WO2019107015A1 - Composition, film, infrared transmission filter, solid state imaging device, and optical sensor - Google Patents

Composition, film, infrared transmission filter, solid state imaging device, and optical sensor Download PDF

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Publication number
WO2019107015A1
WO2019107015A1 PCT/JP2018/039289 JP2018039289W WO2019107015A1 WO 2019107015 A1 WO2019107015 A1 WO 2019107015A1 JP 2018039289 W JP2018039289 W JP 2018039289W WO 2019107015 A1 WO2019107015 A1 WO 2019107015A1
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group
compound
mass
composition
compounds
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PCT/JP2018/039289
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French (fr)
Japanese (ja)
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全弘 森
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富士フイルム株式会社
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Priority to KR1020207010272A priority Critical patent/KR102311924B1/en
Priority to JP2019557069A priority patent/JP6931717B2/en
Publication of WO2019107015A1 publication Critical patent/WO2019107015A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/24—Disazo or polyazo compounds
    • C09B45/28—Disazo or polyazo compounds containing copper
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/24—Disazo or polyazo compounds
    • C09B45/32—Disazo or polyazo compounds containing other metals
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details

Definitions

  • the present invention relates to a composition used for producing an infrared transmission filter and the like, and a film using the composition described above.
  • the present invention also relates to an infrared transmission filter, a solid-state imaging device, and an optical sensor having the above-described film.
  • Yellow pigments are used as color materials for producing basic colors or complementary colors in color filters and the like.
  • an azobarbituric acid nickel complex such as Color Index (C.I.) Pigment Yellow 150 is known.
  • Patent documents 1 to 4 disclose inventions on metal azo pigments containing azobarbituric acid, two or more types of metal ions, and a melamine compound.
  • the metal azo pigments described in Patent Documents 1 to 4 are considered to have improved coloring performance to conventional azobarbituric acid nickel complexes and the like.
  • the inventor of the present invention has intensively studied a film using a metal azo pigment containing azobarbituric acid, two or more metal ions and a melamine compound. When the film is exposed to a high temperature and high humidity environment, It was found that foreign matter defects tend to occur.
  • an object of the present invention is to provide a composition capable of producing a film having high uniformity of film thickness and in which the occurrence of foreign matter defects in a high temperature and high humidity environment is suppressed.
  • Another object of the present invention is to provide a film, an infrared transmission filter, a solid-state image sensor and an optical sensor using this composition.
  • a composition comprising a compound having an ethylenically unsaturated bonding group, and at least one compound selected from a compound having a cyclic ether group, A composition wherein A / B, which is a ratio of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm and the maximum value B of the absorbance in the range of wavelength 1000 to 1300 nm, is 4.5 or more;
  • R 1 and R 2 are each independently OH or NR 5
  • a ⁇ 2> metal azo pigment contains the said anion, the metal ion which contains Zn2 + and Cu2 + at least, and a melamine compound.
  • ⁇ 4> The composition according to ⁇ 2> or ⁇ 3>, wherein the molar ratio of Zn 2+ to Cu 2+ in the metal azo pigment is Zn 2+ : Cu 2+ 199: 1 to 1:15.
  • R 11 to R 13 each independently represent a hydrogen atom or an alkyl group.
  • ⁇ 7> The composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a near infrared absorbing dye.
  • ⁇ 10> The composition according to any one of ⁇ 1> to ⁇ 9>, which is for an infrared transmission filter.
  • the infrared rays permeable filter which has a film
  • the solid-state image sensor which has a film
  • the optical sensor which has a film
  • a composition, a film, an infrared transmission filter, a solid-state imaging device, and an optical sensor capable of manufacturing a film having high uniformity of film thickness and suppressed generation of foreign matter defects under high temperature and high humidity environment are provided. be able to.
  • FIG. 2 is a schematic diagram illustrating an embodiment of a light sensor.
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like can be mentioned.
  • (meth) acrylate represents both or either of acrylate and methacrylate
  • (meth) acryl” represents both or either of acrylic and methacryl
  • Acryloyl represents either or both of acryloyl and methacryloyl.
  • the weight average molecular weight and the number average molecular weight are defined as polystyrene equivalent values in gel permeation chromatography (GPC) measurement.
  • GPC gel permeation chromatography
  • Me in the chemical formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • infrared light refers to light (electromagnetic wave) having a wavelength of 700 to 2500 nm.
  • total solids refers to the total mass of all components of the composition excluding the solvent.
  • the term "process” is included in the term if the intended function of the process is achieved, even if it can not be clearly distinguished from other processes, not only the independent process. .
  • composition of the present invention comprises at least one anion selected from an azo compound represented by the formula (I) described later and an azo compound of a tautomeric structure thereof, two or more metal ions, and a melamine compound.
  • a composition comprising a compound having an ethylenically unsaturated bonding group, and at least one compound selected from a compound having a cyclic ether group, It is characterized in that A / B which is a ratio of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm and the maximum value B of the absorbance in the range of wavelength 1000 to 1300 nm is 4.5 or more.
  • this metal azo pigment contains two or more types of metal ions, but the conformation of the metal azo compound (metal complex) composed of the above-mentioned anion and metal ion differs depending on the type of metal ion.
  • the metal azo pigment mentioned above exists in an unstable state. Therefore, it is presumed that the above-mentioned metal azo pigment tends to promote aggregation under a high temperature and high humidity environment.
  • a coloring material other than the metal azo pigment described above and the metal azo pigment described above and having an absorption maximum in the wavelength range of 400 to 700 nm (hereinafter also referred to as another coloring material) And a composition having an A / B ratio of 4.5 or more, which is a ratio of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm and the maximum value B of the absorbance in the range of the wavelength 1000 to 1300 nm.
  • composition of the present invention is at least one selected from a compound having an ethylenically unsaturated bond group and a compound having a cyclic ether group, in addition to the metal azo pigment described above and other coloring materials.
  • Such variations in film thickness can be effectively suppressed by containing the compound of the type. The reason why such an effect can be obtained is presumed to be as follows.
  • the composition contains a compound having an ethylenically unsaturated bond group
  • the compound having an ethylenically unsaturated bond group interacts with the pigment active surface (in particular, azo moiety) of the metal azo pigment
  • a compound having an unsaturated unsaturated bond group is adsorbed on the surface of the metal azo pigment and can stabilize the metal azo pigment.
  • the composition contains a compound having a cyclic ether group
  • the cyclic ether group coordinates to the metal azo pigment to act as a chelating agent, as a result, the metal azo pigment is stabilized. It is speculated that you can. Therefore, according to the composition of the present invention, it is presumed that the uniformity of the film thickness is improved.
  • the composition of the present invention it is possible to produce a film having high film thickness uniformity and in which the occurrence of foreign matter defects in a high temperature and high humidity environment is suppressed.
  • the film obtained using this composition has a high light shielding property for light of wavelength 400 to 600 nm and is excellent in the transmission of light of wavelength 1000 to 1300 nm, so it can be preferably used for an infrared transmission filter etc. .
  • the metal azo pigment contained in the composition of the present invention is a coloring material having high coloring power. Therefore, by using the composition of the present invention, a film having a high light shielding property in the wavelength range of 400 to 600 nm can be formed even if the film thickness is thin. In addition, since the content of the color material in the composition can be reduced, the degree of freedom in formulation design is also excellent.
  • the composition of the present invention has a ratio A / B of 4.5 or more, which is the ratio of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the range of wavelength 1000 to 1300 nm. It is preferably 5 or more, more preferably 15 or more, and still more preferably 30 or more. If the above absorbance ratio is 4.5 or more, a film having high light shielding properties for light with a wavelength of 400 to 600 nm and excellent transmittance for light with a wavelength of 1000 to 1300 nm can be formed.
  • the absorbance can be measured using a conventionally known spectrophotometer.
  • the measurement conditions of the absorbance are not particularly limited, but under the conditions adjusted so that the minimum value A of the absorbance in the wavelength range of 400 to 600 nm is 0.1 to 3.0, the absorbance in the wavelength range of 1000 to 1300 nm is It is preferable to measure the maximum value B. The measurement error can be further reduced by measuring the absorbance under such conditions.
  • the method of adjusting the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to be 0.1 to 3.0 is not particularly limited. For example, in the case of measuring the absorbance in the state of a solution, there is a method of adjusting the optical path length of the sample cell. Moreover, when measuring a light absorbency in the state of a film
  • A1 / B1 which is a ratio of the minimum value A1 of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B1 of the absorbance in the range of wavelength 800 to 1300 nm is 4.5 or more, 7.5 or more Is more preferably 15 or more, still more preferably 30 or more. According to this aspect, it is possible to shield the light in the wavelength range of 400 to 600 nm, and to form a film capable of transmitting light in excess of the wavelength of 650 nm.
  • A2 / B2 which is a ratio of the minimum value A2 of the absorbance in the wavelength range of 400 to 720 nm to the maximum value B2 of the absorbance in the range of wavelength 900 to 1300 nm is 4.5 or more, 7.5 or more Is more preferably 15 or more, still more preferably 30 or more. According to this aspect, it is possible to block light in the wavelength range of 400 to 750 nm, and to form a film capable of transmitting light in excess of the wavelength of 800 nm.
  • A3 / B3 which is the ratio of the minimum value A3 of the absorbance in the wavelength range of 400 to 830 nm to the maximum value B3 of the absorbance in the range of wavelength 1000 to 1300 nm is 4.5 or more, 7.5 or more Is more preferably 15 or more, still more preferably 30 or more. According to this aspect, it is possible to block light in the wavelength range of 400 to 830 nm to form a film capable of transmitting light in excess of the wavelength of 900 nm.
  • the composition of the present invention has a film thickness after drying of 10.0 ⁇ m or less (preferably 5.0 ⁇ m or less, more preferably 3.0 ⁇ m or less, still more preferably 2.5 ⁇ m or less, and still more preferably Is preferably 2.0 ⁇ m or less, more preferably 1.5 ⁇ m or less, and the lower limit value may be 0.4 ⁇ m or more, 0.5 ⁇ m or more, 0.6 ⁇ m or more Or at least 0.8 ⁇ m, or at least 0.8 ⁇ m, or at least 0.9 ⁇ m.
  • the maximum value of light transmittance in the thickness direction of the film in a wavelength range of 400 to 600 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and a wavelength of 1000 to 1300 nm Minimum 70% of the circumference (preferably 75% or more, more preferably 80% or more) preferably satisfy the spectral characteristics it is.
  • the film thickness after drying using the composition of the present invention is 0.4 to 3.0 ⁇ m (preferably 0.5 to 2.5 ⁇ m, more preferably 0.6 to 2.0 ⁇ m, still more preferably When a film of 0.7 to 1.5 ⁇ m) is produced, the maximum value of light transmittance in the thickness direction of the film in the wavelength range of 400 to 600 nm is 20% or less (preferably 15% or less, more preferably)
  • An embodiment in which the minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more)).
  • the film thickness after drying using the composition of the present invention is 0.6 to 10 ⁇ m (preferably 0.7 to 5.0 ⁇ m, more preferably 0.8 to 3.0 ⁇ m, still more preferably 0.
  • the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10%)
  • the minimum value in the wavelength range of 1000 to 1300 nm of the light transmittance in the film thickness direction is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the composition of the present invention comprises at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof, two or more metal ions, and a melamine compound.
  • Metal azo pigment A is included.
  • R 1 and R 2 are each independently OH or NR 5 R 6
  • R 5 to R 7 are each Independently, it is a hydrogen atom or an alkyl group.
  • the carbon number of the alkyl group represented by R 5 to R 7 is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4.
  • the alkyl group may be linear, branched or cyclic, but linear or branched is preferable, and linear is more preferable.
  • the alkyl group may have a substituent.
  • the below-mentioned substituent T is mentioned, A halogen atom, a hydroxyl group, an alkoxy group, a cyano group, and an amino group are preferable.
  • the melamine compound in the metal azo pigment A is preferably a compound represented by the following formula (II).
  • the metal azo pigment A is preferably a melamine compound (preferably represented by the formula (II), per mole of at least one anion selected from the azo compound represented by the formula (I) and the azo compound of the tautomeric structure thereof. Is preferably contained in an amount of 0.05 to 4 mol, more preferably 0.5 to 2.5 mol, and still more preferably 1.0 to 2.0 mol.
  • the specific surface area of the metal azo pigment A is preferably 20 to 200 m 2 / g.
  • the lower limit is preferably 60 m 2 / g or more, and more preferably 90 m 2 / g or more.
  • the upper limit is preferably 160 m 2 / g or less, more preferably 150 m 2 / g or less.
  • the value of the specific surface area of metal azo pigment A is measured according to DIN 66131: determination of the specific surface area of solids by gas adsorption (measurement of specific surface area of solid by gas adsorption) according to the BET (Brunauer, Emmett and Teller) method. Value.
  • a metal complex is preferably formed of at least one anion selected from an azo compound represented by the formula (I) and an azo compound having a tautomeric structure thereof and a metal ion.
  • a metal complex having a structure represented by the following formula (Ia) can be formed by the above anion and the metal ion Me.
  • the metal ion Me may be bonded via a nitrogen atom in the tautomeric notation of the formula (Ia) to form a complex.
  • Preferred embodiments of the metal azo pigment A include the metal azo pigments of the following embodiments (Az1) to (Az4), and the effects of the present invention are more easily obtained, and the spectral characteristics can be further improved. It is preferable that it is a metal azo pigment of the aspect of (Az1) from the reason.
  • (Az1) At least one anion selected from the azo compound represented by the formula (I) and the azo compound of the tautomeric structure described above, a metal ion containing at least Zn 2+ and Cu 2+ , and a melamine compound
  • the metal azo pigment of the aspect containing.
  • the total content of Zn 2+ and Cu 2+ is preferably 95 to 100 mol%, more preferably 98 to 100 mol%, based on 1 mol of the total metal ions of the metal azo pigment. It is more preferable to contain 99.9 to 100 mol%, and it is particularly preferable to be 100 mol%.
  • the metal azo pigment may further contain a divalent or trivalent metal ion other than Zn 2+ and Cu 2+ (hereinafter also referred to as a metal ion Me1).
  • metal ion Me1 is, Ni 2+, Al 3+, Fe 2+, Fe 3+, Co 2+, Co 3+, La 3+, Ce 3+, Pr 3+, Nd 2+, Nd 3+, Sm 2+, Sm 3+, Eu 2+, Eu 3+ , Gd3 + , Tb3 + , Dy3 + , Ho3 + , Yb2 + , Yb3 + , Er3 + , Tm3 + , Mg2 + , Ca2 + , Sr2 + , Mn2 + , Y3 + , Sc3 + , Ti2 + , Ti3 + , Nb 3+, Mo 2+, Mo 3+, V 2+, V 3+, Zr 2+, Zr 3+, Cd 2+, Cr 3+, Pb 2+, Ba 2+ are mentioned, Al 3+, Fe 2+, Fe 3+, Co 2+, Co 3+, la 3+, Ce 3+, Pr 3+ , Nd 3+,
  • the content of the metal ion Me1 is preferably 5 mol% or less, more preferably 2 mol% or less, and more preferably 0.1 mol% or less based on 1 mol of all metal ions of the metal azo pigment. It is further preferred that
  • the metal ion contains at least one anion selected from the azo compound represented by the formula (I) and the azo compound of the tautomeric structure described above, a metal ion, and a melamine compound, and the metal ion is Ni 2+ , Zn 2+ and at least one further metal ion Me 2, wherein the metal ion Me 2 is La 3+ , Ce 3+ , Pr 3+ , Nd 2+ , Nd 3+ , Sm 2+ , Sm 3+ , Eu 2+ , Eu 3+ , Gd 3+ , Tb3 + , Dy3 + , Ho3 + , Er3 + , Tm3 + , Yb2 + , Yb3 + , Mg2 + , Ca2 + , Sr2 + , Ba2 + , Sc3 + , Y3 + , Ti2 + , Ti3 + , Zr2 + , Zr3 + , V 2+, V 3+, N
  • the metal ion Me2 is La3 + , Ce3 + , Pr3 + , Nd3 + , Sm3 + , Eu3 + , Gd3 + , Tb3 + , Dy3 + , Ho3 + , Er3 + , Tm3 + , Yb3 + , Mg2 + , Ca2 + , Ca2 + , Ca2 + , Ca2 + , It is preferably at least one selected from Sr 2+ , Y 3+ , and Mn 2+ , and at least one selected from La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Tb 3+ , Ho 3+ , and Sr 2+ More preferably, it is a species.
  • the metal azo pigment contains 75 to 99.5 mole% in total of Zn 2+ and Ni 2+ and 0.5 to 25 mole% of metal ion Me preferably it contains, contains 78 to 95 mol% of Zn 2+ and Ni 2+ in total, and more preferably containing metal ions Me2 5 - 22 mol%, 82 to the Zn 2+ and Ni 2+ in total It is more preferable to contain 90 mol% and to contain 10 to 18 mol% of metal ion Me2.
  • the metal ion contains at least one anion selected from the azo compound represented by the formula (I) and the azo compound of the tautomeric structure described above, a metal ion, and a melamine compound, and the metal ion is Ni 2+ , Cu 2+ and at least one further metal ion Me 3 , wherein the metal ion Me 3 is La 3+ , Ce 3+ , Pr 3+ , Nd 2+ , Nd 3+ , Sm 2+ , Sm 3+ , Eu 2+ , Eu 3+ , Gd 3+ , Tb 3 3+ , Dy3 + , Ho3 + , Yb2 + , Yb3 + , Er3 + , Tm3 + , Mg2 + , Ca2 + , Ca2 + , Sr2 + , Mn2 + , Y3 + , Sc3 + , Ti2 + , Ti3 + , Nb3 + , Mo2 + , Mo 3
  • the metal ion Me3 is La3 + , Ce3 + , Pr3 + , Nd3 + , Sm3 + , Eu3 + , Gd3 + , Tb3 + , Dy3 + , Ho3 + , Yb3 + , Er3 + , Tm3 + , Mg2 + , Ca2 + , Ca2 + , Ca2 + , It is preferably at least one selected from Sr 2+ , Mn 2+ , and Y 3+ , and at least one selected from La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Tb 3+ , Ho 3+ , and Sr 2+. More preferably, it is a species.
  • the total content of Cu 2+ and Ni 2+ is 70 to 99.5 mol%, and 0.5 to 30 mol% of the metal ion Me3. preferably contains contains 75-95 mol% of Cu 2+ and Ni 2+ in total, and more preferably containing metal ions Me3 5 - 25 mol%, 80 to the Cu 2+ and Ni 2+ in total It is more preferable to contain 90 mol% and to contain 10 to 20 mol% of metal ion Me3.
  • Metal ions Me4a is, La 3+, Ce 3+, Pr 3+, Nd 3+, Sm 3+, Eu 3+, Gd 3+, Tb 3+, Dy 3+, Ho 3+, Er 3+, at least one selected from the Tm 3+ and Yb 3+ It is preferably at least one selected from La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Tb 3+ and Ho 3+ .
  • the total content of Ni 2+ and metal ion Me 4 a is preferably 95 to 100 mol%, more preferably 98 to 100 mol%, based on 1 mol of the total metal ions of the metal azo pigment.
  • the metal azo pigment may further contain metal ions other than Ni 2+ and metal ion Me4a (hereinafter also referred to as metal ion Me4b).
  • the metal ions Me4b is, Mg 2+, Ca 2+, Sr 2+, Ba 2+, Sc 3+, Y 3+, Ti 2+, Ti 3+, Zr 2+, Zr 3+, V 2+, V 3+, Nb 3+, Cr 3+, Mo 2+ , Mo 3+ , Mn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Cu 2+ , Zn 2+ , Cd 2+ , Al 3+ and Pb 2+ , and Mg 2+ , Ca 2+ , Sr 2+ , Y 3+ , Mn It is preferably at least one selected from 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Cu 2+ , Zn 2+ and Al 3+ , and Sr 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Cu More preferably, it is at least one selected from 2+ , Zn 2
  • the content of the metal ion Me4b is preferably 5 mol% or less, more preferably 2 mol% or less, based on 1 mol of the total metal ions of the metal azo pigment, more preferably 0.1 mol% It is more preferable that it is the following.
  • the metal azo pigment A is a metal azo compound composed of at least one anion selected from the azo compound represented by the above-mentioned formula (I) and an azo compound of the tautomeric structure thereof and a metal ion, and a melamine compound It is preferable that an adduct is formed with (preferably a compound represented by the above formula (II)).
  • An adduct is understood to mean a molecular assembly. The bond between these molecules may be, for example, an intermolecular interaction, a Lewis acid-base interaction, or a coordinate bond or a chain bond.
  • the adduct may also have a structure such as a clathrate in which a guest molecule is incorporated in a lattice constituting a host molecule.
  • the adduct may also have a structure such as a complex intercalated crystal (including an interstitial compound).
  • Composite intercalated crystals are chemically non-stoichiometric crystalline compounds consisting of at least two components.
  • the adduct may be a mixed substituted crystal in which two substances form a co-crystal and the atom of the second component is located at the regular lattice position of the first component.
  • the metal azo pigment used in the present invention may be a physical mixture or a chemically complex compound. Preferably, it is a physical mixture.
  • Preferred examples of the physical mixture in the case of the metal azo pigment of the embodiment of the above (Az1) include the following (Az1-1) and (Az1-2). Also, when the metal azo pigment of the embodiment of (Az1) is a chemical complex compound, it is preferable that Zn 2+ , Cu 2+ and optional additional metal ion Me1 be incorporated in a common crystal lattice.
  • (Az1-1) An adduct of the metal azo compound composed of the anion and Zn 2+ , an adduct 1a of a melamine compound, a metal azo compound composed of the anion and Cu 2+ , and the melamine compound Physical mixture of 1b.
  • Az1-2 A physical mixture containing, in the physical mixture of (Az1-1), an adduct 1c of a metal azo compound composed of the anion and the metal ion Me1 and a melamine compound.
  • Preferred examples of the physical mixture in the case of the metal azo pigment of the aspect of the above (Az2) include the following (Az2-1).
  • the metal azo pigment of the aspect of (Az2) is a chemical complex compound, it is preferable that Ni 2+ , Zn 2+ and metal ion Me2 be incorporated in a common crystal lattice.
  • Preferred examples of the physical mixture in the case of the metal azo pigment of the aspect of the above (Az3) include the following (Az3-1).
  • the metal azo pigment of the aspect of (Az3) is a chemical complex compound, it is preferable that Ni 2+ , Cu 2+ and metal ion Me 3 be incorporated in a common crystal lattice.
  • Preferred examples of the physical mixture in the case of the metal azo pigment of the embodiment (Az4) described above include the following (Az4-1) and (Az4-2). Also, when the metal azo pigment of the embodiment of (Az4) is a chemical complex compound, it is preferable that Ni 2+ , metal ion Me4a and optional additional metal ion Me4b be incorporated in a common crystal lattice.
  • (Az4-1) Addition of a metal azo compound composed of the above anion and Ni 2+ , an adduct 4a of a melamine compound, a metal azo compound composed of the above anion and a metal ion Me4a, and a melamine compound Physical mixture of body 4b.
  • Az4-2) A physical mixture containing, in the physical mixture of (Az4-1), an adduct 4c of a metal azo compound composed of the anion and a metal ion Me4b, and a melamine compound.
  • the metal azo pigment according to the above aspect (Az1) comprises a compound of the formula (III) or a tautomer thereof, a zinc salt and a zinc salt in the presence of a melamine compound (preferably a compound represented by the formula (II)) It can be produced by reacting with a copper salt, and optionally also with the above mentioned salts of the metal ion Me1.
  • the amount of the zinc salt used is preferably 0.05 to 0.995 mol, more preferably 0.05 to 0.5 mol, per 1 mol of the compound of the formula (III) or a tautomer thereof. More preferably, it is 0.1 to 0.3 mol.
  • the amount of the copper salt used is preferably 0.005 to 0.95 mol, preferably 0.49 to 0.95 mol, per 1 mol of the compound of the formula (III) or a tautomer thereof. Is more preferably 0.7 to 0.9 mole.
  • the amount of the metal ion Me1 salt used is preferably 0.05 moles or less, and preferably 0.01 moles or less, per mole of the compound of the formula (III) or a tautomer thereof. Is more preferred.
  • the total amount of a zinc salt, a copper salt, and the metal ion Me1 salt is 1 mol with respect to 1 mol of compounds of Formula (III).
  • the amount of the melamine compound used is preferably 0.05 to 4 moles, and more preferably 0.5 to 2.5 moles relative to 1 mole of the compound of the formula (III) or a tautomer thereof. Is more preferably 1.0 to 2.0 mol.
  • X 1 and X 2 each independently represent a hydrogen atom or an alkali metal ion, and at least one of X 1 and X 2 is an alkali metal ion.
  • R 1 and R 2 are each independently OH or NR 5 R 6 .
  • R 5 to R 7 are each independently a hydrogen atom or an alkyl group.
  • R 1 ⁇ R 7 has the same meaning as R 1 ⁇ R 7 of formula (I), preferred ranges are also the same. Examples of the alkali metal ions which X 1 and X 2 represent, Na + and K + are preferred.
  • the metal azo pigment of the aspect of said (Az1) can also be manufactured by mixing the adduct 1a mentioned above, the adduct 1b, and the adduct 1c.
  • the metal azo pigment of the embodiment (Az2), the metal azo pigment of the embodiment (Az3), and the metal azo pigment of the embodiment (Az4) can also be produced by the same method as described above.
  • paragraphs 0011 to 0062 and 0139 to 0190 of the gazettes and paragraphs 0010 to 0065 and 0142 to 2222 of JP-A-2017-171915 can be referred to, and the contents thereof are incorporated herein.
  • the content of the metal azo pigment A is preferably 1 to 50% by mass in the total solid content of the composition of the present invention.
  • the lower limit is preferably 2% by mass or more, and more preferably 3% by mass or more.
  • the upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less.
  • the composition of the present invention is a coloring material other than the above-mentioned metal azo pigment A, and contains a coloring material having an absorption maximum in the wavelength range of 400 to 700 nm (hereinafter also referred to as another coloring material).
  • Other coloring materials include chromatic coloring agents, black coloring agents and the like.
  • the chromatic coloring agent used as another coloring material is a coloring material other than the above-mentioned metal azo pigment A, and red coloring agent, green coloring agent, blue coloring agent, yellow coloring agent, purple coloring Agents, orange coloring agents and the like.
  • the composition of the present invention preferably contains two or more other colorants.
  • the metal azo pigment A can be further stabilized, and the generation of foreign matter defects in a high temperature and high humidity environment can be more effectively suppressed.
  • the composition of the present invention contains two or more other colorants, it is preferable to contain two or more colorants of different hues.
  • the composition of the present invention preferably contains at least one selected from blue colorants and violet colorants as another colorant.
  • Color materials of these hues have an absorption maximum on the long wavelength side in the visible light wavelength range, and thus have a relatively wide conjugated system. Therefore, these colorants easily interact with the metal azo pigment A, can stabilize the metal azo pigment A more, and can more effectively suppress the generation of foreign matter defects in a high temperature and high humidity environment.
  • a composition having a spectral characteristic of A / B of 4.5 or more, which is the ratio of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm and the maximum value B of the absorbance in the range of wavelength 1000 to 1300 nm It is easy to obtain.
  • a blue coloring agent a triarylmethane compound, a phthalocyanine compound, etc. are mentioned, A phthalocyanine compound is preferable from the reason that the effect of this invention is easy to be acquired more notably.
  • a purple coloring agent a xanthene compound, a triarylmethane compound, an anthraquinone compound, an oxazine compound, a quinacridone compound, a benzimidazolone compound etc. are mentioned, An oxazine compound is preferable from the reason that the effect of this invention is easily obtained notably. .
  • the content of the blue coloring agent in the total amount of the other coloring materials is 5% by mass or more
  • the content is preferably 10% by mass or more, and more preferably 20% by mass or more.
  • the upper limit is not particularly limited. It can be 100% by mass, can be 90% by mass or less, and can be 80% by mass or less.
  • the content of the purple colorant in the total amount of the other coloring materials is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more.
  • the upper limit is not particularly limited. It can be 100% by mass, can be 90% by mass or less, and can be 80% by mass or less.
  • the total content of the blue colorant and the purple colorant in the total amount of the other coloring materials is preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass or more. It is further preferred that The upper limit is not particularly limited. It can be 100% by mass, can be 90% by mass or less, and can be 80% by mass or less.
  • the chromatic coloring agent used as another coloring material may be a pigment, may be a dye, and is preferably a pigment.
  • Pigments include organic pigments and inorganic pigments, with organic pigments being preferred. Examples of the organic pigment include the following.
  • red pigment a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is introduced is bonded to a diketopyrrolopyrrole skeleton is also used. It can.
  • a compound represented by the formula (DPP1) is preferable, and a compound represented by the formula (DPP2) is more preferable.
  • R 11 and R 13 each independently represent a substituent
  • R 12 and R 14 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group
  • n 11 and n 13 are each independently
  • X 12 and X 14 each independently represent an oxygen atom, a sulfur atom or a nitrogen atom
  • m 12 represents 1 and X is an integer of 0 to 4
  • X 14 is a nitrogen atom
  • m14 represents 2
  • Examples of the substituent represented by R 11 and R 13 include the groups listed above as the substituent T, and an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbon
  • the dye is not particularly limited, and known dyes can be used.
  • pyrazole azo type anilino azo type, triarylmethane type, anthraquinone type, anthrapyridone type, benzylidene type, oxonol type, pyrazolotriazole azo type, pyridone azo type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, Dyes of phthalocyanine type, benzopyran type, indigo type, and pyromethene type can be used.
  • dye multimer can also be used as another coloring material.
  • the dye multimer is preferably a dye used by being dissolved in a solvent, but the dye multimer may form particles, and when the dye multimer is particles, it is usually dispersed in a solvent. Used.
  • the dye multimer in a particulate state can be obtained, for example, by emulsion polymerization, and the compounds and production methods described in JP-A-2015-214682 can be mentioned as specific examples.
  • compounds described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742 and the like can also be used.
  • Black coloring agent examples of black colorants used as other colorants include organic black colorants such as bisbenzofuranone compounds, azomethine compounds, perylene compounds and azo compounds.
  • the black colorant is preferably a bisbenzofuranone compound or a perylene compound.
  • the bisbenzofuranone compounds include the compounds described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, etc.
  • Irgaphor Black manufactured by BASF Corp. It is available.
  • perylene compounds C.I. I. Pigment Black 31, 32 and the like.
  • Examples of the azomethine compound include compounds described in JP-A-1-170601, JP-A-2-32664 and the like, and can be obtained, for example, as "Chromofine Black A1103" manufactured by Dainichiseika.
  • the bisbenzofuranone compound is preferably a compound represented by the following formula and a mixture thereof.
  • the substituent represented by R 1 to R 4 is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, -OR 301 , -COR 302 , -COOR 303 , -OCOR 304 , -NR 305 R 306 , -NHCOR 307 , -CONR 308 R 309 , -NHCONR 310 R 311 , -NHCOOR 312 , -SR 313 , -SO 2 R 314 , -SO 2 OR 315 , -NHSO 2 R 316 or -SO 2 NR 317 R 318 is represented, and R 301 to R 318 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group
  • a black color is formed by the combination of the metal azo pigment A and another coloring material.
  • Preferred combinations of the metal azo pigment A and the other colorants include the following (C1) to (C6).
  • C1 a composition having the above-described spectral characteristics of (1) is easily obtained.
  • C2 a composition having the above-mentioned spectral characteristics of (2).
  • (C1) An embodiment containing metal azo pigment A and a purple colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
  • (C2) An embodiment containing metal azo pigment A, a red colorant, a blue colorant and a purple colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
  • (C3) An embodiment containing metal azo pigment A, a red colorant and a blue colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
  • (C4) An embodiment containing metal azo pigment A, a blue colorant and a purple colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
  • (C5) An embodiment containing metal azo pigment A, a purple colorant and a black colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
  • (C6) An embodiment containing metal azo pigment A, a blue colorant and a black colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
  • the metal azo pigment A is preferably the metal azo pigment of the embodiment (Az1) described above.
  • a purple coloring agent C.I. I. Pigment Violet 23 is preferred.
  • yellow colorants C.I. I. Pigment Yellow 139, 150, 185 are preferable, and C.I. I. Pigment Yellow 139, 150 is more preferable, C.I. I. Pigment Yellow 139 is more preferable.
  • a red coloring agent Pigment Red 122, 177, 224, 254, 264 is preferable, Pigment Red 122, 177, 254, 264 is more preferable, and Pigment Red 254 is still more preferable.
  • a blue coloring agent C.I. I. Pigment Blue 15: 6, 16 is preferred.
  • a black coloring agent Irgaphor Black (BASF), C.I. I. Pigment Black 31, 32 is preferred.
  • the purple colorant is preferably contained in an amount of 50 to 500 parts by mass, more preferably 75 to 400 parts by mass, with respect to 100 parts by mass of the metal azo pigment A, and more preferably 100 to 350 More preferably, it is contained in parts by mass.
  • the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
  • the red colorant is preferably contained in an amount of 100 to 800 parts by mass, more preferably 200 to 700 parts by mass, with respect to 100 parts by mass of the metal azo pigment A.
  • the blue colorant is preferably contained in an amount of 100 to 1000 parts by mass, and more preferably 200 to 800 parts by mass. Further, it is preferable to contain 50 to 500 parts by mass of a purple colorant, and it is more preferable to contain 70 to 400 parts by mass.
  • the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
  • the red colorant is preferably contained in an amount of 100 to 800 parts by mass, more preferably 200 to 700 parts by mass, with respect to 100 parts by mass of the metal azo pigment A.
  • the blue colorant is preferably contained in an amount of 100 to 1000 parts by mass, and more preferably 200 to 800 parts by mass.
  • the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
  • the blue colorant is preferably contained in an amount of 100 to 1000 parts by mass, more preferably 200 to 800 parts by mass, with respect to 100 parts by mass of the metal azo pigment A. Further, it is preferable to contain 50 to 500 parts by mass of a purple colorant, and it is more preferable to contain 75 to 400 parts by mass. In the case of further including a yellow colorant as another colorant, the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
  • the purple colorant is preferably contained in an amount of 50 to 500 parts by mass, and more preferably 75 to 400 parts by mass with respect to 100 parts by mass of the metal azo pigment A.
  • the black colorant is preferably contained in an amount of 50 to 1000 parts by mass, and more preferably 100 to 800 parts by mass.
  • the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
  • the blue colorant is preferably contained in an amount of 100 to 1000 parts by mass, more preferably 200 to 800 parts by mass, with respect to 100 parts by mass of the metal azo pigment A.
  • the black colorant is preferably contained in an amount of 50 to 1000 parts by mass, and more preferably 100 to 800 parts by mass.
  • the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
  • the content of the other coloring material is preferably 10 to 80% by mass in the total solid content of the composition of the present invention.
  • the lower limit is preferably 20% by mass or more, and more preferably 30% by mass or more.
  • the upper limit is preferably 70% by mass or less and more preferably 60% by mass or less.
  • the content of the other coloring material is preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the metal azo pigment A.
  • the lower limit is preferably 70 parts by mass or more, and more preferably 100 parts by mass or more.
  • the upper limit is preferably 500 parts by mass or less.
  • the total content of the metal azo pigment A and the other colorant is preferably 10 to 70% by mass in the total solid content of the composition of the present invention.
  • the lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. When the composition of the present invention contains two or more other colorants, the total amount thereof is preferably in the above range.
  • the composition of the present invention can contain a near infrared absorbing dye.
  • the near infrared absorbing dye has a role of limiting the transmitted light (infrared) to a longer wavelength side.
  • a composition having the above-mentioned spectral characteristics of (3) can be easily obtained.
  • the metal azo pigment A and the other coloring material are contained in the combination of the above (C2) to (C6), the composition having the spectral characteristics of the above (3) by further containing a near infrared absorbing dye Is easy to obtain.
  • the composition of the present invention contains a near infrared absorbing dye, the occurrence of foreign matter defects in a high temperature and high humidity environment can be more effectively suppressed.
  • examples of the near infrared absorbing dye include compounds having an absorption maximum in the near infrared region (preferably, wavelength 700 to 1100 nm, more preferably wavelength 700 to 1000 nm, and still more preferably wavelength 800 to 900 nm).
  • the near infrared absorbing dye may be a pigment or a dye.
  • the near infrared absorbing dye a compound having a ⁇ conjugated plane including an aromatic ring of a single ring or a condensed ring can be preferably used. It is preferable that the number of atoms other than hydrogen which comprises the pi conjugation plane which a near-infrared absorption pigment has is 14 or more, It is more preferable that it is 20 or more, It is still more preferable that it is 25 or more, 30 It is particularly preferable to be the above.
  • the upper limit is, for example, preferably 80 or less, and more preferably 50 or less.
  • the above-mentioned aromatic ring includes benzene ring, naphthalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, quaterylene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, Triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzoimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzooxazole ring, imidazoline ring, pyrazine And rings, quinoxaline rings, pyrimidine rings, quin
  • Near infrared absorbing dyes include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diimonium compounds, dithiol compounds, triarylmethane compounds, piromethene compounds, azomethine
  • At least one selected from a compound, an anthraquinone compound, an indigo compound and a dibenzofuranone compound is preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squalilium compound, a phthalocyanine compound, a naphthalocyanine compound, a croconium compound and an indigo compound is more preferable
  • it is selected from pyrrolopyrrole compounds, cyanine compounds and squarylium compounds At least one more preferably, pyrrolo-
  • the indigo compound is preferably an indigo boron complex compound.
  • examples of indigo compounds include the compounds described in Japanese Patent No. 5642013, the contents of which are incorporated herein.
  • the near-infrared absorbing dye compounds described in JP-A-2016-146619, compounds described in JP-A-2016-79331, compounds described in JP-A-2017-82029, JP-A-2015 It is also possible to use the compounds described in -40176 and the compounds described in Japanese Patent No. 5539676.
  • the compound of a following structure can also be used for a near-infrared absorption pigment
  • dye can also be used for a near-infrared absorption pigment
  • R 1a and R 1b include an aryl group having an alkoxy group as a substituent, an aryl group having a hydroxyl group as a substituent, an aryl group having an acyloxy group as a substituent and the like.
  • R 2 and R 3 each independently represent a hydrogen atom or a substituent.
  • the substituent include the above-mentioned substituent T.
  • At least one of R 2 and R 3 is preferably an electron-withdrawing group.
  • a substituent having a positive Hammett's substituent constant ⁇ value acts as an electron-withdrawing group.
  • the substituent constants determined by the Hammett rule include ⁇ p values and ⁇ m values. These values can be found in many general books.
  • a substituent having a Hammett's substituent constant ⁇ value of 0.2 or more can be exemplified as the electron-withdrawing group.
  • the ⁇ value is preferably 0.25 or more, more preferably 0.3 or more, and still more preferably 0.35 or more.
  • the upper limit is not particularly limited, but is preferably 0.80 or less.
  • Me represents a methyl group
  • Ph represents a phenyl group.
  • the Hammett's substituent constant ⁇ value can be referred to, for example, paragraph Nos. 0017 to 0018 of JP-A-2011-68731, the contents of which are incorporated herein.
  • R 2 preferably represents an electron-withdrawing group (preferably a cyano group) and R 3 preferably represents a heteroaryl group.
  • the heteroaryl group is preferably a 5- or 6-membered ring.
  • the heteroaryl group is preferably a single ring or a fused ring, preferably a single ring or a fused ring having 2 to 8 condensations, and more preferably a single ring or a fused ring having 2 to 4 condensations.
  • the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2.
  • a hetero atom a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, for example.
  • the heteroaryl group preferably has one or more nitrogen atoms.
  • Two R 2 s in Formula (PP) may be identical to or different from each other.
  • two R 3 's in Formula (PP) may be the same or different.
  • each of A 1 and A 2 independently represents an aryl group, a heteroaryl group or a group represented by formula (A-1);
  • Z 1 represents a nonmetal atomic group forming a nitrogen-containing heterocyclic ring
  • R 2 represents an alkyl group, an alkenyl group or an aralkyl group
  • d represents 0 or 1.
  • the wavy line represents a connecting hand.
  • near infrared absorbing dyes can also be used.
  • SDO-C33 Arimoto Chemical Industries Co., Ltd.
  • EEX Color IR-14 EEX Color IR-10A
  • EEX Color TX-EX-801B EEX Color TX-EX-805K
  • Shigenox NIA-8041 Shigenox NIA-8042
  • Shigenox NIA-814 Shigenox NIA-820
  • Shigenox NIA-839 Hakoko Chemical Co., Ltd.
  • Epolite V-63 Epolight 3801, Epolight 3036 (EPOLIN)
  • PRO-JET 825 LDI Film manufactured by KK
  • NK-3027 NK-5060
  • Hayashibara YKR-3070
  • FDN-003 Manufactured by Yamada Chemical Industries, Ltd.
  • the content of the near infrared absorbing dye is preferably 1 to 30% by mass in the total solid content of the composition of the present invention. 20 mass% or less is preferable, and, as for the upper limit, 10 mass% or less is more preferable. 3 mass% or more is preferable, and, as for a lower limit, 5 mass% or more is more preferable. Further, the content of the near-infrared absorbing dye is preferably 5 to 50 parts by mass with respect to 100 parts by mass in total of the metal azo pigment A and the other coloring material. 45 mass% or less is preferable, and, as for the upper limit, 40 mass% or less is more preferable.
  • the molecular weight of the polymerizable monomer is preferably less than 3000.
  • the upper limit is more preferably 2000 or less, still more preferably 1500 or less.
  • the lower limit is preferably 100 or more, more preferably 150 or more, and still more preferably 250 or more.
  • the polymerizable monomer is preferably a compound containing 3 or more ethylenic unsaturated bonding groups, more preferably a compound containing 3 to 15 ethylenic unsaturated bonding groups, and an ethylenic unsaturated bonding group. More preferably, it is a compound containing 3 to 6.
  • the polymerizable monomer is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
  • Specific examples of the polymerizable monomer are described in paragraph Nos. 0095 to 0108 of JP2009-288705A, paragraph 0227 of JP2013-29760A, and paragraph 0254-0257 of JP2008-292970A. Compounds are included, the contents of which are incorporated herein.
  • the lower limit is preferably 60 or more, and more preferably 70 or more.
  • dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd.)
  • Dipentaerythritol penta (meth) acrylate (Commercial product: KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) acrylate
  • KAYARAD DPHA Nippon Kayaku ( Ltd.
  • trimethylolpropane tri (meth) acrylate trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) acrylate
  • a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate.
  • Commercially available products of trifunctional (meth) acrylate compounds include Alonics M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305.
  • M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And TMPEOTA (manufactured by Daicel Ornex Co., Ltd.).
  • a polymerizable monomer having an acid group As the polymerizable monomer, the composition layer in the unexposed area is easily removed during development, and the generation of development residues can be effectively suppressed.
  • an acid group a carboxyl group, a sulfo group, a phosphoric acid group etc. are mentioned, A carboxyl group is preferable.
  • Commercially available products of the polymerizable monomer having an acid group include ALONIX M-510, M-520, ALONIX TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.
  • n 0-14 and m is 1-8.
  • a plurality of R and T in one molecule may be identical to or different from each other.
  • Specific examples of the polymerizable compounds represented by the above formulas (MO-1) to (MO-6) include the compounds described in paragraphs 0248 to 0251 of JP-A-2007-269779.
  • the compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, and dipentaerythritol. Mention ⁇ -caprolactone modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as tripentaerythritol, glycerol, diglycerol, trimethylolmelamine and (meth) acrylic acid and ⁇ -caprolactone; Can.
  • the compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • “*” represents a bond.
  • R 1 represents a hydrogen atom or a methyl group
  • “*” represents a bond
  • each E is independently-((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH (CH 3 ) O)- And y each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom or a carboxyl group.
  • the total of (meth) acryloyl groups is three or four, m each independently represents an integer of 0 to 10, and the sum of each m is an integer of 0 to 40.
  • the total of (meth) acryloyl groups is five or six, n independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
  • a compound having an alkyleneoxy group can also be used as the polymerizable monomer.
  • the polymerizable monomer having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and having 4 to 20 ethyleneoxy groups. More preferably, it is a 3- to 6-functional (meth) acrylate compound.
  • SR-494 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, a trifunctional (meth) having three isobutylene oxy groups
  • examples thereof include KAYARAD TPA-330 which is an acrylate.
  • the compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-260909 and JP-A-1-105238 can also be mentioned, and use of these compounds is also preferable.
  • the weight average molecular weight of the polymerizable polymer is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 7,000 or more, and particularly preferably 10,000 or more.
  • the weight average molecular weight of the polymerizable polymer is preferably 50,000 or less, more preferably 40,000 or less, and still more preferably 30,000 or less.
  • the lower limit is preferably 150 or more, and more preferably 200 or more.
  • the upper limit is preferably 4500 or less, more preferably 4000 or less.
  • the polymerizable polymer preferably contains a repeating unit having an ethylenically unsaturated bonding group in a side chain, and more preferably contains a repeating unit represented by the following formula (A-1-1).
  • the polymerizable polymer preferably contains 10 mol% or more, more preferably 10 to 80 mol%, of repeating units having an ethylenically unsaturated bond group in all repeating units of the polymerizable polymer. It is more preferable to contain 70 mol%.
  • X 1 represents a main chain of a repeating unit
  • L 1 represents a single bond or a divalent linking group
  • Y 1 represents an ethylenically unsaturated bonding group.
  • examples of the ethylenically unsaturated bonding group represented by Y 1 include a vinyl group, a (meth) allyl group, a (meth) acryloyl group and the like, and a (meth) acryloyl group is preferable.
  • An acryloyl group is more preferred.
  • the polymerizable polymer preferably further contains a repeating unit having a graft chain.
  • the polymerizable polymer preferably contains a repeating unit having a graft chain in an amount of 1.0 to 60% by mole, and more preferably 1.5 to 50% by mole, based on all repeating units of the polymerizable polymer.
  • a polymerizable polymer containing a repeating unit having a graft chain is preferably used as a dispersant.
  • a graft chain means a polymer chain which branches and extends from the main chain of a repeating unit.
  • the length of the graft chain is not particularly limited, but the longer the graft chain, the higher the steric repulsion effect, and the dispersibility of the metal azo pigment A or the like can be enhanced.
  • the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and 60 to 60 atoms excluding hydrogen atoms. More preferably, it is 500.
  • the graft chains possessed by the polymerizable polymer preferably include at least one structure selected from polyester structure, polyether structure, poly (meth) acrylic structure, polyurethane structure, polyurea structure and polyamide structure, and polyester structure, polyether It is more preferable to include at least one structure selected from a structure and a poly (meth) acrylic structure, and it is further preferable to include a polyester structure.
  • the polyester structure include structures represented by the following Formula (G-1), Formula (G-4) or Formula (G-5).
  • the polyether structure a structure represented by the following formula (G-2) can be mentioned.
  • examples of the poly (meth) acrylic structure include a structure represented by the following formula (G-3).
  • R G1 and R G2 each represent an alkylene group.
  • the alkylene group represented by R G1 and R G2 is not particularly limited, but a linear or branched alkylene group having 1 to 20 carbon atoms is preferable, and a linear or branched alkylene having 2 to 16 carbon atoms is preferable. A group is more preferable, and a linear or branched alkylene group having 3 to 12 carbon atoms is further preferable.
  • R G3 represents a hydrogen atom or a methyl group.
  • Q G1 represents -O- or -NH-
  • L G1 represents a single bond or a divalent linking group.
  • Examples of the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), and an oxyalkylene carbonyl group (preferably having 1 carbon atom).
  • an alkylene group preferably an alkylene group having 1 to 12 carbon atoms
  • an alkyleneoxy group preferably an alkyleneoxy group having 1 to 12 carbon atoms
  • an oxyalkylene carbonyl group preferably having 1 carbon atom.
  • arylene group preferably arylene group having 6 to 20 carbon atoms
  • R G4 represents a hydrogen atom or a substituent.
  • substituents examples include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like.
  • the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
  • substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like.
  • a group having a steric repulsion effect is preferable, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferable, from the viewpoint of improving the dispersibility of the coloring material and the like.
  • the alkyl group and the alkoxy group may be linear, branched or cyclic, and linear or branched is preferable.
  • R G1 and R G2 each independently represent an alkylene group
  • R G3 represents a hydrogen atom or a methyl group
  • Q G1 represents -O- or -NH-
  • L G1 represents a single bond or 2
  • R G4 represents a hydrogen atom or a substituent
  • W 100 represents a hydrogen atom or a substituent.
  • n1 to n5 each independently represent an integer of 2 or more.
  • Q G1 , L G1 , Formula (G1) ⁇ (G-5 ) has the same meaning as R G1 ⁇ R G4, Q G1 , L G1 described in, the preferred range is also the same is there.
  • W 100 is preferably a substituent.
  • the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like.
  • a group having a steric repulsion effect is preferable, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferable, from the viewpoint of improving the dispersibility of the coloring material and the like.
  • the alkyl group and the alkoxy group may be linear, branched or cyclic, and linear or branched is preferable.
  • n1 to n5 each independently represent an integer of 2 or more, more preferably 3 or more, and still more preferably 5 or more.
  • the upper limit is preferably 100 or less, more preferably 80 or less, and still more preferably 60 or less.
  • repeating unit having a graft chain examples include repeating units represented by the following formula (A-1-2).
  • X 2 represents a main chain of a repeating unit
  • L 2 represents a single bond or a divalent linking group
  • W 1 represents a graft chain.
  • Examples of the main chain of the repeating unit represented by X 2 in Formula (A-1-2) include the structures described in X 1 of Formula (A-1-1), and preferred ranges are also the same.
  • the divalent linking group represented by L 2 in Formula (A-1-2) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an arylene group (preferably an arylene group having 6 to 20 carbon atoms) And -NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, OCO-, -S- and a group formed by combining two or more of these.
  • Examples of the graft chain represented by W 1 in formula (A-1-2) include the graft chains described above.
  • the weight average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10000, and 1000 to 7500. It is further preferred that In the present invention, the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for polymerization of the same repeating unit.
  • a repeating unit having a graft chain can be formed by polymerizing a macromonomer.
  • the macromonomer means a polymer compound in which a polymerizable group is introduced at the polymer end.
  • the weight average molecular weight of the macromonomer corresponds to the weight average molecular weight of the repeating unit having a graft chain.
  • the polymerizable polymer further contains a repeating unit having an acid group.
  • the dispersibility of the metal azo pigment A and the like can be further improved.
  • developability can also be improved.
  • the acid group include a carboxyl group, a sulfo group and a phosphate group.
  • repeating unit having an acid group examples include repeating units represented by the following formula (A-1-3).
  • X 3 represents a main chain of a repeating unit
  • L 3 represents a single bond or a divalent linking group
  • a 1 represents an acid group.
  • Examples of the main chain of the repeating unit represented by X 3 in formula (A-1-3) include the structures described in X 1 of formula (A-1-1), and the preferred range is also the same.
  • the divalent linking group represented by L 3 in formula (A-1-3) an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) or an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms) Group), an oxyalkylene carbonyl group (preferably an oxyalkylene carbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2- , And -CO-, -O-, -COO-, OCO-, -S- and a group formed by combining two or more of these.
  • the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylene carbonyl group may be linear, branched or cyclic, and is preferably linear or branched. Further, the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylene carbonyl group may have a substituent or may be unsubstituted. As a substituent, a hydroxy group etc. are mentioned.
  • Examples of the acid group represented by A 1 in formula (A-1-3) include a carboxyl group, a sulfo group and a phosphoric acid group.
  • the acid value of the polymerizable polymer is preferably 20 to 150 mg KOH / g.
  • the upper limit is more preferably 100 mg KOH / g or less.
  • the lower limit is preferably 30 mg KOH / g or more, and more preferably 35 mg KOH / g or more. If the acid value of the polymerizable polymer is in the above range, particularly excellent dispersibility is easily obtained. Furthermore, excellent developability is easily obtained.
  • polymerizable polymer may also be referred to as a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) as another repeating unit (hereinafter, these compounds are referred to as “ether dimer” And B.) can be included.
  • ED1 a compound represented by the following formula
  • ED2 a compound represented by the following formula
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the description in JP-A-2010-168539 can be referred to.
  • ether dimer for example, paragraph “0317” of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification.
  • the ether dimer may be only one type, or two or more types.
  • Compound having a cyclic ether group As a compound which has a cyclic ether group used in this invention, the compound which has 2 or more of cyclic ether groups in 1 molecule is mentioned.
  • the number of cyclic ether groups contained in the compound having a cyclic ether group is preferably 100 or less, more preferably 10 or less, and still more preferably 5 or less.
  • the cyclic ether group may, for example, be an epoxy group or an oxetanyl group, and is preferably an epoxy group. That is, the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter, also referred to as an epoxy compound).
  • the epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 1000) or a macromolecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more).
  • the molecular weight (weight average molecular weight in the case of a polymer) of the epoxy compound is preferably 200 to 100,000, and more preferably 500 to 50,000. 3000 or less is preferable, as for the upper limit of molecular weight (in the case of a polymer, weight average molecular weight), 2000 or less is more preferable, and 1500 or less is still more preferable.
  • the epoxy compounds are compounds described in paragraphs 0034 to 0036 in JP 2013-011869A, paragraphs 0147 to 0156 in JP 2014-043556 A, and paragraphs 0085 to 0092 in JP 2014-089408 A. Can also be used. The contents of these are incorporated herein.
  • epoxy compound for example, as bisphenol A type epoxy resin, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (all manufactured by DIC Corporation) and the like, and as a bisphenol F-type epoxy resin, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (all, manufactured by Mitsubishi Chemical Corporation), EPICLON 830, EPICLON 835 (above, DIC Corporation), LCE-21, RE-602S (above, Japan Drugs, etc., and as phenol novolac type epoxy resins, jER152, jER154, jER157S70, jER157S65 (
  • EPICLON N-695 (all, DIC Corporation), EOCN-1020 (Nippon Kayaku Co., Ltd.), etc.
  • ADEKA RESIN EP-4080S As aliphatic epoxy resins, ADEKA RESIN EP-4080S, EP 4085S, EP-4088S (above, made by ADEKA Co., Ltd.), Celoxide 2021 P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE 3150, EPOLEAD PB 3600, same PB 4700 (above, made by Daicel Co., Ltd.), Denacol EX- 212L, EX-214L, EX-216L, EX-321L, EX-850L (all manufactured by Nagase ChemteX Co., Ltd.) and the like.
  • ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.), jER1031S (manufactured by Mitsubishi Chemical Corporation), merproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G And -1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group-containing polymer) and the like.
  • the content of the compound having an ethylenically unsaturated bonding group is preferably 1 to 50% by mass in the total solid content of the composition.
  • the lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more.
  • the upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less.
  • the content of the compound having an ethylenically unsaturated bond group is preferably 30 parts by mass or more, and more preferably 40 parts by mass or more with respect to 100 parts by mass of the metal azo pigment A described above. More preferably, it is 50 parts by mass or more.
  • the upper limit is preferably 750 parts by mass or less, more preferably 700 parts by mass or less, still more preferably 650 parts by mass or less, and particularly preferably 600 parts by mass or less. If the ratio of the metal azo pigment A and the compound having an ethylenic unsaturated bond group is in the above range, the effects of the present invention can be obtained more remarkably.
  • the content of the polymerizable polymer is 5 to 500 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Is preferred.
  • the lower limit is preferably 8 parts by mass or more, and more preferably 10 parts by mass or more.
  • the upper limit is preferably 450 parts by mass or less, and more preferably 400 parts by mass or less.
  • the content of the compound having a cyclic ether group is preferably 1 to 50% by mass in the total solid content of the composition.
  • the lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more.
  • the upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less.
  • the content of the compound having a cyclic ether group is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and 50 parts by mass with respect to 100 parts by mass of the metal azo pigment A described above. It is more preferable that it is more than.
  • the total content of the compound having an ethylenically unsaturated bond group and the compound having a cyclic ether group is preferably 30 parts by mass or more with respect to 100 parts by mass of the metal azo pigment A described above, It is more preferable that it is a mass part or more, and it is still more preferable that it is 50 mass parts or more.
  • the upper limit is preferably 750 parts by mass or less, more preferably 700 parts by mass or less, still more preferably 650 parts by mass or less, and particularly preferably 600 parts by mass or less. If the content is in the above range, the effects of the present invention can be more remarkably obtained.
  • the cyclic ether group is used per 100 parts by mass of the compound having an ethylenically unsaturated bond group. It is preferable to contain 1 to 50 parts by mass of the compound contained therein.
  • the upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.
  • the lower limit is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and still more preferably 10 parts by mass or more.
  • the composition of the present invention can further contain a resin other than the above-described curable compound (hereinafter, also referred to as another resin).
  • a resin other than the above-described curable compound hereinafter, also referred to as another resin.
  • Other resins are blended, for example, in applications in which particles such as pigments are dispersed in a composition and applications in binders.
  • grains, such as a pigment is also called dispersing agent.
  • such application of the resin is an example, and the resin can also be used for purposes other than such application.
  • the weight average molecular weight (Mw) of the other resin is preferably 2,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, and more preferably 500000 or less. 3000 or more are preferable and, as for a lower limit, 5000 or more are more preferable.
  • (meth) acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide Imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, etc. may be mentioned.
  • One of these resins may be used alone, or two or more thereof may be mixed and used.
  • resin a resin described in an example of International Publication WO 2016/088645, a resin described in JP-A-2017-57265, a resin described in JP-A-2017-32685, JP-A-2017 It is also possible to use the resin described in JP-A-075248 and the resin described in JP-A-2017-066240. Further, a resin having a fluorene skeleton can also be used. As resin which has fluorene frame, resin of the following structure is mentioned.
  • A represents the residue of a carboxylic acid dianhydride selected from pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride and diphenyl ether tetracarboxylic acid dianhydride
  • M is a phenyl or benzyl group.
  • the resin having a fluorene skeleton can be referred to the description of US Patent Application Publication No. 2017/0102610, the contents of which are incorporated herein.
  • resins may have an acid group.
  • an acid group a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group etc. are mentioned, for example, A carboxyl group is preferable.
  • These acid groups may be of only one type, or of two or more types.
  • the resin having an acid group can also be used as an alkali-soluble resin.
  • a polymer having a carboxyl group in a side chain is preferable.
  • alkali-soluble polymers such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, novolac resin, etc.
  • a phenolic resin, an acidic cellulose derivative having a carboxyl group in a side chain, and a resin obtained by adding an acid anhydride to a polymer having a hydroxy group are mentioned.
  • copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are suitable as the alkali-soluble resin.
  • Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like.
  • alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, etc.
  • Resin having an acid group is benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth)
  • a multicomponent copolymer consisting of acrylate / (meth) acrylic acid / other monomers can be preferably used. Further, those obtained by copolymerizing 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A No.
  • the resin having an acid group is a polymer containing a repeating unit derived from a monomer component including the above-mentioned ether dimer.
  • the resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 has a hydrogen atom or 1 to 20 carbon atoms which may contain a benzene ring.
  • Represents an alkyl group of n represents an integer of 1 to 15.
  • the resin having an acid group is described in JP-A-2012-208494, paragraphs 0558 to 0571 (corresponding US patent application publication No. 2012/0235099, paragraphs 0685 to 0700), JP-A-2012-198408. No. 0076-0099 can be referred to, and the contents thereof are incorporated herein. Moreover, the resin which has an acidic radical can also use a commercial item.
  • the acid value of the resin having an acid group is preferably 30 to 200 mg KOH / g.
  • the lower limit is preferably 50 mg KOH / g or more, and more preferably 70 mg KOH / g or more.
  • 150 mgKOH / g or less is preferable and 120 mgKOH / g or less of an upper limit is more preferable.
  • resin which has an acidic radical resin of the following structure, etc. are mentioned, for example.
  • the composition of the present invention can also contain a resin as a dispersant.
  • the dispersant includes an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol% Resins consisting only of groups are more preferred.
  • the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • the resin used as the dispersant is preferably a resin containing a repeating unit having a graft chain in its side chain (hereinafter, also referred to as a graft resin).
  • a graft chain means a polymer chain which branches and extends from the main chain of the repeating unit.
  • the length of the graft chain is not particularly limited, but as the graft chain becomes longer, the steric repulsion effect becomes higher, and the dispersibility of the pigment etc. can be enhanced.
  • the number of atoms excluding hydrogen atoms is preferably 40 to 10,000, and the number of atoms excluding hydrogen atoms is more preferably 50 to 2,000, and the number of atoms excluding hydrogen atoms is 60 to 60 More preferably, it is 500.
  • the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
  • substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like.
  • a group having a steric repulsion effect is preferable, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferable.
  • the alkyl group and the alkoxy group may be linear, branched or cyclic, and linear or branched is preferable.
  • graft resin resin of the following structure etc. are mentioned, for example. Further, the details of the graft resin can be referred to the description of Paragraph Nos. 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
  • Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series (eg, Disperbyk-111 etc.) manufactured by BYK Chemie, the Solsperse series manufactured by Nippon Lubrizol Corporation (eg, And so forth).
  • pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used.
  • resin which has an acidic radical mentioned above, a polymeric polymer, etc. can also be used as a dispersing agent.
  • the resin demonstrated as the said dispersing agent can also be used for uses other than a dispersing agent. For example, it can also be used as a binder.
  • the content of the other resin is preferably 1 to 50% by mass in the total solid content of the composition of the present invention.
  • the upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less.
  • the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more.
  • the total amount of those becomes the said range.
  • the composition of the present invention can also be substantially free of other resins.
  • the composition of the present invention can contain a solvent.
  • the solvent is preferably an organic solvent.
  • the solvent is not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied.
  • organic solvent examples include, for example, the following organic solvents.
  • esters for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkyl oxyacetate alkylate (Eg, methyl alkyl oxyacetate, ethyl alkyl oxyacetate, butyl alkyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate,
  • 2-alkyloxypropionic acid alkyl esters eg methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate etc.
  • ethers for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like can be mentioned.
  • ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
  • Preferred examples of the aromatic hydrocarbons include toluene and xylene.
  • 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable from the viewpoint of solubility improvement.
  • An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • a solvent having a low metal content as the solvent.
  • the metal content in the solvent is preferably, for example, 10 parts by weight (pps) or less.
  • a solvent having a metal content of mass ppt (parts per trillion) level may be used, and such a high purity solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Journal, November 13, 2015) Day).
  • As a method of removing impurities such as metal from the solvent for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter can be mentioned.
  • a filter hole diameter of a filter used for filtration 10 micrometers or less are preferred, 5 micrometers or less are more preferred, and 3 micrometers or less are still more preferred.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only one type of isomer may be contained, or two or more types may be contained.
  • the content rate of a peroxide is 0.8 mmol / L or less, and it is more preferable that the organic solvent used by this invention does not contain a peroxide substantially.
  • the content of the solvent is preferably such that the solid content concentration (total solid content) of the composition is 5 to 50% by mass.
  • the upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less.
  • the lower limit is preferably 8% by mass or more, and more preferably 10% by mass or more.
  • the composition of this invention does not contain an environmental control substance substantially from a viewpoint of an environmental regulation.
  • not containing substantially the environmental regulation substance means that the content of the environmental regulation substance in the composition is 50 mass ppm or less, and preferably 30 mass ppm or less, It is more preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less.
  • the environmental control substance include benzene; alkyl benzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene and the like.
  • distillation methods may be carried out at the stage of the raw material, the stage of the product obtained by reacting the raw material (for example, the resin solution after polymerization or the polyfunctional monomer solution), or the stage of the composition prepared by mixing these compounds. Stages are also possible.
  • the composition of the present invention can further contain a photopolymerization initiator.
  • a photopolymerization initiator in the case where the composition of the present invention contains a compound having an ethylenically unsaturated bonding group, it is preferable to include a photopolymerization initiator.
  • a photoinitiator There is no restriction
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • a halogenated hydrocarbon derivative for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.
  • an acylphosphine compound for example, a hexaarylbiimidazole, an oxime compound, an organic peroxide, Thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxy ketone compounds, ⁇ -amino ketone compounds and the like
  • an organic peroxide for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.
  • an acylphosphine compound for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.
  • an acylphosphine compound for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.
  • the photopolymerization initiator is a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxy ketone compound, an ⁇ -amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole from the viewpoint of exposure sensitivity.
  • Dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyl oxadiazole compounds and 3-aryl substituted coumarin compounds are preferred, and oxime compounds, ⁇ -hydroxy ketone compounds, ⁇ -hydroxy ketone compounds More preferred are compounds selected from amino ketone compounds and acyl phosphine compounds, and more preferred are oxime compounds.
  • an oxime compound as the photopolymerization initiator, excellent curability can be obtained. Furthermore, even when the composition is stored for a long time in a low temperature environment, a film with more suppressed defects can be produced.
  • the metal azo pigment A contained in the composition of the present invention contains two or more metal ions, but depending on the type of metal ion, the arrangement of the metal azo compound (metal complex) composed of the anion and the metal ion described above The seat is different.
  • Cu 2+ forms a metal complex in a planar conformation
  • Zn 2+ forms a metal complex in octahedral conformation.
  • the metal azo pigment A mentioned above is presumed to be present in an unstable state which is difficult to associate, and the metal azo pigment A tends to easily aggregate during storage of the composition. Is presumed to be.
  • the composition is energetically unstable, particularly when the content of nickel ions (Ni 2+ ) in metal azo pigment A is low or metal azo pigment A does not contain nickel ions. It is inferred that the metal azo pigment A tends to be more prone to aggregation during storage of.
  • the oxime compound coordinates to the metal azo pigment A to act as a chelating agent by blending the oxime compound, and as a result, the metal azo pigment A can be stabilized. It is speculated that cohesion and the like can be suppressed more effectively. Therefore, even if the composition is stored for a long time under a low temperature environment, it is presumed that a film with more suppressed defects can be produced.
  • Examples of commercially available ⁇ -hydroxy ketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (manufactured by BASF Corporation) and the like.
  • Examples of commercially available ⁇ -amino ketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF Corporation).
  • Examples of commercially available products of acyl phosphine compounds include IRGACURE-819, DAROCUR-TPO (all manufactured by BASF Corp.) and the like.
  • Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, the compounds described in JP-A-2006-342166, and the like.
  • C. S. Perkin II (1979, pp. 1653-1660) a compound described in J. Am. C. S. A compound described in Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pp.
  • oxime compound examples include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3- On, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy Examples include carbonyloxyimino-1-phenylpropan-1-one and the like.
  • oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF Corporation), TRONLY TR-PBG-304, TRONLY TR-PBG-309, and TRONLY TR-PBG- 305 (made by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), Adeka Arkles NCI-930, Adeka Optomer N-1919 (photopolymerization initiator 2 of JP 2012-14052 A) And the like) (manufactured by ADEKA Co., Ltd.) and the like.
  • an oxime compound having a fluorene ring can also be used as a photopolymerization initiator.
  • the oxime compound having a fluorene ring compounds described in JP-A-2014-137466 can be mentioned.
  • an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator.
  • Specific examples thereof include the compounds OE-01 to OE-75 described in International Publication WO 2015/036910.
  • an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used as a photopolymerization initiator.
  • an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring
  • the compound described in International Publication WO 2013/083505 can be mentioned.
  • an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, the compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. And the like (C-3) and the like.
  • an oxime compound having a nitro group can be used as a photopolymerization initiator. It is also preferable that the oxime compound having a nitro group is a dimer.
  • the oxime compound having a nitro group compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, and patent 4223071 Compounds described in Paragraph Nos. 0007 to 0025 of the gazette, Adeka Arkles NCI-831 (manufactured by ADEKA Co., Ltd.), and the like.
  • oxime compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.
  • the oxime compound is preferably a compound having an absorption maximum in a wavelength range of 350 to 500 nm, and more preferably a compound having an absorption maximum in a wavelength range of 360 to 480 nm.
  • the oxime compound is preferably a compound having high absorbance at 365 nm and 405 nm.
  • the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, Particularly preferred is 000.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a difunctional or trifunctional or higher functional photopolymerization initiator may be used.
  • a photopolymerization initiator two or more radicals are generated from one molecule of the photopolymerization initiator, so that good sensitivity can be obtained.
  • crystallinity is reduced and solubility in a solvent or the like is improved, so that it becomes difficult to precipitate with time, and the stability with time of the composition can be improved.
  • paragraphs of JP-A-2010-527339, JP-A-2011-524436, International Publication WO2015 / 004565, and JP-A-2016-532675 can be used.
  • the content of the photopolymerization initiator is preferably 0.1 to 30% by mass in the total solid content of the composition.
  • the lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more.
  • the upper limit is, for example, more preferably 20% by mass or less and still more preferably 10% by mass or less.
  • the content of the photopolymerization initiator is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A described above.
  • the lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more.
  • the upper limit is preferably 100 parts by mass or more, and more preferably 80 parts by mass or less.
  • the content of the oxime compound is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A described above.
  • the lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more.
  • the upper limit is preferably 100 parts by mass or more, and more preferably 80 parts by mass or less. According to this aspect, the effects of the present invention described above tend to be obtained more significantly.
  • the composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When 2 or more types of photoinitiators are included, it is preferable that the total amount of them becomes said range.
  • the compositions of the invention can contain multifunctional thiols.
  • the multifunctional thiol is a compound having two or more thiol (SH) groups.
  • the multifunctional thiol functions as a chain transfer agent in the radical polymerization process after light irradiation by using it together with the above-mentioned photopolymerization initiator and generates a thiyl radical which is less susceptible to inhibition of polymerization by oxygen, thereby enhancing the sensitivity of the composition.
  • polyfunctional aliphatic thiols in which an SH group is bonded to an aliphatic group such as a methylene or ethylene group are preferable.
  • polyfunctional thiol for example, hexane dithiol, decane dithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bis thioglycolate, ethylene glycol bis thiopropio , Trimethylolpropane tristhioglycollate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercapto propionate), pentaerythritol tetrakis thioglycolate, pentaerythritol tetrakis thiopropionate, pentaerythritol tetrakis (3-mercapto propio) ), Dipentaerythritol t
  • the content of the multifunctional thiol is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass, based on the total solid content of the composition of the present invention .
  • the composition of the present invention may contain only one type of multifunctional thiol, or may contain two or more types. When two or more polyfunctional thiols are contained, the total amount thereof is preferably in the above range.
  • the composition of the present invention can contain a pigment derivative. According to this aspect, it is possible to form a film in which the fluctuation of the spectrum is suppressed with respect to the temperature change.
  • the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acid group, a basic group or a phthalimide group.
  • the pigment derivative is preferably a compound represented by the following formula (syn1).
  • P represents a dye structure
  • L represents a single bond or a linking group
  • X represents an acid group, a basic group or a phthalimide group
  • m represents an integer of 1 or more
  • n is 1 or more
  • the plurality of L and X may be different from each other, and when n is 2 or more, the plurality of X may be different from each other.
  • the dye structure represented by P in the formula (syn1) includes pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinoline dye structure, quinacridone dye structure, isoindoline dye structure, isoindolinone dye structure, anthraquinone dye structure, dianthraquinone Dye structure, benzoisoindole dye structure, thiazine indigo dye structure, azo dye structure, quinophthalone dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, dioxazine dye structure, perylene dye structure, perinone dye structure, benzimidazolone dye structure, At least one selected from benzothiazole dye structure, benzoimidazole dye structure and benzoxazole dye structure is preferable, and pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure And at least one more preferably selected from benzimidazolone pigment
  • the linking group represented by L in formula (syn1) is a hydrocarbon group, a heterocyclic group, -NR-, -SO 2- , -S-, -O-, -CO-, -COO-, -OCO-, Or the group which consists of these combination is mentioned.
  • R represents a hydrogen atom, an alkyl group or an aryl group.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Moreover, the group which combined the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be sufficient.
  • the carbon number of the hydrocarbon group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 10.
  • the heterocyclic group is preferably a 5- or 6-membered ring.
  • the heterocyclic group may be a single ring or may be a fused ring.
  • the number of condensations of the fused ring is preferably 2 to 8, more preferably 2 to 4.
  • a nitrogen atom is preferable.
  • X represents an acid group, a basic group or a phthalimide group.
  • the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imidic acid group.
  • the carboxamide group a group represented by -NHCOR X1 is preferable.
  • the sulfonic acid amide group is preferably a group represented by —NHSO 2 R X2 .
  • the imide group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or —SO 2 NHCOR X6 .
  • R X1 to R X6 independently represents a hydrocarbon group or a heterocyclic group.
  • the hydrocarbon group and the heterocyclic group which R X1 to R X6 represent may have a substituent.
  • the above-mentioned substituent T is mentioned, It is preferable that it is a halogen atom, and it is more preferable that it is a fluorine atom.
  • An amino group is mentioned as a basic group which X represents.
  • the amino group is preferably a group represented by -NR 100 R 101 .
  • R 100 and R 101 independently represents a hydrogen atom, a hydrocarbon group or a heterocyclic group.
  • the hydrocarbon group and the heterocyclic group which R 100 and R 101 represent may have a substituent. Examples of the substituent include the above-mentioned substituent T.
  • the phthalimide group represented by X may be unsubstituted or may have a substituent. Examples of the substituent include the above-mentioned substituent T.
  • m is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 2.
  • n is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
  • pigment derivative the compound of the following structure is mentioned.
  • Me represents a methyl group
  • Ph represents a phenyl group.
  • JP-A-56-118462, JP-A-63-264674, JP-A-1-217077, JP-A-3-9961, JP-A-3-26767, and the like can be used as pigment derivatives.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment contained in the composition.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the metal azo pigment A.
  • the composition of the present invention may contain only one type of pigment derivative, or may contain two or more types. When two or more pigment derivatives are contained, the total amount thereof is preferably in the above range.
  • the composition of the present invention can contain a surfactant.
  • a surfactant As for the surfactant, the description in paragraphs [0238] to [0245] of International Publication WO 2015/166779 can be referred to, and the contents thereof are incorporated herein.
  • the surfactant include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants and the like, with fluorine-based surfactants being preferred.
  • liquid properties in particular, fluidity
  • liquid saving can be further improved.
  • a film with small thickness unevenness can also be formed.
  • the content of fluorine in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass.
  • the fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of the thickness of the coating film and liquid saving.
  • the fluorine-based surfactant As the fluorine-based surfactant, the surfactant described in paragraph Nos. 0060 to 0064 of JP-A-2014-41318 (paragraph number 0060 to 0064 of corresponding international publication WO 2014/17669), JP-A-2011-132503 And the like described in paragraph Nos. 0117 to 0132 of the gazette.
  • the fluorine-based surfactant is an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved to volatilize the fluorine atom Acrylic compounds can be used.
  • a fluorochemical surfactant Megafuck DS series (eg Megafuck DS-21) manufactured by DIC Corporation can be mentioned.
  • fluorine-based surfactant a copolymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound can be used.
  • the description of JP-A-2016-216602 can be referred to for such a fluorine-based surfactant, the contents of which are incorporated herein.
  • the fluorine-based surfactant a block polymer can be used.
  • block polymers include compounds described in JP-A-2011-89090.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy groups) (A fluorine-containing copolymer including a repeating unit derived from a meta) acrylate compound can be used.
  • the following compounds are also exemplified as the fluorinated surfactant used in the present invention.
  • the weight average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the proportion of repeating units is mol%.
  • a fluorine-based surfactant a fluorine-containing copolymer including a repeating unit having an ethylenically unsaturated group in the side chain can be used.
  • compounds described in paragraph Nos. 0050 to 0090 and paragraphs 0289 to 0295 of JP 2010-164965A, Megaface RS-101, RS-102, RS-718K, manufactured by DIC Corporation. RS-72-K etc. are mentioned.
  • the fluorine-based surfactant the compounds described in paragraphs [0015] to [0158] of JP-A-2015-117327 can also be used.
  • nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Company company), Tetronics 304, 701, 704, 901, 904, 150R1 (BAS).
  • glycerol trimethylolpropane
  • the content of the surfactant is preferably 0.001 to 5% by mass in the total solid content of the composition. 3 mass% or less is preferable, and, as for the upper limit, 1 mass% or less is more preferable. 0.05 mass% or more is preferable, and, as for a lower limit, 0.01 mass% or more is more preferable.
  • the composition of the present invention may contain only one surfactant or two or more surfactants. When two or more surfactants are contained, the total amount thereof is preferably in the above range.
  • the composition of the present invention can contain an ultraviolet absorber.
  • an ultraviolet absorber conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds, indole compounds, triazine compounds, and the like can be used. Details of these are described in paragraphs 0052 to 0072 in JP 2012-208374 A, paragraphs 0317 to 0334 in JP 2013-68814 A, and paragraphs 0061 to 0080 in JP 2016-162946 A. The contents of which are incorporated herein by reference. Specific examples of the ultraviolet absorber include compounds having the following structure.
  • UV-503 manufactured by Daito Kagaku Co., Ltd.
  • MYUA series made from Miyoshi Yushi (Chemical Industry Daily, February 1, 2016) is mentioned.
  • the content of the UV absorber is preferably 0.1 to 10% by mass, and more preferably 0.1 to 5% by mass, based on the total solid content of the composition. 0.1 to 3% by weight is particularly preferred.
  • the composition of the present invention may contain only one type of UV absorber, or may contain two or more types. When 2 or more types of ultraviolet absorbers are contained, it is preferable that the total amount of them becomes the said range.
  • the composition of the present invention can contain a silane coupling agent.
  • the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
  • the hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
  • a hydrolysable group a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • a vinyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group etc. are mentioned, for example Meta) acryloyl and epoxy are preferred.
  • the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP 2009-288703, and compounds described in paragraphs 0056 to 0066 of JP 2009-242604, the contents of which are It is incorporated in the specification.
  • the content of the silane coupling agent is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass, based on the total solid content of the composition of the present invention.
  • the composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types. When 2 or more types of silane coupling agents are contained, it is preferable that the total amount of them becomes the said range.
  • the composition of the present invention preferably contains a polymerization inhibitor.
  • the composition of the present invention makes it possible to produce a film in which defects are more suppressed even when the composition is stored for a long time in a low temperature environment. Although the detailed reason why such an effect is obtained is unknown, it is presumed to be due to the following.
  • the metal azo pigment A contained in the composition of the present invention contains two or more types of metal ions, metal azo compounds composed of the anion and the metal ion described above during storage of the composition It is speculated that exchange will occur and precipitates will form, but the inclusion of a polymerization inhibitor will reduce the degree of activation of the metal azo compound, making it difficult to cause metal exchange between metal azo compounds, resulting in It is assumed that the above-mentioned effect is obtained.
  • the content of the polymerization inhibitor is preferably 0.0001 to 1% by mass in the composition.
  • composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more polymerization inhibitors are contained, the total amount thereof is preferably in the above range.
  • an antioxidant for example, a phenol compound and a phosphorus compound (for example, paragraph 004 of JP-A-2011-90147) Compounds described in 2), thioether compounds and the like can be used.
  • Adekastab series AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60G, AO-60, AO-80, AO-A manufactured by ADEKA Co., Ltd.
  • a latent antioxidant is a compound in which the site that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C., or heated at 80 to 200 ° C. in the presence of an acid / base catalyst.
  • compounds in which the protective group is eliminated to function as an antioxidant can be mentioned.
  • the latent antioxidant include compounds described in International Publication WO 2014/021023, International Publication WO 2017/030005, and Japanese Unexamined Patent Publication No. 2017-008219.
  • commercially available products include Adeka ARKRUZ GPA-5001 (manufactured by ADEKA Co., Ltd.) and the like.
  • a thermal polymerization initiator a pinacol compound, an organic peroxide, an azo compound etc. are mentioned, A pinacol compound is preferable.
  • JP-A-2014-521772, JP-A-2014-523939, and JP-A-2014-521772 can be referred to, and the contents thereof are incorporated in the present specification.
  • the solid content concentration of the composition of the present invention is preferably 5 to 50% by mass.
  • the upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less.
  • the lower limit is preferably 8% by mass or more, and more preferably 10% by mass or more.
  • the viscosity (23 ° C.) of the composition of the present invention is preferably, for example, 1 to 100 mPa ⁇ s when a film is formed by coating.
  • the lower limit is preferably 2 mPa ⁇ s or more, and more preferably 3 mPa ⁇ s or more.
  • the upper limit is more preferably 50 mPa ⁇ s or less, still more preferably 30 mPa ⁇ s or less, and particularly preferably 15 mPa ⁇ s or less.
  • a storage container of the composition of this invention A well-known storage container can be used.
  • a container for the purpose of suppressing the mixing of impurities into the raw materials and the composition, a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin or a bottle in which six types of resin are seven layers It is also preferred to use.
  • a container for example, the container described in JP-A-2015-123351 can be mentioned.
  • composition of the present invention can be preferably used as a composition for forming an infrared transmission filter.
  • the composition of the present invention can be prepared by mixing the aforementioned components. At the time of preparation of the composition, all the components may be simultaneously dissolved or dispersed in a solvent to prepare the composition, or, if necessary, two or more solutions or dispersions in which the respective components are appropriately blended in advance.
  • the composition may be prepared by mixing it at the time of use (at the time of application).
  • distributes a pigment in preparation of a composition includes compression, squeezing, impact, shearing, cavitation and the like.
  • mechanical force used to disperse the pigment includes compression, squeezing, impact, shearing, cavitation and the like.
  • means for carrying out these processes include bead mill, sand mill, roll mill, ball mill, paint shaker, microfluidizer, high speed impeller, sand grinder, flow jet mixer, high pressure wet atomization, ultrasonic dispersion, etc.
  • JP-A-2015-157893 can be used.
  • the pigment In the process of dispersing the pigment, the pigment may be subjected to a refining treatment in a salt milling step.
  • the materials, devices, processing conditions, and the like used in the salt milling step can be referred to, for example, the descriptions of JP-A-2015-194521 and JP-A-2012-04629.
  • the composition is preferably filtered with a filter for the purpose of removing foreign matter and reducing defects.
  • a filter if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular.
  • a fluorocarbon resin such as polytetrafluoroethylene (PTFE), a polyamide-based resin such as nylon (for example, nylon-6, nylon-6, 6), or a polyolefin resin such as polyethylene or polypropylene (PP)
  • Filters made of materials such as polyolefin resins of Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
  • the pore size of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, and still more preferably 0.05 to 0.5 ⁇ m. If the pore size of the filter is in the above range, fine foreign particles can be removed more reliably.
  • filter manufacturer's nominal value As the filter, various filters provided by Nippon Paul Co., Ltd. (DFA 4201 NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (old Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used.
  • a fiber-like filter medium as a filter.
  • the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like.
  • SBP type series SBP 008 etc.
  • TPR type series TPR 002, TPR 005 etc.
  • SHPX type series SHPX 003 etc.
  • filters When using filters, different filters (eg, a first filter, a second filter, etc.) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more. Moreover, you may combine the filter of a different hole diameter within the range mentioned above. In addition, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration may be performed with the second filter.
  • filters eg, a first filter, a second filter, etc.
  • the membrane of the present invention is obtained from the composition of the present invention described above.
  • the film of the present invention can be preferably used as an infrared ray transmission filter.
  • the film of the present invention has a maximum value of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 600 nm of the light transmittance in the film thickness direction. It is preferable to satisfy the spectral characteristics that the minimum value in the range of 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the film of the present invention more preferably satisfies the spectral characteristics of any of the following (111) to (113).
  • the maximum value of light transmittance in the film thickness direction in the wavelength range of 400 to 600 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and in the film thickness direction
  • the embodiment in which the minimum value of light transmittance in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it is possible to shield the light in the wavelength range of 400 to 600 nm to make the film capable of transmitting light in excess of the wavelength of 650 nm.
  • the film of the present invention can be produced through the process of applying the composition of the present invention.
  • the composition is preferably coated on a support.
  • the support include a substrate made of a material such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass and the like.
  • An organic film, an inorganic film, or the like may be formed on these substrates.
  • the material of the organic film include the resins described in the section of the composition described above.
  • the support body can also use the board
  • a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support.
  • a black matrix may be formed on the support to separate each pixel.
  • the support may be provided with a subbing layer for the purpose of improving the adhesion with the upper layer, preventing the diffusion of substances or flattening the surface of the substrate.
  • a subbing layer for the purpose of improving the adhesion with the upper layer, preventing the diffusion of substances or flattening the surface of the substrate.
  • a method of applying the composition known methods can be used. For example, dropping method (drop casting); slit coating method; spraying method; roll coating method; spin coating method (spin coating method); cast coating method; slit and spin method; pre-wet method (for example, JP 2009-145395) Methods described in the publication); inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Printing methods; transfer methods using a mold or the like; nanoimprint methods and the like.
  • the application by the ink jet is not particularly limited.
  • coating by spin coating is preferably performed at a rotational speed of 1000 to 2000 rpm. Further, as to coating by spin coating, as described in JP-A-10-142603, JP-A-11-302413 and JP-A-2000-157922, the rotational speed is increased during coating. Also good.
  • the composition layer (coated film) formed by applying the composition may be dried (prebaked).
  • the prebaking may not be performed.
  • the prebaking temperature is preferably 150 ° C. or less, more preferably 120 ° C. or less, and still more preferably 110 ° C. or less.
  • the lower limit may be, for example, 50 ° C. or more, and may be 80 ° C. or more.
  • the pre-bake time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and still more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.
  • the method for producing a film further includes the step of forming a pattern.
  • the pattern formation method includes a pattern formation method using a photolithography method and a pattern formation method using a dry etching method, and a pattern formation method using a photolithography method is preferable.
  • the step of forming a pattern may not be performed.
  • the process of forming a pattern will be described in detail.
  • the pattern formation method by the photolithography method is a step of exposing the composition layer formed by applying the composition of the present invention in a pattern (exposure step) and developing and removing the composition layer in the unexposed area. It is preferable to include the step of forming a pattern (development step). If necessary, a step (post-baking step) may be provided to bake the developed pattern. Each step will be described below.
  • ⁇ exposure step the composition layer is exposed in a pattern.
  • pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using a stepper exposure device, a scanner exposure device, or the like. Thereby, the exposed portion can be cured.
  • radiation (light) that can be used for exposure include g-rays and i-rays. Further, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used.
  • Examples of light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and the like, and KrF rays (wavelength 248 nm) are preferable.
  • Irradiation dose for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2, most preferably 0.08 ⁇ 0.5J / cm 2 .
  • the oxygen concentration at the time of exposure can be selected appropriately. For example, exposure may be performed in the atmosphere, or exposure may be performed in a low oxygen atmosphere (for example, 15% by volume, 5% by volume, substantially no oxygen) in which the oxygen concentration is 19% by volume or less.
  • Exposure may be performed under a high oxygen atmosphere (eg, 22% by volume, 30% by volume, 50% by volume) exceeding 21% by volume. Further, the exposure illuminance can be set as appropriate, and is preferably selected from the range of 1000 to 100000 W / m 2 . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
  • the composition layer in the unexposed area of the composition layer after exposure is developed and removed to form a pattern.
  • the development removal of the composition layer in the unexposed area can be carried out using a developer.
  • the composition layer in the unexposed area in the exposure step is eluted into the developer, and only the photocured area remains on the support.
  • the temperature of the developing solution is preferably, for example, 20 to 30.degree.
  • the development time is preferably 20 to 180 seconds.
  • the process of shaking off the developer every 60 seconds and further supplying the developer anew may be repeated several times.
  • the developing solution is preferably an alkaline aqueous solution in which an alkaline agent is diluted with pure water.
  • an alkaline agent for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide
  • Organic compounds such as ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo [5.4.0] -7-undecene
  • Alkaline compounds sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate Um, and inorganic al
  • the alkaline agent is preferably a compound having a large molecular weight in terms of the environment and safety.
  • concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.
  • the developer may further contain a surfactant.
  • surfactant the surfactant mentioned above is mentioned and nonionic surfactant is preferable.
  • the developer may be prepared once as a concentrate and diluted to a concentration required for use, from the viewpoint of transportation and storage convenience.
  • the dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times.
  • the rinse is preferably performed by supplying a rinse liquid to the composition layer after development while rotating the support on which the composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral portion of the support. Under the present circumstances, when moving from the support center part of a nozzle to a peripheral part, you may make it move, reducing the moving speed of a nozzle gradually. By performing the rinse in this manner, the in-plane variation of the rinse can be suppressed. Also, the same effect can be obtained by gradually reducing the rotational speed of the support while moving from the center of the support to the periphery of the nozzle.
  • Post-baking is a post-development heat treatment to complete film curing.
  • the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 200 to 230 ° C. is more preferable.
  • Post-baking should be performed continuously or batchwise on the film after development, using heating means such as a hot plate, convection oven (hot air circulation dryer), high frequency heater, etc., so as to satisfy the above conditions. Can.
  • Patterning by the dry etching method is to apply a composition of the present invention on a support to cure a composition layer formed to form a cured product layer, and then to form a resist patterned on the cured product layer.
  • a layer can be formed, and then, the patterned resist layer can be used as a mask to dry-etch the cured product layer using an etching gas.
  • the description in paragraphs “0010” to “0067” of JP 2013-064993 can be referred to, and the contents thereof are incorporated in the present specification.
  • the infrared transmission filter of the present invention has the above-described film of the present invention.
  • the solid-state imaging device of the present invention includes the film of the present invention described above.
  • a structure of a solid-state image sensor it is a structure which has a film
  • a light shield comprising a plurality of photodiodes constituting the light receiving area of the solid-state imaging device and transfer electrodes made of polysilicon and the like on the support, light shielding made of tungsten or the like in which only the light receiving portion of the photodiode and the transfer electrodes are opened. It has a film, has a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the photodiode light receiving part, and has the film of the present invention on the device protection film. is there. Furthermore, a configuration having a condensing means (for example, a micro lens etc.
  • the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned into, for example, a grid shape by partition walls.
  • the partition walls in this case preferably have a lower refractive index than each pixel.
  • An optical sensor of the present invention includes the film of the present invention described above.
  • the configuration of the light sensor is not particularly limited as long as it functions as a light sensor.
  • an embodiment of an optical sensor of the present invention will be described using the drawings.
  • reference numeral 110 denotes a solid-state imaging device.
  • An imaging region provided on the solid-state imaging device 110 includes a near infrared cut filter 111 and an infrared transmission filter 114. Further, on the near infrared cut filter 111, a color filter 112 is laminated. A microlens 115 is disposed on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed to cover the microlenses 115.
  • the spectral characteristics of the near infrared cut filter 111 are selected according to the emission wavelength of the infrared light emitting diode (infrared LED) to be used.
  • the color filter 112 is a color filter in which a pixel for transmitting and absorbing light of a specific wavelength in the visible region is formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used.
  • a color filter in which red (R), green (G), and blue (B) pixels are formed is used.
  • the description in paragraph Nos. 0214 to 0263 of JP-A-2014-043556 can be referred to, the contents of which are incorporated herein.
  • the characteristic of the infrared transmission filter 114 is selected according to the emission wavelength of the infrared LED to be used.
  • a near infrared cut filter (another near infrared cut filter) different from the near infrared cut filter 111 may be further disposed on the planarization layer 116.
  • Other near infrared cut filters include those having a copper-containing layer and / or a dielectric multilayer film. The details of these may be mentioned above.
  • a dual band pass filter may be used as another near infrared cut filter.
  • the aqueous solution of potassium hydroxide was added to the solution after the heat treatment to adjust the pH to about 5.
  • the pigment was then isolated from the solution on a suction filter, washed, dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce metal azo pigment 1.
  • the aqueous solution of potassium hydroxide was added to the solution after the heat treatment to adjust the pH to about 5.
  • the pigment was then isolated from the solution on a suction filter, washed and dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce metal azo pigment 2.
  • the aqueous solution of potassium hydroxide was added to the solution after the heat treatment to adjust the pH to about 5.
  • the pigment was then isolated from the solution on a suction filter, washed, dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce metal azo pigment 3.
  • the solution to which these were added was maintained at 82 ° C. for 3 hours, and then KOH was added to adjust the pH to about 5.5. Then, the temperature of the solution was raised to 90 ° C., and while maintaining the temperature of 90 ° C., 1000 g of distilled water was added for dilution. Subsequently, 113 g of 30% hydrochloric acid was added dropwise to this solution, and then heat treated at a temperature of 90 ° C. for 12 hours. Subsequently, the aqueous solution of potassium hydroxide was added to the solution after the heat treatment to adjust the pH to about 5. The pigment was then isolated from the solution on a suction filter, washed, dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce metal azo pigment 4.
  • Multifunctional Acrylate Solution 1 (polymerizable monomer D5).
  • the amount of residual solvent (toluene) contained in the polyfunctional acrylate solution 1 was measured by gas chromatography, and it was confirmed to be reduced to 11 mass ppm.
  • a peak derived from a polyfunctional acrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) was detected by 1 H-NMR (nuclear magnetic resonance), and it was confirmed that no crosslinking reaction was caused by radical polymerization.
  • Dispersant C5 50 g of an acrylate compound (Alonix M-5300, manufactured by Toagosei Co., Ltd.) containing 835 mass ppm of toluene as a residual solvent in a flask, 50 g of PGMEA, and 40 mg of TEMPO
  • the external temperature was set to 90.degree. C.
  • the pressure inside the flask was gradually reduced from normal pressure to 66 mmHg, and reduced-pressure distillation was performed over 4 hours. Thereafter, the weight of the system was adjusted to 100 g with PGMEA to obtain a monomer solution 1.
  • the molecular weight of the obtained compound by GPC method It measured. After confirming that the molecular weight of the compound reached the desired value, 0.35 g of 2,6-di-t-butyl-4-methylphenol was added to the mixture containing the compound. After that, 87.0 g of 2-methacryloyloxyethyl isocyanate was added dropwise over 30 minutes to the obtained mixture.
  • Metal azo pigments 1-4 the above-mentioned metal azo pigments 1-4 PR254: C. I. Pigment Red 254 PY 139: C.I. I. Pigment Yellow 139 PV23: C.I. I. Pigment Violet 23 PB 15: 6: C.I. I. Pigment Blue 15: 6 PB16: C.I. I. Pigment Blue 16 IB: Irgaphor Black (manufactured by BASF) PBk 32: C. I. Pigment Black 32
  • K1, K2, K5, K6, K7, K8, K10 compounds of the following structures.
  • Me represents a methyl group
  • Ph represents a phenyl group.
  • (Pigment derivative) B1, K3 and K4 compounds of the following structures.
  • Ph represents a phenyl group and Me represents a methyl group.
  • P3 Cyclomer ACA 250 (solid content concentration 45% by mass, manufactured by Daicel Corporation)
  • D4 Compound of the following structure
  • D5 The polymerizable monomer D5 produced in the above Production Example 1 (solid content concentration 50% by mass)
  • D6 Alonics M-520 (manufactured by Toagosei Co., Ltd.)
  • Silane coupling agent H1 compound of the following structure (in the following structural formula, Et is an ethyl group)
  • Each composition was applied on a glass substrate using a spin coater such that the film thickness after post-baking was the film thickness described in the following table, and prebaked for 120 seconds using a hot plate at 100 ° C.
  • the entire surface of the coated film after prebaking was irradiated with i-ray at an exposure dose of 1000 mJ / cm 2 for exposure, and then post-baked at 220 ° C. for 5 minutes using a hot plate to form a film.
  • the absorbance and the transmittance of the obtained film are measured at a wavelength of 400 to 1300 nm, and the maximum transmittance in the wavelength range of 400 to 600 nm Value (transmittance T1), minimum value of transmittance in the wavelength range of 1000 to 1300 nm (transmittance T2), minimum value of absorbance in the range of wavelength 400 to 600 nm (absorbance A), absorbance in the range of wavelength 1000 to 1300 nm
  • the maximum value (absorbance B) the ratio of the minimum value of absorbance in the wavelength range of 400 to 600 nm to the maximum value of absorbance in the range of wavelength of 1000 to 1300 nm (absorbance A / absorbance B) was measured.
  • the film thickness difference is more than 0.02 ⁇ m and not more than 0.03 ⁇ m 3: The film thickness difference is more than 0.03 ⁇ m and not more than 0.04 ⁇ m 2: The film thickness difference is more than 0.04 ⁇ m and not more than 0.05 ⁇ m Certain 1: Film thickness difference is greater than 0.05 ⁇ m
  • Number of defects is 0: Number of defects is 1 to 4 3: Number of defects is 5 to 9 2: Number of defects is 10 to 15 1: Number of defects is 16 or more
  • the examples were excellent in film thickness uniformity and moisture resistance.
  • the compositions of the examples were excellent in the light shielding property of light in the wavelength range of 400 to 600 nm, and could be preferably used as an infrared ray transmission filter.
  • the compositions of Examples 1 to 4 blocked the light in the wavelength range of 400 to 600 nm and could form a film capable of transmitting light in excess of the wavelength of 650 nm.
  • the compositions of Examples 5 to 13 blocked the light in the wavelength range of 400 to 720 nm and could form a film capable of transmitting light in excess of the wavelength of 800 nm.
  • the compositions of Examples 14 to 25 could block light having a wavelength of 400 to 830 nm and form a film capable of transmitting light having a wavelength of more than 900 nm.
  • compositions of Examples 1 to 25 are coated on a silicon wafer using a spin coater so that the film thickness after post-baking becomes each of the film thicknesses described in Table 6, and a hot plate of 100 ° C. for 120 seconds Prebaked.
  • the entire surface of the coated film after prebaking was irradiated with i-ray at an exposure dose of 1000 mJ / cm 2 for exposure, and then post-baked at 220 ° C. for 5 minutes using a hot plate to form a film.
  • the following composition for formation of an absorption layer was applied to the surface of the obtained film using a spin coater, and prebaked for 120 seconds using a hot plate at 100 ° C.
  • the entire surface of the coating film after prebaking is exposed by irradiating i-rays at an exposure dose of 1000 mJ / cm 2 , and then post-baked at 220 ° C. for 5 minutes using a hot plate to form an absorption layer A laminate was formed.
  • This laminate was able to block and transmit light in the same wavelength range as in Test Example 1. Furthermore, it was excellent also in light resistance.
  • composition for forming an absorption layer C.
  • a 2 ⁇ m square Bayer pattern (near infrared cut filter) was formed by heating at 200 ° C. for 5 minutes using a hot plate.
  • the red composition was applied by spin coating so that the film thickness after film formation was 1.0 ⁇ m. Subsequently, it heated at 100 degreeC for 2 minutes using the hotplate.
  • an i-line stepper exposure apparatus FPA-3000i5 +, manufactured by Canon Inc.
  • exposure was performed at a dose of 1000 mJ / cm 2 through a mask having a 2 ⁇ m square pattern. Subsequently, paddle development was performed at 23 ° C.
  • TMAH tetramethylammonium hydroxide
  • the red composition was patterned on the Bayer pattern of the near-infrared cut filter by heating at 200 ° C. for 5 minutes using a hot plate.
  • the Green composition and the Blue composition were sequentially patterned to form colored patterns of red, green and blue.
  • the compositions of Examples 14 to 25 were coated on the patterned film by spin coating so that the film thickness after film formation was 2.0 ⁇ m. Subsequently, it heated at 100 degreeC for 2 minutes using the hotplate.
  • the obtained solid-state imaging device was irradiated with light from an infrared light emitting diode (infrared LED) light source under a low illuminance environment (0.001 Lux), an image was captured, and the image performance was evaluated. The subject was clearly recognized on the image. In addition, the incident angle dependency was good.
  • the infrared transmission filter can achieve the same effect even if the film thickness is achieved by multilayer coating. For example, in the case of Example 14, the composition is applied by spin coating to form a coated film, and then the coated film is heated at 100 ° C. for 120 seconds, then exposed and developed, and then at 200 ° C. The film thickness may be adjusted to 2.0 ⁇ m by repeating a series of operations of heating for a plurality of times.
  • the Red composition, Green composition, Blue composition and IR composition used in Test Example 3 are as follows.
  • Red composition The following components were mixed and stirred, and then filtered through a nylon filter with a pore size of 0.45 ⁇ m (manufactured by Nippon Pall Co., Ltd.) to prepare a red composition.
  • Red pigment dispersion liquid 51.7 parts by mass
  • Resin P1 0.6 parts by mass
  • Polymerizable monomer D6 0.6 parts by mass
  • Photopolymerization initiator I1 0.4 parts by mass Surfactant F1 ... 0.2 parts by mass UV absorber (UV-503, manufactured by Daito Chemical Industries, Ltd.) ... 0.3 parts by mass PGMEA ... 46.6 parts by mass
  • Green composition The following components were mixed and stirred, followed by filtration using a nylon filter with a pore size of 0.45 ⁇ m (manufactured by Nippon Pall Co., Ltd.) to prepare a Green composition.
  • Green pigment dispersion ... 73.7 parts by mass Resin P1 ... 0.3 parts by mass Polymerizable monomer D6 ... 1.2 parts by mass Photopolymerization initiator I1 ... 0.6 parts by mass Surfactant F1 ⁇ 0.2 parts by mass Ultraviolet absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ⁇ 0.5 parts by mass PGMEA ⁇ ⁇ 23.5 parts by mass
  • Blue composition The following components were mixed and stirred, and then filtered through a nylon filter with a pore size of 0.45 ⁇ m (manufactured by Nippon Pall Co., Ltd.) to prepare a Blue composition.
  • Surfactant F1 -0.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ... 0.3 parts by mass PGMEA ... 49.8 parts by mass
  • IR composition The following components were mixed and stirred, and then filtered through a nylon filter (made by Nippon Pall Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare an IR composition.
  • IR pigment dispersion liquid 85 parts by mass Polymerizable monomer D6: 1.8 parts by mass Resin P1: 1.1 parts by mass Photopolymerization initiator I1: 0.9 parts by mass Surfactant F1 .. 0.2 parts by mass polymerization inhibitor (p-methoxyphenol)... 0.001 parts by mass PGMEA. 11.0 parts by mass
  • the pigment dispersions used for the Red composition, the Green composition, the Blue composition and the IR composition are as follows.
  • Red pigment dispersion C.I. I. Pigment Red 254, 9.6 parts by mass
  • C.I. I. A mixed solution of 4.3 parts by mass of Pigment Yellow 139, 6.8 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was used as a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours according to 3 mm diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a red pigment dispersion.
  • a mixed solution of 5.3 parts by mass of Pigment Yellow 150, 5.2 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA was added to a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours according to 3 mm diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a green pigment dispersion.
  • -IR pigment dispersion liquid mixed liquid consisting of 6.25 parts by mass of near infrared absorbing dye K2, 1.25 parts by mass of pigment derivative K4, 6 parts by mass of dispersant C3, and 86.5 parts by mass of PGMEA
  • a bead mill zirconia beads 0.3 mm in diameter
  • dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain an IR pigment dispersion.

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Abstract

Provided are: a composition capable of producing a film which has a uniform thickness and has a suppressed occurrence of foreign matter defects under a high temperature and high humidity environment; an infrared transmission filter; a solid state imaging device; and an optical sensor. This composition contains: a specific metal azo pigment; a coloring material having a maximum absorption in the wavelength range of 400-700 nm; and a compound having an ethylenically unsaturated bonding group and/or a compound having a cyclic ether group. In this composition, A/B, which is the ratio of a minimum absorbance value A in the wavelength range of 400-600 nm to a maximum absorbance value B in the wavelength range of 1000-1300 nm, is at least 4.5. Said metal azo pigment contains: at least one anion species selected from among an azo compound represented by formula (I) and a tautomeric azo compound thereof; two or more kinds of metal ions; and a melamine compound.

Description

組成物、膜、赤外線透過フィルタ、固体撮像素子および光センサComposition, film, infrared transmission filter, solid-state imaging device and optical sensor
　本発明は、赤外線透過フィルタなどの製造に用いられる組成物、および前述の組成物を用いた膜に関する。また、前述の膜を有する赤外線透過フィルタ、固体撮像素子および光センサに関する。 The present invention relates to a composition used for producing an infrared transmission filter and the like, and a film using the composition described above. The present invention also relates to an infrared transmission filter, a solid-state imaging device, and an optical sensor having the above-described film.
　黄色顔料は、カラーフィルタ等において、基本色または補色を出すための色材として用いられている。黄色顔料の１種として、カラーインデックス（Ｃ．Ｉ．）Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ１５０などのアゾバルビツール酸ニッケル錯体が知られている。 Yellow pigments are used as color materials for producing basic colors or complementary colors in color filters and the like. As one type of yellow pigment, an azobarbituric acid nickel complex such as Color Index (C.I.) Pigment Yellow 150 is known.
　また、特許文献１～４には、アゾバルビツール酸と、２種以上の金属イオンと、メラミン化合物とを含む金属アゾ顔料に関する発明が記載されている。特許文献１～４に記載された金属アゾ顔料は、従来のアゾバルビツール酸ニッケル錯体などに対して、改良された着色性能を有しているとされている。 Patent documents 1 to 4 disclose inventions on metal azo pigments containing azobarbituric acid, two or more types of metal ions, and a melamine compound. The metal azo pigments described in Patent Documents 1 to 4 are considered to have improved coloring performance to conventional azobarbituric acid nickel complexes and the like.
特開２０１７－１７１９１２号公報JP, 2017-171912, A 特開２０１７－１７１９１３号公報JP, 2017-171913, A 特開２０１７－１７１９１４号公報JP, 2017-171914, A 特開２０１７－１７１９１５号公報JP, 2017-171915, A
　本発明者が、アゾバルビツール酸と２種以上の金属イオンとメラミン化合物とを含む金属アゾ顔料を用いた膜について鋭意検討を進めたところ、この膜を高温高湿環境下に曝した場合、異物欠陥が発生し易い傾向にあることが分かった。 The inventor of the present invention has intensively studied a film using a metal azo pigment containing azobarbituric acid, two or more metal ions and a melamine compound. When the film is exposed to a high temperature and high humidity environment, It was found that foreign matter defects tend to occur.
　また、アゾバルビツール酸と２種以上の金属イオンとメラミン化合物とを含む色材を含む組成物を用いて膜を製造する場合、組成物を塗布して塗布膜を形成した時に、膜厚にばらつきが生じやすいことが分かった。 When a film is produced using a composition containing a coloring material containing azobarbituric acid, two or more types of metal ions, and a melamine compound, when the composition is applied to form a coating film, It turned out that variation is likely to occur.
　よって、本発明の目的は、膜厚均一性が高く、高温高湿環境下での異物欠陥の発生が抑制された膜を製造できる組成物を提供することにある。また、この組成物を用いた膜、赤外線透過フィルタ、固体撮像素子および光センサを提供することにある。 Therefore, an object of the present invention is to provide a composition capable of producing a film having high uniformity of film thickness and in which the occurrence of foreign matter defects in a high temperature and high humidity environment is suppressed. Another object of the present invention is to provide a film, an infrared transmission filter, a solid-state image sensor and an optical sensor using this composition.
　本発明者の検討によれば、後述する組成物を用いることにより上記目的を達成できることを見出し、本発明を完成するに至った。本発明は以下を提供する。
　＜１＞　下記式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、２種以上の金属イオンと、メラミン化合物とを含む金属アゾ顔料と、
　上記金属アゾ顔料以外の色材であって、波長４００～７００ｎｍの範囲に吸収極大を有する色材と、
　エチレン性不飽和結合基を有する化合物、および、環状エーテル基を有する化合物から選ばれる少なくとも１種の化合物と、を含む組成物であり、
　組成物の波長４００～６００ｎｍの範囲における吸光度の最小値Ａと、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂとの比であるＡ／Ｂが４．５以上である、組成物；
Figure JPOXMLDOC01-appb-C000003
 　式中、Ｒ１およびＲ２はそれぞれ独立して、ＯＨまたはＮＲ５Ｒ６であり、
　Ｒ３およびＲ４はそれぞれ独立して、＝Ｏまたは＝ＮＲ７であり、
　Ｒ５～Ｒ７はそれぞれ独立して、水素原子またはアルキル基である。
　＜２＞　金属アゾ顔料は、上記アニオンと、Ｚｎ２＋およびＣｕ２＋を少なくとも含む金属イオンと、メラミン化合物とを含む、＜１＞に記載の組成物。
　＜３＞　金属アゾ顔料中の全金属イオンの１モルを基準として、Ｚｎ２＋およびＣｕ２＋を合計で９５～１００モル％含有する、＜２＞に記載の組成物。
　＜４＞　金属アゾ顔料中のＺｎ２＋とＣｕ２＋とのモル比が、Ｚｎ２＋：Ｃｕ２＋＝１９９：１～１：１５である、＜２＞または＜３＞に記載の組成物。
　＜５＞　金属アゾ顔料におけるメラミン化合物が、下記式（ＩＩ）で表される化合物である、＜１＞～＜４＞のいずれかに記載の組成物；
Figure JPOXMLDOC01-appb-C000004
 　式中Ｒ１１～Ｒ１３は、それぞれ独立して水素原子またはアルキル基である。
　＜６＞　波長４００～７００ｎｍの範囲に吸収極大を有する色材は、青色着色剤および紫色着色剤から選ばれる少なくとも１種を含む、＜１＞～＜５＞のいずれかに記載の組成物。
　＜７＞　更に、近赤外線吸収色素を含む、＜１＞～＜６＞のいずれかに記載の組成物。
　＜８＞　近赤外線吸収色素は波長８００～９００ｎｍの範囲に吸収極大を有する、＜７＞に記載の組成物。
　＜９＞　近赤外線吸収色素はピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物、および、クロコニウム化合物から選ばれる少なくとも１種である、＜７＞または＜８＞に記載の組成物。
　＜１０＞　赤外線透過フィルタ用である、＜１＞～＜９＞のいずれかに組成物。
　＜１１＞　＜１＞～＜１０＞のいずれかに記載の組成物を用いて得られる膜。
　＜１２＞　＜１１＞に記載の膜を有する赤外線透過フィルタ。
　＜１３＞　＜１１＞に記載の膜を有する固体撮像素子。
　＜１４＞　＜１１＞に記載の膜を有する光センサ。 According to the study of the present inventor, it has been found that the above object can be achieved by using the composition described later, and the present invention has been completed. The present invention provides the following.
<1> A metal azo pigment containing at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof, two or more metal ions, and a melamine compound ,
A coloring material other than the metal azo pigment and having an absorption maximum in a wavelength range of 400 to 700 nm;
A composition comprising a compound having an ethylenically unsaturated bonding group, and at least one compound selected from a compound having a cyclic ether group,
A composition wherein A / B, which is a ratio of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm and the maximum value B of the absorbance in the range of wavelength 1000 to 1300 nm, is 4.5 or more;
Figure JPOXMLDOC01-appb-C000003
 In the formula, R 1 and R 2 are each independently OH or NR 5 R 6 ,
R 3 and R 4 are each independently = O or NRNR 7 ,
R 5 to R 7 are each independently a hydrogen atom or an alkyl group.
The composition as described in <1> in which a <2> metal azo pigment contains the said anion, the metal ion which contains Zn2 + and Cu2 + at least, and a melamine compound.
<3> The composition according to <2>, containing a total of 95 to 100 mol% of Zn 2+ and Cu 2+ based on 1 mol of all metal ions in the metal azo pigment.
<4> The composition according to <2> or <3>, wherein the molar ratio of Zn 2+ to Cu 2+ in the metal azo pigment is Zn 2+ : Cu 2+ = 199: 1 to 1:15.
The composition in any one of <1>-<4> whose melamine compound in <5> metal azo pigment is a compound represented by following formula (II);
Figure JPOXMLDOC01-appb-C000004
 In the formula, R 11 to R 13 each independently represent a hydrogen atom or an alkyl group.
<6> The composition according to any one of <1> to <5>, wherein the colorant having an absorption maximum in a wavelength range of 400 to 700 nm includes at least one selected from a blue colorant and a violet colorant.
<7> The composition according to any one of <1> to <6>, further comprising a near infrared absorbing dye.
<8> The composition according to <7>, wherein the near infrared absorbing dye has an absorption maximum in a wavelength range of 800 to 900 nm.
<9> The composition according to <7> or <8>, wherein the near-infrared absorbing dye is at least one selected from pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, and croconium compounds. .
<10> The composition according to any one of <1> to <9>, which is for an infrared transmission filter.
<11> A film obtained using the composition according to any one of <1> to <10>.
The infrared rays permeable filter which has a film | membrane as described in <12><11>.
The solid-state image sensor which has a film | membrane as described in <13><11>.
The optical sensor which has a film | membrane as described in <14><11>.
　本発明によれば、膜厚均一性が高く、高温高湿環境下での異物欠陥の発生が抑制された膜を製造できる組成物、膜、赤外線透過フィルタ、固体撮像素子および光センサを提供することができる。 According to the present invention, a composition, a film, an infrared transmission filter, a solid-state imaging device, and an optical sensor capable of manufacturing a film having high uniformity of film thickness and suppressed generation of foreign matter defects under high temperature and high humidity environment are provided. be able to.
光センサの一実施形態を示す概略図である。FIG. 2 is a schematic diagram illustrating an embodiment of a light sensor.
　以下において、本発明の内容について詳細に説明する。
　本明細書において、「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含する。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「（メタ）アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「（メタ）アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「（メタ）アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
　本明細書において、重量平均分子量および数平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）測定でのポリスチレン換算値として定義される。
　本明細書において、化学式中のＭｅはメチル基を表し、Ｅｔはエチル基を表し、Ｂｕはブチル基を表し、Ｐｈはフェニル基を表す。
　本明細書において、赤外線とは、波長７００～２５００ｎｍの光（電磁波）をいう。
　本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。 Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.
In the notation of the group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Moreover, as light used for exposure, active ray or radiation such as a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like can be mentioned.
In the present specification, “(meth) acrylate” represents both or either of acrylate and methacrylate, “(meth) acryl” represents both or either of acrylic and methacryl, “(meth) acrylate” ) Acryloyl represents either or both of acryloyl and methacryloyl.
In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene equivalent values in gel permeation chromatography (GPC) measurement.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, infrared light refers to light (electromagnetic wave) having a wavelength of 700 to 2500 nm.
As used herein, total solids refers to the total mass of all components of the composition excluding the solvent.
In the present specification, the term "process" is included in the term if the intended function of the process is achieved, even if it can not be clearly distinguished from other processes, not only the independent process. .
＜組成物＞
　本発明の組成物は、後述する式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、２種以上の金属イオンと、メラミン化合物とを含む金属アゾ顔料と、
　上記金属アゾ顔料以外の色材であって、波長４００～７００ｎｍの範囲に吸収極大を有する色材と、
　エチレン性不飽和結合基を有する化合物、および、環状エーテル基を有する化合物から選ばれる少なくとも１種の化合物と、を含む組成物であり、
　組成物の波長４００～６００ｎｍの範囲における吸光度の最小値Ａと、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂとの比であるＡ／Ｂが４．５以上であることを特徴とする。 <Composition>
The composition of the present invention comprises at least one anion selected from an azo compound represented by the formula (I) described later and an azo compound of a tautomeric structure thereof, two or more metal ions, and a melamine compound. Containing metal azo pigments,
A coloring material other than the metal azo pigment and having an absorption maximum in a wavelength range of 400 to 700 nm;
A composition comprising a compound having an ethylenically unsaturated bonding group, and at least one compound selected from a compound having a cyclic ether group,
It is characterized in that A / B which is a ratio of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm and the maximum value B of the absorbance in the range of wavelength 1000 to 1300 nm is 4.5 or more.
　本発明者が、アゾバルビツール酸と２種以上の金属イオンとメラミン化合物とを含む金属アゾ顔料について鋭意検討を進めたところ、この金属アゾ顔料は硬度が低い傾向にあり、微細化し易いものの、活性面が生じて凝集し易い傾向にあることが分かった。また、金属アゾ顔料におけるニッケルイオン（Ｎｉ２＋）の含有量が少ないか、あるいは金属アゾ顔料がニッケルイオンを含まない場合においては、エネルギー的に不安定な状態であると推測され、金属アゾ顔料がより凝集し易い傾向にあると推測される。また、この金属アゾ顔料は、２種以上の金属イオンを含むが、金属イオンの種類により、上述したアニオンと金属イオンとで構成される金属アゾ化合物（金属錯体）の配座が異なる。例えば、Ｃｕ２＋の場合は平面配座の金属錯体を形成し、Ｚｎ２＋の場合は正八面体配座の金属錯体を形成する。このため、上述した金属アゾ顔料は、不安定な状態で存在していると推測される。そのため、上述した金属アゾ顔料は、高温高湿環境下において凝集が促進されやすい傾向にあると推測される。
　本発明者の検討によれば、上述した金属アゾ顔料と、上述した金属アゾ顔料以外の色材であって波長４００～７００ｎｍの範囲に吸収極大を有する色材（以下他の色材ともいう）とを併用して、波長４００～６００ｎｍの範囲における吸光度の最小値Ａと、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂとの比であるＡ／Ｂが４．５以上である組成物を調製したところ、驚くべきことに、この組成物を用いて得られる膜を高温高湿環境下に曝しても、異物欠陥が生じにくいことを見出した。この様な効果が得られた理由としては、推測であるが、金属アゾ顔料以外の他の色材が金属アゾ顔料のアゾ部位と相互作用して金属アゾ顔料の安定性を向上できたためであると考えられる。 The inventors of the present invention have intensively studied metal azo pigments containing azobarbituric acid, two or more metal ions, and a melamine compound. As a result, the metal azo pigments tend to have low hardness and are easily miniaturized, It was found that an active surface was formed and tended to aggregate. In addition, when the content of the nickel ion (Ni 2+ ) in the metal azo pigment is small or when the metal azo pigment does not contain the nickel ion, it is estimated that the state is energetically unstable, and the metal azo pigment is It is presumed that they tend to aggregate more easily. Moreover, this metal azo pigment contains two or more types of metal ions, but the conformation of the metal azo compound (metal complex) composed of the above-mentioned anion and metal ion differs depending on the type of metal ion. For example, Cu 2+ forms a metal complex in a planar conformation, and Zn 2+ forms a metal complex in octahedral conformation. For this reason, it is presumed that the metal azo pigment mentioned above exists in an unstable state. Therefore, it is presumed that the above-mentioned metal azo pigment tends to promote aggregation under a high temperature and high humidity environment.
According to the study of the present inventor, a coloring material other than the metal azo pigment described above and the metal azo pigment described above and having an absorption maximum in the wavelength range of 400 to 700 nm (hereinafter also referred to as another coloring material) And a composition having an A / B ratio of 4.5 or more, which is a ratio of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm and the maximum value B of the absorbance in the range of the wavelength 1000 to 1300 nm. When prepared, it was surprisingly found that foreign matter defects hardly occur even when a film obtained using this composition is exposed to a high temperature and high humidity environment. The reason why such an effect is obtained is that it is presumed that other coloring materials other than the metal azo pigment were able to interact with the azo site of the metal azo pigment to improve the stability of the metal azo pigment it is conceivable that.
　一方、上述した金属アゾ顔料と他の色材とを含む組成物を塗布して膜を形成した場合、膜厚のばらつきが生じやすい傾向にあることが分かった。他の色材等の影響で、組成物中における金属アゾ顔料の分散状態が不安定化していることが原因と考えられる。また、上述した分光特性を有する組成物は、色材を比較的多く含む傾向にあるため、金属アゾ顔料の分散状態がより不安定化し易く、膜厚のばらつきが生じやすい傾向にあることが分かった。しかしながら、本発明の組成物は、上述した金属アゾ顔料と、他の色材との他に、さらに、エチレン性不飽和結合基を有する化合物、および、環状エーテル基を有する化合物から選ばれる少なくとも１種の化合物を含有させたことにより、このような膜厚のばらつきも効果的に抑制できた。このような効果が得られる理由としては以下によるものであると推測される。すなわち、組成物中にエチレン性不飽和結合基を有する化合物を含む場合においては、エチレン性不飽和結合基を有する化合物が金属アゾ顔料の顔料活性面（特にアゾ部位）と相互作用して、エチレン性不飽和結合基を有する化合物が金属アゾ顔料の表面に吸着され、金属アゾ顔料を安定化させることができると推測される。また、組成物中に環状エーテル基を有する化合物を含む場合においては、環状エーテル基が金属アゾ顔料に対して配位してキレート剤として作用すると推測され、その結果、金属アゾ顔料を安定化させることができると推測される。このため、本発明の組成物によれば、膜厚の均一性が良化したと推測される。 On the other hand, when a film was formed by applying a composition containing the metal azo pigment described above and another coloring material, it was found that the film thickness tended to easily vary. It is considered that the cause is that the dispersion state of the metal azo pigment in the composition is unstable due to the influence of other coloring materials and the like. In addition, since the composition having the above-mentioned spectral characteristics tends to contain a relatively large amount of coloring material, it is understood that the dispersion state of the metal azo pigment is more likely to be destabilized, and the film thickness tends to vary. The However, the composition of the present invention is at least one selected from a compound having an ethylenically unsaturated bond group and a compound having a cyclic ether group, in addition to the metal azo pigment described above and other coloring materials. Such variations in film thickness can be effectively suppressed by containing the compound of the type. The reason why such an effect can be obtained is presumed to be as follows. That is, in the case where the composition contains a compound having an ethylenically unsaturated bond group, the compound having an ethylenically unsaturated bond group interacts with the pigment active surface (in particular, azo moiety) of the metal azo pigment, It is speculated that a compound having an unsaturated unsaturated bond group is adsorbed on the surface of the metal azo pigment and can stabilize the metal azo pigment. In the case where the composition contains a compound having a cyclic ether group, it is presumed that the cyclic ether group coordinates to the metal azo pigment to act as a chelating agent, as a result, the metal azo pigment is stabilized. It is speculated that you can. Therefore, according to the composition of the present invention, it is presumed that the uniformity of the film thickness is improved.
　このため、本発明の組成物によれば、膜厚均一性が高く、高温高湿環境下での異物欠陥の発生が抑制された膜を製造できる。また、この組成物を用いて得られる膜は、波長４００～６００ｎｍの光の遮光性が高く、かつ、波長１０００～１３００ｎｍの光の透過性に優れるので、赤外線透過フィルタなどに好ましく用いることができる。また、本発明の組成物に含まれる上記金属アゾ顔料は、着色力の高い色材である。このため、本発明の組成物を用いることで、膜厚が薄くても、波長４００～６００ｎｍの範囲における遮光性の高い膜を形成することができる。また、組成物中の色材の含有量を低減させることもできるので、処方設計の自由度にも優れる。 For this reason, according to the composition of the present invention, it is possible to produce a film having high film thickness uniformity and in which the occurrence of foreign matter defects in a high temperature and high humidity environment is suppressed. Further, the film obtained using this composition has a high light shielding property for light of wavelength 400 to 600 nm and is excellent in the transmission of light of wavelength 1000 to 1300 nm, so it can be preferably used for an infrared transmission filter etc. . Further, the metal azo pigment contained in the composition of the present invention is a coloring material having high coloring power. Therefore, by using the composition of the present invention, a film having a high light shielding property in the wavelength range of 400 to 600 nm can be formed even if the film thickness is thin. In addition, since the content of the color material in the composition can be reduced, the degree of freedom in formulation design is also excellent.
　本発明の組成物は、波長４００～６００ｎｍの範囲における吸光度の最小値Ａと、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂとの比であるＡ／Ｂが４．５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。上記の吸光度比が４．５以上であれば、波長４００～６００ｎｍの光の遮光性が高く、かつ、波長１０００～１３００ｎｍの光の透過性に優れる膜を形成することができる。 The composition of the present invention has a ratio A / B of 4.5 or more, which is the ratio of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the range of wavelength 1000 to 1300 nm. It is preferably 5 or more, more preferably 15 or more, and still more preferably 30 or more. If the above absorbance ratio is 4.5 or more, a film having high light shielding properties for light with a wavelength of 400 to 600 nm and excellent transmittance for light with a wavelength of 1000 to 1300 nm can be formed.
　ある波長λにおける吸光度Ａλは、以下の式（１）により定義される。
　Ａλ＝－ｌｏｇ（Ｔλ／１００）　　　・・・（１）
　Ａλは、波長λにおける吸光度であり、Ｔλは、波長λにおける透過率（％）である。
　本発明において、吸光度の値は、溶液の状態で測定した値であってもよく、組成物を用いて製膜した膜の値であってもよい。膜の状態で吸光度を測定する場合は、ガラス基板上にスピンコート等の方法によって組成物を塗布し、ホットプレート等を用いて１００℃、１２０秒間乾燥して得られた膜を用いて測定することが好ましい。 The absorbance Aλ at a certain wavelength λ is defined by the following equation (1).
Aλ = -log (Tλ / 100) (1)
Aλ is the absorbance at wavelength λ, and Tλ is the transmittance (%) at wavelength λ.
In the present invention, the value of absorbance may be a value measured in the state of a solution, or may be a value of a film formed using a composition. In the case of measuring the absorbance in the state of a film, the composition is applied on a glass substrate by a method such as spin coating, and dried using a hot plate etc. and measured at 100 ° C. for 120 seconds. Is preferred.
　また、吸光度は従来公知の分光光度計を用いて測定できる。吸光度の測定条件は特に限定はないが、波長４００～６００ｎｍの範囲における吸光度の最小値Ａが、０．１～３．０になるように調整した条件で、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂを測定することが好ましい。このような条件で吸光度を測定することで、測定誤差をより小さくできる。波長４００～６００ｎｍの範囲における吸光度の最小値Ａが、０．１～３．０になるように調整する方法としては、特に限定はない。例えば、溶液の状態で吸光度を測定する場合は、試料セルの光路長を調整する方法が挙げられる。また、膜の状態で吸光度を測定する場合は、膜厚を調整する方法などが挙げられる。 Also, the absorbance can be measured using a conventionally known spectrophotometer. The measurement conditions of the absorbance are not particularly limited, but under the conditions adjusted so that the minimum value A of the absorbance in the wavelength range of 400 to 600 nm is 0.1 to 3.0, the absorbance in the wavelength range of 1000 to 1300 nm is It is preferable to measure the maximum value B. The measurement error can be further reduced by measuring the absorbance under such conditions. The method of adjusting the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to be 0.1 to 3.0 is not particularly limited. For example, in the case of measuring the absorbance in the state of a solution, there is a method of adjusting the optical path length of the sample cell. Moreover, when measuring a light absorbency in the state of a film | membrane, the method of adjusting a film thickness etc. are mentioned.
　本発明の組成物は、以下の（１）～（３）のいずれかの分光特性を満たしていることが好ましく、高温高湿環境下での異物欠陥の発生がより抑制された膜を製造し易いという理由から、（２）または（３）の分光特性を満たしていることがより好ましく、（３）の分光特性を満たしていることが更に好ましい。このような効果が得られる理由としては以下によるものであると推測される。（１）、（２）、（３）の順に、より長波長側までの光を遮光できる膜を形成することができるが、より長波長までの光を遮光させるには、他の色材としてより長波長に吸収のある色材が用いられたり、更に近赤外線吸収色素を含有させることがある。このような素材は、広い共役系を有していることが多く、金属アゾ顔料と相互作用し易い傾向にあると推測される。そのため、金属アゾ顔料をより安定化させることができ、その結果、高温高湿環境下での異物欠陥の発生がより抑制された膜を製造することができると推測される。 The composition of the present invention preferably satisfies any of the following spectral characteristics (1) to (3), and produces a film in which the occurrence of foreign matter defects in a high temperature and high humidity environment is further suppressed. It is more preferable that the spectral characteristics of (2) or (3) be satisfied, and it is further preferable that the spectral characteristics of (3) be satisfied because it is easy. The reason why such an effect can be obtained is presumed to be as follows. It is possible to form a film that can block light up to the longer wavelength side in the order of (1), (2), and (3), but to block light up to longer wavelength side, as other color materials Colorants having absorption at longer wavelengths may be used, or near infrared absorbing dyes may be further contained. Such materials often have a wide conjugated system and are presumed to tend to interact with metal azo pigments. Therefore, it is presumed that the metal azo pigment can be further stabilized, and as a result, it is possible to produce a film in which the occurrence of foreign matter defects in a high temperature and high humidity environment is further suppressed.
　（１）：波長４００～６００ｎｍの範囲における吸光度の最小値Ａ１と、波長８００～１３００ｎｍの範囲における吸光度の最大値Ｂ１との比であるＡ１／Ｂ１が４．５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。この態様によれば、波長４００～６００ｎｍの範囲の光を遮光して、波長６５０ｎｍを超える光を透過可能な膜を形成することができる。
　（２）：波長４００～７２０ｎｍの範囲における吸光度の最小値Ａ２と、波長９００～１３００ｎｍの範囲における吸光度の最大値Ｂ２との比であるＡ２／Ｂ２が４．５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。この態様によれば、波長４００～７５０ｎｍの範囲の光を遮光して、波長８００ｎｍを超える光を透過可能な膜を形成することができる。
　（３）：波長４００～８３０ｎｍの範囲における吸光度の最小値Ａ３と、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂ３との比であるＡ３／Ｂ３が４．５以上であり、７．５以上であることが好ましく、１５以上であることがより好ましく、３０以上であることが更に好ましい。この態様によれば、波長４００～８３０ｎｍの範囲の光を遮光して、波長９００ｎｍを超える光を透過可能な膜を形成することができる。 (1): A1 / B1 which is a ratio of the minimum value A1 of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B1 of the absorbance in the range of wavelength 800 to 1300 nm is 4.5 or more, 7.5 or more Is more preferably 15 or more, still more preferably 30 or more. According to this aspect, it is possible to shield the light in the wavelength range of 400 to 600 nm, and to form a film capable of transmitting light in excess of the wavelength of 650 nm.
(2): A2 / B2 which is a ratio of the minimum value A2 of the absorbance in the wavelength range of 400 to 720 nm to the maximum value B2 of the absorbance in the range of wavelength 900 to 1300 nm is 4.5 or more, 7.5 or more Is more preferably 15 or more, still more preferably 30 or more. According to this aspect, it is possible to block light in the wavelength range of 400 to 750 nm, and to form a film capable of transmitting light in excess of the wavelength of 800 nm.
(3): A3 / B3 which is the ratio of the minimum value A3 of the absorbance in the wavelength range of 400 to 830 nm to the maximum value B3 of the absorbance in the range of wavelength 1000 to 1300 nm is 4.5 or more, 7.5 or more Is more preferably 15 or more, still more preferably 30 or more. According to this aspect, it is possible to block light in the wavelength range of 400 to 830 nm to form a film capable of transmitting light in excess of the wavelength of 900 nm.
　本発明の組成物は、乾燥後の膜厚が１０．０μｍ以下（好ましくは５．０μｍ以下であり、より好ましくは３．０μｍ以下であり、更に好ましくは２．５μｍ以下であり、より一層好ましくは２．０μｍ以下であり、特に好ましくは１．５μｍ以下である。また、下限値は、０．４μｍ以上とすることができ、０．５μｍ以上とすることもでき、０．６μｍ以上とすることもでき、０．７μｍ以上とすることもでき、０．８μｍ以上とすることもでき、０．９μｍ以上とすることもできる。）の膜を製膜した際に、前述の膜厚の少なくとも１つにおいて、膜の厚み方向における光の透過率の、波長４００～６００ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１０００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である分光特性を満たしていることが好ましい。 The composition of the present invention has a film thickness after drying of 10.0 μm or less (preferably 5.0 μm or less, more preferably 3.0 μm or less, still more preferably 2.5 μm or less, and still more preferably Is preferably 2.0 μm or less, more preferably 1.5 μm or less, and the lower limit value may be 0.4 μm or more, 0.5 μm or more, 0.6 μm or more Or at least 0.8 μm, or at least 0.8 μm, or at least 0.9 μm. In one of them, the maximum value of light transmittance in the thickness direction of the film in a wavelength range of 400 to 600 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and a wavelength of 1000 to 1300 nm Minimum 70% of the circumference (preferably 75% or more, more preferably 80% or more) preferably satisfy the spectral characteristics it is.
　また、本発明の組成物は、以下の（１１）～（１３）のいずれかの分光特性を満たしていることが好ましく、高温高湿環境下での異物欠陥の発生がより抑制された膜を製造し易いという理由から、（１２）または（１３）の分光特性を満たしていることがより好ましく、（１３）の分光特性を満たしていることが更に好ましい。 In addition, the composition of the present invention preferably satisfies the following spectral characteristics (11) to (13), and a film in which the occurrence of foreign matter defects in a high temperature and high humidity environment is further suppressed: It is more preferable that the spectral characteristics of (12) or (13) be satisfied, and it is further preferable that the spectral characteristics of (13) be satisfied because it is easy to manufacture.
　（１１）：本発明の組成物を用いて乾燥後の膜厚が０．４～３．０μｍ（好ましくは０．５～２．５μｍ、より好ましくは０．６～２．０μｍ、更に好ましくは０．７～１．５μｍ）の膜を製造した際に、膜の厚み方向における光の透過率の、波長４００～６００ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、膜の厚み方向における光の透過率の、波長８００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である態様。
　（１２）：本発明の組成物を用いて乾燥後の膜厚が０．５～５．０μｍ（好ましくは０．６～３．０μｍ、より好ましくは０．７～２．５μｍ、更に好ましくは０．８～２．０μｍ）の膜を製造した際に、膜の厚み方向における光の透過率の、波長４００～７２０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、膜の厚み方向における光の透過率の、波長９００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である態様。
　（１３）：本発明の組成物を用いて乾燥後の膜厚が０．６～１０μｍ（好ましくは０．７～５．０μｍ、より好ましくは０．８～３．０μｍ、更に好ましくは０．９～２．５μｍ）の膜を製造した際に、膜の厚み方向における光の透過率の、波長４００～８３０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、膜の厚み方向における光の透過率の、波長１０００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である態様。 (11): The film thickness after drying using the composition of the present invention is 0.4 to 3.0 μm (preferably 0.5 to 2.5 μm, more preferably 0.6 to 2.0 μm, still more preferably When a film of 0.7 to 1.5 μm) is produced, the maximum value of light transmittance in the thickness direction of the film in the wavelength range of 400 to 600 nm is 20% or less (preferably 15% or less, more preferably) An embodiment in which the minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more)).
(12): The film thickness after drying using the composition of the present invention is 0.5 to 5.0 μm (preferably 0.6 to 3.0 μm, more preferably 0.7 to 2.5 μm, still more preferably When a film of 0.8 to 2.0 μm) is produced, the maximum value of light transmittance in the thickness direction of the film in the wavelength range of 400 to 720 nm is 20% or less (preferably 15% or less, more preferably) 10% or less) and an embodiment in which the minimum value of the light transmittance in the thickness direction of the film in the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
(13): The film thickness after drying using the composition of the present invention is 0.6 to 10 μm (preferably 0.7 to 5.0 μm, more preferably 0.8 to 3.0 μm, still more preferably 0. When a film of 9 to 2.5 μm) is produced, the maximum value of the light transmittance in the thickness direction of the film in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10%) The following is an embodiment in which the minimum value in the wavelength range of 1000 to 1300 nm of the light transmittance in the film thickness direction is 70% or more (preferably 75% or more, more preferably 80% or more).
　以下、本発明の組成物に用いられる各成分について説明する。 Hereinafter, each component used for the composition of this invention is demonstrated.
＜＜金属アゾ顔料Ａ＞＞
　本発明の組成物は、下記式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、２種以上の金属イオンと、メラミン化合物とを含む金属アゾ顔料Ａを含む。
Figure JPOXMLDOC01-appb-C000005
 << Metal azo pigment A >>
The composition of the present invention comprises at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure thereof, two or more metal ions, and a melamine compound. Metal azo pigment A is included.
Figure JPOXMLDOC01-appb-C000005
　式中、Ｒ１およびＲ２はそれぞれ独立して、ＯＨまたはＮＲ５Ｒ６であり、Ｒ３およびＲ４はそれぞれ独立して、＝Ｏまたは＝ＮＲ７であり、Ｒ５～Ｒ７はそれぞれ独立して、水素原子またはアルキル基である。Ｒ５～Ｒ７が表すアルキル基の炭素数は１～１０が好ましく、１～６がより好ましく、１～４が更に好ましい。アルキル基は、直鎖、分岐および環状のいずれであってもよいが、直鎖または分岐が好ましく、直鎖がより好ましい。アルキル基は置換基を有していてもよい。置換基としては、後述の置換基Ｔが挙げられ、ハロゲン原子、ヒドロキシ基、アルコキシ基、シアノ基およびアミノ基が好ましい。 In the formula, R 1 and R 2 are each independently OH or NR 5 R 6 , R 3 and R 4 are each independently = O or NRNR 7 , and R 5 to R 7 are each Independently, it is a hydrogen atom or an alkyl group. The carbon number of the alkyl group represented by R 5 to R 7 is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. The alkyl group may be linear, branched or cyclic, but linear or branched is preferable, and linear is more preferable. The alkyl group may have a substituent. As a substituent, the below-mentioned substituent T is mentioned, A halogen atom, a hydroxyl group, an alkoxy group, a cyano group, and an amino group are preferable.
　式（Ｉ）において、Ｒ１およびＲ２はＯＨであることが好ましい。また、Ｒ３およびＲ４は＝Ｏであることが好ましい。 In formula (I), R 1 and R 2 are preferably OH. Further, R 3 and R 4 are preferably = O.
　金属アゾ顔料Ａにおけるメラミン化合物は、下記式（ＩＩ）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000006
 The melamine compound in the metal azo pigment A is preferably a compound represented by the following formula (II).
Figure JPOXMLDOC01-appb-C000006
　式中Ｒ１１～Ｒ１３は、それぞれ独立して水素原子またはアルキル基である。アルキル基の炭素数は１～１０が好ましく、１～６がより好ましく、１～４が更に好ましい。アルキル基は、直鎖、分岐および環状のいずれであってもよいが、直鎖または分岐が好ましく、直鎖がより好ましい。アルキル基は置換基を有していてもよい。置換基としては、後述の置換基Ｔが挙げられ、ヒドロキシ基が好ましい。Ｒ１１～Ｒ１３の少なくとも一つは水素原子であることが好ましく、Ｒ１１～Ｒ１３の全てが水素原子であることがより好ましい。 In the formula, R 11 to R 13 each independently represent a hydrogen atom or an alkyl group. The carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. The alkyl group may be linear, branched or cyclic, but linear or branched is preferable, and linear is more preferable. The alkyl group may have a substituent. As a substituent, the below-mentioned substituent T is mentioned and a hydroxyl group is preferable. Preferably, at least one of R 11 ~ R 13 is a hydrogen atom, more preferably all of R 11 ~ R 13 is a hydrogen atom.
　金属アゾ顔料Ａは、式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンの１モル当たり、メラミン化合物（好ましくは式（ＩＩ）で表される化合物）を０．０５～４モル含有することが好ましく、０．５～２．５モル含有することがより好ましく、１．０～２．０モル含有することが更に好ましい。 The metal azo pigment A is preferably a melamine compound (preferably represented by the formula (II), per mole of at least one anion selected from the azo compound represented by the formula (I) and the azo compound of the tautomeric structure thereof. Is preferably contained in an amount of 0.05 to 4 mol, more preferably 0.5 to 2.5 mol, and still more preferably 1.0 to 2.0 mol.
　金属アゾ顔料Ａの比表面積は２０～２００ｍ２／ｇであることが好ましい。下限は６０ｍ２／ｇ以上であることが好ましく、９０ｍ２／ｇ以上であることがより好ましい。上限は、１６０ｍ２／ｇ以下であることが好ましく、１５０ｍ２／ｇ以下であることがより好ましい。金属アゾ顔料Ａの比表面積の値は、ＢＥＴ（Ｂｒｕｎａｕｅｒ、ＥｍｍｅｔｔおよびＴｅｌｌｅｒ）法に準じてＤＩＮ　６６１３１：ｄｅｔｅｒｍｉｎａｔｉｏｎ　ｏｆ　ｔｈｅ　ｓｐｅｃｉｆｉｃ　ｓｕｒｆａｃｅ　ａｒｅａ　　ｏｆ　ｓｏｌｉｄｓ　ｂｙ　ｇａｓ　ａｄｓｏｒｐｔｉｏｎ（ガス吸着による固体の比表面積の測定）に従って測定した値である。 The specific surface area of the metal azo pigment A is preferably 20 to 200 m 2 / g. The lower limit is preferably 60 m 2 / g or more, and more preferably 90 m 2 / g or more. The upper limit is preferably 160 m 2 / g or less, more preferably 150 m 2 / g or less. The value of the specific surface area of metal azo pigment A is measured according to DIN 66131: determination of the specific surface area of solids by gas adsorption (measurement of specific surface area of solid by gas adsorption) according to the BET (Brunauer, Emmett and Teller) method. Value.
　（置換基Ｔ）
　上述の置換基Ｔとして、次の基が挙げられる。アルキル基（好ましくは炭素数１～３０のアルキル基）、アルケニル基（好ましくは炭素数２～３０のアルケニル基）、アルキニル基（好ましくは炭素数２～３０のアルキニル基）、アリール基（好ましくは炭素数６～３０のアリール基）、アミノ基（好ましくは炭素数０～３０のアミノ基）、アルコキシ基（好ましくは炭素数１～３０のアルコキシ基）、アリールオキシ基（好ましくは炭素数６～３０のアリールオキシ基）、ヘテロアリールオキシ基、アシル基（好ましくは炭素数１～３０のアシル基）、アルコキシカルボニル基（好ましくは炭素数２～３０のアルコキシカルボニル基）、アリールオキシカルボニル基（好ましくは炭素数７～３０のアリールオキシカルボニル基）、ヘテロアリールオキシカルボニル基、アシルオキシ基（好ましくは炭素数２～３０のアシルオキシ基）、アシルアミノ基（好ましくは炭素数２～３０のアシルアミノ基）、アルコキシカルボニルアミノ基（好ましくは炭素数２～３０のアルコキシカルボニルアミノ基）、アリールオキシカルボニルアミノ基（好ましくは炭素数７～３０のアリールオキシカルボニルアミノ基）、スルファモイル基（好ましくは炭素数０～３０のスルファモイル基）、カルバモイル基（好ましくは炭素数１～３０のカルバモイル基）、アルキルチオ基（好ましくは炭素数１～３０のアルキルチオ基）、アリールチオ基（好ましくは炭素数６～３０のアリールチオ基）、ヘテロアリールチオ基（好ましくは炭素数１～３０）、アルキルスルホニル基（好ましくは炭素数１～３０）、アリールスルホニル基（好ましくは炭素数６～３０）、ヘテロアリールスルホニル基（好ましくは炭素数１～３０）、アルキルスルフィニル基（好ましくは炭素数１～３０）、アリールスルフィニル基（好ましくは炭素数６～３０）、ヘテロアリールスルフィニル基（好ましくは炭素数１～３０）、ウレイド基（好ましくは炭素数１～３０）、ヒドロキシ基、カルボキシル基、スルホ基、リン酸基、カルボン酸アミド基、スルホン酸アミド基、イミド酸基、メルカプト基、ハロゲン原子、シアノ基、アルキルスルフィノ基、アリールスルフィノ基、ヒドラジノ基、イミノ基、ヘテロアリール基（好ましくは炭素数１～３０）。これらの基は、さらに置換可能な基である場合、さらに置換基を有してもよい。さらなる置換基としては、上述した置換基Ｔで説明した基が挙げられる。 (Substituent T)
The following groups may be mentioned as the aforementioned substituent T. An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably An aryl group having 6 to 30 carbon atoms, an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably 6 to carbon atoms 30) aryloxy group), heteroaryloxy group, acyl group (preferably having 1 to 30 carbon atoms), alkoxycarbonyl group (preferably having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably having 2 to 30 carbon atoms) Is an aryloxycarbonyl group having 7 to 30 carbon atoms, a heteroaryloxycarbonyl group, an acyloxy group Preferably, it is an acyloxy group having 2 to 30 carbon atoms, an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonyl Amino group (preferably aryloxycarbonylamino group having 7 to 30 carbon atoms), sulfamoyl group (preferably sulfamoyl group having 0 to 30 carbon atoms), carbamoyl group (preferably carbamoyl group having 1 to 30 carbon atoms), alkylthio group (Preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heteroarylthio group (preferably having a carbon number of 1 to 30), an alkylsulfonyl group (preferably having a carbon number 1 to 30), an arylsulfonyl group (preferably charcoal) 6 to 30), heteroarylsulfonyl (preferably having a carbon number of 1 to 30), alkylsulfinyl (preferably having a carbon number of 1 to 30), arylsulfinyl (preferably having a carbon number of 6 to 30), heteroarylsulfinyl group (Preferably 1 to 30 carbon atoms), ureido group (preferably 1 to 30 carbon atoms), hydroxy group, carboxyl group, sulfo group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imidic acid group, mercapto Group, halogen atom, cyano group, alkylsulfino group, arylsulfino group, hydrazino group, imino group, heteroaryl group (preferably having a carbon number of 1 to 30). When these groups are further substitutable groups, they may further have a substituent. As the further substituent, the groups described for the above-mentioned substituent T can be mentioned.
　金属アゾ顔料Ａは、式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと金属イオンとで金属錯体が形成されていることが好ましい。例えば、２価の金属イオンＭｅの場合は、上記のアニオンと金属イオンＭｅとで下記式（Ｉａ）で表される構造の金属錯体を形成することができる。金属イオンＭｅは、式（Ｉａ）の互変異性表記における窒素原子を介して結合して錯体を形成していてもよい。
Figure JPOXMLDOC01-appb-C000007
 In the metal azo pigment A, a metal complex is preferably formed of at least one anion selected from an azo compound represented by the formula (I) and an azo compound having a tautomeric structure thereof and a metal ion. For example, in the case of the divalent metal ion Me, a metal complex having a structure represented by the following formula (Ia) can be formed by the above anion and the metal ion Me. The metal ion Me may be bonded via a nitrogen atom in the tautomeric notation of the formula (Ia) to form a complex.
Figure JPOXMLDOC01-appb-C000007
　金属アゾ顔料Ａの好ましい態様としては、以下の（Ａｚ１）～（Ａｚ４）の態様の金属アゾ顔料が挙げられ、本発明の効果がより顕著に得られやすく、更には、分光特性をより向上できるという理由から（Ａｚ１）の態様の金属アゾ顔料であることが好ましい。 Preferred embodiments of the metal azo pigment A include the metal azo pigments of the following embodiments (Az1) to (Az4), and the effects of the present invention are more easily obtained, and the spectral characteristics can be further improved. It is preferable that it is a metal azo pigment of the aspect of (Az1) from the reason.
　（Ａｚ１）　上述した式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、Ｚｎ２＋およびＣｕ２＋を少なくとも含む金属イオンと、メラミン化合物とを含む態様の金属アゾ顔料。この態様においては、金属アゾ顔料の全金属イオンの１モルを基準として、Ｚｎ２＋およびＣｕ２＋を合計で９５～１００モル％含有することが好ましく、９８～１００モル％含有することがより好ましく、９９．９～１００モル％含有することが更に好ましく、１００モル％であることが特に好ましい。また、金属アゾ顔料中のＺｎ２＋とＣｕ２＋とのモル比は、Ｚｎ２＋：Ｃｕ２＋＝１９９：１～１：１５であることが好ましく、１９：１～１：１であることがより好ましく、９：１～２：１であることが更に好ましい。また、この態様において、金属アゾ顔料は、更にＺｎ２＋およびＣｕ２＋以外の二価もしくは三価の金属イオン（以下、金属イオンＭｅ１ともいう）を含んでいてもよい。金属イオンＭｅ１としては、Ｎｉ２＋、Ａｌ３＋、Ｆｅ２＋、Ｆｅ３＋、Ｃｏ２＋、Ｃｏ３＋、Ｌａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ２＋、Ｎｄ３＋、Ｓｍ２＋、Ｓｍ３＋、Ｅｕ２＋、Ｅｕ３＋、Ｇｄ３＋、Ｔｂ３＋、Ｄｙ３＋、Ｈｏ３＋、Ｙｂ２＋、Ｙｂ３＋、Ｅｒ３＋、Ｔｍ３＋、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋、Ｍｎ２＋、Ｙ３＋、Ｓｃ３＋、Ｔｉ２＋、Ｔｉ３＋、Ｎｂ３＋、Ｍｏ２＋、Ｍｏ３＋、Ｖ２＋、Ｖ３＋、Ｚｒ２＋、Ｚｒ３＋、Ｃｄ２＋、Ｃｒ３＋、Ｐｂ２＋、Ｂａ２＋が挙げられ、Ａｌ３＋、Ｆｅ２＋、Ｆｅ３＋、Ｃｏ２＋、Ｃｏ３＋、Ｌａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ３＋、Ｓｍ３＋、Ｅｕ３＋、Ｇｄ３＋、Ｔｂ３＋、Ｄｙ３＋、Ｈｏ３＋、Ｙｂ３＋、Ｅｒ３＋、Ｔｍ３＋、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋、Ｍｎ２＋およびＹ３＋から選ばれる少なくとも１種であることが好ましく、Ａｌ３＋、Ｆｅ２＋、Ｆｅ３＋、Ｃｏ２＋、Ｃｏ３＋、Ｌａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ３＋、Ｓｍ３＋、Ｔｂ３＋、Ｈｏ３＋およびＳｒ２＋から選ばれる少なくとも１種であることが更に好ましく、Ａｌ３＋、Ｆｅ２＋、Ｆｅ３＋、Ｃｏ２＋およびＣｏ３＋から選ばれる少なくとも１種であることが特に好ましい。金属イオンＭｅ１の含有量は、金属アゾ顔料の全金属イオンの１モルを基準として、５モル％以下であることが好ましく、２モル％以下であることがより好ましく、０．１モル％以下であることが更に好ましい。 (Az1) At least one anion selected from the azo compound represented by the formula (I) and the azo compound of the tautomeric structure described above, a metal ion containing at least Zn 2+ and Cu 2+ , and a melamine compound The metal azo pigment of the aspect containing. In this aspect, the total content of Zn 2+ and Cu 2+ is preferably 95 to 100 mol%, more preferably 98 to 100 mol%, based on 1 mol of the total metal ions of the metal azo pigment. It is more preferable to contain 99.9 to 100 mol%, and it is particularly preferable to be 100 mol%. In addition, the molar ratio of Zn 2+ to Cu 2+ in the metal azo pigment is preferably Zn 2+ : Cu 2+ = 199: 1 to 1:15, and more preferably 19: 1 to 1: 1. And 9: 1 to 2: 1. Moreover, in this embodiment, the metal azo pigment may further contain a divalent or trivalent metal ion other than Zn 2+ and Cu 2+ (hereinafter also referred to as a metal ion Me1). As the metal ion Me1 is, Ni 2+, Al 3+, Fe 2+, Fe 3+, Co 2+, Co 3+, La 3+, Ce 3+, Pr 3+, Nd 2+, Nd 3+, Sm 2+, Sm 3+, Eu 2+, Eu 3+ , Gd3 + , Tb3 + , Dy3 + , Ho3 + , Yb2 + , Yb3 + , Er3 + , Tm3 + , Mg2 + , Ca2 + , Sr2 + , Mn2 + , Y3 + , Sc3 + , Ti2 + , Ti3 + , Nb 3+, Mo 2+, Mo 3+, V 2+, V 3+, Zr 2+, Zr 3+, Cd 2+, Cr 3+, Pb 2+, Ba 2+ are mentioned, Al 3+, Fe 2+, Fe 3+, Co 2+, Co 3+, la 3+, Ce 3+, Pr 3+ , Nd 3+, Sm 3+, Eu 3+, Gd 3+, Tb 3+, Dy 3+, H 3+, Yb 3+, Er 3+, Tm 3+, Mg 2+, Ca 2+, Sr 2+, is preferably at least one selected from Mn 2+ and Y 3+, Al 3+, Fe 2+ , Fe 3+, Co 2+, Co 3+, La 3+, Ce 3+, Pr 3+, Nd 3+, Sm 3+, Tb 3+, more preferably at least one selected from Ho 3+ and Sr 2+, Al 3+, Fe 2+ , Fe 3+, Co 2+ and It is particularly preferable that it is at least one selected from Co 3+ . The content of the metal ion Me1 is preferably 5 mol% or less, more preferably 2 mol% or less, and more preferably 0.1 mol% or less based on 1 mol of all metal ions of the metal azo pigment. It is further preferred that
　（Ａｚ２）　上述した式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、金属イオンと、メラミン化合物とを含み、金属イオンは、Ｎｉ２＋、Ｚｎ２＋および少なくとも１種のさらなる金属イオンＭｅ２を含み、金属イオンＭｅ２は、Ｌａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ２＋、Ｎｄ３＋、Ｓｍ２＋、Ｓｍ３＋、Ｅｕ２＋、Ｅｕ３＋、Ｇｄ３＋、Ｔｂ３＋、Ｄｙ３＋、Ｈｏ３＋、Ｅｒ３＋、Ｔｍ３＋、Ｙｂ２＋、Ｙｂ３＋、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋、Ｂａ２＋、Ｓｃ３＋、Ｙ３＋、Ｔｉ２＋、Ｔｉ３＋、Ｚｒ２＋、Ｚｒ３＋、Ｖ２＋、Ｖ３＋、Ｎｂ３＋、Ｃｒ３＋、Ｍｏ２＋、Ｍｏ３＋、Ｍｎ２＋、Ｃｄ２＋、およびＰｂ２＋から選ばれる少なくとも１種である態様の金属アゾ顔料。金属イオンＭｅ２は、Ｌａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ３＋、Ｓｍ３＋、Ｅｕ３＋、Ｇｄ３＋、Ｔｂ３＋、Ｄｙ３＋、Ｈｏ３＋、Ｅｒ３＋、Ｔｍ３＋、Ｙｂ３＋、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋、Ｙ３＋、およびＭｎ２＋から選ばれる少なくとも１種であることが好ましく、Ｌａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ３＋、Ｓｍ３＋、Ｔｂ３＋、Ｈｏ３＋、およびＳｒ２＋から選ばれる少なくとも１種であることがより好ましい。この態様においては、金属アゾ顔料の全金属イオンの１モルを基準として、Ｚｎ２＋およびＮｉ２＋を合計で７５～９９．５モル％含有し、かつ、金属イオンＭｅ２を０．５～２５モル％含有することが好ましく、Ｚｎ２＋およびＮｉ２＋を合計で７８～９５モル％含有し、かつ、金属イオンＭｅ２を５～２２モル％含有することがより好ましく、Ｚｎ２＋およびＮｉ２＋を合計で８２～９０モル％含有し、かつ、金属イオンＭｅ２を１０～１８モル％含有することが更に好ましい。また、金属アゾ顔料中のＺｎ２＋とＮｉ２＋とのモル比は、Ｚｎ２＋：Ｎｉ２＋＝９０：３～３：９０であることが好ましく、８０：５～５：８０であることがより好ましく、６０：３３～３３：６０であることが更に好ましい。 (Az2) The metal ion contains at least one anion selected from the azo compound represented by the formula (I) and the azo compound of the tautomeric structure described above, a metal ion, and a melamine compound, and the metal ion is Ni 2+ , Zn 2+ and at least one further metal ion Me 2, wherein the metal ion Me 2 is La 3+ , Ce 3+ , Pr 3+ , Nd 2+ , Nd 3+ , Sm 2+ , Sm 3+ , Eu 2+ , Eu 3+ , Gd 3+ , Tb3 + , Dy3 + , Ho3 + , Er3 + , Tm3 + , Yb2 + , Yb3 + , Mg2 + , Ca2 + , Sr2 + , Ba2 + , Sc3 + , Y3 + , Ti2 + , Ti3 + , Zr2 + , Zr3 + , V 2+, V 3+, Nb 3+, Cr 3+, Mo 2+, Mo 3+, Mn 2+, Cd 2+, and P Aspect of the azo pigment is at least one selected from 2+. The metal ion Me2 is La3 + , Ce3 + , Pr3 + , Nd3 + , Sm3 + , Eu3 + , Gd3 + , Tb3 + , Dy3 + , Ho3 + , Er3 + , Tm3 + , Yb3 + , Mg2 + , Ca2 + , Ca2 + , Ca2 + , It is preferably at least one selected from Sr 2+ , Y 3+ , and Mn 2+ , and at least one selected from La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Tb 3+ , Ho 3+ , and Sr 2+ More preferably, it is a species. In this embodiment, based on 1 mole of the total metal ions of the metal azo pigment, it contains 75 to 99.5 mole% in total of Zn 2+ and Ni 2+ and 0.5 to 25 mole% of metal ion Me preferably it contains, contains 78 to 95 mol% of Zn 2+ and Ni 2+ in total, and more preferably containing metal ions Me2 5 - 22 mol%, 82 to the Zn 2+ and Ni 2+ in total It is more preferable to contain 90 mol% and to contain 10 to 18 mol% of metal ion Me2. Further, the molar ratio of Zn 2+ to Ni 2+ in the metal azo pigment is preferably Zn 2+ : Ni 2+ = 90: 3 to 3:90 , and more preferably 80: 5 to 5:80. And 60:33 to 33:60.
　（Ａｚ３）　上述した式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、金属イオンと、メラミン化合物とを含み、金属イオンは、Ｎｉ２＋、Ｃｕ２＋および少なくとも１種のさらなる金属イオンＭｅ３を含み、金属イオンＭｅ３がＬａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ２＋、Ｎｄ３＋、Ｓｍ２＋、Ｓｍ３＋、Ｅｕ２＋、Ｅｕ３＋、Ｇｄ３＋、Ｔｂ３＋、Ｄｙ３＋、Ｈｏ３＋、Ｙｂ２＋、Ｙｂ３＋、Ｅｒ３＋、Ｔｍ３＋、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋、Ｍｎ２＋、Ｙ３＋、Ｓｃ３＋、Ｔｉ２＋、Ｔｉ３＋、Ｎｂ３＋、Ｍｏ２＋、Ｍｏ３＋、Ｖ２＋、Ｖ３＋、Ｚｒ２＋、Ｚｒ３＋、Ｃｄ２＋、Ｃｒ３＋、Ｐｂ２＋およびＢａ２＋から選ばれる少なくとも１種である態様の金属アゾ顔料。金属イオンＭｅ３は、Ｌａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ３＋、Ｓｍ３＋、Ｅｕ３＋、Ｇｄ３＋、Ｔｂ３＋、Ｄｙ３＋、Ｈｏ３＋、Ｙｂ３＋、Ｅｒ３＋、Ｔｍ３＋、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋、Ｍｎ２＋、およびＹ３＋から選ばれる少なくとも１種であることが好ましく、Ｌａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ３＋、Ｓｍ３＋、Ｔｂ３＋、Ｈｏ３＋、およびＳｒ２＋から選ばれる少なくとも１種であることがより好ましい。この態様においては、金属アゾ顔料の全金属イオンの１モルを基準として、Ｃｕ２＋およびＮｉ２＋を合計で７０～９９．５モル％含有し、かつ、金属イオンＭｅ３を０．５～３０モル％含有することが好ましく、Ｃｕ２＋およびＮｉ２＋を合計で７５～９５モル％含有し、かつ、金属イオンＭｅ３を５～２５モル％含有することがより好ましく、Ｃｕ２＋およびＮｉ２＋を合計で８０～９０モル％含有し、かつ、金属イオンＭｅ３を１０～２０モル％含有することが更に好ましい。また、金属アゾ顔料中のＣｕ２＋とＮｉ２＋とのモル比は、Ｃｕ２＋：Ｎｉ２＋＝４２：１～１：４２であることが好ましく、１０：１～１：１０であることがより好ましく、３：１～１：３であることが更に好ましい。 (Az3) The metal ion contains at least one anion selected from the azo compound represented by the formula (I) and the azo compound of the tautomeric structure described above, a metal ion, and a melamine compound, and the metal ion is Ni 2+ , Cu 2+ and at least one further metal ion Me 3 , wherein the metal ion Me 3 is La 3+ , Ce 3+ , Pr 3+ , Nd 2+ , Nd 3+ , Sm 2+ , Sm 3+ , Eu 2+ , Eu 3+ , Gd 3+ , Tb 3 3+ , Dy3 + , Ho3 + , Yb2 + , Yb3 + , Er3 + , Tm3 + , Mg2 + , Ca2 + , Ca2 + , Sr2 + , Mn2 + , Y3 + , Sc3 + , Ti2 + , Ti3 + , Nb3 + , Mo2 + , Mo 3+, V 2+, V 3+ , Zr 2+, Zr 3+, Cd 2+, Cr 3+, Pb 2+ and Ba 2 Aspect of the azo pigment is at least one selected from the. The metal ion Me3 is La3 + , Ce3 + , Pr3 + , Nd3 + , Sm3 + , Eu3 + , Gd3 + , Tb3 + , Dy3 + , Ho3 + , Yb3 + , Er3 + , Tm3 + , Mg2 + , Ca2 + , Ca2 + , Ca2 + , It is preferably at least one selected from Sr 2+ , Mn 2+ , and Y 3+ , and at least one selected from La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Tb 3+ , Ho 3+ , and Sr 2+. More preferably, it is a species. In this embodiment, based on 1 mole of the total metal ions of the metal azo pigment, the total content of Cu 2+ and Ni 2+ is 70 to 99.5 mol%, and 0.5 to 30 mol% of the metal ion Me3. preferably contains contains 75-95 mol% of Cu 2+ and Ni 2+ in total, and more preferably containing metal ions Me3 5 - 25 mol%, 80 to the Cu 2+ and Ni 2+ in total It is more preferable to contain 90 mol% and to contain 10 to 20 mol% of metal ion Me3. Further, the molar ratio of Cu 2+ to Ni 2+ in the metal azo pigment is preferably Cu 2+ : Ni 2+ = 42: 1 to 1:42, and more preferably 10: 1 to 1:10. More preferably, 3: 1 to 1: 3.
　（Ａｚ４）　上述した式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、金属イオンと、メラミン化合物とを含み、金属イオンは、Ｎｉ２＋と金属イオンＭｅ４ａを含み、金属イオンＭｅ４ａがＬａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ２＋、Ｎｄ３＋、Ｓｍ２＋、Ｓｍ３＋、Ｅｕ２＋、Ｅｕ３＋、Ｇｄ３＋、Ｔｂ３＋、Ｄｙ３＋、Ｈｏ３＋、Ｅｒ３＋、Ｔｍ３＋、Ｙｂ２＋およびＹｂ３＋から選ばれる少なくとも１種である態様の金属アゾ顔料。金属イオンＭｅ４ａは、Ｌａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ３＋、Ｓｍ３＋、Ｅｕ３＋、Ｇｄ３＋、Ｔｂ３＋、Ｄｙ３＋、Ｈｏ３＋、Ｅｒ３＋、Ｔｍ３＋およびＹｂ３＋から選ばれる少なくとも１種であることが好ましく、Ｌａ３＋、Ｃｅ３＋、Ｐｒ３＋、Ｎｄ３＋、Ｓｍ３＋、Ｔｂ３＋およびＨｏ３＋から選ばれる少なくとも１種であることがより好ましい。この態様においては、金属アゾ顔料の全金属イオンの１モルを基準として、Ｎｉ２＋および金属イオンＭｅ４ａを合計で９５～１００モル％含有することが好ましく、９８～１００モル％含有することがより好ましく、９９．９～１００モル％含有することが更に好ましく、１００モル％であることが特に好ましい。また、金属アゾ顔料中のＮｉ２＋と金属イオンＭｅ４ａとのモル比は、Ｎｉ２＋：金属イオンＭｅ４ａ＝１：１～１９：１であることが好ましく、２：１～４：１であることがより好ましく、２．３：１～３：１であることが更に好ましい。また、この態様において、金属アゾ顔料は、更にＮｉ２＋および金属イオンＭｅ４ａ以外の金属イオン（以下、金属イオンＭｅ４ｂともいう）を含んでいてもよい。金属イオンＭｅ４ｂとしては、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋、Ｂａ２＋、Ｓｃ３＋、Ｙ３＋、Ｔｉ２＋、Ｔｉ３＋、Ｚｒ２＋、Ｚｒ３＋、Ｖ２＋、Ｖ３＋、Ｎｂ３＋、Ｃｒ３＋、Ｍｏ２＋、Ｍｏ３＋、Ｍｎ２＋、Ｆｅ２＋、Ｆｅ３＋、Ｃｏ２＋、Ｃｏ３＋、Ｃｕ２＋、Ｚｎ２＋、Ｃｄ２＋、Ａｌ３＋およびＰｂ２＋が挙げられ、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋、Ｙ３＋、Ｍｎ２＋、Ｆｅ２＋、Ｆｅ３＋、Ｃｏ２＋、Ｃｏ３＋、Ｃｕ２＋、Ｚｎ２＋およびＡｌ３＋から選ばれる少なくとも１種であることが好ましく、Ｓｒ２＋、Ｆｅ２＋、Ｆｅ３＋、Ｃｏ２＋、Ｃｏ３＋、Ｃｕ２＋、Ｚｎ２＋およびＡｌ３＋から選ばれる少なくとも１種であることがより好ましい。また、金属イオンＭｅ４ｂの含有量は、金属アゾ顔料の全金属イオンの１モルを基準として、５モル％以下であることが好ましく、２モル％以下であることがより好ましく、０．１モル％以下であることが更に好ましい。 (Az4) The metal ion contains at least one anion selected from the azo compound represented by the formula (I) and the azo compound of the tautomeric structure described above, a metal ion, and a melamine compound, and the metal ion is Ni 2+ and comprises a metal ion Me4a, metal ions Me4a is La 3+, Ce 3+, Pr 3+ , Nd 2+, Nd 3+, Sm 2+, Sm 3+, Eu 2+, Eu 3+, Gd 3+, Tb 3+, Dy 3+, Ho 3+, The metal azo pigment of the aspect which is an at least 1 sort (s) chosen from Er < 3 +> , Tm < 3 + > , Yb <2+> and Yb < 3+ >. Metal ions Me4a is, La 3+, Ce 3+, Pr 3+, Nd 3+, Sm 3+, Eu 3+, Gd 3+, Tb 3+, Dy 3+, Ho 3+, Er 3+, at least one selected from the Tm 3+ and Yb 3+ It is preferably at least one selected from La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Tb 3+ and Ho 3+ . In this embodiment, the total content of Ni 2+ and metal ion Me 4 a is preferably 95 to 100 mol%, more preferably 98 to 100 mol%, based on 1 mol of the total metal ions of the metal azo pigment. It is more preferable to contain 99.9 to 100% by mole, and it is particularly preferable to be 100% by mole. The molar ratio of Ni 2+ to metal ion Me 4 a in the metal azo pigment is preferably Ni 2+ : metal ion Me 4 a = 1: 1 to 19: 1, and 2: 1 to 4: 1. More preferably, 2.3: 1 to 3: 1. In this embodiment, the metal azo pigment may further contain metal ions other than Ni 2+ and metal ion Me4a (hereinafter also referred to as metal ion Me4b). The metal ions Me4b is, Mg 2+, Ca 2+, Sr 2+, Ba 2+, Sc 3+, Y 3+, Ti 2+, Ti 3+, Zr 2+, Zr 3+, V 2+, V 3+, Nb 3+, Cr 3+, Mo 2+ , Mo 3+ , Mn 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Cu 2+ , Zn 2+ , Cd 2+ , Al 3+ and Pb 2+ , and Mg 2+ , Ca 2+ , Sr 2+ , Y 3+ , Mn It is preferably at least one selected from 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Cu 2+ , Zn 2+ and Al 3+ , and Sr 2+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Cu More preferably, it is at least one selected from 2+ , Zn 2+ and Al 3+ . The content of the metal ion Me4b is preferably 5 mol% or less, more preferably 2 mol% or less, based on 1 mol of the total metal ions of the metal azo pigment, more preferably 0.1 mol% It is more preferable that it is the following.
　金属アゾ顔料Ａは、上述した式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと金属イオンとで構成される金属アゾ化合物と、メラミン化合物（好ましくは上記式（ＩＩ）で表される化合物）とで付加体が形成されていることが好ましい。付加体とは、分子集合体を意味すると理解される。これらの分子間の結合は、例えば、分子間相互作用によるものであってもよく、ルイス酸－塩基相互作用によるものであってもよく、配位結合または鎖結合によるものであってもよい。また、付加体は、ゲスト分子がホスト分子を構成する格子に組み込まれている包接化合物（クラスレート）のような構造であっても良い。また、付加体は、複合層間結晶（格子間化合物を含む）のような構造であってもよい。複合層間結晶とは、少なくとも２つの要素からなる化学的な非化学量論的結晶化合物のことである。また、付加体は、２つの物質が共同結晶を形成し、第一の成分の規則的な格子の位置に第二の成分の原子が位置しているような混合置換結晶であってもよい。 The metal azo pigment A is a metal azo compound composed of at least one anion selected from the azo compound represented by the above-mentioned formula (I) and an azo compound of the tautomeric structure thereof and a metal ion, and a melamine compound It is preferable that an adduct is formed with (preferably a compound represented by the above formula (II)). An adduct is understood to mean a molecular assembly. The bond between these molecules may be, for example, an intermolecular interaction, a Lewis acid-base interaction, or a coordinate bond or a chain bond. The adduct may also have a structure such as a clathrate in which a guest molecule is incorporated in a lattice constituting a host molecule. The adduct may also have a structure such as a complex intercalated crystal (including an interstitial compound). Composite intercalated crystals are chemically non-stoichiometric crystalline compounds consisting of at least two components. Also, the adduct may be a mixed substituted crystal in which two substances form a co-crystal and the atom of the second component is located at the regular lattice position of the first component.
　本発明で用いられる金属アゾ顔料は、物理的混合物であってもよく、化学的複合化合物であってもよい。好ましくは、物理的混合物である。 The metal azo pigment used in the present invention may be a physical mixture or a chemically complex compound. Preferably, it is a physical mixture.
　上記の（Ａｚ１）の態様の金属アゾ顔料の場合における物理的混合物の好ましい例としては、以下の（Ａｚ１－１）、（Ａｚ１－２）が挙げられる。また、（Ａｚ１）の態様の金属アゾ顔料が化学的複合化合物である場合、Ｚｎ２＋、Ｃｕ２＋ならびに任意のさらなる金属イオンＭｅ１は、共通の結晶格子に組み込まれていることが好ましい。
　（Ａｚ１－１）上記アニオンとＺｎ２＋とで構成される金属アゾ化合物と、メラミン化合物との付加体１ａと、上記アニオンとＣｕ２＋とで構成される金属アゾ化合物と、メラミン化合物との付加体１ｂの物理的混合物。
　（Ａｚ１－２）　（Ａｚ１－１）の物理的混合物において、更に、上記アニオンと金属イオンＭｅ１とで構成される金属アゾ化合物と、メラミン化合物との付加体１ｃを含む物理的混合物。 Preferred examples of the physical mixture in the case of the metal azo pigment of the embodiment of the above (Az1) include the following (Az1-1) and (Az1-2). Also, when the metal azo pigment of the embodiment of (Az1) is a chemical complex compound, it is preferable that Zn 2+ , Cu 2+ and optional additional metal ion Me1 be incorporated in a common crystal lattice.
(Az1-1) An adduct of the metal azo compound composed of the anion and Zn 2+ , an adduct 1a of a melamine compound, a metal azo compound composed of the anion and Cu 2+ , and the melamine compound Physical mixture of 1b.
(Az1-2) A physical mixture containing, in the physical mixture of (Az1-1), an adduct 1c of a metal azo compound composed of the anion and the metal ion Me1 and a melamine compound.
　上記の（Ａｚ２）の態様の金属アゾ顔料の場合における物理的混合物の好ましい例としては、以下の（Ａｚ２－１）が挙げられる。また、（Ａｚ２）の態様の金属アゾ顔料が化学的複合化合物である場合、Ｎｉ２＋、Ｚｎ２＋および金属イオンＭｅ２は、共通の結晶格子に組み込まれていることが好ましい。
　（Ａｚ２－１）上記アニオンとＮｉ２＋とで構成される金属アゾ化合物と、メラミン化合物との付加体２ａと、上記アニオンとＺｎ２＋とで構成される金属アゾ化合物と、メラミン化合物との付加体２ｂと、上記アニオンと金属イオンＭｅ２とで構成される金属アゾ化合物と、メラミン化合物との付加体２ｃを含む物理的混合物。 Preferred examples of the physical mixture in the case of the metal azo pigment of the aspect of the above (Az2) include the following (Az2-1). In addition, when the metal azo pigment of the aspect of (Az2) is a chemical complex compound, it is preferable that Ni 2+ , Zn 2+ and metal ion Me2 be incorporated in a common crystal lattice.
(Az2-1) An adduct of a metal azo compound composed of the anion and Ni 2+ , an adduct 2a of a melamine compound, a metal azo compound composed of the anion and Zn 2+ , and a melamine compound A physical mixture comprising an adduct 2c of a metal azo compound composed of 2b, the above anion and a metal ion Me2, and a melamine compound.
　上記の（Ａｚ３）の態様の金属アゾ顔料の場合における物理的混合物の好ましい例としては、以下の（Ａｚ３－１）が挙げられる。また、（Ａｚ３）の態様の金属アゾ顔料が化学的複合化合物である場合、Ｎｉ２＋、Ｃｕ２＋および金属イオンＭｅ３は、共通の結晶格子に組み込まれていることが好ましい。
　（Ａｚ３－１）上記アニオンとＮｉ２＋とで構成される金属アゾ化合物と、メラミン化合物との付加体３ａと、上記アニオンとＣｕ２＋とで構成される金属アゾ化合物と、メラミン化合物との付加体３ｂと、上記アニオンと金属イオンＭｅ３とで構成される金属アゾ化合物と、メラミン化合物との付加体３ｃを含む物理的混合物。 Preferred examples of the physical mixture in the case of the metal azo pigment of the aspect of the above (Az3) include the following (Az3-1). In addition, when the metal azo pigment of the aspect of (Az3) is a chemical complex compound, it is preferable that Ni 2+ , Cu 2+ and metal ion Me 3 be incorporated in a common crystal lattice.
(Az3-1) An adduct of the metal azo compound composed of the anion and Ni 2+ , an adduct 3a of a melamine compound, a metal azo compound composed of the anion and Cu 2+ , and a melamine compound A physical mixture comprising an adduct 3c of a metal azo compound composed of 3b, the above anion and a metal ion Me3, and a melamine compound.
　上記の（Ａｚ４）の態様の金属アゾ顔料の場合における物理的混合物の好ましい例としては、以下の（Ａｚ４－１）、（Ａｚ４－２）が挙げられる。また、（Ａｚ４）の態様の金属アゾ顔料が化学的複合化合物である場合、Ｎｉ２＋、金属イオンＭｅ４ａならびに任意のさらなる金属イオンＭｅ４ｂは、共通の結晶格子に組み込まれていることが好ましい。
　（Ａｚ４－１）上記アニオンとＮｉ２＋とで構成される金属アゾ化合物と、メラミン化合物との付加体４ａと、上記アニオンと金属イオンＭｅ４ａとで構成される金属アゾ化合物と、メラミン化合物との付加体４ｂの物理的混合物。
　（Ａｚ４－２）　（Ａｚ４－１）の物理的混合物において、更に、上記アニオンと、金属イオンＭｅ４ｂとで構成される金属アゾ化合物と、メラミン化合物との付加体４ｃを含む物理的混合物。 Preferred examples of the physical mixture in the case of the metal azo pigment of the embodiment (Az4) described above include the following (Az4-1) and (Az4-2). Also, when the metal azo pigment of the embodiment of (Az4) is a chemical complex compound, it is preferable that Ni 2+ , metal ion Me4a and optional additional metal ion Me4b be incorporated in a common crystal lattice.
(Az4-1) Addition of a metal azo compound composed of the above anion and Ni 2+ , an adduct 4a of a melamine compound, a metal azo compound composed of the above anion and a metal ion Me4a, and a melamine compound Physical mixture of body 4b.
(Az4-2) A physical mixture containing, in the physical mixture of (Az4-1), an adduct 4c of a metal azo compound composed of the anion and a metal ion Me4b, and a melamine compound.
　上記の（Ａｚ１）の態様の金属アゾ顔料は、式（ＩＩＩ）またはその互変異性体の化合物を、メラミン化合物（好ましくは式（ＩＩ）で表される化合物）の存在下で、亜鉛塩および銅塩、ならびに任意で更に、上述した金属イオンＭｅ１の塩と反応させることによって製造することができる。亜鉛塩の使用量は、式（ＩＩＩ）またはその互変異性体の化合物の１モルに対して、０．０５～０．９９５モルであることが好ましく、０．０５～０．５モルであることがより好ましく、０．１～０．３モルであることが更に好ましい。また、銅塩の使用量は、式（ＩＩＩ）またはその互変異性体の化合物の１モルに対して、０．００５～０．９５モルであることが好ましく、０．４９～０．９５モルであることがより好ましく、０．７～０．９モルであることが更に好ましい。また、金属イオンＭｅ１の塩の使用量は、式（ＩＩＩ）またはその互変異性体の化合物の１モルに対して、０．０５モル以下であることが好ましく、０．０１モル以下であることがより好ましい。また、式（ＩＩＩ）の化合物１モルに対して、亜鉛塩と銅塩と金属イオンＭｅ１の塩との合計量は１モルであることが好ましい。また、メラミン化合物の使用量は、式（ＩＩＩ）またはその互変異性体の化合物の１モルに対して、０．０５～４モルであることが好ましく、０．５～２．５モルであることがより好ましく、１．０～２．０モルであることが更に好ましい。 The metal azo pigment according to the above aspect (Az1) comprises a compound of the formula (III) or a tautomer thereof, a zinc salt and a zinc salt in the presence of a melamine compound (preferably a compound represented by the formula (II)) It can be produced by reacting with a copper salt, and optionally also with the above mentioned salts of the metal ion Me1. The amount of the zinc salt used is preferably 0.05 to 0.995 mol, more preferably 0.05 to 0.5 mol, per 1 mol of the compound of the formula (III) or a tautomer thereof. More preferably, it is 0.1 to 0.3 mol. The amount of the copper salt used is preferably 0.005 to 0.95 mol, preferably 0.49 to 0.95 mol, per 1 mol of the compound of the formula (III) or a tautomer thereof. Is more preferably 0.7 to 0.9 mole. The amount of the metal ion Me1 salt used is preferably 0.05 moles or less, and preferably 0.01 moles or less, per mole of the compound of the formula (III) or a tautomer thereof. Is more preferred. Moreover, it is preferable that the total amount of a zinc salt, a copper salt, and the metal ion Me1 salt is 1 mol with respect to 1 mol of compounds of Formula (III). The amount of the melamine compound used is preferably 0.05 to 4 moles, and more preferably 0.5 to 2.5 moles relative to 1 mole of the compound of the formula (III) or a tautomer thereof. Is more preferably 1.0 to 2.0 mol.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　式中、Ｘ１およびＸ２はそれぞれ独立して水素原子またはアルカリ金属イオンであり、Ｘ１およびＸ２の少なくとも一方がアルカリ金属イオンである。Ｒ１およびＲ２はそれぞれ独立して、ＯＨまたはＮＲ５Ｒ６である。Ｒ３およびＲ４はそれぞれ独立して、＝Ｏまたは＝ＮＲ７であり、Ｒ５～Ｒ７はそれぞれ独立して、水素原子またはアルキル基である。Ｒ１～Ｒ７については、式（Ｉ）のＲ１～Ｒ７と同義であり、好ましい範囲も同様である。Ｘ１およびＸ２が表すアルカリ金属イオンとしては、Ｎａ＋およびＫ＋が好ましい。 In the formula, X 1 and X 2 each independently represent a hydrogen atom or an alkali metal ion, and at least one of X 1 and X 2 is an alkali metal ion. R 1 and R 2 are each independently OH or NR 5 R 6 . R 3 and R 4 are each independently = O or NRNR 7 , and R 5 to R 7 are each independently a hydrogen atom or an alkyl group. For R 1 ~ R 7 has the same meaning as R 1 ~ R 7 of formula (I), preferred ranges are also the same. Examples of the alkali metal ions which X 1 and X 2 represent, Na + and K + are preferred.
　また、上記の（Ａｚ１）の態様の金属アゾ顔料は、上述した付加体１ａと、付加体１ｂと、付加体１ｃとを混合することによって製造することもできる。 Moreover, the metal azo pigment of the aspect of said (Az1) can also be manufactured by mixing the adduct 1a mentioned above, the adduct 1b, and the adduct 1c.
　上記の（Ａｚ２）の態様の金属アゾ顔料、（Ａｚ３）の態様の金属アゾ顔料、および（Ａｚ４）の態様の金属アゾ顔料についても上述した方法等と同様の方法で製造することができる。 The metal azo pigment of the embodiment (Az2), the metal azo pigment of the embodiment (Az3), and the metal azo pigment of the embodiment (Az4) can also be produced by the same method as described above.
　上記の金属アゾ顔料については、特開２０１７－１７１９１２号公報の段落番号００１１～００６２、０１３７～０２７６、特開２０１７－１７１９１３号公報の段落番号００１０～００６２、０１３８～０２９５、特開２０１７－１７１９１４号公報の段落番号００１１～００６２、０１３９～０１９０、特開２０１７－１７１９１５号公報の段落番号００１０～００６５、０１４２～０２２２の記載を参酌でき、これらの内容は本明細書に組み込まれる。 With regard to the above-mentioned metal azo pigments, paragraph Nos. 0011 to 0062 and 0137 to 0276 of JP-A-2017-171912 and paragraph Nos. 0010 to 0062 and 0138 to 0295 of JP-A-2017-171913 and JP-A-2017-171914. The descriptions of paragraphs 0011 to 0062 and 0139 to 0190 of the gazettes and paragraphs 0010 to 0065 and 0142 to 2222 of JP-A-2017-171915 can be referred to, and the contents thereof are incorporated herein.
　本発明の組成物において、金属アゾ顔料Ａの含有量は、本発明の組成物の全固形分中１～５０質量％であることが好ましい。下限は、２質量％以上であることが好ましく、３質量％以上であることがより好ましい。上限は、４５質量％以下であることが好ましく、４０質量％以下であることがより好ましい。本発明の組成物が金属アゾ顔料Ａを２種以上含む場合はそれらの合計量が上記範囲であることが好ましい。 In the composition of the present invention, the content of the metal azo pigment A is preferably 1 to 50% by mass in the total solid content of the composition of the present invention. The lower limit is preferably 2% by mass or more, and more preferably 3% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. When the composition of the present invention contains two or more metal azo pigments A, the total amount thereof is preferably in the above range.
＜＜他の色材＞＞
　本発明の組成物は、上述した金属アゾ顔料Ａ以外の色材であって、波長４００～７００ｎｍの範囲に吸収極大を有する色材（以下、他の色材ともいう）を含有する。他の色材としては、有彩色着色剤、黒色着色剤などが挙げられる。他の色材として用いられる有彩色着色剤としては、上述した金属アゾ顔料Ａ以外の色材であれば特に限定は無く、赤色着色剤、緑色着色剤、青色着色剤、黄色着色剤、紫色着色剤、オレンジ色着色剤などが挙げられる。本発明の組成物は、他の色材を２種以上含むことが好ましい。この態様によれば、金属アゾ顔料Ａをより安定化でき、高温高湿環境下での異物欠陥の発生をより効果的に抑制できる。また、本発明の組成物が他の色材を２種以上含む場合、異なる色相の色材を２種以上含むことが好ましい。 << Other color materials >>
The composition of the present invention is a coloring material other than the above-mentioned metal azo pigment A, and contains a coloring material having an absorption maximum in the wavelength range of 400 to 700 nm (hereinafter also referred to as another coloring material). Other coloring materials include chromatic coloring agents, black coloring agents and the like. There is no particular limitation on the chromatic coloring agent used as another coloring material, as long as it is a coloring material other than the above-mentioned metal azo pigment A, and red coloring agent, green coloring agent, blue coloring agent, yellow coloring agent, purple coloring Agents, orange coloring agents and the like. The composition of the present invention preferably contains two or more other colorants. According to this aspect, the metal azo pigment A can be further stabilized, and the generation of foreign matter defects in a high temperature and high humidity environment can be more effectively suppressed. When the composition of the present invention contains two or more other colorants, it is preferable to contain two or more colorants of different hues.
　本発明の組成物は、他の色材として青色着色剤および紫色着色剤から選ばれる少なくとも１種を含むことが好ましい。これらの色相の色材は、可視光の波長領域において長波長側に吸収極大を有するので、比較的広い共役系を有している。このため、これらの色材は、金属アゾ顔料Ａと相互作用し易く、金属アゾ顔料Ａをより安定化でき、高温高湿環境下での異物欠陥の発生をより効果的に抑制できる。さらには、波長４００～６００ｎｍの範囲における吸光度の最小値Ａと、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂとの比であるＡ／Ｂが４．５以上の分光特性を有する組成物が得られやすい。青色着色剤としては、トリアリールメタン化合物、フタロシアニン化合物等が挙げられ、本発明の効果がより顕著に得られやすいという理由からフタロシアニン化合物が好ましい。紫色着色剤としては、キサンテン化合物、トリアリールメタン化合物、アントラキノン化合物、オキサジン化合物、キナクリドン化合物、ベンズイミダゾロン化合物等が挙げられ、本発明の効果がより顕著に得られやすいという理由からオキサジン化合物が好ましい。 The composition of the present invention preferably contains at least one selected from blue colorants and violet colorants as another colorant. Color materials of these hues have an absorption maximum on the long wavelength side in the visible light wavelength range, and thus have a relatively wide conjugated system. Therefore, these colorants easily interact with the metal azo pigment A, can stabilize the metal azo pigment A more, and can more effectively suppress the generation of foreign matter defects in a high temperature and high humidity environment. Furthermore, a composition having a spectral characteristic of A / B of 4.5 or more, which is the ratio of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm and the maximum value B of the absorbance in the range of wavelength 1000 to 1300 nm It is easy to obtain. As a blue coloring agent, a triarylmethane compound, a phthalocyanine compound, etc. are mentioned, A phthalocyanine compound is preferable from the reason that the effect of this invention is easy to be acquired more notably. As a purple coloring agent, a xanthene compound, a triarylmethane compound, an anthraquinone compound, an oxazine compound, a quinacridone compound, a benzimidazolone compound etc. are mentioned, An oxazine compound is preferable from the reason that the effect of this invention is easily obtained notably. .
　本発明の組成物が、他の色材として青色着色剤および紫色着色剤から選ばれる少なくとも１種を含む場合、他の色材の全量中における青色着色剤の含有量は、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、２０質量％以上であることが更に好ましい。上限は特に限定はない。１００質量％とすることができ、９０質量％以下とすることもでき、８０質量％以下とすることもできる。また、他の色材の全量中における紫色着色剤の含有量は、１質量％以上であることが好ましく、５質量％以上であることがより好ましく、１０質量％以上であることが更に好ましい。上限は特に限定はない。１００質量％とすることができ、９０質量％以下とすることもでき、８０質量％以下とすることもできる。また、他の色材の全量中における青色着色剤と紫色着色剤との合計の含有量は、１０質量％以上であることが好ましく、２０質量％以上であることがより好ましく、３０質量％以上であることが更に好ましい。上限は特に限定はない。１００質量％とすることができ、９０質量％以下とすることもでき、８０質量％以下とすることもできる。 When the composition of the present invention contains at least one selected from a blue coloring agent and a purple coloring agent as another coloring material, the content of the blue coloring agent in the total amount of the other coloring materials is 5% by mass or more The content is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is not particularly limited. It can be 100% by mass, can be 90% by mass or less, and can be 80% by mass or less. The content of the purple colorant in the total amount of the other coloring materials is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. The upper limit is not particularly limited. It can be 100% by mass, can be 90% by mass or less, and can be 80% by mass or less. In addition, the total content of the blue colorant and the purple colorant in the total amount of the other coloring materials is preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass or more. It is further preferred that The upper limit is not particularly limited. It can be 100% by mass, can be 90% by mass or less, and can be 80% by mass or less.
（有彩色着色剤）
　他の色材として用いられる有彩色着色剤は、顔料であってもよく、染料であってもよく、顔料であることが好ましい。顔料としては、有機顔料および無機顔料が挙げられ、有機顔料が好ましい。有機顔料としては以下のものが挙げられる。 (Achromatic coloring agent)
The chromatic coloring agent used as another coloring material may be a pigment, may be a dye, and is preferably a pigment. Pigments include organic pigments and inorganic pigments, with organic pigments being preferred. Examples of the organic pigment include the following.
　カラーインデックス（Ｃ．Ｉ．）Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４等（以上、黄色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等（以上、オレンジ色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２７０，２７２，２７９等（以上、赤色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７，１０，３６，３７，５８，５９等（以上、緑色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　１，１９，２３，２７，３２，３７，４２等（以上、紫色顔料）、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，６０，６４，６６，７９，８０等（以上、青色顔料）、 Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 35, 53, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170 171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 like (or more, and yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 13, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Above, orange pigment),
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 25: 2, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 208, 209, 210, 216, 220, 224, 242, 246, 254, 255, 264, 270, 272, 279, etc. (above, red Pigment)
C. I. Pigment Green 7, 10, 36, 37, 58, 59 (above, green pigment),
C. I. Pigment Violet 1,19,23,27,32,37,42 etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 22, 60, 64, 66, 79, 80 (the above, blue pigment),
　また、赤色顔料として、芳香族環に対して、酸素原子、硫黄原子または窒素原子が結合した基が導入された芳香族環基がジケトピロロピロール骨格に結合した構造を有する化合物を用いることもできる。このような化合物としては、式（ＤＰＰ１）で表される化合物であることが好ましく、式（ＤＰＰ２）で表される化合物であることがより好ましい。
Figure JPOXMLDOC01-appb-C000009
 In addition, as a red pigment, a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is introduced is bonded to a diketopyrrolopyrrole skeleton is also used. it can. As such a compound, a compound represented by the formula (DPP1) is preferable, and a compound represented by the formula (DPP2) is more preferable.
Figure JPOXMLDOC01-appb-C000009
　上記式中、Ｒ１１およびＲ１３はそれぞれ独立して置換基を表し、Ｒ１２およびＲ１４はそれぞれ独立して水素原子、アルキル基、アリール基またはヘテロアリール基を表し、ｎ１１およびｎ１３はそれぞれ独立して０～４の整数を表し、Ｘ１２およびＸ１４はそれぞれ独立して酸素原子、硫黄原子または窒素原子を表し、Ｘ１２が酸素原子または硫黄原子の場合は、ｍ１２は１を表し、Ｘ１２が窒素原子の場合は、ｍ１２は２を表し、Ｘ１４が酸素原子または硫黄原子の場合は、ｍ１４は１を表し、Ｘ１４が窒素原子の場合は、ｍ１４は２を表す。Ｒ１１およびＲ１３が表す置換基としては、上述した置換基Ｔで挙げた基が挙げられ、アルキル基、アリール基、ハロゲン原子、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、ヘテロアリールオキシカルボニル基、アミド基、シアノ基、ニトロ基、トリフルオロメチル基、スルホキシド基、スルホ基などが好ましい具体例として挙げられる。 In the above formulas, R 11 and R 13 each independently represent a substituent, R 12 and R 14 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and n 11 and n 13 are each independently And X 12 and X 14 each independently represent an oxygen atom, a sulfur atom or a nitrogen atom, and when X 12 is an oxygen atom or a sulfur atom, m 12 represents 1 and X is an integer of 0 to 4; When 12 is a nitrogen atom, m12 represents 2; when X 14 is an oxygen atom or a sulfur atom, m14 represents 1; when X 14 is a nitrogen atom, m14 represents 2; Examples of the substituent represented by R 11 and R 13 include the groups listed above as the substituent T, and an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl Preferred examples are groups, amido groups, cyano groups, nitro groups, trifluoromethyl groups, sulfoxide groups, sulfo groups and the like.
　染料としては特に制限はなく、公知の染料が使用できる。例えば、ピラゾールアゾ系、アニリノアゾ系、トリアリールメタン系、アントラキノン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ベンゾピラン系、インジゴ系、ピロメテン系等の染料が使用できる。 The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo type, anilino azo type, triarylmethane type, anthraquinone type, anthrapyridone type, benzylidene type, oxonol type, pyrazolotriazole azo type, pyridone azo type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, Dyes of phthalocyanine type, benzopyran type, indigo type, and pyromethene type can be used.
　また、他の色材として色素多量体を用いることもできる。色素多量体は、溶剤に溶解して用いられる染料であることが好ましいが、色素多量体は、粒子を形成していてもよく、色素多量体が粒子である場合は通常溶剤に分散した状態で用いられる。粒子状態の色素多量体は、例えば乳化重合によって得ることができ、特開２０１５－２１４６８２号公報に記載されている化合物および製造方法が具体例として挙げられる。色素多量体は、特開２０１１－２１３９２５号公報、特開２０１３－０４１０９７号公報、特開２０１５－０２８１４４号公報、特開２０１５－０３０７４２号公報等に記載されている化合物を用いることもできる。 Moreover, a pigment | dye multimer can also be used as another coloring material. The dye multimer is preferably a dye used by being dissolved in a solvent, but the dye multimer may form particles, and when the dye multimer is particles, it is usually dispersed in a solvent. Used. The dye multimer in a particulate state can be obtained, for example, by emulsion polymerization, and the compounds and production methods described in JP-A-2015-214682 can be mentioned as specific examples. As the dye multimer, compounds described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742 and the like can also be used.
（黒色着色剤）
　他の色材として用いられる黒色着色剤としては、ビスベンゾフラノン化合物、アゾメチン化合物、ペリレン化合物、アゾ化合物などの有機黒色着色剤が挙げられる。黒色着色剤は、ビスベンゾフラノン化合物、ペリレン化合物が好ましい。ビスベンゾフラノン化合物としては、特表２０１０－５３４７２６号公報、特表２０１２－５１５２３３号公報、特表２０１２－５１５２３４号公報などに記載の化合物が挙げられ、例えば、ＢＡＳＦ社製の「Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ」として入手可能である。ペリレン化合物としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　３１、３２などが挙げられる。アゾメチン化合物としては、特開平１－１７０６０１号公報、特開平２－３４６６４号公報などに記載の化合物が挙げられ、例えば、大日精化社製の「クロモファインブラックＡ１１０３」として入手できる。ビスベンゾフラノン化合物は、下記式で表される化合物およびこれらの混合物が好ましい。
Figure JPOXMLDOC01-appb-C000010
 (Black coloring agent)
Examples of black colorants used as other colorants include organic black colorants such as bisbenzofuranone compounds, azomethine compounds, perylene compounds and azo compounds. The black colorant is preferably a bisbenzofuranone compound or a perylene compound. Examples of the bisbenzofuranone compounds include the compounds described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, etc. For example, as "Irgaphor Black" manufactured by BASF Corp. It is available. As perylene compounds, C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include compounds described in JP-A-1-170601, JP-A-2-32664 and the like, and can be obtained, for example, as "Chromofine Black A1103" manufactured by Dainichiseika. The bisbenzofuranone compound is preferably a compound represented by the following formula and a mixture thereof.
Figure JPOXMLDOC01-appb-C000010
　式中、Ｒ１およびＲ２はそれぞれ独立して水素原子又は置換基を表し、Ｒ３およびＲ４はそれぞれ独立して置換基を表し、ａおよびｂはそれぞれ独立して０～４の整数を表し、ａが２以上の場合、複数のＲ３は、同一であってもよく、異なってもよく、複数のＲ３は結合して環を形成していてもよく、ｂが２以上の場合、複数のＲ４は、同一であってもよく、異なってもよく、複数のＲ４は結合して環を形成していてもよい。Ｒ１～Ｒ４が表す置換基は、ハロゲン原子、シアノ基、ニトロ基、アルキル基、アルケニル基、アルキニル基、アラルキル基、アリール基、ヘテロアリール基、－ＯＲ３０１、－ＣＯＲ３０２、－ＣＯＯＲ３０３、－ＯＣＯＲ３０４、－ＮＲ３０５Ｒ３０６、－ＮＨＣＯＲ３０７、－ＣＯＮＲ３０８Ｒ３０９、－ＮＨＣＯＮＲ３１０Ｒ３１１、－ＮＨＣＯＯＲ３１２、－ＳＲ３１３、－ＳＯ２Ｒ３１４、－ＳＯ２ＯＲ３１５、－ＮＨＳＯ２Ｒ３１６または－ＳＯ２ＮＲ３１７Ｒ３１８を表し、Ｒ３０１～Ｒ３１８は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アルキニル基、アリール基またはヘテロアリール基を表す。ビスベンゾフラノン化合物の詳細については、特表２０１０－５３４７２６号公報の段落番号００１４～００３７の記載を参酌でき、この内容は本明細書に組み込まれる。 In the formula, R 1 and R 2 each independently represent a hydrogen atom or a substituent, R 3 and R 4 each independently represent a substituent, and a and b each independently represent an integer of 0 to 4 And when a is 2 or more, plural R 3 s may be the same or different, and plural R 3 s may combine to form a ring, and b is 2 or more The plurality of R 4 may be identical or different, and the plurality of R 4 may be combined to form a ring. The substituent represented by R 1 to R 4 is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, -OR 301 , -COR 302 , -COOR 303 , -OCOR 304 , -NR 305 R 306 , -NHCOR 307 , -CONR 308 R 309 , -NHCONR 310 R 311 , -NHCOOR 312 , -SR 313 , -SO 2 R 314 , -SO 2 OR 315 , -NHSO 2 R 316 or -SO 2 NR 317 R 318 is represented, and R 301 to R 318 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group. The details of the bisbenzofuranone compound can be referred to the description in paragraphs [0014] to [0037] of JP-A-2010-534726, the contents of which are incorporated herein.
　本発明の組成物においては、金属アゾ顔料Ａと他の色材との組み合わせで黒色が形成されていることが好ましい。金属アゾ顔料Ａと他の色材との好ましい組み合わせとしては、以下の（Ｃ１）～（Ｃ６）が挙げられる。以下の（Ｃ１）の組み合わせの場合、上述した（１）の分光特性の組成物が得られやすい。以下の（Ｃ２）～（Ｃ６）の組み合わせの場合、上述した（２）の分光特性の組成物が得られやすい。 In the composition of the present invention, it is preferable that a black color is formed by the combination of the metal azo pigment A and another coloring material. Preferred combinations of the metal azo pigment A and the other colorants include the following (C1) to (C6). In the case of the combination of (C1) below, a composition having the above-described spectral characteristics of (1) is easily obtained. In the case of the following combinations of (C2) to (C6), it is easy to obtain a composition having the above-mentioned spectral characteristics of (2).
　（Ｃ１）金属アゾ顔料Ａと紫色着色剤とを含有する態様。更に、他の色材としての黄色着色剤を含んでいてもよい。
　（Ｃ２）金属アゾ顔料Ａと赤色着色剤と青色着色剤と紫色着色剤とを含有する態様。更に、他の色材としての黄色着色剤を含んでいてもよい。
　（Ｃ３）金属アゾ顔料Ａと赤色着色剤と青色着色剤とを含有する態様。更に、他の色材としての黄色着色剤を含んでいてもよい。
　（Ｃ４）金属アゾ顔料Ａと青色着色剤と紫色着色剤とを含有する態様。更に、他の色材としての黄色着色剤を含んでいてもよい。
　（Ｃ５）金属アゾ顔料Ａと紫色着色剤と黒色着色剤とを含有する態様。更に、他の色材としての黄色着色剤を含んでいてもよい。
　（Ｃ６）金属アゾ顔料Ａと青色着色剤と黒色着色剤とを含有する態様。更に、他の色材としての黄色着色剤を含んでいてもよい。 (C1) An embodiment containing metal azo pigment A and a purple colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
(C2) An embodiment containing metal azo pigment A, a red colorant, a blue colorant and a purple colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
(C3) An embodiment containing metal azo pigment A, a red colorant and a blue colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
(C4) An embodiment containing metal azo pigment A, a blue colorant and a purple colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
(C5) An embodiment containing metal azo pigment A, a purple colorant and a black colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
(C6) An embodiment containing metal azo pigment A, a blue colorant and a black colorant. Furthermore, it may contain a yellow coloring agent as another coloring material.
　金属アゾ顔料Ａとしては、上述した（Ａｚ１）の態様の金属アゾ顔料であることが好ましい。紫色着色剤としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３が好ましい。黄色着色剤としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９，１５０，１８５が好ましく、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９，１５０がより好ましく、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９が更に好ましい。赤色着色剤としては、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１２２，１７７，２２４，２５４，２６４が好ましく、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１２２，１７７、２５４，２６４がより好ましく、Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４が更に好ましい。青色着色剤としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６，１６が好ましい。黒色着色剤としては、Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ（ＢＡＳＦ社）、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　３１、３２が好ましい。 The metal azo pigment A is preferably the metal azo pigment of the embodiment (Az1) described above. As a purple coloring agent, C.I. I. Pigment Violet 23 is preferred. As yellow colorants, C.I. I. Pigment Yellow 139, 150, 185 are preferable, and C.I. I. Pigment Yellow 139, 150 is more preferable, C.I. I. Pigment Yellow 139 is more preferable. As a red coloring agent, Pigment Red 122, 177, 224, 254, 264 is preferable, Pigment Red 122, 177, 254, 264 is more preferable, and Pigment Red 254 is still more preferable. As a blue coloring agent, C.I. I. Pigment Blue 15: 6, 16 is preferred. As a black coloring agent, Irgaphor Black (BASF), C.I. I. Pigment Black 31, 32 is preferred.
　上記（Ｃ１）の組み合わせにおいては、金属アゾ顔料Ａの１００質量部に対して紫色着色剤を５０～５００質量部含有することが好ましく、７５～４００質量部含有することがより好ましく、１００～３５０質量部含有することが更に好ましい。また、他の色材としての黄色着色剤をさらに含む場合は、他の色材としての黄色着色剤の含有量は、金属アゾ顔料Ａの１００質量部に対して１０～２００質量部であることが好ましく、２０～１５０質量部であることがより好ましい。他の色材としての黄色着色剤は含有しない態様とすることもできる。 In the combination of the above (C1), the purple colorant is preferably contained in an amount of 50 to 500 parts by mass, more preferably 75 to 400 parts by mass, with respect to 100 parts by mass of the metal azo pigment A, and more preferably 100 to 350 More preferably, it is contained in parts by mass. In the case of further including a yellow colorant as another colorant, the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
　上記（Ｃ２）の組み合わせにおいては、金属アゾ顔料Ａの１００質量部に対して赤色着色剤を１００～８００質量部含有することが好ましく、２００～７００質量部含有することがより好ましい。また、青色着色剤を１００～１０００質量部含有することが好ましく、２００～８００質量部含有することがより好ましい。また、紫色着色剤を５０～５００質量部含有することが好ましく、７０～４００質量部含有することがより好ましい。また、他の色材としての黄色着色剤をさらに含む場合は、他の色材としての黄色着色剤の含有量は、金属アゾ顔料Ａの１００質量部に対して１０～２００質量部であることが好ましく、２０～１５０質量部であることがより好ましい。他の色材としての黄色着色剤は含有しない態様とすることもできる。 In the combination of (C2), the red colorant is preferably contained in an amount of 100 to 800 parts by mass, more preferably 200 to 700 parts by mass, with respect to 100 parts by mass of the metal azo pigment A. The blue colorant is preferably contained in an amount of 100 to 1000 parts by mass, and more preferably 200 to 800 parts by mass. Further, it is preferable to contain 50 to 500 parts by mass of a purple colorant, and it is more preferable to contain 70 to 400 parts by mass. In the case of further including a yellow colorant as another colorant, the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
　上記（Ｃ３）の組み合わせにおいては、金属アゾ顔料Ａの１００質量部に対して赤色着色剤を１００～８００質量部含有することが好ましく、２００～７００質量部含有することがより好ましい。また、青色着色剤を１００～１０００質量部含有することが好ましく、２００～８００質量部含有することがより好ましい。また、他の色材としての黄色着色剤をさらに含む場合は、他の色材としての黄色着色剤の含有量は、金属アゾ顔料Ａの１００質量部に対して１０～２００質量部であることが好ましく、２０～１５０質量部であることがより好ましい。他の色材としての黄色着色剤は含有しない態様とすることもできる。 In the combination of the above (C3), the red colorant is preferably contained in an amount of 100 to 800 parts by mass, more preferably 200 to 700 parts by mass, with respect to 100 parts by mass of the metal azo pigment A. The blue colorant is preferably contained in an amount of 100 to 1000 parts by mass, and more preferably 200 to 800 parts by mass. In the case of further including a yellow colorant as another colorant, the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
　上記（Ｃ４）の組み合わせにおいては、金属アゾ顔料Ａの１００質量部に対して青色着色剤を１００～１０００質量部含有することが好ましく、２００～８００質量部含有することがより好ましい。また、紫色着色剤を５０～５００質量部含有することが好ましく、７５～４００質量部含有することがより好ましい。また、他の色材としての黄色着色剤をさらに含む場合は、他の色材としての黄色着色剤の含有量は、金属アゾ顔料Ａの１００質量部に対して１０～２００質量部であることが好ましく、２０～１５０質量部であることがより好ましい。他の色材としての黄色着色剤は含有しない態様とすることもできる。 In the combination of (C4), the blue colorant is preferably contained in an amount of 100 to 1000 parts by mass, more preferably 200 to 800 parts by mass, with respect to 100 parts by mass of the metal azo pigment A. Further, it is preferable to contain 50 to 500 parts by mass of a purple colorant, and it is more preferable to contain 75 to 400 parts by mass. In the case of further including a yellow colorant as another colorant, the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
　上記（Ｃ５）の組み合わせにおいては、金属アゾ顔料Ａの１００質量部に対して紫色着色剤を５０～５００質量部含有することが好ましく、７５～４００質量部含有することがより好ましい。また、黒色着色剤を５０～１０００質量部含有することが好ましく、１００～８００質量部含有することがより好ましい。また、他の色材としての黄色着色剤をさらに含む場合は、他の色材としての黄色着色剤の含有量は、金属アゾ顔料Ａの１００質量部に対して１０～２００質量部であることが好ましく、２０～１５０質量部であることがより好ましい。他の色材としての黄色着色剤は含有しない態様とすることもできる。 In the combination of (C5), the purple colorant is preferably contained in an amount of 50 to 500 parts by mass, and more preferably 75 to 400 parts by mass with respect to 100 parts by mass of the metal azo pigment A. The black colorant is preferably contained in an amount of 50 to 1000 parts by mass, and more preferably 100 to 800 parts by mass. In the case of further including a yellow colorant as another colorant, the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
　上記（Ｃ６）の組み合わせにおいては、金属アゾ顔料Ａの１００質量部に対して青色着色剤を１００～１０００質量部含有することが好ましく、２００～８００質量部含有することがより好ましい。また、黒色着色剤を５０～１０００質量部含有することが好ましく、１００～８００質量部含有することがより好ましい。また、他の色材としての黄色着色剤をさらに含む場合は、他の色材としての黄色着色剤の含有量は、金属アゾ顔料Ａの１００質量部に対して１０～２００質量部であることが好ましく、２０～１５０質量部であることがより好ましい。他の色材としての黄色着色剤は含有しない態様とすることもできる。 In the combination of (C6), the blue colorant is preferably contained in an amount of 100 to 1000 parts by mass, more preferably 200 to 800 parts by mass, with respect to 100 parts by mass of the metal azo pigment A. The black colorant is preferably contained in an amount of 50 to 1000 parts by mass, and more preferably 100 to 800 parts by mass. In the case of further including a yellow colorant as another colorant, the content of the yellow colorant as another colorant is 10 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A. Is preferable, and 20 to 150 parts by mass is more preferable. It is also possible to use an embodiment that does not contain a yellow colorant as another coloring material.
　本発明の組成物において、他の色材の含有量は、本発明の組成物の全固形分中１０～８０質量％であることが好ましい。下限は、２０質量％以上であることが好ましく、３０質量％以上であることがより好ましい。上限は、７０質量％以下であることが好ましく、６０質量％以下であることがより好ましい。また、他の色材の含有量は、金属アゾ顔料Ａの１００質量部に対して５０～１０００質量部であることが好ましい。下限は、７０質量部以上であることが好ましく、１００質量部以上であることがより好ましい。上限は、５００質量部以下であることが好ましい。また、金属アゾ顔料Ａと他の色材との合計の含有量は、本発明の組成物の全固形分中１０～７０質量％であることが好ましい。下限は、２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることが更に好ましい。本発明の組成物が他の色材を２種以上含む場合はそれらの合計量が上記範囲であることが好ましい。 In the composition of the present invention, the content of the other coloring material is preferably 10 to 80% by mass in the total solid content of the composition of the present invention. The lower limit is preferably 20% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably 70% by mass or less and more preferably 60% by mass or less. The content of the other coloring material is preferably 50 to 1000 parts by mass with respect to 100 parts by mass of the metal azo pigment A. The lower limit is preferably 70 parts by mass or more, and more preferably 100 parts by mass or more. The upper limit is preferably 500 parts by mass or less. Further, the total content of the metal azo pigment A and the other colorant is preferably 10 to 70% by mass in the total solid content of the composition of the present invention. The lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more. When the composition of the present invention contains two or more other colorants, the total amount thereof is preferably in the above range.
＜＜近赤外線吸収色素＞＞
　本発明の組成物は近赤外線吸収色素を含有することができる。赤外線透過フィルタにおいて、近赤外線吸収色素は、透過する光（赤外線）をより長波長側に限定する役割を有している。本発明の組成物が近赤外線吸収色素を含有する場合においては、上述した（３）の分光特性の組成物が得られやすい。特に、金属アゾ顔料Ａと他の色材を上記の（Ｃ２）～（Ｃ６）の組み合わせで含む場合において、更に近赤外線吸収色素を含有することで、上述した（３）の分光特性の組成物が得られやすい。また、本発明の組成物が近赤外線吸収色素を含有する場合においては、高温高湿環境下での異物欠陥の発生をより効果的に抑制できる。 << Near Infrared Absorbing Dyes >>
The composition of the present invention can contain a near infrared absorbing dye. In the infrared transmission filter, the near infrared absorbing dye has a role of limiting the transmitted light (infrared) to a longer wavelength side. In the case where the composition of the present invention contains a near infrared absorbing dye, a composition having the above-mentioned spectral characteristics of (3) can be easily obtained. In particular, when the metal azo pigment A and the other coloring material are contained in the combination of the above (C2) to (C6), the composition having the spectral characteristics of the above (3) by further containing a near infrared absorbing dye Is easy to obtain. When the composition of the present invention contains a near infrared absorbing dye, the occurrence of foreign matter defects in a high temperature and high humidity environment can be more effectively suppressed.
　本発明において、近赤外線吸収色素としては、近赤外領域（好ましくは、波長７００～１１００ｎｍ、より好ましくは波長７００～１０００ｎｍ、更に好ましくは波長８００～９００ｎｍ）の範囲に吸収極大を有する化合物が挙げられる。近赤外線吸収色素は、顔料であってもよく、染料であってもよい。 In the present invention, examples of the near infrared absorbing dye include compounds having an absorption maximum in the near infrared region (preferably, wavelength 700 to 1100 nm, more preferably wavelength 700 to 1000 nm, and still more preferably wavelength 800 to 900 nm). Be The near infrared absorbing dye may be a pigment or a dye.
　近赤外線吸収色素は、単環または縮合環の芳香族環を含むπ共役平面を有する化合物を好ましく用いることができる。近赤外線吸収色素が有するπ共役平面を構成する水素以外の原子数は、１４個以上であることが好ましく、２０個以上であることがより好ましく、２５個以上であることが更に好ましく、３０個以上であることが特に好ましい。上限は、例えば、８０個以下であることが好ましく、５０個以下であることがより好ましい。また、近赤外線吸収色素が有するπ共役平面は、単環または縮合環の芳香族環を２個以上含むことが好ましく、前述の芳香族環を３個以上含むことがより好ましく、前述の芳香族環を４個以上含むことが更に好ましく、前述の芳香族環を５個以上含むことが特に好ましい。上限は、１００個以下が好ましく、５０個以下がより好ましく、３０個以下が更に好ましい。前述の芳香族環としては、ベンゼン環、ナフタレン環、インデン環、アズレン環、ヘプタレン環、インダセン環、ペリレン環、ペンタセン環、クアテリレン環、アセナフテン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ピリジン環、キノリン環、イソキノリン環、イミダゾール環、ベンゾイミダゾール環、ピラゾール環、チアゾール環、ベンゾチアゾール環、トリアゾール環、ベンゾトリアゾール環、オキサゾール環、ベンゾオキサゾール環、イミダゾリン環、ピラジン環、キノキサリン環、ピリミジン環、キナゾリン環、ピリダジン環、トリアジン環、ピロール環、インドール環、イソインドール環、カルバゾール環、および、これらの環を有する縮合環が挙げられる。 As the near infrared absorbing dye, a compound having a π conjugated plane including an aromatic ring of a single ring or a condensed ring can be preferably used. It is preferable that the number of atoms other than hydrogen which comprises the pi conjugation plane which a near-infrared absorption pigment has is 14 or more, It is more preferable that it is 20 or more, It is still more preferable that it is 25 or more, 30 It is particularly preferable to be the above. The upper limit is, for example, preferably 80 or less, and more preferably 50 or less. The π conjugated plane of the near infrared absorbing dye preferably contains two or more single rings or two or more aromatic rings of a fused ring, more preferably three or more of the above aromatic rings, and the above aromatic More preferably, it contains 4 or more rings, and particularly preferably 5 or more of the above-mentioned aromatic rings. The upper limit is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less. The above-mentioned aromatic ring includes benzene ring, naphthalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, quaterylene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, Triphenylene ring, fluorene ring, pyridine ring, quinoline ring, isoquinoline ring, imidazole ring, benzoimidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, triazole ring, benzotriazole ring, oxazole ring, benzooxazole ring, imidazoline ring, pyrazine And rings, quinoxaline rings, pyrimidine rings, quinazoline rings, pyridazine rings, triazine rings, pyrrole rings, indole rings, isoindole rings, carbazole rings, and fused rings having these rings.
　近赤外線吸収色素は、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物、クアテリレン化合物、メロシアニン化合物、クロコニウム化合物、オキソノール化合物、ジイモニウム化合物、ジチオール化合物、トリアリールメタン化合物、ピロメテン化合物、アゾメチン化合物、アントラキノン化合物、インジゴ化合物およびジベンゾフラノン化合物から選ばれる少なくとも１種が好ましく、ピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物、クロコニウム化合物およびインジゴ化合物から選ばれる少なくとも１種がより好ましく、ピロロピロール化合物、シアニン化合物およびスクアリリウム化合物から選ばれる少なくとも１種が更に好ましく、ピロロピロール化合物が特に好ましい。ジイモニウム化合物としては、例えば、特表２００８－５２８７０６号公報に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。フタロシアニン化合物としては、例えば、特開２０１２－７７１５３号公報の段落番号００９３に記載の化合物、特開２００６－３４３６３１号公報に記載のオキシチタニウムフタロシアニン、特開２０１３－１９５４８０号公報の段落番号００１３～００２９に記載の化合物、特許第６０８１７７１号公報に記載のバナジウムフタロシアニンが挙げられ、これらの内容は本明細書に組み込まれる。ナフタロシアニン化合物としては、例えば、特開２０１２－７７１５３号公報の段落番号００９３に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。インジゴ化合物は、インジゴホウ素錯体化合物が好ましい。インジゴ化合物としては、特許第５６４２０１３号公報に記載された化合物が挙げられ、この内容は本明細書に組み込まれる。また、近赤外線吸収色素は、特開２０１６－１４６６１９号公報に記載された化合物、特開２０１６－７９３３１号公報に記載された化合物、特開２０１７－８２０２９号公報に記載された化合物、特開２０１５－４０１７６号公報に記載された化合物、特許第５５３９６７６号公報に記載された化合物を用いることもできる。また、近赤外線吸収色素は下記構造の化合物を用いることもできる。
Figure JPOXMLDOC01-appb-C000011
 Near infrared absorbing dyes include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diimonium compounds, dithiol compounds, triarylmethane compounds, piromethene compounds, azomethine At least one selected from a compound, an anthraquinone compound, an indigo compound and a dibenzofuranone compound is preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squalilium compound, a phthalocyanine compound, a naphthalocyanine compound, a croconium compound and an indigo compound is more preferable Preferably, it is selected from pyrrolopyrrole compounds, cyanine compounds and squarylium compounds At least one more preferably, pyrrolo-pyrrole compounds are particularly preferred. Examples of diimmonium compounds include the compounds described in JP-A-2008-528706, the contents of which are incorporated herein. As the phthalocyanine compound, for example, a compound described in paragraph 0093 of JP-A-2012-77153, an oxytitanium phthalocyanine described in JP-A-2006-343631, a paragraph number 0013 to 0029 of JP-A-2013-195480. And vanadium phthalocyanine described in Japanese Patent No. 6081771, the contents of which are incorporated herein. As a naphthalocyanine compound, the compound as described in stage number 0093 of Unexamined-Japanese-Patent No. 2012-77153 is mentioned, for example, This content is integrated in this specification. The indigo compound is preferably an indigo boron complex compound. Examples of indigo compounds include the compounds described in Japanese Patent No. 5642013, the contents of which are incorporated herein. Further, as the near-infrared absorbing dye, compounds described in JP-A-2016-146619, compounds described in JP-A-2016-79331, compounds described in JP-A-2017-82029, JP-A-2015 It is also possible to use the compounds described in -40176 and the compounds described in Japanese Patent No. 5539676. Moreover, the compound of a following structure can also be used for a near-infrared absorption pigment | dye.
Figure JPOXMLDOC01-appb-C000011
　ピロロピロール化合物としては、式（ＰＰ）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000012
 　式中、Ｒ１ａおよびＲ１ｂは、各々独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ２およびＲ３は、各々独立に水素原子または置換基を表し、Ｒ２およびＲ３は、互いに結合して環を形成してもよく、Ｒ４は、各々独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、－ＢＲ４ＡＲ４Ｂ、または金属原子を表し、Ｒ４は、Ｒ１ａ、Ｒ１ｂおよびＲ３から選ばれる少なくとも一つと共有結合もしくは配位結合していてもよく、Ｒ４ＡおよびＲ４Ｂは、各々独立に置換基を表す。式（ＰＰ）の詳細については、特開２００９－２６３６１４号公報の段落番号００１７～００４７、特開２０１１－６８７３１号公報の段落番号００１１～００３６、国際公開ＷＯ２０１５／１６６８７３号公報の段落番号００１０～００２４の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The pyrrolopyrrole compound is preferably a compound represented by the formula (PP).
Figure JPOXMLDOC01-appb-C000012
 In the formula, R 1a and R 1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R 2 and R 3 each independently represent a hydrogen atom or a substituent, and R 2 and R 3 represent R 4 may be combined with each other to form a ring, and each R 4 independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4A R 4B , or a metal atom, and R 4 is an R R 4A and R 4B may each independently represent a substituent, which may be covalently bonded or coordinated with at least one selected from 1 a 1 , R 1 b and R 3 . About the detail of Formula (PP), Paragraph No. 0017 of the Unexamined-Japanese-Patent No. 2009-263614, Paragraph No. 0011 of the Unexamined-Japanese-Patent No. 2011-68731, Paragraph No. 0010 of the international publication WO2015 / 166873, 0024 The contents of which are incorporated herein by reference.
　式（ＰＰ）において、Ｒ１ａおよびＲ１ｂは、各々独立に、アリール基またはヘテロアリール基が好ましく、アリール基がより好ましい。また、Ｒ１ａおよびＲ１ｂが表すアルキル基、アリール基およびヘテロアリール基は、置換基を有していてもよく、無置換であってもよい。置換基としては、特開２００９－２６３６１４号公報の段落番号００２０～００２２に記載された置換基や、上述した置換基Ｔが挙げられる。また、Ｒ１ａおよびＲ１ｂが表すアルキル基、アリール基およびヘテロアリール基が２個以上の置換基を有している場合、置換基同士が結合して環を形成していてもよい。 In formula (PP), R 1a and R 1b are each independently preferably an aryl group or a heteroaryl group, and more preferably an aryl group. In addition, the alkyl group, the aryl group and the heteroaryl group represented by R 1a and R 1b may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described in Paragraph Nos. 0020 to 0022 of JP-A-2009-263614, and the above-mentioned substituent T. When the alkyl group, aryl group and heteroaryl group represented by R 1a and R 1b have two or more substituents, the substituents may be combined to form a ring.
　Ｒ１ａ、Ｒ１ｂで表される基の具体例としては、アルコキシ基を置換基として有するアリール基、水酸基を置換基として有するアリール基、アシルオキシ基を置換基として有するアリール基などが挙げられる。 Specific examples of the group represented by R 1a and R 1b include an aryl group having an alkoxy group as a substituent, an aryl group having a hydroxyl group as a substituent, an aryl group having an acyloxy group as a substituent and the like.
　式（ＰＰ）において、Ｒ２およびＲ３は、各々独立に水素原子または置換基を表す。置換基としては上述した置換基Ｔが挙げられる。Ｒ２およびＲ３の少なくとも一方は電子求引性基が好ましい。ハメットの置換基定数σ値（シグマ値）が正の置換基は、電子求引性基として作用する。ここで、ハメット則で求められた置換基定数にはσｐ値とσｍ値がある。これらの値は多くの一般的な成書に見出すことができる。本発明においては、ハメットの置換基定数σ値が０．２以上の置換基を電子求引性基として例示することができる。σ値は、０．２５以上が好ましく、０．３以上がより好ましく、０．３５以上が更に好ましい。上限は特に制限はないが、好ましくは０．８０以下である。電子求引性基の具体例としては、シアノ基（－ＣＮ：σｐ値＝０．６６）、カルボキシル基（－ＣＯＯＨ：σｐ値＝０．４５）、アルコキシカルボニル基（例えば、－ＣＯＯＭｅ：σｐ値＝０．４５）、アリールオキシカルボニル基（例えば、－ＣＯＯＰｈ：σｐ値＝０．４４）、カルバモイル基（例えば、－ＣＯＮＨ２：σｐ値＝０．３６）、アルキルカルボニル基（例えば、－ＣＯＭｅ：σｐ値＝０．５０）、アリールカルボニル基（例えば、－ＣＯＰｈ：σｐ値＝０．４３）、アルキルスルホニル基（例えば、－ＳＯ２Ｍｅ：σｐ値＝０．７２）、アリールスルホニル基（例えば、－ＳＯ２Ｐｈ：σｐ値＝０．６８）などが挙げられ、シアノ基が好ましい。ここで、Ｍｅはメチル基を、Ｐｈはフェニル基を表す。なお、ハメットの置換基定数σ値については、例えば、特開２０１１－６８７３１号公報の段落番号００１７～００１８を参酌でき、この内容は本明細書に組み込まれる。 In formula (PP), R 2 and R 3 each independently represent a hydrogen atom or a substituent. Examples of the substituent include the above-mentioned substituent T. At least one of R 2 and R 3 is preferably an electron-withdrawing group. A substituent having a positive Hammett's substituent constant σ value (sigma value) acts as an electron-withdrawing group. Here, the substituent constants determined by the Hammett rule include σp values and σm values. These values can be found in many general books. In the present invention, a substituent having a Hammett's substituent constant σ value of 0.2 or more can be exemplified as the electron-withdrawing group. The σ value is preferably 0.25 or more, more preferably 0.3 or more, and still more preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less. Specific examples of the electron withdrawing group include a cyano group (-CN: σp value = 0.66), a carboxyl group (-COOH: σp value = 0.45), and an alkoxycarbonyl group (eg, -COOMe: σp value) = 0.45), an aryloxycarbonyl group (for example, -COOPh: σp value = 0.44), a carbamoyl group (for example, -CONH 2 : σp value = 0.36), an alkylcarbonyl group (for example, -COMe: σp value = 0.50), arylcarbonyl group (eg, -COPh: σp value = 0.43), alkylsulfonyl group (eg, -SO 2 Me: σp value = 0.72), arylsulfonyl group (eg, -SO 2 Ph: σp value = 0.68) and the like, and a cyano group is preferable. Here, Me represents a methyl group, and Ph represents a phenyl group. The Hammett's substituent constant σ value can be referred to, for example, paragraph Nos. 0017 to 0018 of JP-A-2011-68731, the contents of which are incorporated herein.
　式（ＰＰ）において、Ｒ２は電子求引性基（好ましくはシアノ基）を表し、Ｒ３はヘテロアリール基を表すことが好ましい。ヘテロアリール基は、５員環または６員環が好ましい。また、ヘテロアリール基は、単環または縮合環が好ましく、単環または縮合数が２～８の縮合環が好ましく、単環または縮合数が２～４の縮合環がより好ましい。ヘテロアリール基を構成するヘテロ原子の数は、１～３が好ましく、１～２がより好ましい。ヘテロ原子としては、例えば、窒素原子、酸素原子、硫黄原子が例示される。ヘテロアリール基は、窒素原子を１個以上有することが好ましい。式（ＰＰ）における２個のＲ２同士は同一であってもよく、異なっていてもよい。また、式（ＰＰ）における２個のＲ３同士は同一であってもよく、異なっていてもよい。 In formula (PP), R 2 preferably represents an electron-withdrawing group (preferably a cyano group) and R 3 preferably represents a heteroaryl group. The heteroaryl group is preferably a 5- or 6-membered ring. The heteroaryl group is preferably a single ring or a fused ring, preferably a single ring or a fused ring having 2 to 8 condensations, and more preferably a single ring or a fused ring having 2 to 4 condensations. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, for example. The heteroaryl group preferably has one or more nitrogen atoms. Two R 2 s in Formula (PP) may be identical to or different from each other. Moreover, two R 3 's in Formula (PP) may be the same or different.
　式（ＰＰ）において、Ｒ４は、水素原子、アルキル基、アリール基、ヘテロアリール基または－ＢＲ４ＡＲ４Ｂで表される基であることが好ましく、水素原子、アルキル基、アリール基または－ＢＲ４ＡＲ４Ｂで表される基であることがより好ましく、－ＢＲ４ＡＲ４Ｂで表される基であることが更に好ましい。Ｒ４ＡおよびＲ４Ｂが表す置換基としては、ハロゲン原子、アルキル基、アルコキシ基、アリール基、または、ヘテロアリール基が好ましく、アルキル基、アリール基、または、ヘテロアリール基がより好ましく、アリール基が特に好ましい。これらの基はさらに置換基を有していてもよい。式（ＰＰ）における２個のＲ４同士は同一であってもよく、異なっていてもよい。Ｒ４ＡおよびＲ４Ｂは互いに結合して環を形成していてもよい。 In formula (PP), R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or a group represented by —BR 4A R 4B , and a hydrogen atom, an alkyl group, an aryl group or —BR The group represented by 4A R 4B is more preferably a group represented by -BR 4A R 4B . The substituent represented by R 4A and R 4B is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group, more preferably an alkyl group, an aryl group or a heteroaryl group, and an aryl group Particularly preferred. These groups may further have a substituent. Two R 4 's in the formula (PP) may be the same or different. R 4A and R 4B may be bonded to each other to form a ring.
　式（ＰＰ）で表される化合物の具体例としては、下記化合物が挙げられる。以下の構造式中、Ｍｅはメチル基を表し、Ｐｈはフェニル基を表す。また、ピロロピロール化合物としては、特開２００９－２６３６１４号公報の段落番号００１６～００５８に記載の化合物、特開２０１１－６８７３１号公報の段落番号００３７～００５２に記載の化合物、国際公開ＷＯ２０１５／１６６８７３号公報の段落番号００１０～００３３に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。
Figure JPOXMLDOC01-appb-C000013
 The following compounds may be mentioned as specific examples of the compound represented by the formula (PP). In the following structural formulae, Me represents a methyl group and Ph represents a phenyl group. As pyrrolopyrrole compounds, compounds described in paragraphs 0016 to 0058 of JP 2009-263614 A, compounds described in paragraphs 0037 to 0052 of JP 2011-68731 A, WO 2015/166873 And the compounds described in Paragraph No. 0010 to 0033 of the publication, the contents of which are incorporated herein.
Figure JPOXMLDOC01-appb-C000013
　スクアリリウム化合物としては、下記式（ＳＱ）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000014
 　式（ＳＱ）中、Ａ１およびＡ２は、それぞれ独立に、アリール基、ヘテロアリール基または式（Ａ－１）で表される基を表す；
Figure JPOXMLDOC01-appb-C000015
 　式（Ａ－１）中、Ｚ１は、含窒素複素環を形成する非金属原子団を表し、Ｒ２は、アルキル基、アルケニル基またはアラルキル基を表し、ｄは、０または１を表し、波線は連結手を表す。式（ＳＱ）の詳細については、特開２０１１－２０８１０１号公報の段落番号００２０～００４９、特許第６０６５１６９号公報の段落番号００４３～００６２、国際公開ＷＯ２０１６／１８１９８７号公報の段落番号００２４～００４０の記載を参酌でき、これらの内容は本明細書に組み込まれる。 As the squarylium compound, a compound represented by the following formula (SQ) is preferable.
Figure JPOXMLDOC01-appb-C000014
 In formula (SQ), each of A 1 and A 2 independently represents an aryl group, a heteroaryl group or a group represented by formula (A-1);
Figure JPOXMLDOC01-appb-C000015
 In formula (A-1), Z 1 represents a nonmetal atomic group forming a nitrogen-containing heterocyclic ring, R 2 represents an alkyl group, an alkenyl group or an aralkyl group, and d represents 0 or 1. The wavy line represents a connecting hand. The details of the formula (SQ) are described in paragraph Nos. 0020 to 0049 of JP2011-208101A, paragraph Nos. 0043 to 0062 of Patent No. 6065169, and paragraph Nos. 0024 to 0040 of International Publication WO2016 / 181987. The contents of these are incorporated herein by reference.
　なお、式（ＳＱ）においてカチオンは、以下のように非局在化して存在している。
Figure JPOXMLDOC01-appb-C000016
 In the formula (SQ), the cation is present in a delocalized manner as follows.
Figure JPOXMLDOC01-appb-C000016
　スクアリリウム化合物としては、下記構造の化合物が挙げられる。また、特開２０１１－２０８１０１号公報の段落番号００４４～００４９に記載の化合物、特許第６０６５１６９号公報の段落番号００６０～００６１に記載の化合物、国際公開ＷＯ２０１６／１８１９８７号公報の段落番号００４０に記載の化合物、国際公開ＷＯ２０１３／１３３０９９号公報に記載の化合物、国際公開ＷＯ２０１４／０８８０６３号公報に記載の化合物、特開２０１４－１２６６４２号公報に記載の化合物、特開２０１６－１４６６１９号公報に記載の化合物、特開２０１５－１７６０４６号公報に記載の化合物、特開２０１７－２５３１１号公報に記載の化合物、国際公開ＷＯ２０１６／１５４７８２号公報に記載の化合物、特許第５８８４９５３号公報に記載の化合物、特許第６０３６６８９号公報に記載の化合物、特許第５８１０６０４号公報に記載の化合物、特開２０１７－０６８１２０号公報に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。
Figure JPOXMLDOC01-appb-C000017
 As a squarylium compound, the compound of the following structure is mentioned. Further, compounds described in paragraphs 0044 to 0049 of JP2011-208101A, compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, described in paragraph 0040 of International Publication WO2016 / 181987A. Compound, compound described in International Publication WO 2013/133099, compound described in International Publication WO 2014/088063, compound described in Japanese Patent Laid-Open No. 2014-126642, compound described in Japanese Patent Laid-Open No. 2016-146619, Compound described in JP-A-2015-176046, Compound described in JP-A-2017-25311, Compound described in International Publication WO2016 / 154782, Compound described in JP-A-5884953, JP-A-6036689 Compounds described in the official gazette Compounds described in Japanese Patent No. 5810604, can be mentioned compounds described in JP-A-2017-068120, the contents of which are incorporated herein.
Figure JPOXMLDOC01-appb-C000017
　シアニン化合物は、式（Ｃ）で表される化合物が好ましい。
式（Ｃ）
Figure JPOXMLDOC01-appb-C000018
 　式中、Ｚ１およびＺ２は、それぞれ独立に、縮環してもよい５員または６員の含窒素複素環を形成する非金属原子団であり、
　Ｒ１０１およびＲ１０２は、それぞれ独立に、アルキル基、アルケニル基、アルキニル基、アラルキル基またはアリール基を表し、
　Ｌ１は、奇数個のメチン基を有するメチン鎖を表し、
　ａおよびｂは、それぞれ独立に、０または１であり、
　ａが０の場合は、炭素原子と窒素原子とが二重結合で結合し、ｂが０の場合は、炭素原子と窒素原子とが単結合で結合し、
　式中のＣｙで表される部位がカチオン部である場合、Ｘ１はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ１はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、ｃは０である。 The cyanine compound is preferably a compound represented by the formula (C).
Formula (C)
Figure JPOXMLDOC01-appb-C000018
 In the formula, each of Z 1 and Z 2 independently represents a nonmetallic atomic group forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be condensed.
R 101 and R 102 each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,
L 1 represents a methine chain having an odd number of methine groups,
a and b are each independently 0 or 1;
When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,
When the site represented by Cy in the formula is a cation moiety, X 1 represents an anion, c represents the number necessary to balance the charge, and the site represented by Cy in the formula is an anion moiety Where X 1 represents a cation, c represents the number necessary to balance the charge, and c is a molecule in which the charge at the site represented by Cy in the formula is neutralized within the molecule It is 0.
　シアニン化合物としては、特開２００９－１０８２６７号公報の段落番号００４４～００４５に記載の化合物、特開２００２－１９４０４０号公報の段落番号００２６～００３０に記載の化合物、特開２０１５－１７２００４号公報に記載の化合物、特開２０１５－１７２１０２号公報に記載の化合物、特開２００８－８８４２６号公報に記載の化合物、特開２０１７－０３１３９４号公報に記載の化合物などが挙げられ、これらの内容は本明細書に組み込まれる。 As cyanine compounds, compounds described in paragraphs 0044 to 0045 of JP 2009-108267 A, compounds described in paragraphs 0026 to 0030 of JP 2002-194040 A, described in JP 2015-172004 A Compounds described in JP-A-2015-172102, compounds described in JP-A-2008-88426, and compounds described in JP-A-2017-031394, the contents of which are incorporated herein by reference. Incorporated into
　本発明において、近赤外線吸収色素は市販品を用いることもできる。例えば、ＳＤＯ－Ｃ３３（有本化学工業（株）製）、イーエクスカラーＩＲ－１４、イーエクスカラーＩＲ－１０Ａ、イーエクスカラーＴＸ－ＥＸ－８０１Ｂ、イーエクスカラーＴＸ－ＥＸ－８０５Ｋ（（株）日本触媒製）、ＳｈｉｇｅｎｏｘＮＩＡ－８０４１、ＳｈｉｇｅｎｏｘＮＩＡ－８０４２、ＳｈｉｇｅｎｏｘＮＩＡ－８１４、ＳｈｉｇｅｎｏｘＮＩＡ－８２０、ＳｈｉｇｅｎｏｘＮＩＡ－８３９（ハッコーケミカル社製）、ＥｐｏｌｉｔｅＶ－６３、Ｅｐｏｌｉｇｈｔ３８０１、Ｅｐｏｌｉｇｈｔ３０３６（ＥＰＯＬＩＮ社製）、ＰＲＯ－ＪＥＴ８２５ＬＤＩ（富士フイルム（株）製）、ＮＫ－３０２７、ＮＫ－５０６０（（株）林原製）、ＹＫＲ－３０７０（三井化学（株）製）、ＦＤＮ－００３（山田化学工業（株）製）などが挙げられる。 In the present invention, commercially available near infrared absorbing dyes can also be used. For example, SDO-C33 (Arimoto Chemical Industries Co., Ltd.), EEX Color IR-14, EEX Color IR-10A, EEX Color TX-EX-801B, EEX Color TX-EX-805K ( A product of Nippon Shokubai), Shigenox NIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820, Shigenox NIA-839 (Hakoko Chemical Co., Ltd.), Epolite V-63, Epolight 3801, Epolight 3036 (EPOLIN), PRO-JET 825 LDI Film (manufactured by KK), NK-3027, NK-5060 (manufactured by Hayashibara), YKR-3070 (manufactured by Mitsui Chemicals, Inc.), FDN-003 (manufactured by Yamada Chemical Industries, Ltd.), etc. And the like.
　本発明の組成物が近赤外線吸収色素を含有する場合、近赤外線吸収色素の含有量は、本発明の組成物の全固形分中１～３０質量％であることが好ましい。上限は、２０質量％以下が好ましく、１０質量％以下がより好ましい。下限は、３質量％以上が好ましく、５質量％以上がより好ましい。また、近赤外線吸収色素の含有量は、金属アゾ顔料Ａと他の色材との合計１００質量部に対し５～５０質量部であることが好ましい。上限は、４５質量％以下が好ましく、４０質量％以下がより好ましい。下限は、１０質量％以上が好ましく、１５質量％以上がより好ましい。また、金属アゾ顔料Ａと、他の色材と、近赤外線吸収色素との合計の含有量は、本発明の組成物の全固形分中１０～７０質量％であることが好ましい。下限は、２０質量％以上が好ましく、３０質量％以上がより好ましく、４０質量％以上が更に好ましい。本発明の組成物は、近赤外線吸収色素を１種のみ含んでいてもよいし、２種以上含んでいてもよい。近赤外線吸収色素を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 When the composition of the present invention contains a near infrared absorbing dye, the content of the near infrared absorbing dye is preferably 1 to 30% by mass in the total solid content of the composition of the present invention. 20 mass% or less is preferable, and, as for the upper limit, 10 mass% or less is more preferable. 3 mass% or more is preferable, and, as for a lower limit, 5 mass% or more is more preferable. Further, the content of the near-infrared absorbing dye is preferably 5 to 50 parts by mass with respect to 100 parts by mass in total of the metal azo pigment A and the other coloring material. 45 mass% or less is preferable, and, as for the upper limit, 40 mass% or less is more preferable. 10 mass% or more is preferable, and, as for a lower limit, 15 mass% or more is more preferable. In addition, the total content of the metal azo pigment A, the other coloring material, and the near infrared absorbing dye is preferably 10 to 70% by mass in the total solid content of the composition of the present invention. 20 mass% or more is preferable, 30 mass% or more is more preferable, and 40 mass% or more is still more preferable for a minimum. The composition of the present invention may contain only one type of near infrared absorbing dye, or may contain two or more types. When two or more near infrared absorbing dyes are contained, the total amount thereof is preferably in the above range.
＜＜硬化性化合物＞＞
　本発明の組成物は、エチレン性不飽和結合基を有する化合物、および、環状エーテル基を有する化合物から選ばれる少なくとも１種の化合物を含有する。以下、両者を合わせて硬化性化合物ともいう。エチレン性不飽和結合基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられる。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられる。 << Curable compound >>
The composition of the present invention contains at least one compound selected from a compound having an ethylenically unsaturated bonding group and a compound having a cyclic ether group. Hereinafter, both are put together and it is also called a curable compound. As an ethylenically unsaturated bond group, a vinyl group, a (meth) allyl group, a (meth) acryloyl group etc. are mentioned. The cyclic ether group may, for example, be an epoxy group or an oxetanyl group.
（エチレン性不飽和結合基を有する化合物）
　本発明において用いられるエチレン性不飽和結合基を有する化合物は、モノマーであってもよく、ポリマーであってもよい。以下、エチレン性不飽和結合基を有するモノマーを重合性モノマーともいう。また、エチレン性不飽和結合基を有するポリマーを重合性ポリマーともいう。 (Compounds Having an Ethylenically Unsaturated Bonding Group)
The compound having an ethylenically unsaturated bonding group used in the present invention may be a monomer or a polymer. Hereinafter, a monomer having an ethylenically unsaturated bond group is also referred to as a polymerizable monomer. In addition, a polymer having an ethylenically unsaturated bond group is also referred to as a polymerizable polymer.
　重合性モノマーの分子量は、３０００未満であることが好ましい。上限は、２０００以下がより好ましく、１５００以下が更に好ましい。下限は、１００以上が好ましく、１５０以上がより好ましく、２５０以上が更に好ましい。重合性モノマーは、エチレン性不飽和結合基を３個以上含む化合物であることが好ましく、エチレン性不飽和結合基を３～１５個含む化合物であることがより好ましく、エチレン性不飽和結合基を３～６個含む化合物であることが更に好ましい。また、重合性モノマーは、３～１５官能の（メタ）アクリレート化合物であることが好ましく、３～６官能の（メタ）アクリレート化合物であることがより好ましい。重合性モノマーの具体例としては、特開２００９－２８８７０５号公報の段落番号００９５～０１０８、特開２０１３－２９７６０号公報の段落０２２７、特開２００８－２９２９７０号公報の段落番号０２５４～０２５７に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。 The molecular weight of the polymerizable monomer is preferably less than 3000. The upper limit is more preferably 2000 or less, still more preferably 1500 or less. The lower limit is preferably 100 or more, more preferably 150 or more, and still more preferably 250 or more. The polymerizable monomer is preferably a compound containing 3 or more ethylenic unsaturated bonding groups, more preferably a compound containing 3 to 15 ethylenic unsaturated bonding groups, and an ethylenic unsaturated bonding group. More preferably, it is a compound containing 3 to 6. Further, the polymerizable monomer is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound. Specific examples of the polymerizable monomer are described in paragraph Nos. 0095 to 0108 of JP2009-288705A, paragraph 0227 of JP2013-29760A, and paragraph 0254-0257 of JP2008-292970A. Compounds are included, the contents of which are incorporated herein.
　重合性モノマーのＣ＝Ｃ当量（重合性モノマーの分子量［ｇ／ｍｏｌ］／重合性モノマーに含まれるエチレン性不飽和結合基の数）は、５０～１０００であることが好ましい。下限は、６０以上であることが好ましく、７０以上であることがより好ましい。上限は、７００以下であることが好ましく、５００以下であることがより好ましく、２００以下であることが更に好ましく、１５０以下であることがより一層好ましく、１４０以下であることが特に好ましい。重合性モノマーのＣ＝Ｃ当量が上記範囲であれば、顔料活性面に効果的に吸着でき、金属アゾ顔料Ａの凝集をより顕著に抑制できる。 The C = C equivalent of the polymerizable monomer (molecular weight of the polymerizable monomer [g / mol] / number of ethylenically unsaturated bond groups contained in the polymerizable monomer) is preferably 50 to 1,000. The lower limit is preferably 60 or more, and more preferably 70 or more. The upper limit is preferably 700 or less, more preferably 500 or less, still more preferably 200 or less, still more preferably 150 or less, and particularly preferably 140 or less. If the C = C equivalent of the polymerizable monomer is in the above-mentioned range, it can be effectively adsorbed to the pigment active surface, and the aggregation of the metal azo pigment A can be more remarkably suppressed.
　重合性モノマーとして、ジペンタエリスリトールトリアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、ＮＫエステルＡ－ＤＰＨ－１２Ｅ；新中村化学工業（株）製）、およびこれらの（メタ）アクリロイル基がエチレングリコールおよび／またはプロピレングリコール残基を介して結合している構造の化合物（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）、ＮＫエステルＡ－ＴＭＭＴ（新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＲＰ－１０４０、ＤＰＣＡ－２０（日本化薬（株）製）などが挙げられる。また、重合性化合物として、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンプロピレンオキシ変性トリ（メタ）アクリレート、トリメチロールプロパンエチレンオキシ変性トリ（メタ）アクリレート、イソシアヌル酸エチレンオキシ変性トリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートなどの３官能の（メタ）アクリレート化合物を用いることも好ましい。３官能の（メタ）アクリレート化合物の市販品としては、アロニックスＭ－３０９、Ｍ－３１０、Ｍ－３２１、Ｍ－３５０、Ｍ－３６０、Ｍ－３１３、Ｍ－３１５、Ｍ－３０６、Ｍ－３０５、Ｍ－３０３、Ｍ－４５２、Ｍ－４５０（東亞合成（株）製）、ＮＫエステル　Ａ９３００、Ａ－ＧＬＹ－９Ｅ、Ａ－ＧＬＹ－２０Ｅ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、Ａ－ＴＭＰＴ、ＴＭＰＴ（新中村化学工業（株）製）、ＫＡＹＡＲＡＤ　ＧＰＯ－３０３、ＴＭＰＴＡ、ＴＨＥ－３３０、ＴＰＡ－３３０、ＰＥＴ－３０（日本化薬（株）製）、ＴＭＰＥＯＴＡ（ダイセル・オルネクス（株）製）などが挙げられる。 As polymerizable monomers, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd.) Made, Dipentaerythritol penta (meth) acrylate (Commercial product: KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) acrylate (Commercial product: KAYARAD DPHA; Nippon Kayaku ( Ltd. product, NK ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd. product, and the compound of the structure where these (meth) acryloyl groups are linked via ethylene glycol and / or propylene glycol residue (For example, commercially available from Sartmar And has, SR454, SR499), NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Industry Co.), manufactured KAYARAD RP-1040, DPCA-20 (Nippon Kayaku Co.) and the like. Moreover, as a polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth) acrylate It is also preferable to use a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate. Commercially available products of trifunctional (meth) acrylate compounds include Alonics M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And TMPEOTA (manufactured by Daicel Ornex Co., Ltd.).
　重合性モノマーとして、酸基を有する重合性モノマーを用いることも好ましい。酸基を有する重合性モノマーを用いることで、現像時に未露光部の組成物層が除去されやすく、現像残渣の発生を効果的に抑制できる。酸基としては、カルボキシル基、スルホ基、リン酸基等が挙げられ、カルボキシル基が好ましい。酸基を有する重合性モノマーの市販品としては、アロニックスＭ－５１０、Ｍ－５２０、アロニックスＴＯ－２３４９（東亞合成（株）製）等が挙げられる。酸基を有する重合性モノマーの酸価は、０．１～４０ｍｇＫＯＨ／ｇであることが好ましく、５～３０ｍｇＫＯＨ／ｇがより好ましい。重合性モノマーの酸価が０．１ｍｇＫＯＨ／ｇ以上であれば、現像液に対する溶解性が良好であり、より優れた現像性が得られる。重合性モノマーの酸価が４０ｍｇＫＯＨ／ｇ以下であれば、製造や取扱い上、有利である。 It is also preferable to use a polymerizable monomer having an acid group as the polymerizable monomer. By using the polymerizable monomer having an acid group, the composition layer in the unexposed area is easily removed during development, and the generation of development residues can be effectively suppressed. As an acid group, a carboxyl group, a sulfo group, a phosphoric acid group etc. are mentioned, A carboxyl group is preferable. Commercially available products of the polymerizable monomer having an acid group include ALONIX M-510, M-520, ALONIX TO-2349 (manufactured by Toagosei Co., Ltd.), and the like. The acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40 mg KOH / g, and more preferably 5 to 30 mg KOH / g. When the acid value of the polymerizable monomer is 0.1 mg KOH / g or more, the solubility in a developer is good, and more excellent developability can be obtained. If the acid value of the polymerizable monomer is 40 mg KOH / g or less, it is advantageous in terms of production and handling.
　重合性モノマーとして、下記式（ＭＯ－１）～（ＭＯ－６）で表される化合物を用いることも好ましい。なお、式中、Ｔがオキシアルキレン基の場合には、炭素原子側の末端がＲに結合する。 It is also preferable to use the compounds represented by the following formulas (MO-1) to (MO-6) as the polymerizable monomer. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　上記の式において、ｎは０～１４であり、ｍは１～８である。一分子内に複数存在するＲ、Ｔ、は、各々同一であっても、異なっていてもよい。
　上記式（ＭＯ－１）～（ＭＯ－６）で表される化合物の各々において、複数のＲの内の少なくとも１つは、－ＯＣ（＝Ｏ）ＣＨ＝ＣＨ２、－ＯＣ（＝Ｏ）Ｃ（ＣＨ３）＝ＣＨ２、－ＮＨＣ（＝Ｏ）ＣＨ＝ＣＨ２または－ＮＨＣ（＝Ｏ）Ｃ（ＣＨ３）＝ＣＨ２を表す。上記式（ＭＯ－１）～（ＭＯ－６）で表される重合性化合物の具体例としては、特開２００７－２６９７７９号公報の段落０２４８～０２５１に記載されている化合物が挙げられる。 In the above formula, n is 0-14 and m is 1-8. A plurality of R and T in one molecule may be identical to or different from each other.
In each of the compounds represented by the above formulas (MO-1) to (MO-6), at least one of a plurality of R is —OC (= O) CH = CH 2 , —OC (= O) C (CH 3 ) = CH 2 , —NHC (= O) CH = CH 2 or —NHC (= O) C (CH 3 ) = CH 2 . Specific examples of the polymerizable compounds represented by the above formulas (MO-1) to (MO-6) include the compounds described in paragraphs 0248 to 0251 of JP-A-2007-269779.
　また、重合性モノマーとして、カプロラクトン構造を有する化合物を用いることも好ましい。カプロラクトン構造を有する化合物としては、分子内にカプロラクトン構造を有する限り特に限定されるものではないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと（メタ）アクリル酸及びε－カプロラクトンとをエステル化することにより得られる、ε－カプロラクトン変性多官能（メタ）アクリレートを挙げることができる。カプロラクトン構造を有する化合物は、下記式（Ｚ－１）で表される化合物が好ましい。 It is also preferable to use a compound having a caprolactone structure as the polymerizable monomer. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane, pentaerythritol, and dipentaerythritol. Mention ε-caprolactone modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as tripentaerythritol, glycerol, diglycerol, trimethylolmelamine and (meth) acrylic acid and ε-caprolactone; Can. The compound having a caprolactone structure is preferably a compound represented by the following formula (Z-1).
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　式（Ｚ－１）中、６個のＲの全てが式（Ｚ－２）で表される基であるか、又は６個のＲのうち１～５個が式（Ｚ－２）で表される基であり、残余が式（Ｚ－３）で表される基、酸基またはヒドロキシ基である。 In the formula (Z-1), all of the six R's are a group represented by the formula (Z-2), or 1 to 5 of the six R's are represented by the formula (Z-2) And the remainder is a group represented by formula (Z-3), an acid group or a hydroxy group.
Figure JPOXMLDOC01-appb-C000021
 　式（Ｚ－２）中、Ｒ１は水素原子又はメチル基を示し、ｍは１又は２の数を示し、「＊」は結合手であることを示す。
Figure JPOXMLDOC01-appb-C000021
 In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.
Figure JPOXMLDOC01-appb-C000022
 　式（Ｚ－３）中、Ｒ１は水素原子又はメチル基を示し、「＊」は結合手であることを示す。
Figure JPOXMLDOC01-appb-C000022
 In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
　重合性モノマーとして、式（Ｚ－４）又は（Ｚ－５）で表される化合物も挙げられる。 Examples of the polymerizable monomer also include compounds represented by Formula (Z-4) or (Z-5).
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（Ｚ－４）及び（Ｚ－５）中、Ｅは、各々独立に、－（（ＣＨ２）ｙＣＨ２Ｏ）－、又は－（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－を表し、ｙは、各々独立に０～１０の整数を表し、Ｘは、各々独立に、（メタ）アクリロイル基、水素原子、又はカルボキシル基を表す。式（Ｚ－４）中、（メタ）アクリロイル基の合計は３個又は４個であり、ｍは各々独立に０～１０の整数を表し、各ｍの合計は０～４０の整数である。式（Ｚ－５）中、（メタ）アクリロイル基の合計は５個又は６個であり、ｎは各々独立に０～１０の整数を表し、各ｎの合計は０～６０の整数である。 In the formulas (Z-4) and (Z-5), each E is independently-((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH (CH 3 ) O)- And y each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom or a carboxyl group. In formula (Z-4), the total of (meth) acryloyl groups is three or four, m each independently represents an integer of 0 to 10, and the sum of each m is an integer of 0 to 40. In formula (Z-5), the total of (meth) acryloyl groups is five or six, n independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60.
　式（Ｚ－４）中、ｍは、０～６の整数が好ましく、０～４の整数がより好ましい。また、各ｍの合計は、２～４０の整数が好ましく、２～１６の整数がより好ましく、４～８の整数が特に好ましい。
　式（Ｚ－５）中、ｎは、０～６の整数が好ましく、０～４の整数がより好ましい。また、各ｎの合計は、３～６０の整数が好ましく、３～２４の整数がより好ましく、６～１２の整数が特に好ましい。
　また、式（Ｚ－４）又は式（Ｚ－５）中のＥ、すなわち、－（（ＣＨ２）ｙＣＨ２Ｏ）－又は－（（ＣＨ２）ｙＣＨ（ＣＨ３）Ｏ）－は、酸素原子側の末端がＸに結合する形態が好ましい。 In the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The total of m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
Furthermore, E in the formula (Z-4) or the formula (Z-5), that is,-((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH (CH 3 ) O)- It is preferable that the terminal at the oxygen atom side is bonded to X.
　重合性モノマーとして、アルキレンオキシ基を有する化合物を用いることもできる。アルキレンオキシ基を有する重合性モノマーは、エチレンオキシ基および／またはプロピレンオキシ基を有する化合物であることが好ましく、エチレンオキシ基を有する化合物であることがより好ましく、エチレンオキシ基を４～２０個有する３～６官能（メタ）アクリレート化合物であることがさらに好ましい。アルキレンオキシ基を有する重合性モノマーの市販品としては、例えばサートマー社製のエチレンオキシ基を４個有する４官能（メタ）アクリレートであるＳＲ－４９４、イソブチレンオキシ基を３個有する３官能（メタ）アクリレートであるＫＡＹＡＲＡＤ　ＴＰＡ－３３０などが挙げられる。 A compound having an alkyleneoxy group can also be used as the polymerizable monomer. The polymerizable monomer having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and having 4 to 20 ethyleneoxy groups. More preferably, it is a 3- to 6-functional (meth) acrylate compound. As a commercial item of a polymerizable monomer having an alkyleneoxy group, for example, SR-494 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, a trifunctional (meth) having three isobutylene oxy groups Examples thereof include KAYARAD TPA-330 which is an acrylate.
　重合性モノマーとして、特公昭４８－４１７０８号公報、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報に記載されているエチレンオキサイド系骨格を有するウレタン化合物、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平１－１０５２３８号公報に記載されている分子内にアミノ構造やスルフィド構造を有する化合物も挙げられ、これらの化合物を用いることも好ましい。市販品としては、ＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（共栄社化学（株）製）などが挙げられる。
　また、重合性モノマーは、８ＵＨ－１００６、８ＵＨ－１０１２（以上、大成ファインケミカル（株）製）、ライトアクリレートＰＯＢ－Ａ０（共栄社化学（株）製）などを用いることも好ましい。
　また、重合性モノマーは、特開２０１７－４８３６７号公報、特許第６０５７８９１号公報、特許第６０３１８０７号公報に記載されている化合物を用いることもできる。 As polymerizable monomers, urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765, and JP-B-58 JP-A-63-277653, urethane compounds having an ethylene oxide skeleton described in JP-49-860A, JP-B-56-17654, JP-B-62-39417, JP-B-62-39418 The compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-260909 and JP-A-1-105238 can also be mentioned, and use of these compounds is also preferable. As commercial products, UA-7200 (Shin-Nakamura Chemical Co., Ltd. product), DPHA-40H (Nippon Kayaku Co., Ltd. product), UA-306H, UA-306T, UA-306I, AH-600, T- 600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.
In addition, it is also preferable to use 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. as the polymerizable monomer.
Further, as the polymerizable monomer, compounds described in JP-A-2017-48367, JP-A-6057891, and JP-A-6031807 can also be used.
　重合性ポリマーの重量平均分子量は、３０００以上であることが好ましく、５０００以上であることがより好ましく、７０００以上であることが更に好ましく、１００００以上であることが特に好ましい。また、重合性ポリマーの重量平均分子量は、５００００以下であることが好ましく、４００００以下であることがより好ましく、３００００以下であることが更に好ましい。 The weight average molecular weight of the polymerizable polymer is preferably 3,000 or more, more preferably 5,000 or more, still more preferably 7,000 or more, and particularly preferably 10,000 or more. The weight average molecular weight of the polymerizable polymer is preferably 50,000 or less, more preferably 40,000 or less, and still more preferably 30,000 or less.
　重合性ポリマーのＣ＝Ｃ当量（重合性ポリマーの分子量／重合性ポリマーに含まれるエチレン性不飽和結合基の数）は、１００～５０００であることが好ましい。下限は、１５０以上であることが好ましく、２００以上であることがより好ましい。上限は、４５００以下であることが好ましく、４０００以下であることがより好ましい。重合性ポリマーのＣ＝Ｃ当量が上記範囲であれば、顔料活性面に効果的に吸着でき、金属アゾ顔料Ａの凝集をより顕著に抑制できる。 The C = C equivalent of the polymerizable polymer (molecular weight of the polymerizable polymer / the number of ethylenically unsaturated bonding groups contained in the polymerizable polymer) is preferably 100 to 5,000. The lower limit is preferably 150 or more, and more preferably 200 or more. The upper limit is preferably 4500 or less, more preferably 4000 or less. When the C = C equivalent of the polymerizable polymer is in the above-mentioned range, it can be effectively adsorbed to the pigment active surface, and the aggregation of the metal azo pigment A can be more significantly suppressed.
　重合性ポリマーは、エチレン性不飽和結合基を側鎖に有する繰り返し単位を含むことが好ましく、下記式（Ａ－１－１）で表される繰り返し単位を含むことがより好ましい。また、重合性ポリマーは、エチレン性不飽和結合基を有する繰り返し単位を重合性ポリマーの全繰り返し単位中１０モル％以上含有することが好ましく、１０～８０モル％含有することがより好ましく、２０～７０モル％含有することが更に好ましい。
Figure JPOXMLDOC01-appb-C000024
 　式（Ａ－１－１）において、Ｘ１は繰り返し単位の主鎖を表し、Ｌ１は単結合または２価の連結基を表し、Ｙ１はエチレン性不飽和結合基を表す。 The polymerizable polymer preferably contains a repeating unit having an ethylenically unsaturated bonding group in a side chain, and more preferably contains a repeating unit represented by the following formula (A-1-1). The polymerizable polymer preferably contains 10 mol% or more, more preferably 10 to 80 mol%, of repeating units having an ethylenically unsaturated bond group in all repeating units of the polymerizable polymer. It is more preferable to contain 70 mol%.
Figure JPOXMLDOC01-appb-C000024
 In formula (A-1-1), X 1 represents a main chain of a repeating unit, L 1 represents a single bond or a divalent linking group, and Y 1 represents an ethylenically unsaturated bonding group.
　式（Ａ－１－１）において、Ｘ１が表す繰り返し単位の主鎖としては、特に限定はない。公知の重合可能なモノマーから形成される連結基であれば特に制限ない。例えば、ポリ（メタ）アクリル系連結基、ポリアルキレンイミン系連結基、ポリエステル系連結基、ポリウレタン系連結基、ポリウレア系連結基、ポリアミド系連結基、ポリエーテル系連結基、ポリスチレン系連結基などが挙げられ、原料素材の入手性や製造適性の観点からポリ（メタ）アクリル系連結基、ポリアルキレンイミン系連結基が好ましく、ポリ（メタ）アクリル系連結基がより好ましい。 There is no particular limitation on the main chain of the repeating unit represented by X 1 in formula (A-1-1). There is no particular limitation as long as it is a linking group formed from known polymerizable monomers. For example, poly (meth) acrylic linking groups, polyalkyleneimine linking groups, polyester linking groups, polyurethane linking groups, polyurea linking groups, polyamide linking groups, polyether linking groups, polystyrene linking groups, etc. From the viewpoint of the availability of the raw material and the production suitability, preferred are poly (meth) acrylic based linking groups and polyalkyleneimine based linking groups, and more preferred are poly (meth) acrylic based linking groups.
　式（Ａ－１－１）において、Ｌ１が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アルキレンオキシ基（好ましくは炭素数１～１２のアルキレンオキシ基）、オキシアルキレンカルボニル基（好ましくは炭素数１～１２のオキシアルキレンカルボニル基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。 In the formula (A-1-1), as a divalent linking group represented by L 1 , an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) or an alkyleneoxy group (preferably an alkylene having 1 to 12 carbon atoms) Oxy group), oxyalkylene carbonyl group (preferably oxyalkylene carbonyl group having 1 to 12 carbon atoms), arylene group (preferably arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2- And -CO-, -O-, -COO-, OCO-, -S- and a group formed by combining two or more of these.
　式（Ａ－１－１）において、Ｙ１が表すエチレン性不飽和結合基としては、ビニル基、（メタ）アリル基、（メタ）アクリロイル基などが挙げられ、（メタ）アクリロイル基が好ましく、アクリロイル基がより好ましい。 In the formula (A-1-1), examples of the ethylenically unsaturated bonding group represented by Y 1 include a vinyl group, a (meth) allyl group, a (meth) acryloyl group and the like, and a (meth) acryloyl group is preferable. An acryloyl group is more preferred.
　重合性ポリマーは、更にグラフト鎖を有する繰り返し単位を含むことが好ましい。重合性ポリマーがグラフト鎖を有する繰り返し単位を含むことにより、グラフト鎖による立体障害によって金属アゾ顔料Ａなどの凝集などをより効果的に抑制できる。重合性ポリマーは、グラフト鎖を有する繰り返し単位を、重合性ポリマーの全繰り返し単位中１．０～６０モル％含有することが好ましく、１．５～５０モル％含有することがより好ましい。グラフト鎖を有する繰り返し単位を含む重合性ポリマーは分散剤として好ましく用いられる。 The polymerizable polymer preferably further contains a repeating unit having a graft chain. When the polymerizable polymer contains a repeating unit having a graft chain, aggregation and the like of the metal azo pigment A and the like can be more effectively suppressed by steric hindrance due to the graft chain. The polymerizable polymer preferably contains a repeating unit having a graft chain in an amount of 1.0 to 60% by mole, and more preferably 1.5 to 50% by mole, based on all repeating units of the polymerizable polymer. A polymerizable polymer containing a repeating unit having a graft chain is preferably used as a dispersant.
　本発明において、グラフト鎖とは、繰り返し単位の主鎖から枝分かれして伸びるポリマー鎖のことを意味する。グラフト鎖の長さについては特に制限されないが、グラフト鎖が長くなると立体反発効果が高くなり、金属アゾ顔料Ａなどの分散性を高めることができる。グラフト鎖としては、水素原子を除いた原子数が４０～１００００であることが好ましく、水素原子を除いた原子数が５０～２０００であることがより好ましく、水素原子を除いた原子数が６０～５００であることが更に好ましい。 In the present invention, a graft chain means a polymer chain which branches and extends from the main chain of a repeating unit. The length of the graft chain is not particularly limited, but the longer the graft chain, the higher the steric repulsion effect, and the dispersibility of the metal azo pigment A or the like can be enhanced. The graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and 60 to 60 atoms excluding hydrogen atoms. More preferably, it is 500.
　重合性ポリマーが有するグラフト鎖は、ポリエステル構造、ポリエーテル構造、ポリ（メタ）アクリル構造、ポリウレタン構造、ポリウレア構造およびポリアミド構造から選ばれる少なくとも１種の構造を含むことが好ましく、ポリエステル構造、ポリエーテル構造およびポリ（メタ）アクリル構造から選ばれる少なくとも１種の構造を含むことがより好ましく、ポリエステル構造を含むことが更に好ましい。ポリエステル構造としては、下記の式（Ｇ－１）、式（Ｇ－４）または式（Ｇ－５）で表される構造が挙げられる。また、ポリエーテル構造としては、下記の式（Ｇ－２）で表される構造が挙げられる。また、ポリ（メタ）アクリル構造としては、下記の式（Ｇ－３）で表される構造が挙げられる。
Figure JPOXMLDOC01-appb-C000025
 The graft chains possessed by the polymerizable polymer preferably include at least one structure selected from polyester structure, polyether structure, poly (meth) acrylic structure, polyurethane structure, polyurea structure and polyamide structure, and polyester structure, polyether It is more preferable to include at least one structure selected from a structure and a poly (meth) acrylic structure, and it is further preferable to include a polyester structure. Examples of the polyester structure include structures represented by the following Formula (G-1), Formula (G-4) or Formula (G-5). Further, as the polyether structure, a structure represented by the following formula (G-2) can be mentioned. Further, examples of the poly (meth) acrylic structure include a structure represented by the following formula (G-3).
Figure JPOXMLDOC01-appb-C000025
　上記式において、ＲＧ１およびＲＧ２は、それぞれアルキレン基を表す。ＲＧ１およびＲＧ２で表されるアルキレン基としては特に制限されないが、炭素数１～２０の直鎖状又は分岐状のアルキレン基が好ましく、炭素数２～１６の直鎖状又は分岐状のアルキレン基がより好ましく、炭素数３～１２の直鎖状又は分岐状のアルキレン基が更に好ましい。
　上記式において、ＲＧ３は、水素原子またはメチル基を表す。
　上記式において、ＱＧ１は、－Ｏ－または－ＮＨ－を表し、ＬＧ１は、単結合または２価の連結基を表す。２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アルキレンオキシ基（好ましくは炭素数１～１２のアルキレンオキシ基）、オキシアルキレンカルボニル基（好ましくは炭素数１～１２のオキシアルキレンカルボニル基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。
　上記式において、ＲＧ４は、水素原子または置換基を表す。置換基としては、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基等が挙げられる。 In the above formulas, R G1 and R G2 each represent an alkylene group. The alkylene group represented by R G1 and R G2 is not particularly limited, but a linear or branched alkylene group having 1 to 20 carbon atoms is preferable, and a linear or branched alkylene having 2 to 16 carbon atoms is preferable. A group is more preferable, and a linear or branched alkylene group having 3 to 12 carbon atoms is further preferable.
In the above formulae, R G3 represents a hydrogen atom or a methyl group.
In the above formula, Q G1 represents -O- or -NH-, and L G1 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), and an oxyalkylene carbonyl group (preferably having 1 carbon atom). -12 oxyalkylene carbonyl group), arylene group (preferably arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, OCO And-, -S- and a group formed by combining two or more of them.
In the above formulae, R G4 represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like.
　グラフト鎖の末端構造としては、特に限定されない。水素原子であってもよく、置換基であってもよい。置換基としては、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基等が挙げられる。なかでも、色材などの分散性向上の観点から、立体反発効果を有する基が好ましく、炭素数５～２４のアルキル基又はアルコキシ基が好ましい。アルキル基およびアルコキシ基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。 The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferable, from the viewpoint of improving the dispersibility of the coloring material and the like. The alkyl group and the alkoxy group may be linear, branched or cyclic, and linear or branched is preferable.
　本発明において、グラフト鎖としては、下記式（Ｇ－１ａ）、式（Ｇ－２ａ）、式（Ｇ－３ａ）、式（Ｇ－４ａ）または式（Ｇ－５ａ）で表される構造であることが好ましい。
Figure JPOXMLDOC01-appb-C000026
 In the present invention, as a graft chain, a structure represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a) or formula (G-5a) Is preferred.
Figure JPOXMLDOC01-appb-C000026
　上記式において、ＲＧ１およびＲＧ２はそれぞれ独立してアルキレン基を表し、ＲＧ３は水素原子またはメチル基を表し、ＱＧ１は－Ｏ－または－ＮＨ－を表し、ＬＧ１は単結合または２価の連結基を表し、ＲＧ４は水素原子または置換基を表し、Ｗ１００は水素原子または置換基を表す。ｎ１～ｎ５はそれぞれ独立して２以上の整数を表す。ＲＧ１～ＲＧ４、ＱＧ１、ＬＧ１については、式（Ｇ－１）～（Ｇ－５）で説明したＲＧ１～ＲＧ４、ＱＧ１、ＬＧ１と同義であり、好ましい範囲も同様である。 In the above formulae, R G1 and R G2 each independently represent an alkylene group, R G3 represents a hydrogen atom or a methyl group, Q G1 represents -O- or -NH-, L G1 represents a single bond or 2 R G4 represents a hydrogen atom or a substituent, and W 100 represents a hydrogen atom or a substituent. n1 to n5 each independently represent an integer of 2 or more. For R G1 ~ R G4, Q G1 , L G1 , Formula (G1) ~ (G-5 ) has the same meaning as R G1 ~ R G4, Q G1 , L G1 described in, the preferred range is also the same is there.
　式（Ｇ－１ａ）～（Ｇ－５ａ）において、Ｗ１００は、置換基であることが好ましい。置換基としては、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基等が挙げられる。なかでも、色材などの分散性向上の観点から、立体反発効果を有する基が好ましく、炭素数５～２４のアルキル基又はアルコキシ基が好ましい。アルキル基およびアルコキシ基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。 In formulas (G-1a) to (G-5a), W 100 is preferably a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like. Among them, a group having a steric repulsion effect is preferable, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferable, from the viewpoint of improving the dispersibility of the coloring material and the like. The alkyl group and the alkoxy group may be linear, branched or cyclic, and linear or branched is preferable.
　式（Ｇ－１ａ）～（Ｇ－５ａ）において、ｎ１～ｎ５はそれぞれ独立して２以上の整数を表し、３以上であることがより好ましく、５以上であることが更に好ましい。上限は例えば、１００以下が好ましく、８０以下がより好ましく、６０以下が更に好ましい。 In formulas (G-1a) to (G-5a), n1 to n5 each independently represent an integer of 2 or more, more preferably 3 or more, and still more preferably 5 or more. For example, the upper limit is preferably 100 or less, more preferably 80 or less, and still more preferably 60 or less.
　グラフト鎖を有する繰り返し単位としては、下記式（Ａ－１－２）で表される繰り返し単位が挙げられる。
Figure JPOXMLDOC01-appb-C000027
 Examples of the repeating unit having a graft chain include repeating units represented by the following formula (A-1-2).
Figure JPOXMLDOC01-appb-C000027
　式（Ａ－１－２）において、Ｘ２は繰り返し単位の主鎖を表し、Ｌ２は単結合または２価の連結基を表し、Ｗ１はグラフト鎖を表す。 In formula (A-1-2), X 2 represents a main chain of a repeating unit, L 2 represents a single bond or a divalent linking group, and W 1 represents a graft chain.
　式（Ａ－１－２）におけるＸ２が表す繰り返し単位の主鎖としては、式（Ａ－１－１）のＸ１で説明した構造が挙げられ、好ましい範囲も同様である。式（Ａ－１－２）におけるＬ２が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。式（Ａ－１－２）におけるＷ１が表すグラフト鎖としては、上述したグラフト鎖が挙げられる。 Examples of the main chain of the repeating unit represented by X 2 in Formula (A-1-2) include the structures described in X 1 of Formula (A-1-1), and preferred ranges are also the same. The divalent linking group represented by L 2 in Formula (A-1-2) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an arylene group (preferably an arylene group having 6 to 20 carbon atoms) And -NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, OCO-, -S- and a group formed by combining two or more of these. Examples of the graft chain represented by W 1 in formula (A-1-2) include the graft chains described above.
　重合性ポリマーがグラフト鎖を有する繰り返し単位を含む場合、グラフト鎖を有する繰り返し単位の重量平均分子量（Ｍｗ）は、１０００以上であることが好ましく、１０００～１００００であることがより好ましく、１０００～７５００であることが更に好ましい。なお、本発明において、グラフト鎖を有する繰り返し単位の重量平均分子量は、同繰り返し単位の重合に用いた原料モノマーの重量平均分子量から算出した値である。例えば、グラフト鎖を有する繰り返し単位は、マクロモノマーを重合することで形成できる。ここで、マクロモノマーとは、ポリマー末端に重合性基が導入された高分子化合物を意味する。マクロモノマーを用いてグラフト鎖を有する繰り返し単位を形成した場合においては、マクロモノマーの重量平均分子量がグラフト鎖を有する繰り返し単位の重量平均分子量に該当する。 When the polymerizable polymer contains a repeating unit having a graft chain, the weight average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10000, and 1000 to 7500. It is further preferred that In the present invention, the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for polymerization of the same repeating unit. For example, a repeating unit having a graft chain can be formed by polymerizing a macromonomer. Here, the macromonomer means a polymer compound in which a polymerizable group is introduced at the polymer end. When a macromonomer is used to form a repeating unit having a graft chain, the weight average molecular weight of the macromonomer corresponds to the weight average molecular weight of the repeating unit having a graft chain.
　重合性ポリマーは、更に酸基を有する繰り返し単位を含むことも好ましい。重合性ポリマーが更に酸基を有する繰り返し単位を含むことで、金属アゾ顔料Ａなどの分散性をより向上できる。更には、現像性を向上させることもできる。酸基としては、カルボキシル基、スルホ基、リン酸基が挙げられる。 It is also preferred that the polymerizable polymer further contains a repeating unit having an acid group. When the polymerizable polymer further contains a repeating unit having an acid group, the dispersibility of the metal azo pigment A and the like can be further improved. Furthermore, developability can also be improved. Examples of the acid group include a carboxyl group, a sulfo group and a phosphate group.
　酸基を有する繰り返し単位としては、下記式（Ａ－１－３）で表される繰り返し単位が挙げられる。
Figure JPOXMLDOC01-appb-C000028
 Examples of the repeating unit having an acid group include repeating units represented by the following formula (A-1-3).
Figure JPOXMLDOC01-appb-C000028
　式（Ａ－１－３）において、Ｘ３は繰り返し単位の主鎖を表し、Ｌ３は単結合または２価の連結基を表し、Ａ１は酸基を表す。 In formula (A-1-3), X 3 represents a main chain of a repeating unit, L 3 represents a single bond or a divalent linking group, and A 1 represents an acid group.
　式（Ａ－１－３）におけるＸ３が表す繰り返し単位の主鎖としては、式（Ａ－１－１）のＸ１で説明した構造が挙げられ、好ましい範囲も同様である。
　式（Ａ－１－３）におけるＬ３が表す２価の連結基としては、アルキレン基（好ましくは炭素数１～１２のアルキレン基）、アルキレンオキシ基（好ましくは炭素数１～１２のアルキレンオキシ基）、オキシアルキレンカルボニル基（好ましくは炭素数１～１２のオキシアルキレンカルボニル基）、アリーレン基（好ましくは炭素数６～２０のアリーレン基）、－ＮＨ－、－ＳＯ－、－ＳＯ２－、－ＣＯ－、－Ｏ－、－ＣＯＯ－、ＯＣＯ－、－Ｓ－およびこれらの２以上を組み合わせてなる基が挙げられる。アルキレン基、アルキレンオキシ基におけるアルキレン基、オキシアルキレンカルボニル基におけるアルキレン基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。また、アルキレン基、アルキレンオキシ基におけるアルキレン基、オキシアルキレンカルボニル基におけるアルキレン基は、置換基を有していてもよく、無置換であってもよい。置換基としては、ヒドロキシ基などが挙げられる。
　式（Ａ－１－３）におけるＡ１が表す酸基としては、カルボキシル基、スルホ基、リン酸基が挙げられる。 Examples of the main chain of the repeating unit represented by X 3 in formula (A-1-3) include the structures described in X 1 of formula (A-1-1), and the preferred range is also the same.
As the divalent linking group represented by L 3 in formula (A-1-3), an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) or an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms) Group), an oxyalkylene carbonyl group (preferably an oxyalkylene carbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2- , And -CO-, -O-, -COO-, OCO-, -S- and a group formed by combining two or more of these. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylene carbonyl group may be linear, branched or cyclic, and is preferably linear or branched. Further, the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylene carbonyl group may have a substituent or may be unsubstituted. As a substituent, a hydroxy group etc. are mentioned.
Examples of the acid group represented by A 1 in formula (A-1-3) include a carboxyl group, a sulfo group and a phosphoric acid group.
　重合性ポリマーの酸価は、２０～１５０ｍｇＫＯＨ／ｇであることが好ましい。上限は、１００ｍｇＫＯＨ／ｇ以下であることがより好ましい。下限は、３０ｍｇＫＯＨ／ｇ以上であることが好ましく、３５ｍｇＫＯＨ／ｇ以上であることがより好ましい。重合性ポリマーの酸価が上記範囲であれば、特に優れた分散性が得られやすい。さらには、優れた現像性が得られやすい。 The acid value of the polymerizable polymer is preferably 20 to 150 mg KOH / g. The upper limit is more preferably 100 mg KOH / g or less. The lower limit is preferably 30 mg KOH / g or more, and more preferably 35 mg KOH / g or more. If the acid value of the polymerizable polymer is in the above range, particularly excellent dispersibility is easily obtained. Furthermore, excellent developability is easily obtained.
　また、重合性ポリマーは、他の繰り返し単位として、下記式（ＥＤ１）で示される化合物および／または下記式（ＥＤ２）で表される化合物（以下、これらの化合物を「エーテルダイマー」と称することもある。）を含むモノマー成分に由来する繰り返し単位を含むことができる。 In addition, the polymerizable polymer may also be referred to as a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) as another repeating unit (hereinafter, these compounds are referred to as “ether dimer” And B.) can be included.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　式（ＥＤ１）中、Ｒ１およびＲ２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１～２５の炭化水素基を表す。
　式（ＥＤ２）中、Ｒは、水素原子または炭素数１～３０の有機基を表す。式（ＥＤ２）の具体例としては、特開２０１０－１６８５３９号公報の記載を参酌できる。 In formula (ED1), R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP-A-2010-168539 can be referred to.
　エーテルダイマーの具体例としては、例えば、特開２０１３－２９７６０号公報の段落番号０３１７を参酌することができ、この内容は本明細書に組み込まれる。エーテルダイマーは、１種のみであってもよいし、２種以上であってもよい。 As a specific example of the ether dimer, for example, paragraph “0317” of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification. The ether dimer may be only one type, or two or more types.
　重合性ポリマーの具体例としては以下が挙げられる。
Figure JPOXMLDOC01-appb-C000031
 The following may be mentioned as specific examples of the polymerizable polymer.
Figure JPOXMLDOC01-appb-C000031
（環状エーテル基を有する化合物）
　本発明において用いられる環状エーテル基を有する化合物としては、１分子内に環状エーテル基を２個以上有する化合物が挙げられる。環状エーテル基を有する化合物に含まれる環状エーテル基の数は、１００個以下であることが好ましく、１０個以下であることがより好ましく、５個以下であることが更に好ましい。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられ、エポキシ基であることが好ましい。すなわち、環状エーテル基を有する化合物は、エポキシ基を有する化合物（以下、エポキシ化合物ともいう）であることが好ましい。 (Compound having a cyclic ether group)
As a compound which has a cyclic ether group used in this invention, the compound which has 2 or more of cyclic ether groups in 1 molecule is mentioned. The number of cyclic ether groups contained in the compound having a cyclic ether group is preferably 100 or less, more preferably 10 or less, and still more preferably 5 or less. The cyclic ether group may, for example, be an epoxy group or an oxetanyl group, and is preferably an epoxy group. That is, the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter, also referred to as an epoxy compound).
　エポキシ化合物のエポキシ当量（＝エポキシ基を有する化合物の分子量／エポキシ基の数）は、５００以下であることが好ましく、１００～４００であることがより好ましく、１００～３００であることがさらに好ましい。エポキシ化合物は、低分子化合物（例えば、分子量１０００未満）でもよいし、高分子化合物（ｍａｃｒｏｍｏｌｅｃｕｌｅ）（例えば、分子量１０００以上、ポリマーの場合は、重量平均分子量が１０００以上）であってもよい。エポキシ化合物の分子量（ポリマーの場合は、重量平均分子量）は、２００～１０００００が好ましく、５００～５００００がより好ましい。分子量（ポリマーの場合は、重量平均分子量）の上限は、３０００以下が好ましく、２０００以下がより好ましく、１５００以下が更に好ましい。 The epoxy equivalent of the epoxy compound (= molecular weight of compound having an epoxy group / number of epoxy groups) is preferably 500 or less, more preferably 100 to 400, and still more preferably 100 to 300. The epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 1000) or a macromolecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The molecular weight (weight average molecular weight in the case of a polymer) of the epoxy compound is preferably 200 to 100,000, and more preferably 500 to 50,000. 3000 or less is preferable, as for the upper limit of molecular weight (in the case of a polymer, weight average molecular weight), 2000 or less is more preferable, and 1500 or less is still more preferable.
　エポキシ化合物は、特開２０１３－０１１８６９号公報の段落番号００３４～００３６、特開２０１４－０４３５５６号公報の段落番号０１４７～０１５６、特開２０１４－０８９４０８号公報の段落番号００８５～００９２に記載された化合物を用いることもできる。これらの内容は、本明細書に組み込まれる。エポキシ化合物の市販品としては、例えば、ビスフェノールＡ型エポキシ樹脂としては、ｊＥＲ８２５、ｊＥＲ８２７、ｊＥＲ８２８、ｊＥＲ８３４、ｊＥＲ１００１、ｊＥＲ１００２、ｊＥＲ１００３、ｊＥＲ１０５５、ｊＥＲ１００７、ｊＥＲ１００９、ｊＥＲ１０１０（以上、三菱化学（株）製）、ＥＰＩＣＬＯＮ８６０、ＥＰＩＣＬＯＮ１０５０、ＥＰＩＣＬＯＮ１０５１、ＥＰＩＣＬＯＮ１０５５（以上、ＤＩＣ（株）製）等であり、ビスフェノールＦ型エポキシ樹脂としては、ｊＥＲ８０６、ｊＥＲ８０７、ｊＥＲ４００４、ｊＥＲ４００５、ｊＥＲ４００７、ｊＥＲ４０１０（以上、三菱化学（株）製）、ＥＰＩＣＬＯＮ８３０、ＥＰＩＣＬＯＮ８３５（以上、ＤＩＣ（株）製）、ＬＣＥ－２１、ＲＥ－６０２Ｓ（以上、日本化薬（株）製）等であり、フェノールノボラック型エポキシ樹脂としては、ｊＥＲ１５２、ｊＥＲ１５４、ｊＥＲ１５７Ｓ７０、ｊＥＲ１５７Ｓ６５（以上、三菱化学（株）製）、ＥＰＩＣＬＯＮ　Ｎ－７４０、ＥＰＩＣＬＯＮ　Ｎ－７７０、ＥＰＩＣＬＯＮ　Ｎ－７７５（以上、ＤＩＣ（株）製）等であり、クレゾールノボラック型エポキシ樹脂としては、ＥＰＩＣＬＯＮ　Ｎ－６６０、ＥＰＩＣＬＯＮ　Ｎ－６６５、ＥＰＩＣＬＯＮ　Ｎ－６７０、ＥＰＩＣＬＯＮ　Ｎ－６７３、ＥＰＩＣＬＯＮ　Ｎ－６８０、ＥＰＩＣＬＯＮ　Ｎ－６９０、ＥＰＩＣＬＯＮ　Ｎ－６９５（以上、ＤＩＣ（株）製）、ＥＯＣＮ－１０２０（日本化薬（株）製）等であり、脂肪族エポキシ樹脂としては、ＡＤＥＫＡ　ＲＥＳＩＮ　ＥＰ－４０８０Ｓ、同ＥＰ－４０８５Ｓ、同ＥＰ－４０８８Ｓ（以上、（株）ＡＤＥＫＡ製）、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド２０８３、セロキサイド２０８５、ＥＨＰＥ３１５０、ＥＰＯＬＥＡＤ　ＰＢ　３６００、同ＰＢ　４７００（以上、（株）ダイセル製）、デナコール　ＥＸ－２１２Ｌ、ＥＸ－２１４Ｌ、ＥＸ－２１６Ｌ、ＥＸ－３２１Ｌ、ＥＸ－８５０Ｌ（以上、ナガセケムテックス（株）製）等である。その他にも、ＡＤＥＫＡ　ＲＥＳＩＮ　ＥＰ－４０００Ｓ、同ＥＰ－４００３Ｓ、同ＥＰ－４０１０Ｓ、同ＥＰ－４０１１Ｓ（以上、（株）ＡＤＥＫＡ製）、ＮＣ－２０００、ＮＣ－３０００、ＮＣ－７３００、ＸＤ－１０００、ＥＰＰＮ－５０１、ＥＰＰＮ－５０２（以上、（株）ＡＤＥＫＡ製）、ｊＥＲ１０３１Ｓ（三菱化学（株）製）、マープルーフＧ－０１５０Ｍ、Ｇ－０１０５ＳＡ、Ｇ－０１３０ＳＰ、Ｇ－０２５０ＳＰ、Ｇ－１００５Ｓ、Ｇ－１００５ＳＡ、Ｇ－１０１０Ｓ、Ｇ－２０５０Ｍ、Ｇ－０１１００、Ｇ－０１７５８（以上、日油（株）製、エポキシ基含有ポリマー）等が挙げられる。 The epoxy compounds are compounds described in paragraphs 0034 to 0036 in JP 2013-011869A, paragraphs 0147 to 0156 in JP 2014-043556 A, and paragraphs 0085 to 0092 in JP 2014-089408 A. Can also be used. The contents of these are incorporated herein. As a commercial item of the epoxy compound, for example, as bisphenol A type epoxy resin, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (all manufactured by Mitsubishi Chemical Corporation), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (all manufactured by DIC Corporation) and the like, and as a bisphenol F-type epoxy resin, jER806, jER807, jER4004, jER4005, jER4007, jER4010 (all, manufactured by Mitsubishi Chemical Corporation), EPICLON 830, EPICLON 835 (above, DIC Corporation), LCE-21, RE-602S (above, Japan Drugs, etc., and as phenol novolac type epoxy resins, jER152, jER154, jER157S70, jER157S65 (above, Mitsubishi Chemical Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (Above, DIC Corporation) and the like, and as cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690. EPICLON N-695 (all, DIC Corporation), EOCN-1020 (Nippon Kayaku Co., Ltd.), etc., and as aliphatic epoxy resins, ADEKA RESIN EP-4080S, EP 4085S, EP-4088S (above, made by ADEKA Co., Ltd.), Celoxide 2021 P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE 3150, EPOLEAD PB 3600, same PB 4700 (above, made by Daicel Co., Ltd.), Denacol EX- 212L, EX-214L, EX-216L, EX-321L, EX-850L (all manufactured by Nagase ChemteX Co., Ltd.) and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, made by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Co., Ltd.), jER1031S (manufactured by Mitsubishi Chemical Corporation), merproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G And -1005SA, G-1010S, G-2050M, G-01100, G-01758 (manufactured by NOF Corporation, epoxy group-containing polymer) and the like.
　本発明の組成物において、エチレン性不飽和結合基を有する化合物の含有量は、組成物の全固形分中１～５０質量％であることが好ましい。下限は３質量％以上であることが好ましく、５質量％以上であることがより好ましい。上限は、４５質量％以下であることが好ましく、４０質量％以下であることがより好ましい。また、エチレン性不飽和結合基を有する化合物の含有量は、上述した金属アゾ顔料Ａの１００質量部に対して３０質量部以上であることが好ましく、４０質量部以上であることがより好ましく、５０質量部以上であることが更に好ましい。上限は、７５０質量部以下であることが好ましく、７００質量部以下であることがより好ましく、６５０質量部以下であることが更に好ましく、６００質量部以下であることが特に好ましい。金属アゾ顔料Ａとエチレン性不飽和結合基を有する化合物の割合が上記範囲であれば、本発明の効果がより顕著に得られる。また、エチレン性不飽和結合基を有する化合物として、重合性モノマーと重合性ポリマーとを併用する場合、重合性ポリマーの含有量は、重合性モノマーの１００質量部に対して５～５００質量部であることが好ましい。下限は８質量部以上であることが好ましく、１０質量部以上であることがより好ましい。上限は、４５０質量部以下であることが好ましく、４００質量部以下であることがより好ましい。 In the composition of the present invention, the content of the compound having an ethylenically unsaturated bonding group is preferably 1 to 50% by mass in the total solid content of the composition. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. In addition, the content of the compound having an ethylenically unsaturated bond group is preferably 30 parts by mass or more, and more preferably 40 parts by mass or more with respect to 100 parts by mass of the metal azo pigment A described above. More preferably, it is 50 parts by mass or more. The upper limit is preferably 750 parts by mass or less, more preferably 700 parts by mass or less, still more preferably 650 parts by mass or less, and particularly preferably 600 parts by mass or less. If the ratio of the metal azo pigment A and the compound having an ethylenic unsaturated bond group is in the above range, the effects of the present invention can be obtained more remarkably. When a polymerizable monomer and a polymerizable polymer are used in combination as the compound having an ethylenically unsaturated bond group, the content of the polymerizable polymer is 5 to 500 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Is preferred. The lower limit is preferably 8 parts by mass or more, and more preferably 10 parts by mass or more. The upper limit is preferably 450 parts by mass or less, and more preferably 400 parts by mass or less.
　本発明の組成物において、環状エーテル基を有する化合物の含有量は、組成物の全固形分中１～５０質量％であることが好ましい。下限は３質量％以上であることが好ましく、５質量％以上であることがより好ましい。上限は、４５質量％以下であることが好ましく、４０質量％以下であることがより好ましい。また、環状エーテル基を有する化合物の含有量は、上述した金属アゾ顔料Ａの１００質量部に対して３０質量部以上であることが好ましく、４０質量部以上であることがより好ましく、５０質量部以上であることが更に好ましい。上限は、７５０質量部以下であることが好ましく、７００質量部以下であることがより好ましく、６５０質量部以下であることが更に好ましく、６００質量部以下であることが特に好ましい。金属アゾ顔料Ａと環状エーテル基を有する化合物の割合が上記範囲であれば、本発明の効果がより顕著に得られる。 In the composition of the present invention, the content of the compound having a cyclic ether group is preferably 1 to 50% by mass in the total solid content of the composition. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. The content of the compound having a cyclic ether group is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and 50 parts by mass with respect to 100 parts by mass of the metal azo pigment A described above. It is more preferable that it is more than. The upper limit is preferably 750 parts by mass or less, more preferably 700 parts by mass or less, still more preferably 650 parts by mass or less, and particularly preferably 600 parts by mass or less. If the ratio of the metal azo pigment A and the compound having a cyclic ether group is in the above range, the effects of the present invention can be more remarkably obtained.
　本発明の組成物において、エチレン性不飽和結合基を有する化合物と環状エーテル基を有する化合物との合計の含有量は、組成物の全固形分中１～５０質量％であることが好ましい。下限は３質量％以上であることが好ましく、５質量％以上であることがより好ましい。上限は、４５質量％以下であることが好ましく、４０質量％以下であることがより好ましい。また、エチレン性不飽和結合基を有する化合物と環状エーテル基を有する化合物との合計の含有量は、上述した金属アゾ顔料Ａの１００質量部に対して３０質量部以上であることが好ましく、４０質量部以上であることがより好ましく、５０質量部以上であることが更に好ましい。上限は、７５０質量部以下であることが好ましく、７００質量部以下であることがより好ましく、６５０質量部以下であることが更に好ましく、６００質量部以下であることが特に好ましい。含有量が上記範囲であれば、本発明の効果がより顕著に得られる。また、本発明の組成物が、エチレン性不飽和結合基を有する化合物と環状エーテル基を有する化合物とを含有する場合、エチレン性不飽和結合基を有する化合物１００質量部に対して環状エーテル基を有する化合物を１～５０質量部含有することが好ましい。上限は、４０質量部以下であることが好ましく、３０質量部以下であることがより好ましい。下限は、５質量部以上であることが好ましく、７質量部以上であることがより好ましく、１０質量部以上であることが更に好ましい。 In the composition of the present invention, the total content of the compound having an ethylenically unsaturated bonding group and the compound having a cyclic ether group is preferably 1 to 50% by mass in the total solid content of the composition. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. In addition, the total content of the compound having an ethylenically unsaturated bond group and the compound having a cyclic ether group is preferably 30 parts by mass or more with respect to 100 parts by mass of the metal azo pigment A described above, It is more preferable that it is a mass part or more, and it is still more preferable that it is 50 mass parts or more. The upper limit is preferably 750 parts by mass or less, more preferably 700 parts by mass or less, still more preferably 650 parts by mass or less, and particularly preferably 600 parts by mass or less. If the content is in the above range, the effects of the present invention can be more remarkably obtained. When the composition of the present invention contains a compound having an ethylenically unsaturated bond group and a compound having a cyclic ether group, the cyclic ether group is used per 100 parts by mass of the compound having an ethylenically unsaturated bond group. It is preferable to contain 1 to 50 parts by mass of the compound contained therein. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. The lower limit is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and still more preferably 10 parts by mass or more.
＜＜他の樹脂＞＞
　本発明の組成物は、上述した硬化性化合物以外の樹脂（以下、他の樹脂ともいう）をさらに含有することができる。他の樹脂は、例えば、顔料などの粒子を組成物中で分散させる用途やバインダーの用途で配合される。なお、主に顔料などの粒子を分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で樹脂を使用することもできる。 << Other resin >>
The composition of the present invention can further contain a resin other than the above-described curable compound (hereinafter, also referred to as another resin). Other resins are blended, for example, in applications in which particles such as pigments are dispersed in a composition and applications in binders. In addition, resin used mainly for disperse | distributing particle | grains, such as a pigment, is also called dispersing agent. However, such application of the resin is an example, and the resin can also be used for purposes other than such application.
　他の樹脂の重量平均分子量（Ｍｗ）は、２０００～２００００００が好ましい。上限は、１００００００以下が好ましく、５０００００以下がより好ましい。下限は、３０００以上が好ましく、５０００以上がより好ましい。 The weight average molecular weight (Mw) of the other resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500000 or less. 3000 or more are preferable and, as for a lower limit, 5000 or more are more preferable.
　他の樹脂としては、（メタ）アクリル樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂などが挙げられる。これらの樹脂から１種を単独で使用してもよく、２種以上を混合して使用してもよい。また、樹脂は、国際公開ＷＯ２０１６／０８８６４５号公報の実施例に記載された樹脂、特開２０１７－５７２６５号公報に記載された樹脂、特開２０１７－３２６８５号公報に記載された樹脂、特開２０１７－０７５２４８号公報に記載された樹脂、特開２０１７－０６６２４０号公報に記載された樹脂を用いることもできる。また、フルオレン骨格を有する樹脂を用いることもできる。フルオレン骨格を有する樹脂としては、下記構造の樹脂が挙げられる。以下の構造式中、Ａは、ピロメリット酸二無水物、ベンゾフェノンテトラカルボン酸二無水物、ビフェニルテトラカルボン酸二無水物およびジフェニルエーテルテトラカルボン酸二無水物から選択されるカルボン酸二無水物の残基であり、Ｍはフェニル基またはベンジル基である。フルオレン骨格を有する樹脂については、米国特許出願公開第２０１７／０１０２６１０号公報の記載を参酌でき、この内容は本明細書に組み込まれる。
Figure JPOXMLDOC01-appb-C000032
 As other resin, (meth) acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide Imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, etc. may be mentioned. One of these resins may be used alone, or two or more thereof may be mixed and used. Further, as the resin, a resin described in an example of International Publication WO 2016/088645, a resin described in JP-A-2017-57265, a resin described in JP-A-2017-32685, JP-A-2017 It is also possible to use the resin described in JP-A-075248 and the resin described in JP-A-2017-066240. Further, a resin having a fluorene skeleton can also be used. As resin which has fluorene frame, resin of the following structure is mentioned. In the following structural formulae, A represents the residue of a carboxylic acid dianhydride selected from pyromellitic dianhydride, benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride and diphenyl ether tetracarboxylic acid dianhydride And M is a phenyl or benzyl group. The resin having a fluorene skeleton can be referred to the description of US Patent Application Publication No. 2017/0102610, the contents of which are incorporated herein.
Figure JPOXMLDOC01-appb-C000032
　他の樹脂は、酸基を有していてもよい。酸基としては、例えば、カルボキシル基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられ、カルボキシル基が好ましい。これら酸基は、１種のみであってもよいし、２種以上であってもよい。酸基を有する樹脂はアルカリ可溶性樹脂として用いることもできる。 Other resins may have an acid group. As an acid group, a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group etc. are mentioned, for example, A carboxyl group is preferable. These acid groups may be of only one type, or of two or more types. The resin having an acid group can also be used as an alkali-soluble resin.
　酸基を有する樹脂としては、側鎖にカルボキシル基を有するポリマーが好ましい。具体例としては、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体、ノボラック樹脂などのアルカリ可溶性フェノール樹脂、側鎖にカルボキシル基を有する酸性セルロース誘導体、ヒドロキシ基を有するポリマーに酸無水物を付加させた樹脂が挙げられる。特に、（メタ）アクリル酸と、これと共重合可能な他のモノマーとの共重合体が、アルカリ可溶性樹脂として好適である。（メタ）アクリル酸と共重合可能な他のモノマーとしては、アルキル（メタ）アクリレート、アリール（メタ）アクリレート、ビニル化合物などが挙げられる。アルキル（メタ）アクリレートおよびアリール（メタ）アクリレートとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、トリル（メタ）アクリレート、ナフチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、グリシジル（メタ）アクリレート等が挙げられる。ビニル化合物としては、スチレン、α－メチルスチレン、ビニルトルエン、アクリロニトリル、ビニルアセテート、Ｎ－ビニルピロリドン、ポリスチレンマクロモノマー、ポリメチルメタクリレートマクロモノマー等が挙げられる。また他のモノマーは、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等のマレイミドモノマーを用いることもできる。これらの（メタ）アクリル酸と共重合可能な他のモノマーは１種のみであってもよいし、２種以上であってもよい。 As a resin having an acid group, a polymer having a carboxyl group in a side chain is preferable. Specific examples thereof include alkali-soluble polymers such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, novolac resin, etc. A phenolic resin, an acidic cellulose derivative having a carboxyl group in a side chain, and a resin obtained by adding an acid anhydride to a polymer having a hydroxy group are mentioned. In particular, copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are suitable as the alkali-soluble resin. Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, etc. Be Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like. As other monomers, maleimide monomers such as N-phenyl maleimide and N-cyclohexyl maleimide can also be used. These other monomers copolymerizable with (meth) acrylic acid may be only one type, or two or more types.
　酸基を有する樹脂は、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／２－ヒドロキシエチル（メタ）アクリレート共重合体、ベンジル（メタ）アクリレート／（メタ）アクリル酸／他のモノマーからなる多元共重合体が好ましく用いることができる。また、２－ヒドロキシエチル（メタ）アクリレートを共重合したもの、特開平７－１４０６５４号公報に記載の、２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体なども好ましく用いることができる。 Resin having an acid group is benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) A multicomponent copolymer consisting of acrylate / (meth) acrylic acid / other monomers can be preferably used. Further, those obtained by copolymerizing 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A No. 7-1420654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene Macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like can also be preferably used.
　酸基を有する樹脂は、上述したエーテルダイマーを含むモノマー成分に由来する繰り返し単位を含むポリマーであることも好ましい。 It is also preferable that the resin having an acid group is a polymer containing a repeating unit derived from a monomer component including the above-mentioned ether dimer.
　酸基を有する樹脂は、下記式（Ｘ）で示される化合物に由来する繰り返し単位を含んでいてもよい。
Figure JPOXMLDOC01-appb-C000033
 　式（Ｘ）において、Ｒ１は、水素原子またはメチル基を表し、Ｒ２は炭素数２～１０のアルキレン基を表し、Ｒ３は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。 The resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X).
Figure JPOXMLDOC01-appb-C000033
 In formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 has a hydrogen atom or 1 to 20 carbon atoms which may contain a benzene ring. Represents an alkyl group of n represents an integer of 1 to 15.
　酸基を有する樹脂については、特開２０１２－２０８４９４号公報の段落番号０５５８～０５７１（対応する米国特許出願公開第２０１２／０２３５０９９号明細書の段落番号０６８５～０７００）の記載、特開２０１２－１９８４０８号公報の段落番号００７６～００９９の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、酸基を有する樹脂は市販品を用いることもできる。 The resin having an acid group is described in JP-A-2012-208494, paragraphs 0558 to 0571 (corresponding US patent application publication No. 2012/0235099, paragraphs 0685 to 0700), JP-A-2012-198408. No. 0076-0099 can be referred to, and the contents thereof are incorporated herein. Moreover, the resin which has an acidic radical can also use a commercial item.
　酸基を有する樹脂の酸価は、３０～２００ｍｇＫＯＨ／ｇが好ましい。下限は、５０ｍｇＫＯＨ／ｇ以上が好ましく、７０ｍｇＫＯＨ／ｇ以上がより好ましい。上限は、１５０ｍｇＫＯＨ／ｇ以下が好ましく、１２０ｍｇＫＯＨ／ｇ以下がより好ましい。 The acid value of the resin having an acid group is preferably 30 to 200 mg KOH / g. The lower limit is preferably 50 mg KOH / g or more, and more preferably 70 mg KOH / g or more. 150 mgKOH / g or less is preferable and 120 mgKOH / g or less of an upper limit is more preferable.
　酸基を有する樹脂としては、例えば下記構造の樹脂などが挙げられる。
Figure JPOXMLDOC01-appb-C000034
 As resin which has an acidic radical, resin of the following structure, etc. are mentioned, for example.
Figure JPOXMLDOC01-appb-C000034
　本発明の組成物は、分散剤としての樹脂を含むこともできる。分散剤は、酸性分散剤（酸性樹脂）、塩基性分散剤（塩基性樹脂）が挙げられる。ここで、酸性分散剤（酸性樹脂）とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤（酸性樹脂）は、酸基の量と塩基性基の量の合計量を１００モル％としたときに、酸基の量が７０モル％以上を占める樹脂が好ましく、実質的に酸基のみからなる樹脂がより好ましい。酸性分散剤（酸性樹脂）が有する酸基は、カルボキシル基が好ましい。酸性分散剤（酸性樹脂）の酸価は、４０～１０５ｍｇＫＯＨ／ｇが好ましく、５０～１０５ｍｇＫＯＨ／ｇがより好ましく、６０～１０５ｍｇＫＯＨ／ｇがさらに好ましい。また、塩基性分散剤（塩基性樹脂）とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤（塩基性樹脂）は、酸基の量と塩基性基の量の合計量を１００モル％としたときに、塩基性基の量が５０モル％を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基であることが好ましい。 The composition of the present invention can also contain a resin as a dispersant. The dispersant includes an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol% Resins consisting only of groups are more preferred. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mg KOH / g, more preferably 50 to 105 mg KOH / g, and still more preferably 60 to 105 mg KOH / g. Moreover, a basic dispersing agent (basic resin) represents resin whose quantity of a basic group is larger than the quantity of an acidic radical. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50% by mole, where the total amount of the amount of acid groups and the amount of basic groups is 100% by mole. The basic group possessed by the basic dispersant is preferably an amino group.
　分散剤として用いる樹脂は、酸基を有する繰り返し単位を含むことが好ましい。分散剤として用いる樹脂が酸基を有する繰り返し単位を含むことにより、フォトリソグラフィ法によりパターン形成する際、画素の下地に発生する残渣をより低減することができる。 The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersing agent contains a repeating unit having an acid group, it is possible to further reduce the residue generated on the base of the pixel when forming a pattern by photolithography.
　分散剤として用いる樹脂は、側鎖にグラフト鎖を有する繰り返し単位を含む樹脂（以下、グラフト樹脂ともいう）であることが好ましい。この態様によれば、金属アゾ顔料Ａなどの分散性をより向上させることができる。ここで、グラフト鎖とは、繰り返し単位の主鎖から枝分かれして伸びるポリマー鎖のことを意味する。グラフト鎖の長さについては特に制限されないが、グラフト鎖が長くなると立体反発効果が高くなり、顔料などの分散性を高めることができる。グラフト鎖においては、水素原子を除いた原子数が４０～１００００であることが好ましく、水素原子を除いた原子数が５０～２０００であることがより好ましく、水素原子を除いた原子数が６０～５００であることが更に好ましい。 The resin used as the dispersant is preferably a resin containing a repeating unit having a graft chain in its side chain (hereinafter, also referred to as a graft resin). According to this aspect, the dispersibility of the metal azo pigment A or the like can be further improved. Here, a graft chain means a polymer chain which branches and extends from the main chain of the repeating unit. The length of the graft chain is not particularly limited, but as the graft chain becomes longer, the steric repulsion effect becomes higher, and the dispersibility of the pigment etc. can be enhanced. In the graft chain, the number of atoms excluding hydrogen atoms is preferably 40 to 10,000, and the number of atoms excluding hydrogen atoms is more preferably 50 to 2,000, and the number of atoms excluding hydrogen atoms is 60 to 60 More preferably, it is 500.
　グラフト鎖は、ポリエステル鎖、ポリエーテル鎖、ポリ（メタ）アクリル鎖、ポリウレタン鎖、ポリウレア鎖およびポリアミド鎖から選ばれる少なくとも１種の構造を含むことが好ましく、ポリエステル鎖、ポリエーテル鎖およびポリ（メタ）アクリル鎖から選ばれる少なくとも１種の構造を含むことがより好ましく、ポリエステル鎖を含むことが更に好ましい。 The graft chain preferably includes at least one structure selected from polyester chains, polyether chains, poly (meth) acrylic chains, polyurethane chains, polyurea chains and polyamide chains, and polyester chains, polyether chains and poly (meta It is more preferable to include at least one structure selected from acryl chains, and it is further preferable to include a polyester chain.
　グラフト鎖の末端構造としては、特に限定されない。水素原子であってもよく、置換基であってもよい。置換基としては、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基等が挙げられる。なかでも、金属アゾ顔料Ａなどの分散性向上の観点から、立体反発効果を有する基が好ましく、炭素数５～２４のアルキル基又はアルコキシ基が好ましい。アルキル基およびアルコキシ基は、直鎖状、分岐状、及び、環状のいずれでもよく、直鎖状または分岐状が好ましい。 The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like. Among them, from the viewpoint of improving the dispersibility of the metal azo pigment A and the like, a group having a steric repulsion effect is preferable, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferable. The alkyl group and the alkoxy group may be linear, branched or cyclic, and linear or branched is preferable.
　グラフト樹脂としては、例えば下記構造の樹脂などが挙げられる。また、グラフト樹脂の詳細は、特開２０１２－２５５１２８号公報の段落番号００２５～００９４の記載を参酌でき、この内容は本明細書に組み込まれる。
Figure JPOXMLDOC01-appb-C000035
 As a graft resin, resin of the following structure etc. are mentioned, for example. Further, the details of the graft resin can be referred to the description of Paragraph Nos. 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
Figure JPOXMLDOC01-appb-C000035
　分散剤として用いる樹脂は、主鎖及び側鎖の少なくとも一方に窒素原子を含むオリゴイミン系樹脂であることも好ましい。オリゴイミン系樹脂としては、ｐＫａ１４以下の官能基を有する部分構造Ｘを有する構造単位と、原子数４０～１０，０００の側鎖Ｙを含む側鎖とを有し、かつ主鎖及び側鎖の少なくとも一方に塩基性窒素原子を有する樹脂が好ましい。塩基性窒素原子としては、塩基性を呈する窒素原子であれば特に制限はない。オリゴイミン系樹脂については、特開２０１２－２５５１２８号公報の段落番号０１０２～０１６６の記載を参酌でき、本明細書には上記内容が組み込まれる。オリゴイミン系樹脂の具体例としては、例えば、以下が挙げられる。また、特開２０１２－２５５１２８号公報の段落番号０１６８～０１７４に記載の樹脂を用いることができる。
Figure JPOXMLDOC01-appb-C000036
 The resin used as the dispersant is also preferably an oligoimine resin containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine resin has a structural unit having a partial structure X having a functional group having a pKa of 14 or less and a side chain containing a side chain Y having 40 to 10,000 atoms, and at least a main chain and a side chain Resins having a basic nitrogen atom on one side are preferred. The basic nitrogen atom is not particularly limited as long as it exhibits basicity. With regard to the oligoimine resin, the description in paragraphs [0102] to [0166] of JP-A-2012-255128 can be referred to, and the above contents are incorporated herein. Examples of the oligoimine resin include the following. In addition, the resins described in paragraph Nos. 0168 to 0174 of JP 2012-255128 A can be used.
Figure JPOXMLDOC01-appb-C000036
　分散剤は、市販品としても入手可能であり、そのような具体例としては、ＢＹＫＣｈｅｍｉｅ社製のＤｉｓｐｅｒｂｙｋシリーズ（例えば、Ｄｉｓｐｅｒｂｙｋ－１１１など）、日本ルーブリゾール（株）製のソルスパースシリーズ（例えば、ソルスパース７６５００など）などが挙げられる。また、特開２０１４－１３０３３８号公報の段落番号００４１～０１３０に記載された顔料分散剤を用いることもできる。また、上述した酸基を有する樹脂や重合性ポリマーなどを分散剤として用いることもできる。なお、上記分散剤として説明した樹脂は、分散剤以外の用途で使用することもできる。例えば、バインダーとして用いることもできる。 Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series (eg, Disperbyk-111 etc.) manufactured by BYK Chemie, the Solsperse series manufactured by Nippon Lubrizol Corporation (eg, And so forth). In addition, pigment dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used. Moreover, resin which has an acidic radical mentioned above, a polymeric polymer, etc. can also be used as a dispersing agent. In addition, the resin demonstrated as the said dispersing agent can also be used for uses other than a dispersing agent. For example, it can also be used as a binder.
　本発明の組成物が他の樹脂を含む場合、他の樹脂の含有量は、本発明の組成物の全固形分中１～５０質量％であることが好ましい。上限は、４５質量％以下であることが好ましく、４０質量％以下であることがより好ましい。下限は、２質量％以上であることが好ましく、３質量％以上であることがより好ましく、５質量％以上であることが更に好ましい。また、他の樹脂を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
　また、本発明の組成物は、他の樹脂を実質的に含まないこともできる。本発明の組成物が他の樹脂を実質的に含まない場合とは、本発明の組成物の全固形分中における他の樹脂の含有量が０．１質量％以下であることが好ましく、０．０５質量％以下であることがより好ましく、含有しないことが特に好ましい。
　また、上述した硬化性化合物と他の樹脂との合計の含有量は、本発明の組成物の全固形分中５～５０質量％であることが好ましい。下限は８質量％以上であることが好ましく、１０質量％以上であることがより好ましい。上限は、４５質量％以下であることが好ましく、４０質量％以下であることがより好ましい。また、他の樹脂を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 When the composition of the present invention contains another resin, the content of the other resin is preferably 1 to 50% by mass in the total solid content of the composition of the present invention. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more. Moreover, when 2 or more types of other resin are included, it is preferable that the total amount of those becomes the said range.
The composition of the present invention can also be substantially free of other resins. When the composition of the present invention is substantially free of other resins, the content of the other resins in the total solid content of the composition of the present invention is preferably 0.1% by mass or less, and 0 The content is more preferably 0.05% by mass or less, and particularly preferably not contained.
The total content of the above-mentioned curable compound and other resin is preferably 5 to 50% by mass in the total solid content of the composition of the present invention. The lower limit is preferably 8% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. Moreover, when 2 or more types of other resin are included, it is preferable that the total amount of them becomes said range.
＜＜溶剤＞＞
　本発明の組成物は、溶剤を含有することができる。溶剤は有機溶剤が好ましい。溶剤は、各成分の溶解性や組成物の塗布性を満足すれば特に制限はない。 << solvent >>
The composition of the present invention can contain a solvent. The solvent is preferably an organic solvent. The solvent is not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied.
　有機溶剤の例としては、例えば、以下の有機溶剤が挙げられる。エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、酢酸シクロヘキシル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、アルキルオキシ酢酸アルキル（例えば、アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例えば、３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例えば、２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチル及び２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等が挙げられる。エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等が挙げられる。ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン等が挙げられる。芳香族炭化水素類として、例えば、トルエン、キシレン等が好適に挙げられる。また、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミドも溶解性向上の観点から好ましい。有機溶剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the organic solvent include, for example, the following organic solvents. As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkyl oxyacetate alkylate (Eg, methyl alkyl oxyacetate, ethyl alkyl oxyacetate, butyl alkyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Ethyl, 3-ethoxypropionate etc.), 2-alkyloxypropionic acid alkyl esters (eg methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate etc. (eg Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and Ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, Acetoacetate Le, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like can be mentioned. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like. Preferred examples of the aromatic hydrocarbons include toluene and xylene. Further, 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are also preferable from the viewpoint of solubility improvement. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
　本発明においては、溶剤として金属含有量の少ない溶剤を用いることが好ましい。溶剤中の金属含有量は、例えば１０質量ｐｐｂ（ｐａｒｔｓ　ｐｅｒ　ｂｉｌｌｉｏｎ）以下であることが好ましい。必要に応じて金属含有量が質量ｐｐｔ（ｐａｒｔｓ　ｐｅｒ　ｔｒｉｌｌｉｏｎ）レベルの溶剤を用いてもよく、そのような高純度溶剤は例えば東洋合成社が提供している（化学工業日報、２０１５年１１月１３日）。溶剤から金属等の不純物を除去する方法としては、例えば、蒸留（分子蒸留や薄膜蒸留等）やフィルタを用いたろ過を挙げることができる。ろ過に用いるフィルタのフィルタ孔径としては、１０μｍ以下が好ましく、５μｍ以下がより好ましく、３μｍ以下が更に好ましい。フィルタの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。 In the present invention, it is preferable to use a solvent having a low metal content as the solvent. The metal content in the solvent is preferably, for example, 10 parts by weight (pps) or less. If necessary, a solvent having a metal content of mass ppt (parts per trillion) level may be used, and such a high purity solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Journal, November 13, 2015) Day). As a method of removing impurities such as metal from the solvent, for example, distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter can be mentioned. As a filter hole diameter of a filter used for filtration, 10 micrometers or less are preferred, 5 micrometers or less are more preferred, and 3 micrometers or less are still more preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
　溶剤には、異性体（原子数が同じであるが構造が異なる化合物）が含まれていてもよい。また、異性体は、１種のみが含まれていてもよいし、複数種含まれていてもよい。 The solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only one type of isomer may be contained, or two or more types may be contained.
　本発明で用いられる有機溶剤は、過酸化物の含有率が０．８ｍｍｏｌ／Ｌ以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。 It is preferable that the content rate of a peroxide is 0.8 mmol / L or less, and it is more preferable that the organic solvent used by this invention does not contain a peroxide substantially.
　溶剤の含有量は、組成物の固形分濃度（全固形分）が５～５０質量％となる量であることが好ましい。上限は４５質量％以下であることが好ましく、４０質量％以下であることがより好ましい。下限は８質量％以上であることが好ましく、１０質量％以上であることが好ましい。 The content of the solvent is preferably such that the solid content concentration (total solid content) of the composition is 5 to 50% by mass. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. The lower limit is preferably 8% by mass or more, and more preferably 10% by mass or more.
　また、本発明の組成物は、環境規制の観点から環境規制物質を実質的に含有しないことが好ましい。なお、本発明において、環境規制物質を実質的に含有しないとは、組成物中における環境規制物質の含有量が５０質量ｐｐｍ以下であることを意味し、３０質量ｐｐｍ以下であることが好ましく、１０質量ｐｐｍ以下であることが更に好ましく、１質量ｐｐｍ以下であることが特に好ましい。環境規制物質は、例えばベンゼン；トルエン、キシレン等のアルキルベンゼン類；クロロベンゼン等のハロゲン化ベンゼン類等が挙げられる。これらは、ＲＥＡＣＨ（Ｒｅｇｉｓｔｒａｔｉｏｎ　Ｅｖａｌｕａｔｉｏｎ　Ａｕｔｈｏｒｉｚａｔｉｏｎ　ａｎｄ　Ｒｅｓｔｒｉｃｔｉｏｎ　ｏｆ　ＣＨｅｍｉｃａｌｓ）規則、ＰＲＴＲ（Ｐｏｌｌｕｔａｎｔ　Ｒｅｌｅａｓｅ　ａｎｄ　Ｔｒａｎｓｆｅｒ　Ｒｅｇｉｓｔｅｒ）法、ＶＯＣ（Ｖｏｌａｔｉｌｅ　Ｏｒｇａｎｉｃ　Ｃｏｍｐｏｕｎｄｓ）規制等のもとに環境規制物質として登録されており、使用量や取り扱い方法が厳しく規制されている。これらの化合物は、本発明の組成物に用いられる各成分などを製造する際に溶媒として用いられることがあり、残留溶媒として組成物中に混入することがある。人への安全性、環境への配慮の観点よりこれらの物質は可能な限り低減することが好ましい。環境規制物質を低減する方法としては、系中を加熱や減圧して環境規制物質の沸点以上にして系中から環境規制物質を留去して低減する方法が挙げられる。また、少量の環境規制物質を留去する場合においては、効率を上げる為に該当溶媒と同等の沸点を有する溶媒と共沸させることも有用である。また、ラジカル重合性を有する化合物を含有する場合、減圧留去中にラジカル重合反応が進行して分子間で架橋してしまうことを抑制するために重合禁止剤等を添加して減圧留去してもよい。これらの留去方法は、原料の段階、原料を反応させた生成物（例えば重合した後の樹脂溶液や多官能モノマー溶液）の段階、またはこれらの化合物を混ぜて作製した組成物の段階いずれの段階でも可能である。 Moreover, it is preferable that the composition of this invention does not contain an environmental control substance substantially from a viewpoint of an environmental regulation. In the present invention, not containing substantially the environmental regulation substance means that the content of the environmental regulation substance in the composition is 50 mass ppm or less, and preferably 30 mass ppm or less, It is more preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less. Examples of the environmental control substance include benzene; alkyl benzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene and the like. These are registered as environmentally controlled substances under the Registration Evaluation Authorization and Restriction of Chemical Substances (REACH) rule, Pollutant Release and Transfer Register (PRTR) method, Volatile Organic Compounds (VOC) regulations, etc. The method is strictly regulated. These compounds may be used as a solvent when producing each component etc. which are used for the composition of this invention, and may be mixed in a composition as a residual solvent. It is preferable to reduce these substances as much as possible from the viewpoint of human safety and environmental consideration. As a method of reducing the environmental control substance, there is a method of heating or depressurizing the inside of the system to make the temperature equal to or higher than the boiling point of the environmental control substance and distilling the environmental control substance out of the system to reduce it. When distilling off a small amount of environmental control substance, it is also useful to make it azeotropic with a solvent having a boiling point equivalent to that of the corresponding solvent in order to increase the efficiency. In addition, when a compound having radical polymerization property is contained, a polymerization inhibitor or the like is added in order to suppress the progress of the radical polymerization reaction and crosslinking between molecules during distillation under reduced pressure, May be These distillation methods may be carried out at the stage of the raw material, the stage of the product obtained by reacting the raw material (for example, the resin solution after polymerization or the polyfunctional monomer solution), or the stage of the composition prepared by mixing these compounds. Stages are also possible.
＜＜光重合開始剤＞＞
　本発明の組成物は、更に光重合開始剤を含むことができる。特に、本発明の組成物がエチレン性不飽和結合基を有する化合物を含む場合においては、光重合開始剤を含むことが好ましい。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する化合物が好ましい。光重合開始剤は光ラジカル重合開始剤であることが好ましい。 << photoinitiator >>
The composition of the present invention can further contain a photopolymerization initiator. In particular, in the case where the composition of the present invention contains a compound having an ethylenically unsaturated bonding group, it is preferable to include a photopolymerization initiator. There is no restriction | limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. For example, compounds having photosensitivity to light in the ultraviolet to visible region are preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.
　光重合開始剤としては、例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物など）、アシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、α－ヒドロキシケトン化合物、α－アミノケトン化合物などが挙げられる。光重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン－ベンゼン－鉄錯体、ハロメチルオキサジアゾール化合物および３－アリール置換クマリン化合物が好ましく、オキシム化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、および、アシルホスフィン化合物から選ばれる化合物がより好ましく、オキシム化合物が更に好ましい。光重合開始剤としてオキシム化合物を用いることで優れた硬化性が得られる。更には、低温環境下で組成物を長期間保管した場合であっても、欠陥がより抑制された膜を製造することができる。このような効果が得られる理由としては以下によるものであると推測される。本発明の組成物に含まれる金属アゾ顔料Ａは、２種以上の金属イオンを含むが、金属イオンの種類により、上述したアニオンと金属イオンとで構成される金属アゾ化合物（金属錯体）の配座が異なる。例えば、Ｃｕ２＋の場合は平面配座の金属錯体を形成し、Ｚｎ２＋の場合は正八面体配座の金属錯体を形成する。このため、溶剤などを含む組成物中において、上述した金属アゾ顔料Ａは、会合し難く不安定な状態で存在していると推測され、組成物の保管時に金属アゾ顔料Ａが凝集し易い傾向にあると推測される。また、特に、金属アゾ顔料Ａにおけるニッケルイオン（Ｎｉ２＋）の含有量が少ないか、あるいは金属アゾ顔料Ａがニッケルイオンを含まない場合においては、エネルギー的に不安定であると推測され、組成物の保管時に金属アゾ顔料Ａがより凝集し易い傾向にあると推測される。しかしながら、オキシム化合物を配合することでオキシム化合物が金属アゾ顔料Ａに対して配位してキレート剤として作用すると推測され、その結果、金属アゾ顔料Ａを安定化させることができ、金属アゾ顔料Ａの凝集などをより効果的に抑制できると推測される。そのため、低温環境下で組成物を長期間保管した場合であっても、欠陥がより抑制された膜を製造することができると推測される。 As the photopolymerization initiator, for example, a halogenated hydrocarbon derivative (for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.), an acylphosphine compound, a hexaarylbiimidazole, an oxime compound, an organic peroxide, Thio compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, α-amino ketone compounds and the like can be mentioned. The photopolymerization initiator is a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole from the viewpoint of exposure sensitivity. Dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyl oxadiazole compounds and 3-aryl substituted coumarin compounds are preferred, and oxime compounds, α-hydroxy ketone compounds, α-hydroxy ketone compounds More preferred are compounds selected from amino ketone compounds and acyl phosphine compounds, and more preferred are oxime compounds. By using an oxime compound as the photopolymerization initiator, excellent curability can be obtained. Furthermore, even when the composition is stored for a long time in a low temperature environment, a film with more suppressed defects can be produced. The reason why such an effect can be obtained is presumed to be as follows. The metal azo pigment A contained in the composition of the present invention contains two or more metal ions, but depending on the type of metal ion, the arrangement of the metal azo compound (metal complex) composed of the anion and the metal ion described above The seat is different. For example, Cu 2+ forms a metal complex in a planar conformation, and Zn 2+ forms a metal complex in octahedral conformation. For this reason, in the composition containing a solvent etc., the metal azo pigment A mentioned above is presumed to be present in an unstable state which is difficult to associate, and the metal azo pigment A tends to easily aggregate during storage of the composition. Is presumed to be. In addition, it is presumed that the composition is energetically unstable, particularly when the content of nickel ions (Ni 2+ ) in metal azo pigment A is low or metal azo pigment A does not contain nickel ions. It is inferred that the metal azo pigment A tends to be more prone to aggregation during storage of. However, it is presumed that the oxime compound coordinates to the metal azo pigment A to act as a chelating agent by blending the oxime compound, and as a result, the metal azo pigment A can be stabilized. It is speculated that cohesion and the like can be suppressed more effectively. Therefore, even if the composition is stored for a long time under a low temperature environment, it is presumed that a film with more suppressed defects can be produced.
　α－ヒドロキシケトン化合物の市販品としては、ＩＲＧＡＣＵＲＥ－１８４、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ－１２７（以上、ＢＡＳＦ社製）などが挙げられる。α－アミノケトン化合物の市販品としては、ＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、ＩＲＧＡＣＵＲＥ－３７９、及び、ＩＲＧＡＣＵＲＥ－３７９ＥＧ（以上、ＢＡＳＦ社製）などが挙げられる。アシルホスフィン化合物の市販品としては、ＩＲＧＡＣＵＲＥ－８１９、ＤＡＲＯＣＵＲ－ＴＰＯ（以上、ＢＡＳＦ社製）などが挙げられる。 Examples of commercially available α-hydroxy ketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (manufactured by BASF Corporation) and the like. Examples of commercially available α-amino ketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF Corporation). Examples of commercially available products of acyl phosphine compounds include IRGACURE-819, DAROCUR-TPO (all manufactured by BASF Corp.) and the like.
　オキシム化合物としては、例えば、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１６５３－１６６０）に記載の化合物、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ　ＩＩ（１９７９年、ｐｐ．１５６－１６２）に記載の化合物、Ｊｏｕｒｎａｌ　ｏｆ　Ｐｈｏｔｏｐｏｌｙｍｅｒ　Ｓｃｉｅｎｃｅ　ａｎｄ　Ｔｅｃｈｎｏｌｏｇｙ（１９９５年、ｐｐ．２０２－２３２）に記載の化合物、特開２０００－６６３８５号公報に記載の化合物、特開２０００－８００６８号公報に記載の化合物、特表２００４－５３４７９７号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物、特開２０１７－１９７６６号公報に記載の化合物、特許第６０６５５９６号公報に記載の化合物、国際公開ＷＯ２０１５／１５２１５３号公報に記載の化合物、国際公開ＷＯ２０１７／０５１６８０公報に記載の化合物などが挙げられる。オキシム化合物の具体例としては、例えば、３－ベンゾイルオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、および２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。オキシム化合物の市販品としては、ＩＲＧＡＣＵＲＥ－ＯＸＥ０１、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２、ＩＲＧＡＣＵＲＥ－ＯＸＥ０３、ＩＲＧＡＣＵＲＥ－ＯＸＥ０４（以上、ＢＡＳＦ社製）、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０４、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０９、ＴＲＯＮＬＹ　ＴＲ－ＰＢＧ－３０５（常州強力電子新材料有限公司（ＣＨＡＮＧＺＨＯＵ　ＴＲＯＮＬＹ　ＮＥＷ　ＥＬＥＣＴＲＯＮＩＣ　ＭＡＴＥＲＩＡＬＳ　ＣＯ．，ＬＴＤ）製）、アデカアークルズＮＣＩ－９３０、アデカオプトマーＮ－１９１９（特開２０１２－１４０５２号公報の光重合開始剤２）（（株）ＡＤＥＫＡ製）などが挙げられる。 Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, the compounds described in JP-A-2006-342166, and the like. C. S. Perkin II (1979, pp. 1653-1660), a compound described in J. Am. C. S. A compound described in Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), a compound described in JP-A-2000-66385, Compounds described in JP-A-2000-80068, compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-19766, Patent No. Examples thereof include the compounds described in 6065596, the compounds described in International Publication WO 2015/152153, and the compounds described in International Publication WO 2017/051680. Specific examples of the oxime compound include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3- On, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy Examples include carbonyloxyimino-1-phenylpropan-1-one and the like. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF Corporation), TRONLY TR-PBG-304, TRONLY TR-PBG-309, and TRONLY TR-PBG- 305 (made by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), Adeka Arkles NCI-930, Adeka Optomer N-1919 (photopolymerization initiator 2 of JP 2012-14052 A) And the like) (manufactured by ADEKA Co., Ltd.) and the like.
　また上記以外のオキシム化合物として、カルバゾール環のＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物、ベンゾフェノン部位にヘテロ置換基が導入された米国特許第７６２６９５７号公報に記載の化合物、色素部位にニトロ基が導入された特開２０１０－１５０２５号公報および米国特許公開２００９－２９２０３９号公報に記載の化合物、国際公開ＷＯ２００９／１３１１８９号公報に記載のケトオキシム化合物、トリアジン骨格とオキシム骨格を同一分子内に含有する米国特許７５５６９１０号公報に記載の化合物、４０５ｎｍに吸収極大を有し、ｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報に記載の化合物などが挙げられる。 Further, as oxime compounds other than those described above, compounds described in JP-T-2009-519904, in which an oxime is linked to the N-position of a carbazole ring, and compounds described in US Pat. Compounds described in JP-A-2010-15025 and US Patent Publication 2009-292039 in which a nitro group is introduced at a dye site, a ketoxime compound described in International Publication WO2009 / 131189, a triazine skeleton and an oxime skeleton The compound described in US Pat. No. 7,556,910, which is contained in the same molecule, the compound described in JP2009-221114A, which has an absorption maximum at 405 nm and has a good sensitivity to a g-line light source can be mentioned. .
　本発明は、光重合開始剤として、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開２０１４－１３７４６６号公報に記載の化合物が挙げられる。 In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. As specific examples of the oxime compound having a fluorene ring, compounds described in JP-A-2014-137466 can be mentioned.
　本発明は、光重合開始剤として、ベンゾフラン骨格を有するオキシム化合物を用いることもできる。具体例としては、国際公開ＷＯ２０１５／０３６９１０号公報に記載の化合物ＯＥ－０１～ＯＥ－７５が挙げられる。 In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples thereof include the compounds OE-01 to OE-75 described in International Publication WO 2015/036910.
　本発明は、光重合開始剤として、カルバゾール環の少なくとも１つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。そのようなオキシム化合物の具体例としては、国際公開ＷＯ２０１３／０８３５０５号公報に記載の化合物が挙げられる。 In the present invention, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used as a photopolymerization initiator. As a specific example of such an oxime compound, the compound described in International Publication WO 2013/083505 can be mentioned.
　本発明は、光重合開始剤として、フッ素原子を有するオキシム化合物を用いることもできる。フッ素原子を有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載の化合物、特表２０１４－５００８５２号公報に記載の化合物２４、３６～４０、特開２０１３－１６４４７１号公報に記載の化合物（Ｃ－３）などが挙げられる。 In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, the compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. And the like (C-3) and the like.
　本発明は、光重合開始剤として、ニトロ基を有するオキシム化合物を用いることができる。ニトロ基を有するオキシム化合物は、二量体であることも好ましい。ニトロ基を有するオキシム化合物の具体例としては、特開２０１３－１１４２４９号公報の段落番号００３１～００４７、特開２０１４－１３７４６６号公報の段落番号０００８～００１２、００７０～００７９に記載の化合物、特許４２２３０７１号公報の段落番号０００７～００２５に記載の化合物、アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製）などが挙げられる。 In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. It is also preferable that the oxime compound having a nitro group is a dimer. As specific examples of the oxime compound having a nitro group, compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, and patent 4223071 Compounds described in Paragraph Nos. 0007 to 0025 of the gazette, Adeka Arkles NCI-831 (manufactured by ADEKA Co., Ltd.), and the like.
　本発明において好ましく使用されるオキシム化合物の具体例を以下に示すが、本発明はこれらに限定されるものではない。 Specific examples of oxime compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　オキシム化合物は、波長３５０～５００ｎｍの範囲に吸収極大を有する化合物であることが好ましく、波長３６０～４８０ｎｍの範囲に吸収極大を有する化合物であることがより好ましい。また、オキシム化合物は、３６５ｎｍおよび４０５ｎｍの吸光度が高い化合物であることが好ましい。 The oxime compound is preferably a compound having an absorption maximum in a wavelength range of 350 to 500 nm, and more preferably a compound having an absorption maximum in a wavelength range of 360 to 480 nm. The oxime compound is preferably a compound having high absorbance at 365 nm and 405 nm.
　オキシム化合物の３６５ｎｍまたは４０５ｎｍにおけるモル吸光係数は、感度の観点から、１，０００～３００，０００であることが好ましく、２，０００～３００，０００であることがより好ましく、５，０００～２００，０００であることが特に好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 From the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, Particularly preferred is 000. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
　本発明は、２官能あるいは３官能以上の光重合開始剤を用いてもよい。このような光重合開始剤を用いることにより、光重合開始剤の１分子から２つ以上のラジカルが発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して溶剤などへの溶解性が向上して、経時で析出しにくくなり、組成物の経時安定性を向上させることができる。２官能あるいは３官能以上の光重合開始剤の具体例としては、特表２０１０－５２７３３９号公報、特表２０１１－５２４４３６号公報、国際公開ＷＯ２０１５／００４５６５号公報、特表２０１６－５３２６７５号公報の段落番号０４１７～０４１２、国際公開ＷＯ２０１７／０３３６８０号公報の段落番号００３９～００５５に記載されているオキシム化合物の２量体、特表２０１３－５２２４４５号公報に記載されている化合物（Ｅ）および化合物（Ｇ）、国際公開ＷＯ２０１６／０３４９６３号公報に記載されているＣｍｐｄ１～７、特表２０１７－５２３４６５号公報の段落番号０００７に記載されているオキシムエステル類光開始剤、特開２０１７－１６７３９９号公報の段落番号００２０～００３３に記載されている光開始剤、特開２０１７－１５１３４２号公報の段落番号００１７～００２６に記載されている光重合開始剤（Ａ）などが挙げられる。 In the present invention, a difunctional or trifunctional or higher functional photopolymerization initiator may be used. By using such a photopolymerization initiator, two or more radicals are generated from one molecule of the photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, crystallinity is reduced and solubility in a solvent or the like is improved, so that it becomes difficult to precipitate with time, and the stability with time of the composition can be improved. As specific examples of the difunctional or trifunctional or higher photopolymerization initiator, paragraphs of JP-A-2010-527339, JP-A-2011-524436, International Publication WO2015 / 004565, and JP-A-2016-532675 can be used. No. 0417 to 0412, a dimer of the oxime compound described in Paragraph Nos. 0039 to 0055 of International Publication WO 2017/033680, a compound (E) and a compound (G) described in JP-A-2013-522445 Cmpd 1 to 7 described in International Publication WO 2016/034963; oxime ester photoinitiators described in Paragraph No. 0007 of JP-A-2017-523465; Paragraphs of JP-A-2017-167399 Photoinitiators described in the numbers 0020 to 0033 Patent photopolymerization initiators described in 2017-151342, paragraphs numbers 0017 to 0026 of JP (A), and the like.
　本発明の組成物が光重合開始剤を含有する場合、光重合開始剤の含有量は、組成物の全固形分中０．１～３０質量％が好ましい。下限は、例えば０．５質量％以上がより好ましく、１質量％以上が更に好ましい。上限は、例えば、２０質量％以下がより好ましく、１０質量％以下が更に好ましい。
　また、光重合開始剤の含有量は、上述した金属アゾ顔料Ａの１００質量部に対して１～２００質量部であることが好ましい。下限は、３質量部以上であることが好ましく、５質量部以上であることが更に好ましい。上限は、１００質量部以上であることが好ましく、８０質量部以下であることがより好ましい。
　また、光重合開始剤としてオキシム化合物を用いた場合、オキシム化合物の含有量は、上述した金属アゾ顔料Ａの１００質量部に対して１～２００質量部であることが好ましい。下限は、３質量部以上であることが好ましく、５質量部以上であることが更に好ましい。上限は、１００質量部以上であることが好ましく、８０質量部以下であることがより好ましい。この態様によれば、上述した本発明の効果がより顕著に得られる傾向にある。
　本発明の組成物は、光重合開始剤を１種のみ含んでいてもよいし、２種以上含んでいてもよい。光重合開始剤を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 When the composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 30% by mass in the total solid content of the composition. The lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is, for example, more preferably 20% by mass or less and still more preferably 10% by mass or less.
Further, the content of the photopolymerization initiator is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A described above. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 100 parts by mass or more, and more preferably 80 parts by mass or less.
When an oxime compound is used as the photopolymerization initiator, the content of the oxime compound is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the metal azo pigment A described above. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 100 parts by mass or more, and more preferably 80 parts by mass or less. According to this aspect, the effects of the present invention described above tend to be obtained more significantly.
The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When 2 or more types of photoinitiators are included, it is preferable that the total amount of them becomes said range.
＜＜多官能チオール＞＞
　本発明の組成物は多官能チオールを含有することができる。多官能チオールは、チオール（ＳＨ）基を２個以上有する化合物である。多官能チオールは上述の光重合開始剤とともに使用することにより、光照射後のラジカル重合過程において、連鎖移動剤として働き、酸素による重合阻害を受けにくいチイルラジカルが発生するので、組成物の感度を高めることができる。特にＳＨ基がメチレン、エチレン基等の脂肪族基に結合した多官能脂肪族チオールが好ましい。 << Multifunctional thiols >>
The compositions of the invention can contain multifunctional thiols. The multifunctional thiol is a compound having two or more thiol (SH) groups. The multifunctional thiol functions as a chain transfer agent in the radical polymerization process after light irradiation by using it together with the above-mentioned photopolymerization initiator and generates a thiyl radical which is less susceptible to inhibition of polymerization by oxygen, thereby enhancing the sensitivity of the composition. be able to. In particular, polyfunctional aliphatic thiols in which an SH group is bonded to an aliphatic group such as a methylene or ethylene group are preferable.
　多官能チオールとしては、例えば、ヘキサンジチオール、デカンジチオール、１，４－ブタンジオールビスチオプロピオネート、１，４－ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、エチレングリコールビスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、トリメチロールプロパントリスチオプロピオネート、トリメチロールエタントリス（３－メルカプトブチレート）、トリメチロールプロパントリス（３－メルカプトブチレート）、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）、トリメルカプトプロピオン酸トリス（２－ヒドロキシエチル）イソシアヌレート、１，４－ジメチルメルカプトベンゼン、２、４、６－トリメルカプト－ｓ－トリアジン、２－（Ｎ，Ｎ－ジブチルアミノ）－４，６－ジメルカプト－ｓ－トリアジンなどが挙げられる。また、下記構造の化合物も挙げられる。 As polyfunctional thiol, for example, hexane dithiol, decane dithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bis thioglycolate, ethylene glycol bis thiopropio , Trimethylolpropane tristhioglycollate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercapto propionate), pentaerythritol tetrakis thioglycolate, pentaerythritol tetrakis thiopropionate, pentaerythritol tetrakis (3-mercapto propio) ), Dipentaerythritol hexakis (3-mercaptopropionate), tris (2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s And -triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. Moreover, the compound of the following structure is also mentioned.
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　多官能チオールの含有量は、本発明の組成物の全固形分に対し０．１～２０質量％が好ましく、０．１～１５質量％がより好ましく、０．１～１０質量％が更に好ましい。本発明の組成物は、多官能チオールを、１種のみを含んでいてもよいし、２種以上含んでいてもよい。多官能チオールを２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the multifunctional thiol is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass, based on the total solid content of the composition of the present invention . The composition of the present invention may contain only one type of multifunctional thiol, or may contain two or more types. When two or more polyfunctional thiols are contained, the total amount thereof is preferably in the above range.
＜＜顔料誘導体＞＞
　本発明の組成物は顔料誘導体を含有することができる。この態様によれば、温度変化に対して分光の変動が抑制された膜を形成できる。顔料誘導体としては、顔料の一部が、酸基、塩基性基又はフタルイミド基などで置換された構造を有する化合物が挙げられる。顔料誘導体は下記式（ｓｙｎ１）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000040
 　式（ｓｙｎ１）中、Ｐは色素構造を表し、Ｌは単結合または連結基を表し、Ｘは酸基、塩基性基またはフタルイミド基を表し、ｍは１以上の整数を表し、ｎは１以上の整数を表し、ｍが２以上の場合は複数のＬおよびＸは互いに異なっていてもよく、ｎが２以上の場合は複数のＸは互いに異なってもよい。 << pigment derivative >>
The composition of the present invention can contain a pigment derivative. According to this aspect, it is possible to form a film in which the fluctuation of the spectrum is suppressed with respect to the temperature change. Examples of the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acid group, a basic group or a phthalimide group. The pigment derivative is preferably a compound represented by the following formula (syn1).
Figure JPOXMLDOC01-appb-C000040
 In formula (syn1), P represents a dye structure, L represents a single bond or a linking group, X represents an acid group, a basic group or a phthalimide group, m represents an integer of 1 or more, and n is 1 or more And when m is 2 or more, the plurality of L and X may be different from each other, and when n is 2 or more, the plurality of X may be different from each other.
　式（ｓｙｎ１）におけるＰが表す色素構造としては、ピロロピロール色素構造、ジケトピロロピロール色素構造、キノリン色素構造、キナクリドン色素構造、イソインドリン色素構造、イソインドリノン色素構造、アントラキノン色素構造、ジアントラキノン色素構造、ベンゾイソインドール色素構造、チアジンインジゴ色素構造、アゾ色素構造、キノフタロン色素構造、フタロシアニン色素構造、ナフタロシアニン色素構造、ジオキサジン色素構造、ペリレン色素構造、ペリノン色素構造、ベンゾイミダゾロン色素構造、ベンゾチアゾール色素構造、ベンゾイミダゾール色素構造およびベンゾオキサゾール色素構造から選ばれる少なくとも１種が好ましく、ピロロピロール色素構造、ジケトピロロピロール色素構造、キナクリドン色素構造およびベンゾイミダゾロン色素構造から選ばれる少なくとも１種が更に好ましく、ピロロピロール色素構造が特に好ましい。 The dye structure represented by P in the formula (syn1) includes pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinoline dye structure, quinacridone dye structure, isoindoline dye structure, isoindolinone dye structure, anthraquinone dye structure, dianthraquinone Dye structure, benzoisoindole dye structure, thiazine indigo dye structure, azo dye structure, quinophthalone dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, dioxazine dye structure, perylene dye structure, perinone dye structure, benzimidazolone dye structure, At least one selected from benzothiazole dye structure, benzoimidazole dye structure and benzoxazole dye structure is preferable, and pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure And at least one more preferably selected from benzimidazolone pigment structure, pyrrolo pyrrole pigment structure is particularly preferred.
　式（ｓｙｎ１）においてＬが表す連結基としては、炭化水素基、複素環基、－ＮＲ－、－ＳＯ2－、－Ｓ－、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、もしくはこれらの組み合わせからなる基が挙げられる。Ｒは水素原子、アルキル基またはアリール基を表す。炭化水素基は、脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよい。また、脂肪族炭化水素基と芳香族炭化水素基とを組み合わせた基であってもよい。炭化水素基の炭素数は、１～３０が好ましく、１～１５がより好ましく、１～１０がさらに好ましい。複素環基は、５員環または６員環であることが好ましい。複素環基は、単環であってもよく、縮合環であってもよい。縮合環の縮合数は、２～８が好ましく、２～４がより好ましい。複素環基の環を構成するヘテロ原子としては、窒素原子、硫黄原子および酸素原子が挙げられ、窒素原子が好ましい。 The linking group represented by L in formula (syn1) is a hydrocarbon group, a heterocyclic group, -NR-, -SO 2- , -S-, -O-, -CO-, -COO-, -OCO-, Or the group which consists of these combination is mentioned. R represents a hydrogen atom, an alkyl group or an aryl group. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Moreover, the group which combined the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be sufficient. The carbon number of the hydrocarbon group is preferably 1 to 30, more preferably 1 to 15, and still more preferably 1 to 10. The heterocyclic group is preferably a 5- or 6-membered ring. The heterocyclic group may be a single ring or may be a fused ring. The number of condensations of the fused ring is preferably 2 to 8, more preferably 2 to 4. As a hetero atom which comprises the ring of heterocyclic group, a nitrogen atom, a sulfur atom, and an oxygen atom are mentioned, A nitrogen atom is preferable.
　式（ｓｙｎ１）中、Ｘは、酸基、塩基性基またはフタルイミド基を表す。Ｘが表す酸基としては、カルボキシル基、スルホ基、カルボン酸アミド基、スルホン酸アミド基、イミド酸基等が挙げられる。カルボン酸アミド基としては、－ＮＨＣＯＲＸ１で表される基が好ましい。スルホン酸アミド基としては、－ＮＨＳＯ２ＲＸ２で表される基が好ましい。イミド酸基としては、－ＳＯ２ＮＨＳＯ２ＲＸ３、－ＣＯＮＨＳＯ２ＲＸ４、－ＣＯＮＨＣＯＲＸ５または－ＳＯ２ＮＨＣＯＲＸ６で表される基が好ましい。ＲＸ１～ＲＸ６は、それぞれ独立に、炭化水素基または複素環基を表す。ＲＸ１～ＲＸ６が表す、炭化水素基および複素環基は、置換基を有してもよい。置換基としては、上述した置換基Ｔが挙げられ、ハロゲン原子であることが好ましく、フッ素原子であることがより好ましい。Ｘが表す塩基性基としては、アミノ基が挙げられる。アミノ基は、－ＮＲ１００Ｒ１０１で表される基が好ましい。Ｒ１００およびＲ１０１は、それぞれ独立に、水素原子、炭化水素基または複素環基を表す。Ｒ１００およびＲ１０１が表す、炭化水素基および複素環基は、置換基を有してもよい。置換基としては、上述した置換基Ｔが挙げられる。Ｘが表すフタルイミド基は、無置換であってもよく、置換基を有していてもよい。置換基としては、上述した置換基Ｔが挙げられる。 In formula (syn1), X represents an acid group, a basic group or a phthalimide group. Examples of the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imidic acid group. As the carboxamide group, a group represented by -NHCOR X1 is preferable. The sulfonic acid amide group is preferably a group represented by —NHSO 2 R X2 . The imide group is preferably a group represented by —SO 2 NHSO 2 R X3 , —CONHSO 2 R X4 , —CONHCOR X5 or —SO 2 NHCOR X6 . Each of R X1 to R X6 independently represents a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group which R X1 to R X6 represent may have a substituent. As a substituent, the above-mentioned substituent T is mentioned, It is preferable that it is a halogen atom, and it is more preferable that it is a fluorine atom. An amino group is mentioned as a basic group which X represents. The amino group is preferably a group represented by -NR 100 R 101 . Each of R 100 and R 101 independently represents a hydrogen atom, a hydrocarbon group or a heterocyclic group. The hydrocarbon group and the heterocyclic group which R 100 and R 101 represent may have a substituent. Examples of the substituent include the above-mentioned substituent T. The phthalimide group represented by X may be unsubstituted or may have a substituent. Examples of the substituent include the above-mentioned substituent T.
　式（ｓｙｎ１）において、ｍは１～１０が好ましく、１～５がより好ましく、１～２がさらに好ましい。式（ｓｙｎ１）において、ｎは１～４が好ましく、１～３がより好ましく、１～２がさらに好ましい。 In the formula (syn1), m is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 2. In the formula (syn1), n is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.
　顔料誘導体としては、下記構造の化合物が挙げられる。以下の構造式中、Ｍｅはメチル基を表し、Ｐｈはフェニル基を表す。また、顔料誘導体としては、特開昭５６－１１８４６２号公報、特開昭６３－２６４６７４号公報、特開平１－２１７０７７号公報、特開平３－９９６１号公報、特開平３－２６７６７号公報、特開平３－１５３７８０号公報、特開平３－４５６６２号公報、特開平４－２８５６６９号公報、特開平６－１４５５４６号公報、特開平６－２１２０８８号公報、特開平６－２４０１５８号公報、特開平１０－３００６３号公報、特開平１０－１９５３２６号公報、国際公開ＷＯ２０１１／０２４８９６号公報の段落番号００８６～００９８、国際公開ＷＯ２０１２／１０２３９９号公報の段落番号００６３～００９４、国際公開ＷＯ２０１７／０３８２５２号公報の段落番号００８２、特許第５２９９１５１号公報に記載が挙げられる。
Figure JPOXMLDOC01-appb-C000041
 As a pigment derivative, the compound of the following structure is mentioned. In the following structural formulae, Me represents a methyl group and Ph represents a phenyl group. In addition, as pigment derivatives, JP-A-56-118462, JP-A-63-264674, JP-A-1-217077, JP-A-3-9961, JP-A-3-26767, and the like can be used. JP-A-3-153780, JP-A-4-45662, JP-A-4-285669, JP-A-6-145546, JP-A-6-212088, JP-A-6-240158, JP-A-10. -30063, JP-A-10-195326, International Publication WO 2011/024896, Paragraph Nos. 0086 to 0098, International Publication WO 2012/102399, Paragraph Nos. 0063 to 0094, International Publication WO 2017/038252 No. 0082, and the patent 5299151 gazette mentions.
Figure JPOXMLDOC01-appb-C000041
　本発明の組成物が顔料誘導体を含有する場合、顔料誘導体の含有量は、組成物に含まれる顔料の１００質量部に対し、１～３０質量部が好ましく、３～２０質量部がさらに好ましい。また、顔料誘導体の含有量は、金属アゾ顔料Ａの１００質量部に対し、１～３０質量部が好ましく、３～２０質量部がさらに好ましい。本発明の組成物は、顔料誘導体を、１種のみを含んでいてもよいし、２種以上含んでいてもよい。顔料誘導体を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment contained in the composition. The content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the metal azo pigment A. The composition of the present invention may contain only one type of pigment derivative, or may contain two or more types. When two or more pigment derivatives are contained, the total amount thereof is preferably in the above range.
＜＜界面活性剤＞＞
　本発明の組成物は、界面活性剤を含有することができる。界面活性剤については、国際公開ＷＯ２０１５／１６６７７９号公報の段落番号０２３８～０２４５の記載を参酌でき、この内容は本明細書に組み込まれる。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などが挙げられ、フッ素系界面活性剤が好ましい。本発明の組成物にフッ素系界面活性剤を含有させることで液特性（特に、流動性）が向上し、省液性をより改善できる。また、厚みムラの小さい膜を形成することもできる。 << Surfactant >>
The composition of the present invention can contain a surfactant. As for the surfactant, the description in paragraphs [0238] to [0245] of International Publication WO 2015/166779 can be referred to, and the contents thereof are incorporated herein. Examples of the surfactant include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants and the like, with fluorine-based surfactants being preferred. By containing a fluorine-based surfactant in the composition of the present invention, liquid properties (in particular, fluidity) can be improved, and liquid saving can be further improved. In addition, a film with small thickness unevenness can also be formed.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好ましく、５～３０質量％がより好ましく、７～２５質量％が更に好ましい。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的である。 The content of fluorine in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of the thickness of the coating film and liquid saving.
　フッ素系界面活性剤としては、特開２０１４－４１３１８号公報の段落番号００６０～００６４（対応する国際公開ＷＯ２０１４／１７６６９号公報の段落番号００６０～００６４）に記載の界面活性剤、特開２０１１－１３２５０３号公報の段落番号０１１７～０１３２に記載の界面活性剤などが挙げられる。また、フッ素系界面活性剤の市販品としては、メガファックＦ１７１、Ｆ１７２、Ｆ１７３、Ｆ１７６、Ｆ１７７、Ｆ１４１、Ｆ１４２、Ｆ１４３、Ｆ１４４、Ｒ３０、Ｆ４３７、Ｆ４７５、Ｆ４７９、Ｆ４８２、Ｆ５５４、Ｆ７８０、ＥＸＰ、ＭＦＳ－３３０（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、ＦＣ４３１、ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、ＳＣ－１０１、ＳＣ－１０３、ＳＣ－１０４、ＳＣ－１０５、ＳＣ－１０６８、ＳＣ－３８１、ＳＣ－３８３、Ｓ－３９３、ＫＨ－４０（以上、旭硝子（株）製）、ＰｏｌｙＦｏｘ　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）等が挙げられる。 As the fluorine-based surfactant, the surfactant described in paragraph Nos. 0060 to 0064 of JP-A-2014-41318 (paragraph number 0060 to 0064 of corresponding international publication WO 2014/17669), JP-A-2011-132503 And the like described in paragraph Nos. 0117 to 0132 of the gazette. Further, as commercially available products of fluorinated surfactants, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS -330 (above, DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Corporation), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, made by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, made by OMNOVA Corporation), etc. may be mentioned. .
　また、フッ素系界面活性剤は、フッ素原子を含有する官能基を持つ分子構造のアクリル系化合物であって、熱を加えるとフッ素原子を含有する官能基の部分が切断されてフッ素原子が揮発するアクリル系化合物を用いることができる。このようなフッ素系界面活性剤としては、ＤＩＣ（株）製のメガファックＤＳシリーズ（例えばメガファックＤＳ－２１）が挙げられる。 Further, the fluorine-based surfactant is an acrylic compound having a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing a fluorine atom is cleaved to volatilize the fluorine atom Acrylic compounds can be used. As such a fluorochemical surfactant, Megafuck DS series (eg Megafuck DS-21) manufactured by DIC Corporation can be mentioned.
　また、フッ素系界面活性剤は、フッ素化アルキル基またはフッ素化アルキレンエーテル基を有するフッ素原子含有ビニルエーテル化合物と、親水性のビニルエーテル化合物との共重合体を用いることができる。このようなフッ素系界面活性剤については、特開２０１６－２１６６０２号公報の記載を参酌でき、この内容は本明細書に組み込まれる。 Further, as the fluorine-based surfactant, a copolymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound can be used. The description of JP-A-2016-216602 can be referred to for such a fluorine-based surfactant, the contents of which are incorporated herein.
　フッ素系界面活性剤は、ブロックポリマーを用いることができる。ブロックポリマーとしては、例えば特開２０１１－８９０９０号公報に記載された化合物が挙げられる。また、フッ素系界面活性剤は、フッ素原子を有する（メタ）アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基（好ましくはエチレンオキシ基、プロピレンオキシ基）を２以上（好ましくは５以上）有する（メタ）アクリレート化合物に由来する繰り返し単位と、を含む含フッ素共重合体を用いることができる。下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
Figure JPOXMLDOC01-appb-C000042
 　上記の化合物の重量平均分子量は、好ましくは３，０００～５０，０００であり、例えば、１４，０００である。上記の化合物中、繰り返し単位の割合を示す％はモル％である。 As the fluorine-based surfactant, a block polymer can be used. Examples of block polymers include compounds described in JP-A-2011-89090. Further, the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy groups) ( A fluorine-containing copolymer including a repeating unit derived from a meta) acrylate compound can be used. The following compounds are also exemplified as the fluorinated surfactant used in the present invention.
Figure JPOXMLDOC01-appb-C000042
 The weight average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the proportion of repeating units is mol%.
　また、フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する繰り返し単位を含む含フッ素共重合体を用いることができる。具体例としては、特開２０１０－１６４９６５号公報の段落番号００５０～００９０および段落番号０２８９～０２９５に記載された化合物、ＤＩＣ（株）製のメガファックＲＳ－１０１、ＲＳ－１０２、ＲＳ－７１８Ｋ、ＲＳ－７２－Ｋ等が挙げられる。また、フッ素系界面活性剤は、特開２０１５－１１７３２７号公報の段落番号００１５～０１５８に記載の化合物を用いることもできる。 Further, as the fluorine-based surfactant, a fluorine-containing copolymer including a repeating unit having an ethylenically unsaturated group in the side chain can be used. As specific examples, compounds described in paragraph Nos. 0050 to 0090 and paragraphs 0289 to 0295 of JP 2010-164965A, Megaface RS-101, RS-102, RS-718K, manufactured by DIC Corporation. RS-72-K etc. are mentioned. Further, as the fluorine-based surfactant, the compounds described in paragraphs [0015] to [0158] of JP-A-2015-117327 can also be used.
　ノニオン系界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセロールエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２（ＢＡＳＦ社製）、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１（ＢＡＳＦ社製）、ソルスパース２００００（日本ルーブリゾール（株）製）、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２（和光純薬工業（株）製）、パイオニンＤ－６１１２、Ｄ－６１１２－Ｗ、Ｄ－６３１５（竹本油脂（株）製）、オルフィンＥ１０１０、サーフィノール１０４、４００、４４０（日信化学工業（株）製）などが挙げられる。 Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Company company), Tetronics 304, 701, 704, 901, 904, 150R1 (BAS). Manufactured by Nippon Steel Co., Ltd., Solsparse 20000 (manufactured by Nippon Lubrisol Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D -6315 (manufactured by Takemoto Yushi Co., Ltd.), Olfin E1010, Surfynol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.) and the like.
　界面活性剤の含有量は組成物の全固形分中、０．００１～５質量％が好ましい。上限は、３質量％以下が好ましく、１質量％以下がより好ましい。下限は、０．０５質量％以上が好ましく、０．０１質量％以上がより好ましい。本発明の組成物は、界面活性剤を、１種のみを含んでいてもよいし、２種以上含んでいてもよい。界面活性剤を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the surfactant is preferably 0.001 to 5% by mass in the total solid content of the composition. 3 mass% or less is preferable, and, as for the upper limit, 1 mass% or less is more preferable. 0.05 mass% or more is preferable, and, as for a lower limit, 0.01 mass% or more is more preferable. The composition of the present invention may contain only one surfactant or two or more surfactants. When two or more surfactants are contained, the total amount thereof is preferably in the above range.
＜＜紫外線吸収剤＞＞
　本発明の組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤は、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などを用いることができる。これらの詳細については、特開２０１２－２０８３７４号公報の段落番号００５２～００７２、特開２０１３－６８８１４号公報の段落番号０３１７～０３３４、特開２０１６－１６２９４６号公報の段落番号００６１～００８０の記載を参酌でき、これらの内容は本明細書に組み込まれる。紫外線吸収剤の具体例としては、下記構造の化合物などが挙げられる。紫外線吸収剤の市販品としては、例えば、ＵＶ－５０３（大東化学（株）製）などが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のＭＹＵＡシリーズ（化学工業日報、２０１６年２月１日）が挙げられる。
Figure JPOXMLDOC01-appb-C000043
 << UV Absorbent >>
The composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds, indole compounds, triazine compounds, and the like can be used. Details of these are described in paragraphs 0052 to 0072 in JP 2012-208374 A, paragraphs 0317 to 0334 in JP 2013-68814 A, and paragraphs 0061 to 0080 in JP 2016-162946 A. The contents of which are incorporated herein by reference. Specific examples of the ultraviolet absorber include compounds having the following structure. Examples of commercially available ultraviolet light absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Moreover, as a benzotriazole compound, MYUA series made from Miyoshi Yushi (Chemical Industry Daily, February 1, 2016) is mentioned.
Figure JPOXMLDOC01-appb-C000043
　本発明の組成物が紫外線吸収剤を含有する場合、紫外線吸収剤の含有量は、組成物の全固形分中、０．１～１０質量％が好ましく、０．１～５質量％がより好ましく、０．１～３質量％が特に好ましい。本発明の組成物は、紫外線吸収剤を１種のみを含んでいてもよいし、２種以上含んでいてもよい。紫外線吸収剤を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 When the composition of the present invention contains a UV absorber, the content of the UV absorber is preferably 0.1 to 10% by mass, and more preferably 0.1 to 5% by mass, based on the total solid content of the composition. 0.1 to 3% by weight is particularly preferred. The composition of the present invention may contain only one type of UV absorber, or may contain two or more types. When 2 or more types of ultraviolet absorbers are contained, it is preferable that the total amount of them becomes the said range.
＜＜シランカップリング剤＞＞
　本発明の組成物は、シランカップリング剤を含有することができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれかによってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられ、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、（メタ）アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基などが挙げられ、（メタ）アクリロイル基およびエポキシ基が好ましい。シランカップリング剤は、特開２００９－２８８７０３号公報の段落番号００１８～００３６に記載の化合物、特開２００９－２４２６０４号公報の段落番号００５６～００６６に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。 << Silane coupling agent >>
The composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Moreover, as functional groups other than a hydrolysable group, a vinyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group etc. are mentioned, for example Meta) acryloyl and epoxy are preferred. Examples of the silane coupling agent include compounds described in paragraphs 0018 to 0036 of JP 2009-288703, and compounds described in paragraphs 0056 to 0066 of JP 2009-242604, the contents of which are It is incorporated in the specification.
　シランカップリング剤の含有量は、本発明の組成物の全固形分中、０．００１～２０質量％が好ましく、０．０１～１０質量％がより好ましく、０．１～５質量％が特に好ましい。本発明の組成物は、シランカップリング剤を１種のみ含んでいてもよいし、２種以上含んでいてもよい。シランカップリング剤を２種以上含む場合は、それらの合計量が上記範囲となることが好ましい。 The content of the silane coupling agent is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass, based on the total solid content of the composition of the present invention. preferable. The composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types. When 2 or more types of silane coupling agents are contained, it is preferable that the total amount of them becomes the said range.
＜＜重合禁止剤＞＞
　本発明の組成物は、重合禁止剤を含有することが好ましい。本発明の組成物が重合禁止剤を含有することにより、低温環境下で組成物を長期間保管した場合であっても、欠陥がより抑制された膜を製造することができる。このような効果が得られる詳細な理由は不明であるが、以下によるものであると推測される。すなわち、本発明の組成物に含まれる金属アゾ顔料Ａは、２種以上の金属イオンを含むので、組成物の保管時において、上述したアニオンと金属イオンとで構成される金属アゾ化合物同士で金属交換が生じて析出物が生じると推測されるが、重合禁止剤を含有させることにより、金属アゾ化合物の活性化度を低下させて金属アゾ化合物同士で金属交換が生じにくくなると推測され、その結果、上述した効果が得られたと推測される。 << polymerization inhibitor >>
The composition of the present invention preferably contains a polymerization inhibitor. By containing the polymerization inhibitor, the composition of the present invention makes it possible to produce a film in which defects are more suppressed even when the composition is stored for a long time in a low temperature environment. Although the detailed reason why such an effect is obtained is unknown, it is presumed to be due to the following. That is, since the metal azo pigment A contained in the composition of the present invention contains two or more types of metal ions, metal azo compounds composed of the anion and the metal ion described above during storage of the composition It is speculated that exchange will occur and precipitates will form, but the inclusion of a polymerization inhibitor will reduce the degree of activation of the metal azo compound, making it difficult to cause metal exchange between metal azo compounds, resulting in It is assumed that the above-mentioned effect is obtained.
　重合禁止剤としては、ハイドロキノン、ｐ－メトキシフェノール、ジ－ｔ－ブチル－ｐ－クレゾール、ピロガロール、ｔ－ブチルカテコール、ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、Ｎ－ニトロソフェニルヒドロキシアミン塩（アンモニウム塩、第一セリウム塩等）等、２，２，６，６－テトラメチルピペリジン　１－オキシルなどが挙げられる。
　本発明の組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、組成物中０．０００１～１質量％が好ましい。下限は、０．０００５質量％以上が好ましく、０．００１質量％以上がより好ましい。上限は、０．５質量％以下が好ましく、０．１質量％以下がより好ましい。本発明の組成物は重合禁止剤を１種のみを含んでいてもよいし、２種以上含んでいてもよい。重合禁止剤を２種以上含む場合はそれらの合計量が上記範囲となることが好ましい。 As a polymerization inhibitor, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-Methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, cerous salt etc.), etc., 2,2,6,6-tetramethylpiperidine 1- Oxyl and the like.
When the composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.0001 to 1% by mass in the composition. 0.0005 mass% or more is preferable, and, as for a lower limit, 0.001 mass% or more is more preferable. 0.5 mass% or less is preferable, and, as for the upper limit, 0.1 mass% or less is more preferable. The composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more polymerization inhibitors are contained, the total amount thereof is preferably in the above range.
＜＜その他添加剤＞＞
　本発明の組成物には、必要に応じて、各種添加剤、例えば、充填剤、密着促進剤、酸化防止剤、潜在酸化防止剤、熱重合開始剤等を配合することができる。これらの添加剤については、特開２０１２－００３２２５号公報の段落番号０１８３（対応する米国特許出願公開第２０１３／００３４８１２号明細書の段落番号０２３７）の記載、特開２００８－２５００７４号公報の段落番号０１０１～０１０４、０１０７～０１０９等の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、酸化防止剤としては、例えばフェノール化合物、リン系化合物（例えば特開２０１１－９０１４７号公報の段落番号００４
２に記載の化合物）、チオエーテル化合物などを用いることができる。市販品としては、例えば（株）ＡＤＥＫＡ製のアデカスタブシリーズ（ＡＯ－２０、ＡＯ－３０、ＡＯ－４０、ＡＯ－５０、ＡＯ－５０Ｆ、ＡＯ－６０、ＡＯ－６０Ｇ、ＡＯ－８０、ＡＯ－３３０など）が挙げられる。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開ＷＯ２０１４／０２１０２３号公報、国際公開ＷＯ２０１７／０３０００５号公報、特開２０１７－００８２１９号公報に記載された化合物が挙げられる。市販品としては、アデカアークルズＧＰＡ－５００１（（株）ＡＤＥＫＡ製）等が挙げられる。熱重合開始剤としては、ピナコール化合物、有機過酸化物、アゾ化合物などが挙げられ、ピナコール化合物が好ましい。ピナコール化合物としては、ベンゾピナコール、１，２－ジメトキシ－１，１，２，２－テトラフェニルエタン、１，２－ジエトキシ－１，１，２，２－テトラフェニルエタン、１，２－ジフェノキシ－１，１，２，２－テトラフェニルエタン、１，２－ジメトキシ－１，１，２，２－テトラ（４－メチルフェニル）エタン、１，２－ジフェノキシ－１，１，２，２－テトラ（４－メトキシフェニル）エタン、１，２－ビス（トリメチルシロキシ）－１，１，２，２－テトラフェニルエタン、１，２－ビス（トリエチルシロキシ）－１，１，２，２－テトラフェニルエタン、１，２－ビス（ｔ－ブチルジメチルシロキシ）－１，１，２，２－テトラフェニルエタン、１－ヒドロキシ－２－トリメチルシロキシ－１，１，２，２－テトラフェニルエタン、１－ヒドロキシ－２－トリエチルシロキシ－１，１，２，２－テトラフェニルエタン、１－ヒドロキシ－２－ｔ－ブチルジメチルシロキシ－１，１，２，２－テトラフェニルエタンなどが挙げられる。また、ピナコール化合物については、特表２０１４－５２１７７２号公報、特表２０１４－５２３９３９号公報、および、特表２０１４－５２１７７２号公報の記載を参酌でき、これらの内容は本明細書に組み込まれる。 << Other Additives >>
In the composition of the present invention, various additives such as a filler, an adhesion promoter, an antioxidant, a latent antioxidant, a thermal polymerization initiator and the like can be blended, if necessary. With regard to these additives, the description in paragraph [0183] of JP-A-2012-003225 (paragraph No. 0237 in the corresponding US Patent Application Publication No. 2013/0034812), the paragraph number in JP-A-2008-250074, The descriptions of 0101 to 0104, 0107 to 0109, etc. can be referred to, and the contents thereof are incorporated herein. Moreover, as an antioxidant, for example, a phenol compound and a phosphorus compound (for example, paragraph 004 of JP-A-2011-90147)
Compounds described in 2), thioether compounds and the like can be used. As a commercial item, for example, Adekastab series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60G, AO-60, AO-80, AO-A manufactured by ADEKA Co., Ltd.) 330). A latent antioxidant is a compound in which the site that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C., or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. In some cases, compounds in which the protective group is eliminated to function as an antioxidant can be mentioned. Examples of the latent antioxidant include compounds described in International Publication WO 2014/021023, International Publication WO 2017/030005, and Japanese Unexamined Patent Publication No. 2017-008219. Examples of commercially available products include Adeka ARKRUZ GPA-5001 (manufactured by ADEKA Co., Ltd.) and the like. As a thermal polymerization initiator, a pinacol compound, an organic peroxide, an azo compound etc. are mentioned, A pinacol compound is preferable. As pinacol compounds, benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy- 1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra (4-methylphenyl) ethane, 1,2-diphenoxy-1,1,2,2-tetra (4-Methoxyphenyl) ethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, 1,2-bis (triethylsiloxy) -1,1,2,2-tetraphenyl Ethane, 1,2-bis (t-butyldimethylsiloxy) -1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenyl Ethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethylsiloxy-1,1,2,2-tetraphenylethane and the like. . Further, with regard to the pinacol compound, the descriptions in JP-A-2014-521772, JP-A-2014-523939, and JP-A-2014-521772 can be referred to, and the contents thereof are incorporated in the present specification.
　本発明の組成物の固形分濃度は、５～５０質量％であることが好ましい。上限は４５質量％以下であることが好ましく、４０質量％以下であることがより好ましい。下限は８質量％以上であることが好ましく、１０質量％以上であることが好ましい。 The solid content concentration of the composition of the present invention is preferably 5 to 50% by mass. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. The lower limit is preferably 8% by mass or more, and more preferably 10% by mass or more.
　本発明の組成物の粘度（２３℃）は、例えば、塗布により膜を形成する場合、１～１００ｍＰａ・ｓであることが好ましい。下限は、２ｍＰａ・ｓ以上がより好ましく、３ｍＰａ・ｓ以上が更に好ましい。上限は、５０ｍＰａ・ｓ以下がより好ましく、３０ｍＰａ・ｓ以下が更に好ましく、１５ｍＰａ・ｓ以下が特に好ましい。 The viscosity (23 ° C.) of the composition of the present invention is preferably, for example, 1 to 100 mPa · s when a film is formed by coating. The lower limit is preferably 2 mPa · s or more, and more preferably 3 mPa · s or more. The upper limit is more preferably 50 mPa · s or less, still more preferably 30 mPa · s or less, and particularly preferably 15 mPa · s or less.
　本発明の組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、原材料や組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成する多層ボトルや６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 There is no limitation in particular as a storage container of the composition of this invention, A well-known storage container can be used. In addition, as a container, for the purpose of suppressing the mixing of impurities into the raw materials and the composition, a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin or a bottle in which six types of resin are seven layers It is also preferred to use. As such a container, for example, the container described in JP-A-2015-123351 can be mentioned.
　本発明の組成物は、赤外線透過フィルタの形成用の組成物として好ましく用いることができる。 The composition of the present invention can be preferably used as a composition for forming an infrared transmission filter.
＜組成物の調製方法＞
　本発明の組成物は、前述の成分を混合して調製できる。組成物の調製に際しては、全成分を同時に溶剤に溶解または分散して組成物を調製してもよいし、必要に応じては、各成分を適宜配合した２つ以上の溶液または分散液をあらかじめ調製し、使用時（塗布時）にこれらを混合して組成物として調製してもよい。 <Method of Preparing Composition>
The composition of the present invention can be prepared by mixing the aforementioned components. At the time of preparation of the composition, all the components may be simultaneously dissolved or dispersed in a solvent to prepare the composition, or, if necessary, two or more solutions or dispersions in which the respective components are appropriately blended in advance. The composition may be prepared by mixing it at the time of use (at the time of application).
　また、組成物の調製に際しては、顔料を分散させるプロセスを含むことが好ましい。顔料を分散させるプロセスにおいて、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断、キャビテーションなどが挙げられる。これらプロセスを実施するための手段の具体例としては、ビーズミル、サンドミル、ロールミル、ボールミル、ペイントシェーカー、マイクロフルイダイザー、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化、超音波分散などが挙げられる。またサンドミル（ビーズミル）における顔料の粉砕においては、径の小さいビーズを使用する、ビーズの充填率を大きくする事等により粉砕効率を高めた条件で処理することが好ましい。また、粉砕処理後にろ過、遠心分離などで粗粒子を除去することが好ましい。また、顔料を分散させるプロセスおよび分散機については、「分散技術大全、株式会社情報機構発行、２００５年７月１５日」、「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」、特開２０１５－１５７８９３号公報の段落番号００２２に記載のプロセス及び分散機を使用することができる。また顔料を分散させるプロセスにおいては、ソルトミリング工程にて顔料を微細化処理してもよい。ソルトミリング工程に用いられる素材、機器、処理条件等は、例えば特開２０１５－１９４５２１号公報、特開２０１２－０４６６２９号公報の記載を参酌できる。 Moreover, it is preferable to include the process which disperse | distributes a pigment in preparation of a composition. In the process of dispersing the pigment, mechanical force used to disperse the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of means for carrying out these processes include bead mill, sand mill, roll mill, ball mill, paint shaker, microfluidizer, high speed impeller, sand grinder, flow jet mixer, high pressure wet atomization, ultrasonic dispersion, etc. Be In the pulverization of the pigment in a sand mill (bead mill), it is preferable to use a bead having a small diameter, and to process under conditions in which the pulverization efficiency is enhanced by increasing the packing ratio of the beads. Moreover, it is preferable to remove coarse particles by filtration, centrifugation or the like after the pulverizing treatment. In addition, for the process and disperser to disperse the pigment, “Dispersion Technology Complete, issued by Information Technology Co., Ltd., July 15, 2005”, “Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial Practical Application A collection of general materials, published by the Business Development Center Publishing Department, October 10, 1978 ", and the process and disperser described in paragraph No. 0022 of JP-A-2015-157893 can be used. In the process of dispersing the pigment, the pigment may be subjected to a refining treatment in a salt milling step. The materials, devices, processing conditions, and the like used in the salt milling step can be referred to, for example, the descriptions of JP-A-2015-194521 and JP-A-2012-04629.
　組成物の調製にあたり、異物の除去や欠陥の低減などの目的で、組成物をフィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているフィルタであれば特に限定されることなく用いることができる。例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂、ナイロン（例えばナイロン－６、ナイロン－６，６）等のポリアミド系樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量のポリオレフィン樹脂を含む）等の素材を用いたフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含む）およびナイロンが好ましい。 In preparation of the composition, the composition is preferably filtered with a filter for the purpose of removing foreign matter and reducing defects. As a filter, if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular. For example, a fluorocarbon resin such as polytetrafluoroethylene (PTFE), a polyamide-based resin such as nylon (for example, nylon-6, nylon-6, 6), or a polyolefin resin such as polyethylene or polypropylene (PP) Filters made of materials such as polyolefin resins of Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
　フィルタの孔径は、０．０１～７．０μｍが好ましく、０．０１～３．０μｍがより好ましく、０．０５～０．５μｍが更に好ましい。フィルタの孔径が上記範囲であれば、微細な異物をより確実に除去できる。フィルタの孔径値については、フィルタメーカーの公称値を参照することができる。フィルタは、日本ポール株式会社（ＤＦＡ４２０１ＮＩＥＹなど）、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）および株式会社キッツマイクロフィルタ等が提供する各種フィルタを用いることができる。 The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and still more preferably 0.05 to 0.5 μm. If the pore size of the filter is in the above range, fine foreign particles can be removed more reliably. For filter pore size values, reference can be made to the filter manufacturer's nominal value. As the filter, various filters provided by Nippon Paul Co., Ltd. (DFA 4201 NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (old Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used.
　また、フィルタとしてファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。市販品としては、ロキテクノ社製のＳＢＰタイプシリーズ（ＳＢＰ００８など）、ＴＰＲタイプシリーズ（ＴＰＲ００２、ＴＰＲ００５など）、ＳＨＰＸタイプシリーズ（ＳＨＰＸ００３など）が挙げられる。 Moreover, it is also preferable to use a fiber-like filter medium as a filter. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. As a commercial item, SBP type series (SBP 008 etc.) made by Loki Techno, TPR type series (TPR 002, TPR 005 etc.), SHPX type series (SHPX 003 etc.) are mentioned.
　フィルタを使用する際、異なるフィルタ（例えば、第１のフィルタと第２のフィルタなど）を組み合わせてもよい。その際、各フィルタでのろ過は、１回のみでもよいし、２回以上行ってもよい。また、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。また、第１のフィルタでのろ過は、分散液のみに対して行い、他の成分を混合した後で、第２のフィルタでろ過を行ってもよい。 When using filters, different filters (eg, a first filter, a second filter, etc.) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more. Moreover, you may combine the filter of a different hole diameter within the range mentioned above. In addition, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration may be performed with the second filter.
＜膜＞
　次に、本発明の膜について説明する。本発明の膜は、上述した本発明の組成物から得られるものである。本発明の膜は、赤外線透過フィルタとして好ましく用いることができる。 <Membrane>
Next, the film of the present invention will be described. The membrane of the present invention is obtained from the composition of the present invention described above. The film of the present invention can be preferably used as an infrared ray transmission filter.
　本発明の膜は、膜の厚み方向における光の透過率の、波長４００～６００ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、波長１０００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である分光特性を満たしていることが好ましい。 The film of the present invention has a maximum value of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 600 nm of the light transmittance in the film thickness direction. It is preferable to satisfy the spectral characteristics that the minimum value in the range of 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
　本発明の膜は、以下の（１１１）～（１１３）のいずれかの分光特性を満たしていることがより好ましい。
　（１１１）：膜の厚み方向における光の透過率の、波長４００～６００ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、膜の厚み方向における光の透過率の、波長８００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である態様。この態様によれば、波長４００～６００ｎｍの範囲の光を遮光して、波長６５０ｎｍを超える光を透過可能な膜とすることができる。
　（１１２）：膜の厚み方向における光の透過率の、波長４００～７２０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、膜の厚み方向における光の透過率の、波長９００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である態様。この態様によれば、波長４００～７５０ｎｍの範囲の光を遮光して、波長８００ｎｍを超える光を透過可能な膜とすることができる。
　（１１３）：膜の厚み方向における光の透過率の、波長４００～８３０ｎｍの範囲における最大値が２０％以下（好ましくは１５％以下、より好ましくは１０％以下）であり、膜の厚み方向における光の透過率の、波長１０００～１３００ｎｍの範囲における最小値が７０％以上（好ましくは７５％以上、より好ましくは８０％以上）である態様。この態様によれば、波長４００～８３０ｎｍの範囲の光を遮光して、波長９００ｎｍを超える光を透過可能な膜とすることができる。 The film of the present invention more preferably satisfies the spectral characteristics of any of the following (111) to (113).
(111): The maximum value of light transmittance in the film thickness direction in the wavelength range of 400 to 600 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and in the film thickness direction The embodiment in which the minimum value of light transmittance in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it is possible to shield the light in the wavelength range of 400 to 600 nm to make the film capable of transmitting light in excess of the wavelength of 650 nm.
(112): The maximum value of light transmittance in the film thickness direction in the wavelength range of 400 to 720 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and in the film thickness direction The embodiment in which the minimum value of light transmittance in the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it is possible to shield the light in the wavelength range of 400 to 750 nm to make the film capable of transmitting light in excess of the wavelength of 800 nm.
(113): The maximum value of light transmittance in the film thickness direction in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and in the film thickness direction The embodiment in which the minimum value of light transmittance in the wavelength range of 1000 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this aspect, it is possible to shield the light in the wavelength range of 400 to 830 nm to make the film capable of transmitting light in excess of the wavelength of 900 nm.
　本発明の膜の膜厚は、目的に応じて適宜調整できる。１０．０μｍ以下が好ましく、５．０μｍ以下がより好ましく、３．０μｍ以下が更に好ましく、２．５μｍ以下がより一層好ましく、２．０μｍ以下が更に一層好ましく、１．５μｍ以下が特に好ましい。膜厚の下限は、０．４μｍ以上が好ましく、０．５μｍ以上がより好ましく、０．６μｍ以上が更に好ましく、０．７μｍ以上がより一層好ましく、０．８μｍ以上が更に一層このましく、０．９μｍ以上が特に好ましい。 The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The thickness is preferably 10.0 μm or less, more preferably 5.0 μm or less, still more preferably 3.0 μm or less, still more preferably 2.5 μm or less, still more preferably 2.0 μm or less, and particularly preferably 1.5 μm or less. The lower limit of the film thickness is preferably 0.4 μm or more, more preferably 0.5 μm or more, still more preferably 0.6 μm or more, still more preferably 0.7 μm or more, still more preferably 0.8 μm or more. .9 μm or more is particularly preferred.
＜膜の製造方法＞
　次に、本発明の膜の製造方法について説明する。本発明の膜は、本発明の組成物を塗布する工程を経て製造できる。 <Method of producing membrane>
Next, the method for producing the membrane of the present invention will be described. The film of the present invention can be produced through the process of applying the composition of the present invention.
　本発明の膜の製造方法において、組成物は支持体上に塗布することが好ましい。支持体としては、例えば、シリコン、無アルカリガラス、ソーダガラス、パイレックス（登録商標）ガラス、石英ガラスなどの材質で構成された基板が挙げられる。これらの基板には、有機膜や無機膜など形成されていてもよい。有機膜の材料としては、例えば上述した組成物の欄で説明した樹脂が挙げられる。また、支持体は、樹脂で構成された基板を用いることもできる。また、支持体には、電荷結合素子（ＣＣＤ）、相補型金属酸化膜半導体（ＣＭＯＳ）、透明導電膜などが形成されていてもよい。また、支持体には、各画素を隔離するブラックマトリクスが形成されている場合もある。また、支持体には、必要により、上部の層との密着性改良、物質の拡散防止或いは基板表面の平坦化のために下塗り層を設けてもよい。また、支持体としてガラス基板を用いる場合においては、ガラス基板上に無機膜を形成したり、ガラス基板を脱アルカリ処理して用いることが好ましい。 In the method of producing a film of the present invention, the composition is preferably coated on a support. Examples of the support include a substrate made of a material such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass and the like. An organic film, an inorganic film, or the like may be formed on these substrates. Examples of the material of the organic film include the resins described in the section of the composition described above. Moreover, the support body can also use the board | substrate comprised with resin. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support. In addition, a black matrix may be formed on the support to separate each pixel. In addition, if necessary, the support may be provided with a subbing layer for the purpose of improving the adhesion with the upper layer, preventing the diffusion of substances or flattening the surface of the substrate. Moreover, when using a glass substrate as a support body, it is preferable to form an inorganic film on a glass substrate, or to carry out the de-alkali treatment of the glass substrate, and to use.
　組成物の塗布方法としては、公知の方法を用いることができる。例えば、滴下法（ドロップキャスト）；スリットコート法；スプレー法；ロールコート法；回転塗布法（スピンコート法）；流延塗布法；スリットアンドスピン法；プリウェット法（たとえば、特開２００９－１４５３９５号公報に記載されている方法）；インクジェット（例えばオンデマンド方式、ピエゾ方式、サーマル方式）、ノズルジェット等の吐出系印刷、フレキソ印刷、スクリーン印刷、グラビア印刷、反転オフセット印刷、メタルマスク印刷法などの各種印刷法；金型等を用いた転写法；ナノインプリント法などが挙げられる。インクジェットでの塗布としては、特に限定されず、例えば「広がる・使えるインクジェット－特許に見る無限の可能性－、２００５年２月発行、住ベテクノリサーチ」に示された方法（特に１１５～１３３ページ）や、特開２００３－２６２７１６号公報、特開２００３－１８５８３１号公報、特開２００３－２６１８２７号公報、特開２０１２－１２６８３０号公報、特開２００６－１６９３２５号公報などに記載の方法が挙げられる。また、スピンコート法での塗布は、１０００～２０００ｒｐｍの回転数で行うことが好ましい。また、スピンコート法での塗布については、特開平１０－１４２６０３号公報、特開平１１－３０２４１３号公報、特開２０００－１５７９２２号公報に記載されているように、回転速度を塗布中に高めても良い。また「最先端カラーフィルターのプロセス技術とケミカルス」２００６年１月３１日、シーエムシー出版記載のスピンコートプロセスも好適に使用することができる。また、組成物の塗布方法については、国際公開ＷＯ２０１７／０３０１７４号公報、国際公開ＷＯ２０１７／０１８４１９号公報に記載の方法が挙げられ、これらの内容は本明細書に組み込まれる。 As a method of applying the composition, known methods can be used. For example, dropping method (drop casting); slit coating method; spraying method; roll coating method; spin coating method (spin coating method); cast coating method; slit and spin method; pre-wet method (for example, JP 2009-145395) Methods described in the publication); inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Printing methods; transfer methods using a mold or the like; nanoimprint methods and the like. The application by the ink jet is not particularly limited. For example, the method (in particular, pages 115 to 133) disclosed in "Spread and usable ink jet-Infinite possibilities seen in patent-, issued in February 2005, resident Betechno Research" Methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. . In addition, coating by spin coating is preferably performed at a rotational speed of 1000 to 2000 rpm. Further, as to coating by spin coating, as described in JP-A-10-142603, JP-A-11-302413 and JP-A-2000-157922, the rotational speed is increased during coating. Also good. In addition, the spin coat process described in "Advanced Color Filter Process Technology and Chemicals", Jan. 31, 2006, published by CMC can be suitably used. Moreover, as a method of applying the composition, the methods described in International Publication WO 2017/030174 and International Publication WO 2017/018419 can be mentioned, and the contents thereof are incorporated in the present specification.
　組成物を塗布して形成した組成物層（塗布膜）は、乾燥（プリベーク）してもよい。低温プロセスにより膜を製造する場合は、プリベークを行わなくてもよい。プリベークを行う場合、プリベーク温度は、１５０℃以下が好ましく、１２０℃以下がより好ましく、１１０℃以下が更に好ましい。下限は、例えば、５０℃以上とすることができ、８０℃以上とすることもできる。プリベーク時間は、１０秒～３０００秒が好ましく、４０～２５００秒がより好ましく、８０～２２０秒がさらに好ましい。プリベークは、ホットプレート、オーブン等を用いて行うことができる。 The composition layer (coated film) formed by applying the composition may be dried (prebaked). In the case of producing a film by a low temperature process, the prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150 ° C. or less, more preferably 120 ° C. or less, and still more preferably 110 ° C. or less. The lower limit may be, for example, 50 ° C. or more, and may be 80 ° C. or more. The pre-bake time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and still more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.
　膜の製造方法において、更にパターンを形成する工程を含むことも好ましい。パターン形成方法としては、フォトリソグラフィ法を用いたパターン形成方法、ドライエッチング法を用いたパターン形成方法が挙げられ、フォトリソグラフィ法を用いたパターン形成方法が好ましい。なお、本発明の膜を平坦膜として用いる場合には、パターンを形成する工程を行わなくてもよい。以下、パターンを形成する工程について詳細に説明する。 It is also preferable that the method for producing a film further includes the step of forming a pattern. The pattern formation method includes a pattern formation method using a photolithography method and a pattern formation method using a dry etching method, and a pattern formation method using a photolithography method is preferable. When the film of the present invention is used as a flat film, the step of forming a pattern may not be performed. Hereinafter, the process of forming a pattern will be described in detail.
（フォトリソグラフィ法でパターン形成する場合）
　フォトリソグラフィ法でのパターン形成方法は、本発明の組成物を塗布して形成した組成物層に対しパターン状に露光する工程（露光工程）と、未露光部の組成物層を現像除去してパターンを形成する工程（現像工程）と、を含むことが好ましい。必要に応じて、現像されたパターンをベークする工程（ポストベーク工程）を設けてもよい。以下、各工程について説明する。 (When forming a pattern by photolithography)
The pattern formation method by the photolithography method is a step of exposing the composition layer formed by applying the composition of the present invention in a pattern (exposure step) and developing and removing the composition layer in the unexposed area. It is preferable to include the step of forming a pattern (development step). If necessary, a step (post-baking step) may be provided to bake the developed pattern. Each step will be described below.
＜＜露光工程＞＞
　露光工程では組成物層をパターン状に露光する。例えば、組成物層に対し、ステッパー露光機やスキャナ露光機などを用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン露光することができる。これにより、露光部分を硬化することができる。露光に際して用いることができる放射線（光）としては、ｇ線、ｉ線等が挙げられる。また、波長３００ｎｍ以下の光（好ましくは波長１８０～３００ｎｍの光）を用いることもできる。波長３００ｎｍ以下の光としては、ＫｒＦ線（波長２４８ｎｍ）、ＡｒＦ線（波長１９３ｎｍ）などが挙げられ、ＫｒＦ線（波長２４８ｎｍ）が好ましい。照射量（露光量）は、例えば、０．０３～２．５Ｊ／ｃｍ２が好ましく、０．０５～１．０Ｊ／ｃｍ２がより好ましく、０．０８～０．５Ｊ／ｃｍ２が最も好ましい。露光時における酸素濃度については適宜選択することができる。例えば、大気下で露光してもよく、酸素濃度が１９体積％以下の低酸素雰囲気下（例えば、１５体積％、５体積％、実質的に無酸素）で露光してもよく、酸素濃度が２１体積％を超える高酸素雰囲気下（例えば、２２体積％、３０体積％、５０体積％）で露光してもよい。また、露光照度は適宜設定することができ、１０００～１０００００Ｗ／ｍ２の範囲から選択することが好ましい。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度１０体積％で照度１００００Ｗ／ｍ２、酸素濃度３５体積％で照度２００００Ｗ／ｍ２などとすることができる。 << exposure step >>
In the exposure step, the composition layer is exposed in a pattern. For example, pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using a stepper exposure device, a scanner exposure device, or the like. Thereby, the exposed portion can be cured. Examples of radiation (light) that can be used for exposure include g-rays and i-rays. Further, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and the like, and KrF rays (wavelength 248 nm) are preferable. Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm 2, more preferably 0.05 ~ 1.0J / cm 2, most preferably 0.08 ~ 0.5J / cm 2 . The oxygen concentration at the time of exposure can be selected appropriately. For example, exposure may be performed in the atmosphere, or exposure may be performed in a low oxygen atmosphere (for example, 15% by volume, 5% by volume, substantially no oxygen) in which the oxygen concentration is 19% by volume or less. Exposure may be performed under a high oxygen atmosphere (eg, 22% by volume, 30% by volume, 50% by volume) exceeding 21% by volume. Further, the exposure illuminance can be set as appropriate, and is preferably selected from the range of 1000 to 100000 W / m 2 . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
＜＜現像工程＞＞
　次に、露光後の組成物層における未露光部の組成物層を現像除去してパターンを形成する。未露光部の組成物層の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の組成物層が現像液に溶出し、光硬化した部分だけが支持体上に残る。現像液の温度は、例えば、２０～３０℃が好ましい。現像時間は、２０～１８０秒が好ましい。また、残渣除去性を向上させるため、現像液を６０秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。 << Development Process >>
Next, the composition layer in the unexposed area of the composition layer after exposure is developed and removed to form a pattern. The development removal of the composition layer in the unexposed area can be carried out using a developer. As a result, the composition layer in the unexposed area in the exposure step is eluted into the developer, and only the photocured area remains on the support. The temperature of the developing solution is preferably, for example, 20 to 30.degree. The development time is preferably 20 to 180 seconds. In addition, in order to improve the residue removability, the process of shaking off the developer every 60 seconds and further supplying the developer anew may be repeated several times.
　現像液は、アルカリ剤を純水で希釈したアルカリ性水溶液が好ましい。アルカリ剤としては、例えば、アンモニア、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、ジグリコールアミン、ジエタノールアミン、ヒドロキシアミン、エチレンジアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセンなどの有機アルカリ性化合物や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどの無機アルカリ性化合物が挙げられる。アルカリ剤は、分子量が大きい化合物の方が環境面および安全面で好ましい。アルカリ性水溶液のアルカリ剤の濃度は、０．００１～１０質量％が好ましく、０．０１～１質量％がより好ましい。また、現像液は、さらに界面活性剤を含有していてもよい。界面活性剤としては、上述した界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。現像液は、移送や保管の便宜などの観点より、一旦濃縮液として製造し、使用時に必要な濃度に希釈してもよい。希釈倍率は特に限定されないが、例えば１．５～１００倍の範囲に設定することができる。なお、アルカリ性水溶液を現像液として使用した場合には、現像後純水で洗浄（リンス）することが好ましい。また、リンスは、現像後の組成物層が形成された支持体を回転させつつ、現像後の組成物層へリンス液を供給して行うことが好ましい。また、リンス液を吐出させるノズルを支持体の中心部から支持体の周縁部に移動させて行うことも好ましい。この際、ノズルの支持体中心部から周縁部へ移動させるにあたり、ノズルの移動速度を徐々に低下させながら移動させてもよい。このようにしてリンスを行うことで、リンスの面内ばらつきを抑制できる。また、ノズルの支持体中心部から周縁部へ移動させつつ、支持体の回転速度を徐々に低下させても同様の効果が得られる。 The developing solution is preferably an alkaline aqueous solution in which an alkaline agent is diluted with pure water. As an alkaline agent, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide Organic compounds such as ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo [5.4.0] -7-undecene Alkaline compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate. The alkaline agent is preferably a compound having a large molecular weight in terms of the environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The developer may further contain a surfactant. As surfactant, the surfactant mentioned above is mentioned and nonionic surfactant is preferable. The developer may be prepared once as a concentrate and diluted to a concentration required for use, from the viewpoint of transportation and storage convenience. The dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. When an alkaline aqueous solution is used as a developer, it is preferable to wash (rinse) with pure water after development. The rinse is preferably performed by supplying a rinse liquid to the composition layer after development while rotating the support on which the composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral portion of the support. Under the present circumstances, when moving from the support center part of a nozzle to a peripheral part, you may make it move, reducing the moving speed of a nozzle gradually. By performing the rinse in this manner, the in-plane variation of the rinse can be suppressed. Also, the same effect can be obtained by gradually reducing the rotational speed of the support while moving from the center of the support to the periphery of the nozzle.
　現像後、乾燥を施した後に加熱処理（ポストベーク）を行うこともできる。ポストベークは、膜の硬化を完全なものとするための現像後の加熱処理である。ポストベークを行う場合、ポストベーク温度は、例えば１００～２４０℃が好ましい。膜硬化の観点から、２００～２３０℃がより好ましい。ポストベークは、現像後の膜に対して、上記条件になるようにホットプレートやコンベクションオーブン（熱風循環式乾燥機）、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。 It is also possible to carry out heat treatment (post bake) after drying after development. Post-baking is a post-development heat treatment to complete film curing. When post-baking, the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 200 to 230 ° C. is more preferable. Post-baking should be performed continuously or batchwise on the film after development, using heating means such as a hot plate, convection oven (hot air circulation dryer), high frequency heater, etc., so as to satisfy the above conditions. Can.
（ドライエッチング法でパターン形成する場合）
　ドライエッチング法でのパターン形成は、本発明の組成物を支持体上に塗布して形成した組成物層を硬化して硬化物層を形成し、次いで、この硬化物層上にパターニングされたレジスト層を形成し、次いで、パターニングされたレジスト層をマスクとして硬化物層に対してエッチングガスを用いてドライエッチングするなどの方法で行うことができる。ドライエッチング法でのパターン形成については、特開２０１３－０６４９９３号公報の段落番号００１０～００６７の記載を参酌でき、この内容は本明細書に組み込まれる。 (When patterning by dry etching)
Patterning by the dry etching method is to apply a composition of the present invention on a support to cure a composition layer formed to form a cured product layer, and then to form a resist patterned on the cured product layer. A layer can be formed, and then, the patterned resist layer can be used as a mask to dry-etch the cured product layer using an etching gas. For the pattern formation by the dry etching method, the description in paragraphs “0010” to “0067” of JP 2013-064993 can be referred to, and the contents thereof are incorporated in the present specification.
＜赤外線透過フィルタ＞
　次に、本発明の赤外線透過フィルタについて説明する。本発明の赤外線透過フィルタは、上述した本発明の膜を有する。 <Infrared transmission filter>
Next, the infrared ray transmission filter of the present invention will be described. The infrared transmission filter of the present invention has the above-described film of the present invention.
　本発明の赤外線透過フィルタは、有彩色着色剤を含むカラーフィルタと組み合わせて用いることもできる。カラーフィルタは、有彩色着色剤を含む着色組成物を用いて製造できる。有彩色着色剤としては、本発明の組成物で説明した有彩色着色剤が挙げられる。着色組成物は、硬化性化合物、樹脂、光重合開始剤、界面活性剤、溶剤、重合禁止剤、紫外線吸収剤などを更に含有することができる。これらの詳細については、本発明の組成物で説明した材料が挙げられ、それらを用いることができる。 The infrared transmission filter of the present invention can also be used in combination with a color filter containing a chromatic coloring agent. A color filter can be manufactured using a coloring composition containing a chromatic coloring agent. The chromatic colorants include the chromatic colorants described in the composition of the present invention. The coloring composition may further contain a curable compound, a resin, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet light absorber and the like. These details include the materials described in the compositions of the present invention, which can be used.
　また、本発明の赤外線透過フィルタは、本発明の膜の画素と、赤、緑、青、マゼンタ、黄、シアン、黒および無色から選ばれる画素とを有する態様も好ましい態様である。 In addition, an embodiment in which the infrared ray transmitting filter of the present invention has pixels of the film of the present invention and pixels selected from red, green, blue, magenta, yellow, cyan, black and colorless is also a preferable embodiment.
＜固体撮像素子＞
　本発明の固体撮像素子は、上述した本発明の膜を含む。固体撮像素子の構成としては、本発明の膜を有する構成であり、固体撮像素子として機能する構成であれば特に限定はない。例えば、以下のような構成が挙げられる。 <Solid-state imaging device>
The solid-state imaging device of the present invention includes the film of the present invention described above. As a structure of a solid-state image sensor, it is a structure which has a film | membrane of this invention, and if it is a structure which functions as a solid-state image sensor, there will be no limitation in particular. For example, the following configuration may be mentioned.
　支持体上に、固体撮像素子の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等からなる転送電極を有し、フォトダイオードおよび転送電極上にフォトダイオードの受光部のみ開口したタングステン等からなる遮光膜を有し、遮光膜上に遮光膜全面およびフォトダイオード受光部を覆うように形成された窒化シリコン等からなるデバイス保護膜を有し、デバイス保護膜上に、本発明における膜を有する構成である。さらに、デバイス保護膜上であって、本発明における膜の下（支持体に近い側）に集光手段（例えば、マイクロレンズ等。以下同じ）を有する構成や、本発明における膜上に集光手段を有する構成等であってもよい。また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各画素を形成する膜が埋め込まれた構造を有していてもよい。この場合の隔壁は各画素よりも低屈折率であることが好ましい。このような構造を有する撮像装置の例としては、特開２０１２－２２７４７８号公報、特開２０１４－１７９５７７号公報に記載の装置が挙げられる。 A light shield comprising a plurality of photodiodes constituting the light receiving area of the solid-state imaging device and transfer electrodes made of polysilicon and the like on the support, light shielding made of tungsten or the like in which only the light receiving portion of the photodiode and the transfer electrodes are opened. It has a film, has a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the photodiode light receiving part, and has the film of the present invention on the device protection film. is there. Furthermore, a configuration having a condensing means (for example, a micro lens etc. The same shall apply hereinafter) on the device protective film and under the film of the present invention (closer to the support), or on the film of the present invention It may be a configuration having means. In addition, the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned into, for example, a grid shape by partition walls. The partition walls in this case preferably have a lower refractive index than each pixel. As an example of an imaging device having such a structure, devices described in JP 2012-227478 A and JP 2014-179577 A can be mentioned.
＜光センサ＞
　本発明の光センサは、上述した本発明の膜を含む。光センサの構成としては、光センサとして機能する構成であれば特に限定はない。以下、本発明の光センサの一実施形態について、図面を用いて説明する。 <Optical sensor>
An optical sensor of the present invention includes the film of the present invention described above. The configuration of the light sensor is not particularly limited as long as it functions as a light sensor. Hereinafter, an embodiment of an optical sensor of the present invention will be described using the drawings.
　図１において、符号１１０は、固体撮像素子である。固体撮像素子１１０上に設けられている撮像領域は、近赤外線カットフィルタ１１１と、赤外線透過フィルタ１１４とを有する。また、近赤外線カットフィルタ１１１上には、カラーフィルタ１１２が積層している。カラーフィルタ１１２および赤外線透過フィルタ１１４の入射光ｈν側には、マイクロレンズ１１５が配置されている。マイクロレンズ１１５を覆うように平坦化層１１６が形成されている。 In FIG. 1, reference numeral 110 denotes a solid-state imaging device. An imaging region provided on the solid-state imaging device 110 includes a near infrared cut filter 111 and an infrared transmission filter 114. Further, on the near infrared cut filter 111, a color filter 112 is laminated. A microlens 115 is disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed to cover the microlenses 115.
　近赤外線カットフィルタ１１１の分光特性は、使用する赤外発光ダイオード（赤外ＬＥＤ）の発光波長に応じて選択される。カラーフィルタ１１２は、可視領域における特定波長の光を透過及び吸収する画素が形成されたカラーフィルタであって、特に限定はなく、従来公知の画素形成用のカラーフィルタを用いることができる。例えば、赤色（Ｒ）、緑色（Ｇ）、青色（Ｂ）の画素が形成されたカラーフィルタなどが用いられる。例えば、特開２０１４－０４３５５６号公報の段落番号０２１４～０２６３の記載を参酌することができ、この内容は本明細書に組み込まれる。赤外線透過フィルタ１１４は、使用する赤外ＬＥＤの発光波長に応じてその特性が選択される。 The spectral characteristics of the near infrared cut filter 111 are selected according to the emission wavelength of the infrared light emitting diode (infrared LED) to be used. The color filter 112 is a color filter in which a pixel for transmitting and absorbing light of a specific wavelength in the visible region is formed, and is not particularly limited, and a conventionally known color filter for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description in paragraph Nos. 0214 to 0263 of JP-A-2014-043556 can be referred to, the contents of which are incorporated herein. The characteristic of the infrared transmission filter 114 is selected according to the emission wavelength of the infrared LED to be used.
　図１に示す赤外線センサにおいて、平坦化層１１６上には、近赤外線カットフィルタ１１１とは別の近赤外線カットフィルタ（他の近赤外線カットフィルタ）がさらに配置されていてもよい。他の近赤外線カットフィルタとしては、銅を含有する層および／または誘電体多層膜を有するものなどが挙げられる。これらの詳細については、上述したものが挙げられる。また、他の近赤外線カットフィルタとしては、デュアルバンドパスフィルタを用いてもよい。 In the infrared sensor shown in FIG. 1, a near infrared cut filter (another near infrared cut filter) different from the near infrared cut filter 111 may be further disposed on the planarization layer 116. Other near infrared cut filters include those having a copper-containing layer and / or a dielectric multilayer film. The details of these may be mentioned above. In addition, as another near infrared cut filter, a dual band pass filter may be used.
　以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部」は質量基準である。 Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, unless otherwise indicated, "part" is a mass reference | standard.
＜重量平均分子量の測定＞
　樹脂の重量平均分子量は、以下の条件に従って、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）によって測定した。
　カラムの種類：ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｈと、ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００と、ＴＯＳＯＨ　ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００とを連結したカラム
　展開溶媒：テトラヒドロフラン
　カラム温度：４０℃
　流量（サンプル注入量）：１．０μＬ（サンプル濃度０．１質量％）
　装置名：東ソー（株）製　ＨＬＣ－８２２０ＧＰＣ
　検出器：ＲＩ（屈折率）検出器
　検量線ベース樹脂：ポリスチレン樹脂 <Measurement of weight average molecular weight>
The weight average molecular weight of the resin was measured by gel permeation chromatography (GPC) according to the following conditions.
Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ 4000, and TOSOH TSKgel Super HZ 2000 coupled column Developing solvent: tetrahydrofuran Column temperature: 40 ° C.
Flow rate (sample injection amount): 1.0 μL (sample concentration 0.1 mass%)
Device name: Tosoh Corp. HLC-8220 GPC
Detector: RI (refractive index) detector Calibration curve base resin: polystyrene resin
＜金属アゾ顔料の製造＞
（金属アゾ顔料１の製造）
　４６．２ｇのジアゾバルビツール酸および３８．４ｇのバルビツール酸を、８５℃の蒸留水の１１００ｇ中に添加した。次いで、この溶液に水酸化カリウム水溶液を添加してｐＨを約５とした後、９０分間攪拌してアゾバルビツール酸前駆体を製造した。
　次いで、上記の方法に従って製造されたアゾバルビツール酸前駆体に、８２℃の蒸留水の１５００ｇを添加した。次いで、１０ｇの３０％塩酸を滴下により添加した。次いで、７９．４ｇのメラミンを添加した。次いで、０．２８２モルの約２５％塩化亜鉛溶液と、０．００１５モルの約３０％塩化銅（ＩＩ）溶液との混合物を滴下により添加した。次いで、これらを添加した溶液を８２℃の温度で３時間保持した後、ＫＯＨを添加してｐＨを約５．５とした。次いで、この溶液の温度を９０℃に昇温し、９０℃の温度を維持しつつ、１００ｇの蒸留水を添加して希釈した。次いで、この溶液に２１ｇの３０％塩酸を滴下により添加した後、９０℃の温度で１２時間加熱処理した。次いで、加熱処理後の溶液に水酸化カリウム水溶液を添加してｐＨを約５とした。次いで、この溶液から顔料を吸引フィルタ上で単離し、洗浄し、８０℃での真空乾燥キャビネット中で乾燥させた後、標準実験室ミルで約２分間すり潰して金属アゾ顔料１を製造した。 <Production of metal azo pigment>
(Production of metal azo pigment 1)
46.2 g of diazobarbituric acid and 38.4 g of barbituric acid were added into 1100 g of distilled water at 85.degree. Then, an aqueous potassium hydroxide solution was added to this solution to adjust the pH to about 5, and the mixture was stirred for 90 minutes to produce an azobarbituric acid precursor.
Next, 1500 g of distilled water at 82 ° C. was added to the azobarbituric acid precursor produced according to the method described above. Then 10 g of 30% hydrochloric acid were added dropwise. Then 79.4 g of melamine was added. Then, a mixture of 0.282 mol of about 25% zinc chloride solution and 0.0015 mol of about 30% copper (II) chloride solution was added dropwise. The solutions to which they were added were then held at a temperature of 82 ° C. for 3 hours, after which KOH was added to bring the pH to about 5.5. Then, the temperature of the solution was raised to 90 ° C., and while maintaining the temperature of 90 ° C., 100 g of distilled water was added for dilution. Then, 21 g of 30% hydrochloric acid was added dropwise to this solution, followed by heat treatment at a temperature of 90 ° C. for 12 hours. Subsequently, the aqueous solution of potassium hydroxide was added to the solution after the heat treatment to adjust the pH to about 5. The pigment was then isolated from the solution on a suction filter, washed, dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce metal azo pigment 1.
（金属アゾ顔料２の製造）
　１５４．１ｇのジアゾバルビツール酸および１２８．１ｇのバルビツール酸を、８５℃の蒸留水の３６００ｇ中に添加した。次いで、この溶液に水酸化カリウム水溶液を添加してｐＨを約５とした後、９０分間攪拌してアゾバルビツール酸前駆体を製造した。
　次いで、上記の方法に従って製造されたアゾバルビツール酸前駆体に、８２℃の蒸留水の５０００ｇを添加した。次いで、２５２．２ｇのメラミンを添加した。次いで、０．６８モルの約３０％塩化ニッケル（ＩＩ）溶液、０．０２モルの約３０％塩化銅（ＩＩ）溶液、および０．２００モルの約２０％塩化ランタン（ＩＩＩ）溶液の混合物を滴下により添加した。次いで、これらを添加した溶液を８２℃で３時間保持した後、ＫＯＨを添加してｐＨを約５．５とした。次いで、この溶液の温度を９０℃に昇温し、９０℃の温度を維持しつつ、１０００ｇの蒸留水を添加して希釈した。次いで、この溶液に１１３ｇの３０％塩酸を滴下により添加した後、９０℃の温度で１２時間加熱処理した。次いで、加熱処理後の溶液に水酸化カリウム水溶液を添加してｐＨを約５とした。次いで、この溶液から顔料を吸引フィルタ上で単離し、洗浄し、８０℃での真空乾燥キャビネット中で乾燥させた後、標準実験室ミルで約２分間すり潰して金属アゾ顔料２を製造した。 (Production of metal azo pigment 2)
154.1 g of diazobarbituric acid and 128.1 g of barbituric acid were added into 3600 g of distilled water at 85 ° C. Then, an aqueous potassium hydroxide solution was added to this solution to adjust the pH to about 5, and the mixture was stirred for 90 minutes to produce an azobarbituric acid precursor.
Next, 5000 g of distilled water at 82 ° C. was added to the azobarbituric acid precursor produced according to the method described above. Then 252.2 g of melamine was added. Then, a mixture of 0.68 mole of about 30% nickel (II) chloride solution, 0.02 mole of about 30% copper (II) chloride solution, and 0.200 mole of about 20% lanthanum (III) chloride solution It was added dropwise. Then, the solution to which these were added was maintained at 82 ° C. for 3 hours, and then KOH was added to adjust the pH to about 5.5. Then, the temperature of the solution was raised to 90 ° C., and while maintaining the temperature of 90 ° C., 1000 g of distilled water was added for dilution. Subsequently, 113 g of 30% hydrochloric acid was added dropwise to this solution, and then heat treated at a temperature of 90 ° C. for 12 hours. Subsequently, the aqueous solution of potassium hydroxide was added to the solution after the heat treatment to adjust the pH to about 5. The pigment was then isolated from the solution on a suction filter, washed and dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce metal azo pigment 2.
（金属アゾ顔料３の製造）
　１５４．１ｇのジアゾバルビツール酸および１２８．１ｇのバルビツール酸を、８５℃の蒸留水の３６００ｇ中に添加した。次いで、この溶液に水酸化カリウム水溶液を添加してｐＨを約５とした後、９０分間攪拌してアゾバルビツール酸前駆体を製造した。
　次いで、上記の方法に従って製造されたアゾバルビツール酸前駆体に、８２℃の蒸留水の５０００ｇを添加した。次いで、２５２．２ｇのメラミンを添加した。次いで、０．７０モルの約３０％塩化ニッケル（ＩＩ）溶液、０．０５モルの約３０％塩化亜鉛（ＩＩ）溶液、および０．１６７モルの約２０％塩化ランタン（ＩＩＩ）溶液の混合物を滴下により添加した。次いで、これらを添加した溶液を８２℃で３時間保持した後、ＫＯＨを添加してｐＨを約５．５とした。次いで、この溶液の温度を９０℃に昇温し、９０℃の温度を維持しつつ、１０００ｇの蒸留水を添加して希釈した。次いで、この溶液に１１３ｇの３０％塩酸を滴下により添加した後、９０℃の温度で１２時間加熱処理した。次いで、加熱処理後の溶液に水酸化カリウム水溶液を添加してｐＨを約５とした。次いで、この溶液から顔料を吸引フィルタ上で単離し、洗浄し、８０℃での真空乾燥キャビネット中で乾燥させた後、標準実験室ミルで約２分間すり潰して金属アゾ顔料３を製造した。 (Production of metal azo pigment 3)
154.1 g of diazobarbituric acid and 128.1 g of barbituric acid were added into 3600 g of distilled water at 85 ° C. Then, an aqueous potassium hydroxide solution was added to this solution to adjust the pH to about 5, and the mixture was stirred for 90 minutes to produce an azobarbituric acid precursor.
Next, 5000 g of distilled water at 82 ° C. was added to the azobarbituric acid precursor produced according to the method described above. Then 252.2 g of melamine was added. Then, a mixture of 0.70 moles of about 30% nickel (II) chloride solution, 0.05 moles of about 30% zinc (II) chloride solution, and 0.167 moles of about 20% lanthanum (III) chloride solution It was added dropwise. Then, the solution to which these were added was maintained at 82 ° C. for 3 hours, and then KOH was added to adjust the pH to about 5.5. Then, the temperature of the solution was raised to 90 ° C., and while maintaining the temperature of 90 ° C., 1000 g of distilled water was added for dilution. Subsequently, 113 g of 30% hydrochloric acid was added dropwise to this solution, and then heat treated at a temperature of 90 ° C. for 12 hours. Subsequently, the aqueous solution of potassium hydroxide was added to the solution after the heat treatment to adjust the pH to about 5. The pigment was then isolated from the solution on a suction filter, washed, dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce metal azo pigment 3.
（金属アゾ顔料４の製造）
　４６．２ｇのジアゾバルビツール酸および３８．４ｇのバルビツール酸を、８５℃の蒸留水の１１００ｇ中に添加した。次いで、この溶液に水酸化カリウム水溶液を添加してｐＨを約５とした後、９０分間攪拌してアゾバルビツール酸前駆体を製造した。
　次いで、上記の方法に従って製造されたアゾバルビツール酸前駆体に、８２℃の蒸留水の５０００ｇを添加した。次いで、２５２．２ｇのメラミンを添加した。次いで、０．２８５モルの約２５％塩化ニッケル溶液と０．０１０モルの約１０％塩化ガドリニウム（ＩＩＩ）溶液との混合物を滴下により添加した。次いで、これらを添加した溶液を８２℃で３時間保持した後、ＫＯＨを添加してｐＨを約５．５とした。次いで、この溶液の温度を９０℃に昇温し、９０℃の温度を維持しつつ、１０００ｇの蒸留水を添加して希釈した。次いで、この溶液に１１３ｇの３０％塩酸を滴下により添加した後、９０℃の温度で１２時間加熱処理した。次いで、加熱処理後の溶液に水酸化カリウム水溶液を添加してｐＨを約５とした。次いで、この溶液から顔料を吸引フィルタ上で単離し、洗浄し、８０℃での真空乾燥キャビネット中で乾燥させた後、標準実験室ミルで約２分間すり潰して金属アゾ顔料４を製造した。 (Production of metal azo pigment 4)
46.2 g of diazobarbituric acid and 38.4 g of barbituric acid were added into 1100 g of distilled water at 85.degree. Then, an aqueous potassium hydroxide solution was added to this solution to adjust the pH to about 5, and the mixture was stirred for 90 minutes to produce an azobarbituric acid precursor.
Next, 5000 g of distilled water at 82 ° C. was added to the azobarbituric acid precursor produced according to the method described above. Then 252.2 g of melamine was added. Then, a mixture of 0.285 mole of about 25% nickel chloride solution and 0.010 mole of about 10% gadolinium (III) chloride solution was added dropwise. Then, the solution to which these were added was maintained at 82 ° C. for 3 hours, and then KOH was added to adjust the pH to about 5.5. Then, the temperature of the solution was raised to 90 ° C., and while maintaining the temperature of 90 ° C., 1000 g of distilled water was added for dilution. Subsequently, 113 g of 30% hydrochloric acid was added dropwise to this solution, and then heat treated at a temperature of 90 ° C. for 12 hours. Subsequently, the aqueous solution of potassium hydroxide was added to the solution after the heat treatment to adjust the pH to about 5. The pigment was then isolated from the solution on a suction filter, washed, dried in a vacuum drying cabinet at 80 ° C. and then ground in a standard laboratory mill for about 2 minutes to produce metal azo pigment 4.
＜環境規制物質の留去方法＞
　（製造例１）　重合性モノマーＤ５の製造
　フラスコに、残留溶媒としてトルエンを２３８質量ｐｐｍ含有する多官能アクリレート（ＫＡＹＡＲＡＤ　ＤＰＨＡ、日本化薬（株）製）の５０ｇと、プロピレングリコールモノメチルアセテート（ＰＧＭＥＡ）の５０ｇと、２，２，６，６－テトラメチルピペリジン　１－オキシル（ＴＥＭＰＯ）の８０ｍｇとを入れ、外設温度を９０℃に設定し、フラスコ内部の圧力を常圧から徐々に減圧して６８ｍｍＨｇにし、４時間かけて減圧留去を行った。その後、系内の重量を１００ｇになるようＰＧＭＥＡで調整して、多官能アクリレート溶液１（重合性モノマーＤ５）を得た。ガスクロマトグラフィーにて多官能アクリレート溶液１中に含まれる残留溶媒（トルエン）量を測定したところ１１質量ｐｐｍに低減されていることを確認した。また、１Ｈ－ＮＭＲ（ｎｕｃｌｅａｒ　ｍａｇｎｅｔｉｃ　ｒｅｓｏｎａｎｃｅ）にて多官能アクリレート（ＫＡＹＡＲＡＤ　ＤＰＨＡ、日本化薬（株）製）由来のピークが検出され、ラジカル重合による架橋反応が生じていないことを確認した。 <Distillation method of environmental control substance>
Production Example 1 Production of Polymerizable Monomer D5 In a flask, 50 g of polyfunctional acrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) containing 238 mass ppm of toluene as a residual solvent and propylene glycol monomethyl acetate (PGMEA) Of 50g and 80 mg of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), the external temperature is set to 90 ° C, and the pressure inside the flask is gradually reduced from normal pressure. The pressure was adjusted to 68 mmHg and vacuum distillation was performed over 4 hours. Thereafter, the weight in the system was adjusted with PGMEA to 100 g to obtain Multifunctional Acrylate Solution 1 (polymerizable monomer D5). The amount of residual solvent (toluene) contained in the polyfunctional acrylate solution 1 was measured by gas chromatography, and it was confirmed to be reduced to 11 mass ppm. In addition, a peak derived from a polyfunctional acrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) was detected by 1 H-NMR (nuclear magnetic resonance), and it was confirmed that no crosslinking reaction was caused by radical polymerization.
　（製造例２）　分散剤Ｃ５の製造
　フラスコに残留溶媒としてトルエンを８３５質量ｐｐｍ含有するアクリレート化合物（アロニックスＭ－５３００、東亞合成（株）製）の５０ｇと、ＰＧＭＥＡの５０ｇと、ＴＥＭＰＯの４０ｍｇとを入れ、外設温度を９０℃に設定し、フラスコ内部の圧力を常圧から徐々に減圧して６６ｍｍＨｇにし、４時間かけて減圧留去を行った。その後、系内の重量を１００ｇになるようＰＧＭＥＡで調整し、モノマー溶液１を得た。ガスクロマトグラフィーにてモノマー溶液１中に含まれる残留溶媒（トルエン）量を測定したところ、９質量ｐｐｍに低減されていることを確認した。また、１Ｈ－ＮＭＲにてアクリレート化合物（アロニックスＭ－５３００、東亞合成（株）製）由来のピークが検出され、ラジカル重合による架橋反応が生じていないことを確認した。 Production Example 2 Production of Dispersant C5 50 g of an acrylate compound (Alonix M-5300, manufactured by Toagosei Co., Ltd.) containing 835 mass ppm of toluene as a residual solvent in a flask, 50 g of PGMEA, and 40 mg of TEMPO The external temperature was set to 90.degree. C., the pressure inside the flask was gradually reduced from normal pressure to 66 mmHg, and reduced-pressure distillation was performed over 4 hours. Thereafter, the weight of the system was adjusted to 100 g with PGMEA to obtain a monomer solution 1. When the amount of residual solvent (toluene) contained in the monomer solution 1 was measured by gas chromatography, it was confirmed to be reduced to 9 mass ppm. In addition, a peak derived from an acrylate compound (Alonix M-5300, manufactured by Toagosei Co., Ltd.) was detected by 1 H-NMR, and it was confirmed that a crosslinking reaction by radical polymerization did not occur.
　三口フラスコに、ε－カプロラクトンの１０４４．２ｇと、δ－バレロラクトンの１８４．３ｇと、２－エチル－１－ヘキサノールの７１．６ｇとを導入し、混合物を得た。次に、窒素を吹き込みながら、上記混合物を攪拌した。次に、混合物にモノブチル錫オキシドの０．６１ｇを加え、得られた混合物を９０℃に加熱した。６時間後、１Ｈ－ＮＭＲを用いて、混合物中における２－エチル－１－ヘキサノールに由来するシグナルが消失したのを確認後、混合物を１１０℃に加熱した。窒素下にて１１０℃で１２時間重合反応を続けた後、１Ｈ－ＮＭＲでε－カプロラクトン及びδ－バレロラクトンに由来するシグナルの消失を確認した後、得られた化合物について、ＧＰＣ法により分子量測定を行った。化合物の分子量が所望の値に到達したことを確認した後、上記化合物を含有する混合物に２，６－ジ－ｔ－ブチル－４－メチルフェノールの０．３５ｇを添加した。更にその後、得られた混合物に対して、２－メタクリロイロキシエチルイソシアネートの８７．０ｇを３０分かけて滴下した。滴下終了から６時間後、１Ｈ－ＮＭＲにて２－メタクリロイロキシエチルイソシアネート（ＭＯＩ）に由来するシグナルが消失したのを確認後、ＰＧＭＥＡの１３８７．０ｇを混合物に添加し、濃度が５０質量％のマクロモノマーＡ－１溶液の２７７０ｇを得た。マクロモノマーＡ－１の構造（式（Ａ－１）に示した）は、１Ｈ－ＮＭＲにより確認した。得られたマクロモノマーＡ－１の重量平均分子量は６，０００であった。
Figure JPOXMLDOC01-appb-C000044
 In a three-necked flask, 1044.2 g of ε-caprolactone, 184.3 g of δ-valerolactone, and 71.6 g of 2-ethyl-1-hexanol were introduced to obtain a mixture. The mixture was then stirred while blowing with nitrogen. Next, 0.61 g of monobutyl tin oxide was added to the mixture, and the resulting mixture was heated to 90.degree. After 6 hours, the mixture was heated to 110 ° C. using 1 H-NMR to confirm that the signal derived from 2-ethyl-1-hexanol in the mixture had disappeared. After continuing the polymerization reaction at 110 ° C. under nitrogen for 12 hours, after confirming the disappearance of the signal derived from ε-caprolactone and δ-valerolactone by 1 H-NMR, the molecular weight of the obtained compound by GPC method It measured. After confirming that the molecular weight of the compound reached the desired value, 0.35 g of 2,6-di-t-butyl-4-methylphenol was added to the mixture containing the compound. After that, 87.0 g of 2-methacryloyloxyethyl isocyanate was added dropwise over 30 minutes to the obtained mixture. Six hours after the completion of dropwise addition, after confirming by 1 H-NMR that the signal derived from 2-methacryloyloxyethyl isocyanate (MOI) has disappeared, 1387.0 g of PGMEA is added to the mixture, and the concentration is 50 mass %, Of 2770 g of a solution of macromonomer A-1 were obtained. The structure of macromonomer A-1 (shown in Formula (A-1)) was confirmed by 1 H-NMR. The weight average molecular weight of the obtained macromonomer A-1 was 6,000.
Figure JPOXMLDOC01-appb-C000044
　三口フラスコに、上記マクロモノマーＡ－１溶液の１２０ｇと、上記モノマー溶液１の２８０ｇと、ＰＧＭＥＡの２６６．７ｇとを添加して、混合物を得た。窒素を吹き込みながら、上記混合物を攪拌した。次に、窒素をフラスコ内に流しながら、混合物を７５℃まで昇温した。次に、混合物に、ドデシルメルカプタンの１．６５ｇと、２，２’－アゾビス（２－メチルプロピオン酸メチル）（以下「Ｖ－６０１」ともいう。）の０．８３ｇを添加し、重合反応を開始した。混合物を７５℃で２時間加熱した後、更にＶ－６０１の０．８３ｇを混合物に追加した。２時間後、更にＶ－６０１の０．８３ｇを混合物に追加した。更に２時間反応後、混合物を９０℃に昇温し、３時間攪拌した。上記操作により、重合反応を終了した。
　反応終了後、空気下でジメチルドデシルアミンの６．０ｇと、ＴＥＭＰＯの２．４６ｇを加えた後、メタクリル酸グリシジルの１５．７ｇを添加した。空気下、９０℃で２４時間反応を続けた後、酸価測定により反応終了を確認した。６０℃まで冷却した後、得られた混合物に更に２－イソシアナトエチルアクリラート（ＡＯＩ）の１５．６ｇを添加し、６０℃で６時間反応させた。１Ｈ－ＮＭＲ測定によりＡＯＩの消失を確認した。得られた混合物に適量のＰＧＭＥＡを加えることで分散剤Ｃ－５の２０質量％溶液を得た。得られた樹脂Ｃ－５の重量平均分子量は２５０００、酸価は８０ｍｇＫＯＨ／ｍｇ、Ｃ＝Ｃ価は０．９ｍｍｏｌ／ｇであった。また、樹脂Ｃ－５中に含まれるトルエン量を測定したところ５質量ｐｐｍ以下であることを確認した。 In a three-necked flask, 120 g of the macromonomer A-1 solution, 280 g of the monomer solution 1 and 266.7 g of PGMEA were added to obtain a mixture. The mixture was stirred while blowing with nitrogen. The mixture was then warmed to 75 ° C. while flowing nitrogen into the flask. Next, 1.65 g of dodecyl mercaptan and 0.83 g of methyl 2,2′-azobis (2-methylpropionate) (hereinafter also referred to as “V-601”) are added to the mixture, and a polymerization reaction is It started. After heating the mixture at 75 ° C. for 2 hours, another 0.83 g of V-601 was added to the mixture. After 2 hours, another 0.83 g of V-601 was added to the mixture. After further reacting for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. The polymerization reaction was completed by the above operation.
After completion of the reaction, 6.0 g of dimethyldodecylamine and 2.46 g of TEMPO were added under air, and then 15.7 g of glycidyl methacrylate was added. The reaction was continued at 90 ° C. for 24 hours under air, and the completion of the reaction was confirmed by acid value measurement. After cooling to 60 ° C., 15.6 g of 2-isocyanatoethyl acrylate (AOI) was further added to the obtained mixture and reacted at 60 ° C. for 6 hours. The disappearance of AOI was confirmed by 1 H-NMR measurement. An appropriate amount of PGMEA was added to the resulting mixture to obtain a 20% by mass solution of Dispersant C-5. The weight average molecular weight of the obtained resin C-5 was 25,000, the acid value was 80 mg KOH / mg, and the C = C value was 0.9 mmol / g. In addition, when the amount of toluene contained in the resin C-5 was measured, it was confirmed to be 5 mass ppm or less.
［試験例１］
＜顔料分散液の製造＞
　下記の表１に記載の原料を混合したのち、直径０．３ｍｍのジルコニアビーズ２３０質量部を加えて、ペイントシェーカーを用いて５時間分散処理を行い、ビーズをろ過で分離して顔料分散液を製造した。下記の表に記載の数値は質量部である。 [Test Example 1]
<Production of pigment dispersion>
After mixing the raw materials described in Table 1 below, 230 parts by mass of zirconia beads having a diameter of 0.3 mm are added, dispersion treatment is performed for 5 hours using a paint shaker, and the beads are separated by filtration to obtain a pigment dispersion Manufactured. The numerical values described in the following table are parts by mass.
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000045
＜組成物の調製＞
　下記の表２～５に記載の原料を混合して、実施例１～２５、比較例１～３の組成物を調製した。下記の表に記載の数値は質量部である。 <Preparation of composition>
The raw materials described in Tables 2 to 5 below were mixed to prepare compositions of Examples 1 to 25 and Comparative Examples 1 to 3. The numerical values described in the following table are parts by mass.
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
　上記表１～５に記載の原料は以下の通りである。 The raw materials described in Tables 1 to 5 above are as follows.
　（色材）
　金属アゾ顔料１～４：上述した金属アゾ顔料１～４
　ＰＲ２５４　：　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４
　ＰＹ１３９　：　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９
　ＰＶ２３　：　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３
　ＰＢ１５：６　：　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６
　ＰＢ１６　：　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１６
　ＩＢ：　Ｉｒｇａｐｈｏｒ　Ｂｌａｃｋ（ＢＡＳＦ社製）
　ＰＢｋ３２：　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌａｃｋ　３２ (Color material)
Metal azo pigments 1-4: the above-mentioned metal azo pigments 1-4
PR254: C. I. Pigment Red 254
PY 139: C.I. I. Pigment Yellow 139
PV23: C.I. I. Pigment Violet 23
PB 15: 6: C.I. I. Pigment Blue 15: 6
PB16: C.I. I. Pigment Blue 16
IB: Irgaphor Black (manufactured by BASF)
PBk 32: C. I. Pigment Black 32
（近赤外線吸収色素）
　Ｋ１、Ｋ２、Ｋ５、Ｋ６、Ｋ７、Ｋ８、Ｋ１０：下記構造の化合物。以下の式中、Ｍｅはメチル基を表し、Ｐｈはフェニル基を表す。
　Ｋ９：ＦＤＮ－００３（山田化学工業（株）製）
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
 (Near-infrared absorbing dye)
K1, K2, K5, K6, K7, K8, K10: compounds of the following structures. In the following formulas, Me represents a methyl group and Ph represents a phenyl group.
K9: FDN-003 (manufactured by Yamada Chemical Industry Co., Ltd.)
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
（顔料誘導体）
　Ｂ１、Ｋ３、Ｋ４：下記構造の化合物。以下の構造式中、Ｐｈはフェニル基を表し、Ｍｅはメチル基を表す。
Figure JPOXMLDOC01-appb-C000052
 (Pigment derivative)
B1, K3 and K4: compounds of the following structures. In the following structural formulae, Ph represents a phenyl group and Me represents a methyl group.
Figure JPOXMLDOC01-appb-C000052
（分散剤）
　Ｃ１：下記構造の樹脂（主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ＝２０，０００）
　Ｃ２：下記構造の樹脂（主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ＝２４，０００）
　Ｃ３：下記構造の樹脂（主鎖に付記した数値はモル比であり、側鎖に付記した数値は繰り返し単位の数である。Ｍｗ＝２０，０００）
　Ｃ４：ＢＹＫ２０００（固形分濃度４０質量％、ビックケミージャパン（株）製）
　Ｃ５：上述の製造例２で製造した分散剤Ｃ５（固形分濃度２０質量％）
Figure JPOXMLDOC01-appb-C000053
 (Dispersant)
C1: Resin of the following structure (the numerical value attached to the main chain is a molar ratio, the numerical value attached to the side chain is the number of repeating units, Mw = 20,000)
C2: Resin of the following structure (the numerical value attached to the main chain is a molar ratio, the numerical value attached to the side chain is the number of repeating units, Mw = 24,000)
C3: Resin of the following structure (the numerical value attached to the main chain is a molar ratio, the numerical value attached to the side chain is the number of repeating units, Mw = 20,000)
C4: BYK 2000 (solid content 40% by mass, manufactured by BIC Chemie Japan Ltd.)
C5: Dispersant C5 (solids concentration 20 mass%) produced in the above-mentioned Production Example 2
Figure JPOXMLDOC01-appb-C000053
（樹脂）
　Ｐ１：下記構造の樹脂（Ｍｗ＝１１０００、主鎖に付記した数値はモル比である。Ｍｅはメチル基である。）
　Ｐ２：下記構造の樹脂。（Ｍｗ＝４４００、酸価＝９５ｍｇＫＯＨ／ｇ、以下の構造式中、Ｍはフェニル基であり、Ａはビフェニルテトラカルボン酸無水物残基である。）
　Ｐ３：サイクロマーＡＣＡ２５０（固形分濃度４５質量％、（株）ダイセル製）
　Ｐ４：下記構造の樹脂（Ｍｗ＝３００００、主鎖に付記した数値はモル比である。）
Figure JPOXMLDOC01-appb-C000054
 (resin)
P1: Resin of the following structure (Mw = 11000, the numerical value attached to the main chain is a molar ratio. Me is a methyl group)
P2: Resin of the following structure. (Mw = 4400, acid value = 95 mg KOH / g, in the following structural formula, M is a phenyl group and A is a biphenyltetracarboxylic acid anhydride residue.)
P3: Cyclomer ACA 250 (solid content concentration 45% by mass, manufactured by Daicel Corporation)
P4: Resin of the following structure (Mw = 30,000, the numerical value attached to the main chain is a molar ratio)
Figure JPOXMLDOC01-appb-C000054
（重合性モノマー）
　Ｄ１：下記構造の化合物（ａ＋ｂ＋ｃ＝３）
　Ｄ２：下記構造の化合物（ａ＋ｂ＋ｃ＝４）
　Ｄ３：下記構造の化合物の混合物（ａ＋ｂ＋ｃ＝５の化合物：ａ＋ｂ＋ｃ＝６の化合物＝３：１（モル比））
Figure JPOXMLDOC01-appb-C000055
 　Ｄ４：下記構造の化合物
Figure JPOXMLDOC01-appb-C000056
 　Ｄ５：上記製造例１で製造した重合性モノマーＤ５（固形分濃度５０質量％）
　Ｄ６：アロニックスＭ－５２０（東亞合成（株）製） (Polymerizable monomer)
D1: Compound of the following structure (a + b + c = 3)
D2: Compound of the following structure (a + b + c = 4)
D3: Mixture of compounds of the following structure (compound of a + b + c = 5: compound of a + b + c = 6 = 3: 1 (molar ratio))
Figure JPOXMLDOC01-appb-C000055
 D4: Compound of the following structure
Figure JPOXMLDOC01-appb-C000056
 D5: The polymerizable monomer D5 produced in the above Production Example 1 (solid content concentration 50% by mass)
D6: Alonics M-520 (manufactured by Toagosei Co., Ltd.)
　（シランカップリング剤）
　Ｈ１：下記構造の化合物（以下の構造式中、Ｅｔはエチル基である）
Figure JPOXMLDOC01-appb-C000057
 (Silane coupling agent)
H1: compound of the following structure (in the following structural formula, Et is an ethyl group)
Figure JPOXMLDOC01-appb-C000057
（光重合開始剤）
　Ｉ１～Ｉ５：下記構造の化合物（オキシム化合物）
Figure JPOXMLDOC01-appb-C000058
 　Ｉ６：アデカアークルズＮＣＩ－８３１（（株）ＡＤＥＫＡ製、オキシム化合物）
　Ｉ７：ＩＲＧＡＣＵＲＥ－３７９（ＢＡＳＦ社製、α－アミノケトン化合物）
　Ｉ８：特表２０１７－５２３４６５号公報の段落番号０００７に記載された化合物ＮＯ．１２
　Ｉ９：特開２０１７－１５１３４２号公報の段落番号００２５に記載された式（２）の化合物
　Ｉ１０：特開２０１７－１６７３９９号公報の段落番号００３１に記載された化合物６
（紫外線吸収剤）
　Ｌ１：下記構造の化合物
Figure JPOXMLDOC01-appb-C000059
 (Photopolymerization initiator)
I1 to I5: compounds of the following structures (oxime compounds)
Figure JPOXMLDOC01-appb-C000058
 I6: Adeka ARKRUZ NCI-831 (manufactured by ADEKA CORPORATION, oxime compound)
I7: IRGACURE-379 (manufactured by BASF, α-amino ketone compound)
I8: Compound No. 1 described in paragraph No. 0007 of JP-A-2017-523465. 12
I9: Compound of the formula (2) described in Paragraph No. 0025 of JP-A-2017-151342 I10: Compound 6 described in Paragraph No. 0031 of JP-A-2017-167399
(UV absorber)
L1: compound of the following structure
Figure JPOXMLDOC01-appb-C000059
（多官能チオール）
　Ｍ１：トリメチロールプロパントリス（３－メルカプトブチレート） (Multifunctional thiol)
M1: trimethylolpropane tris (3-mercaptobutyrate)
（界面活性剤）
　Ｆ１：下記混合物（Ｍｗ＝１４０００）。下記の式中、繰り返し単位の割合を示す％はモル％である。
Figure JPOXMLDOC01-appb-C000060
 (Surfactant)
F1: The following mixture (Mw = 14000). In the following formulas,% indicating the proportion of repeating units is mol%.
Figure JPOXMLDOC01-appb-C000060
　（エポキシ化合物）
　Ｎ１：ＥＨＰＥ３１５０（（株）ダイセル製）
（重合禁止剤）
　Ｇ１：ｐ－メトキシフェノール
（溶剤）
　Ｊ１：プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）
　Ｊ２：シクロヘキサノン
　Ｊ３：３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド
　Ｊ４：３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド (Epoxy compound)
N1: EHPE 3150 (manufactured by Daicel Corporation)
(Polymerization inhibitor)
G1: p-methoxyphenol (solvent)
J1: Propylene glycol monomethyl ether acetate (PGMEA)
J2: cyclohexanone J3: 3-methoxy-N, N-dimethylpropanamide J4: 3-butoxy-N, N-dimethylpropanamide
＜分光特性の評価＞
　各組成物を、ガラス基板上にポストベーク後の膜厚が下記表に記載の膜厚になるようにスピンコーターを用いて塗布し、１００℃のホットプレートを用いて１２０秒間プリベークした。次いで、プリベーク後の塗布膜の全面に、ｉ線を１０００ｍＪ／ｃｍ２の露光量で照射して露光した後、ホットプレートを用いて２２０℃で５分間ポストベークを行って膜を形成した。
　分光光度計（Ｕ－４１００、（株）日立ハイテクノロジーズ製）を用いて、得られた膜の波長４００～１３００ｎｍの吸光度及び透過率を測定して、波長４００～６００ｎｍの範囲における透過率の最大値（透過率Ｔ１）、波長１０００～１３００ｎｍの範囲における透過率の最小値（透過率Ｔ２）、波長４００～６００ｎｍの範囲における吸光度の最小値（吸光度Ａ）、波長１０００～１３００ｎｍの範囲における吸光度の最大値（吸光度Ｂ）、波長４００～６００ｎｍの範囲における吸光度の最小値と波長１０００～１３００ｎｍの範囲における吸光度の最大値との比（吸光度Ａ／吸光度Ｂ）を測定した。 <Evaluation of spectral characteristics>
Each composition was applied on a glass substrate using a spin coater such that the film thickness after post-baking was the film thickness described in the following table, and prebaked for 120 seconds using a hot plate at 100 ° C. Next, the entire surface of the coated film after prebaking was irradiated with i-ray at an exposure dose of 1000 mJ / cm 2 for exposure, and then post-baked at 220 ° C. for 5 minutes using a hot plate to form a film.
Using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), the absorbance and the transmittance of the obtained film are measured at a wavelength of 400 to 1300 nm, and the maximum transmittance in the wavelength range of 400 to 600 nm Value (transmittance T1), minimum value of transmittance in the wavelength range of 1000 to 1300 nm (transmittance T2), minimum value of absorbance in the range of wavelength 400 to 600 nm (absorbance A), absorbance in the range of wavelength 1000 to 1300 nm The maximum value (absorbance B), the ratio of the minimum value of absorbance in the wavelength range of 400 to 600 nm to the maximum value of absorbance in the range of wavelength of 1000 to 1300 nm (absorbance A / absorbance B) was measured.
＜膜厚均一性＞
　各組成物を８インチ（２０．３２ｃｍ）のシリコンウエハ上にスピンコート法で塗布した。次いで、ホットプレートを用いて、１００℃で２分間加熱した。得られた膜を光学式膜厚計（フィルメトリクス（株）、Ｆ５０）を用い、膜厚を測定し、最も薄い部分の膜厚と最も厚い部分の膜厚の差（以下、膜厚差という）を算出した。膜厚差が小さいほど膜厚均一性が良好であるといえる。
　５：膜厚差が０．０２μｍ以下である。
　４：膜厚差が０．０２μｍより大きく０．０３μｍ以下である
　３：膜厚差が０．０３μｍより大きく０．０４μｍ以下である
　２：膜厚差が０．０４μｍより大きく０．０５μｍ以下である
　１：膜厚差が０．０５μｍより大きい <Film thickness uniformity>
Each composition was spin coated onto an 8 inch (20.32 cm) silicon wafer. Subsequently, it heated at 100 degreeC for 2 minutes using the hotplate. The film thickness is measured using an optical film thickness meter (Filmetrics, Inc., F50), and the difference between the film thickness of the thinnest portion and the film thickness of the thickest portion (hereinafter referred to as film thickness difference) ) Was calculated. It can be said that the film thickness uniformity is better as the film thickness difference is smaller.
5: The film thickness difference is 0.02 μm or less.
4: The film thickness difference is more than 0.02 μm and not more than 0.03 μm 3: The film thickness difference is more than 0.03 μm and not more than 0.04 μm 2: The film thickness difference is more than 0.04 μm and not more than 0.05 μm Certain 1: Film thickness difference is greater than 0.05 μm
＜耐湿性＞
　各組成物を、ガラス基板上にポストベーク後の膜厚が下記表に記載の膜厚になるようにスピンコーターを用いて塗布し、１００℃のホットプレートを用いて１２０秒間プリベークした。次いで、プリベーク後の塗布膜の全面に、ｉ線を１０００ｍＪ／ｃｍ２の露光量で照射して露光した後、ホットプレートを用いて２２０℃で５分間ポストベークを行って膜を形成した。得られた膜を、温度１３５℃、湿度８５％の条件下で３００時間保管して高温高湿試験を行った。高温高湿試験後の膜について、１ｃｍ四方の部分を光学顕微鏡で観察し、０．５μｍ以上のサイズの結晶状の欠陥の数をカウントして耐湿性を評価した。
　５：欠陥の数が０個
　４：欠陥の数が１～４個
　３：欠陥の数が５～９個
　２：欠陥の数が１０～１５個
　１：欠陥の数が１６個以上 Moisture resistance
Each composition was applied on a glass substrate using a spin coater such that the film thickness after post-baking was the film thickness described in the following table, and prebaked for 120 seconds using a hot plate at 100 ° C. Next, the entire surface of the coated film after prebaking was irradiated with i-ray at an exposure dose of 1000 mJ / cm 2 for exposure, and then post-baked at 220 ° C. for 5 minutes using a hot plate to form a film. The obtained film was stored for 300 hours under the conditions of a temperature of 135 ° C. and a humidity of 85% to conduct a high temperature and high humidity test. With respect to the film after the high temperature and high humidity test, a 1 cm square portion was observed with an optical microscope, and the number of crystalline defects with a size of 0.5 μm or more was counted to evaluate the moisture resistance.
5: Number of defects is 0: Number of defects is 1 to 4 3: Number of defects is 5 to 9 2: Number of defects is 10 to 15 1: Number of defects is 16 or more
Figure JPOXMLDOC01-appb-T000061
Figure JPOXMLDOC01-appb-T000061
　上記表に示すように、実施例は膜厚均一性および耐湿性に優れていた。また、実施例の組成物は、波長４００～６００ｎｍの範囲の光の遮光性に優れており、赤外線透過フィルタとして好ましく用いることができた。
　また、実施例１～４の組成物は、波長４００～６００ｎｍの範囲の光を遮光して、波長６５０ｎｍを超える光を透過可能な膜を形成できた。
　また、実施例５～１３の組成物は、波長４００～７２０ｎｍの範囲の光を遮光して、波長８００ｎｍを超える光を透過可能な膜を形成できた。
　また、実施例１４～２５の組成物は、波長４００～８３０ｎｍの範囲の光を遮光して、波長９００ｎｍを超える光を透過可能な膜を形成できた。 As shown in the above table, the examples were excellent in film thickness uniformity and moisture resistance. In addition, the compositions of the examples were excellent in the light shielding property of light in the wavelength range of 400 to 600 nm, and could be preferably used as an infrared ray transmission filter.
In addition, the compositions of Examples 1 to 4 blocked the light in the wavelength range of 400 to 600 nm and could form a film capable of transmitting light in excess of the wavelength of 650 nm.
In addition, the compositions of Examples 5 to 13 blocked the light in the wavelength range of 400 to 720 nm and could form a film capable of transmitting light in excess of the wavelength of 800 nm.
In addition, the compositions of Examples 14 to 25 could block light having a wavelength of 400 to 830 nm and form a film capable of transmitting light having a wavelength of more than 900 nm.
　各実施例において、更にベンゾピナコールを組成物の全固形分中に１質量％、２質量％、３質量％、４質量％または５質量％含有させた場合であっても、各実施例と同様の効果が得られる。 In each of the examples, even when benzopinacol is further contained in the total solid content of the composition in an amount of 1% by mass, 2% by mass, 3% by mass, 4% by mass or 5% by mass, the same as in each example The effect of
［試験例２］
　実施例１～２５の組成物をシリコンウエハ上にポストベーク後の膜厚がそれぞれ表６に記載の膜厚になるようにスピンコーターを用いて塗布し、１００℃のホットプレートを用いて１２０秒間プリベークした。次いで、プリベーク後の塗布膜の全面に、ｉ線を１０００ｍＪ／ｃｍ２の露光量で照射して露光した後、ホットプレートを用いて２２０℃で５分間ポストベークを行って膜を形成した。次に、得られた膜の表面に、以下の吸収層形成用組成物をスピンコーターを用いて塗布し、１００℃のホットプレートを用いて１２０秒間プリベークした。次いで、プリベーク後の塗布膜の全面に、ｉ線を１０００ｍＪ／ｃｍ２の露光量で照射して露光した後、ホットプレートを用いて２２０℃で５分間ポストベークを行って吸収層を形成して積層体を形成した。この積層体は、試験例１と同様の波長範囲の光を遮光および透過できた。更には、耐光性にも優れていた。 [Test Example 2]
The compositions of Examples 1 to 25 are coated on a silicon wafer using a spin coater so that the film thickness after post-baking becomes each of the film thicknesses described in Table 6, and a hot plate of 100 ° C. for 120 seconds Prebaked. Next, the entire surface of the coated film after prebaking was irradiated with i-ray at an exposure dose of 1000 mJ / cm 2 for exposure, and then post-baked at 220 ° C. for 5 minutes using a hot plate to form a film. Next, the following composition for formation of an absorption layer was applied to the surface of the obtained film using a spin coater, and prebaked for 120 seconds using a hot plate at 100 ° C. Next, the entire surface of the coating film after prebaking is exposed by irradiating i-rays at an exposure dose of 1000 mJ / cm 2 , and then post-baked at 220 ° C. for 5 minutes using a hot plate to form an absorption layer A laminate was formed. This laminate was able to block and transmit light in the same wavelength range as in Test Example 1. Furthermore, it was excellent also in light resistance.
（吸収層形成用組成物）
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１５０の１２質量部と、分散剤Ｃ５の３７質量部と、ＰＧＭＥＡの５１質量部とを、直径０．３ｍｍのジルコニアビーズ２３０質量部に加えて、ペイントシェーカーを用いて５時間分散処理を行い、ビーズをろ過で分離してＹｅｌｌｏｗ顔料分散液を製造した。
　得られたＹｅｌｌｏｗ顔料分散液の３５質量部と、樹脂Ｐ１の１２質量部と、重合性モノマーＤ５の４質量部と、光重合開始剤Ｉ１の１．８質量部と、ＰＧＭＥＡの４７．２質量部とを混合して吸収層形成用組成物を製造した。 (Composition for forming an absorption layer)
C. I. Add 12 parts by mass of Pigment Yellow 150, 37 parts by mass of dispersant C5, and 51 parts by mass of PGMEA to 230 parts by mass of zirconia beads with a diameter of 0.3 mm, and disperse for 5 hours using a paint shaker The beads were separated by filtration to produce a yellow pigment dispersion.
35 parts by mass of the obtained yellow pigment dispersion, 12 parts by mass of the resin P1, 4 parts by mass of the polymerizable monomer D5, 1.8 parts by mass of the photopolymerization initiator I1, and 47.2 parts of PGMEA Parts were mixed to produce an absorbent layer-forming composition.
［試験例３］
　ＩＲ組成物を、製膜後の膜厚が１．０μｍになるように、シリコンウエハ上にスピンコート法で塗布した。次いで、ホットプレートを用いて、１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置（ＦＰＡ－３０００ｉ５＋、Ｃａｎｏｎ（株）製）を用い、１０００ｍＪ／ｃｍ２の露光量にて、２μｍ四方のベイヤーパターンを有するマスクを介して露光した。
　次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、さらに純水にて水洗した。次いで、ホットプレートを用いて、２００℃で５分間加熱することで２μｍ四方のベイヤーパターン（近赤外線カットフィルタ）を形成した。
　次に、近赤外線カットフィルタのベイヤーパターン上に、Ｒｅｄ組成物を製膜後の膜厚が１．０μｍになるようにスピンコート法で塗布した。次いで、ホットプレートを用い、１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置（ＦＰＡ－３０００ｉ５＋、Ｃａｎｏｎ（株）製）を用い、１０００ｍＪ／ｃｍ２の露光量にて、２μｍ四方のパターンを有するマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、さらに純水にて水洗した。次いで、ホットプレートを用い、２００℃で５分間加熱することで、近赤外線カットフィルタのＢａｙｅｒパターン上にＲｅｄ組成物をパターニングした。同様にＧｒｅｅｎ組成物、Ｂｌｕｅ組成物を順次パターニングし、赤、緑および青の着色パターンを形成した。
　次に、上記パターン形成した膜上に、実施例１４～２５の組成物を、製膜後の膜厚が２．０μｍになるようにスピンコート法で塗布した。次いで、ホットプレートを用いて１００℃で２分間加熱した。次いで、ｉ線ステッパー露光装置（ＦＰＡ－３０００ｉ５＋、Ｃａｎｏｎ（株）製）を用い、１０００ｍＪ／ｃｍ２の露光量にて、２μｍ四方のパターンを有するマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム（ＴＭＡＨ）０．３質量％水溶液を用い、２３℃で６０秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、さらに純水にて水洗した。次いで、ホットプレートを用いて、２００℃で５分間加熱することで、近赤外線カットフィルタのＢａｙｅｒパターンの抜け部分に、実施例１４～２５の組成物の膜（赤外線透過フィルタ）を形成した。これを公知の方法に従い固体撮像素子に組み込んだ。
　得られた固体撮像素子について、低照度の環境下（０．００１Ｌｕｘ）で赤外発光ダイオード（赤外ＬＥＤ）光源から光を照射し、画像の取り込みを行い、画像性能を評価した。画像上で被写体をはっきりと認識できた。また、入射角依存性が良好であった。また、赤外線透過フィルタは、多層塗布で記載の膜厚を達成しても同様の効果が得られる。例えば実施例１４の場合、組成物をスピンコート法で塗布して塗布膜を形成し、次いで、塗布膜を１００℃で１２０秒加熱し、次いで、露光および現像を行い、次いで、２００℃で５分加熱する一連の操作を複数回繰り返して膜厚を２．０μｍに調整してもよい。 [Test Example 3]
The IR composition was applied by spin coating on a silicon wafer such that the film thickness after film formation was 1.0 μm. Subsequently, it heated at 100 degreeC for 2 minutes using the hotplate. Next, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Inc.), exposure was performed at a dose of 1000 mJ / cm 2 through a mask having a 2 μm square Bayer pattern.
Subsequently, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed by spin shower and was further rinsed with pure water. Next, a 2 μm square Bayer pattern (near infrared cut filter) was formed by heating at 200 ° C. for 5 minutes using a hot plate.
Next, on the Bayer pattern of the near infrared cut filter, the red composition was applied by spin coating so that the film thickness after film formation was 1.0 μm. Subsequently, it heated at 100 degreeC for 2 minutes using the hotplate. Next, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Inc.), exposure was performed at a dose of 1000 mJ / cm 2 through a mask having a 2 μm square pattern. Subsequently, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed by spin shower and was further rinsed with pure water. Next, the red composition was patterned on the Bayer pattern of the near-infrared cut filter by heating at 200 ° C. for 5 minutes using a hot plate. Similarly, the Green composition and the Blue composition were sequentially patterned to form colored patterns of red, green and blue.
Next, the compositions of Examples 14 to 25 were coated on the patterned film by spin coating so that the film thickness after film formation was 2.0 μm. Subsequently, it heated at 100 degreeC for 2 minutes using the hotplate. Next, using an i-line stepper exposure apparatus (FPA-3000i5 +, manufactured by Canon Inc.), exposure was performed at a dose of 1000 mJ / cm 2 through a mask having a 2 μm square pattern. Subsequently, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed by spin shower and was further rinsed with pure water. Next, by heating for 5 minutes at 200 ° C. using a hot plate, a film (infrared ray transmission filter) of the composition of Examples 14 to 25 was formed on the missing part of the Bayer pattern of the near infrared ray cut filter. This was incorporated into a solid-state imaging device according to a known method.
The obtained solid-state imaging device was irradiated with light from an infrared light emitting diode (infrared LED) light source under a low illuminance environment (0.001 Lux), an image was captured, and the image performance was evaluated. The subject was clearly recognized on the image. In addition, the incident angle dependency was good. In addition, the infrared transmission filter can achieve the same effect even if the film thickness is achieved by multilayer coating. For example, in the case of Example 14, the composition is applied by spin coating to form a coated film, and then the coated film is heated at 100 ° C. for 120 seconds, then exposed and developed, and then at 200 ° C. The film thickness may be adjusted to 2.0 μm by repeating a series of operations of heating for a plurality of times.
　試験例３で使用したＲｅｄ組成物、Ｇｒｅｅｎ組成物、Ｂｌｕｅ組成物およびＩＲ組成物は以下の通りである。 The Red composition, Green composition, Blue composition and IR composition used in Test Example 3 are as follows.
（Ｒｅｄ組成物）
　下記成分を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、Ｒｅｄ組成物を調製した。
　Ｒｅｄ顔料分散液　　・・５１．７質量部
　樹脂Ｐ１　　・・・０．６質量部
　重合性モノマーＤ６　　・・・０．６質量部
　光重合開始剤Ｉ１　　・・・０．４質量部
　界面活性剤Ｆ１　　・・・０．２質量部
　紫外線吸収剤（ＵＶ－５０３、大東化学（株）製）　　・・・０．３質量部
　ＰＧＭＥＡ　　・・・４６．６質量部 (Red composition)
The following components were mixed and stirred, and then filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a red composition.
Red pigment dispersion liquid: 51.7 parts by mass Resin P1: 0.6 parts by mass Polymerizable monomer D6: 0.6 parts by mass Photopolymerization initiator I1: 0.4 parts by mass Surfactant F1 ... 0.2 parts by mass UV absorber (UV-503, manufactured by Daito Chemical Industries, Ltd.) ... 0.3 parts by mass PGMEA ... 46.6 parts by mass
（Ｇｒｅｅｎ組成物）
　下記成分を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、Ｇｒｅｅｎ組成物を調製した。
　Ｇｒｅｅｎ顔料分散液　　・・・７３．７質量部
　樹脂Ｐ１　　・・・０．３質量部
　重合性モノマーＤ６　　・・・１．２質量部
　光重合開始剤Ｉ１　　・・・０．６質量部
　界面活性剤Ｆ１　　・・・０．２質量部
　紫外線吸収剤（ＵＶ－５０３、大東化学（株）製）　　・・・０．５質量部
　ＰＧＭＥＡ　　・・・２３．５質量部 (Green composition)
The following components were mixed and stirred, followed by filtration using a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a Green composition.
Green pigment dispersion ... 73.7 parts by mass Resin P1 ... 0.3 parts by mass Polymerizable monomer D6 ... 1.2 parts by mass Photopolymerization initiator I1 ... 0.6 parts by mass Surfactant F1 ··· 0.2 parts by mass Ultraviolet absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ··· 0.5 parts by mass PGMEA · · 23.5 parts by mass
（Ｂｌｕｅ組成物）
　下記成分を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、Ｂｌｕｅ組成物を調製した。
　Ｂｌｕｅ顔料分散液　　４４．９質量部
　樹脂Ｐ１　　・・・２．１質量部
　重合性モノマーＤ６　　・・・２．２質量部
　光重合開始剤Ｉ１　　・・・０．８質量部
　界面活性剤Ｆ１　　・・・０．２質量部
　紫外線吸収剤（ＵＶ－５０３、大東化学（株）製）　　・・・０．３質量部
　ＰＧＭＥＡ　　・・・４９．８質量部 (Blue composition)
The following components were mixed and stirred, and then filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a Blue composition.
Blue pigment dispersion 44.9 parts by mass Resin P1: 2.1 parts by mass Polymerizable monomer D6: 2.2 parts by mass Photopolymerization initiator I1: 0.8 parts by mass Surfactant F1: -0.2 parts by mass UV absorber (UV-503, manufactured by Daito Kagaku Co., Ltd.) ... 0.3 parts by mass PGMEA ... 49.8 parts by mass
（ＩＲ組成物）
　下記成分を混合し、撹拌した後、孔径０．４５μｍのナイロン製フィルタ（日本ポール（株）製）でろ過して、ＩＲ組成物を調製した。
　ＩＲ顔料分散液　　・・・８５質量部
　重合性モノマーＤ６　　・・・１．８質量部
　樹脂Ｐ１　　・・・１．１質量部
　光重合開始剤Ｉ１　　・・・０．９質量部
　界面活性剤F１　　・・・０．２質量部
　重合禁止剤（ｐ－メトキシフェノール）　　・・・０．００１質量部
　ＰＧＭＥＡ　　・・・１１．０質量部 (IR composition)
The following components were mixed and stirred, and then filtered through a nylon filter (made by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare an IR composition.
IR pigment dispersion liquid: 85 parts by mass Polymerizable monomer D6: 1.8 parts by mass Resin P1: 1.1 parts by mass Photopolymerization initiator I1: 0.9 parts by mass Surfactant F1 .. 0.2 parts by mass polymerization inhibitor (p-methoxyphenol)... 0.001 parts by mass PGMEA. 11.0 parts by mass
　Ｒｅｄ組成物、Ｇｒｅｅｎ組成物、Ｂｌｕｅ組成物およびＩＲ組成物に使用した顔料分散液は以下の通りである。 The pigment dispersions used for the Red composition, the Green composition, the Blue composition and the IR composition are as follows.
・Ｒｅｄ顔料分散液
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４の９．６質量部と、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３９の４．３質量部と、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ＢＹＫＣｈｅｍｉｅ社製）の６．８質量部と、ＰＧＭＥＡの７９．３質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合および分散した。その後さらに、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、Ｒｅｄ顔料分散液を得た。 Red pigment dispersion C.I. I. Pigment Red 254, 9.6 parts by mass, C.I. I. A mixed solution of 4.3 parts by mass of Pigment Yellow 139, 6.8 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA was used as a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours according to 3 mm diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a red pigment dispersion.
・Ｇｒｅｅｎ顔料分散液
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　３６の６．４質量部と、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１５０の５．３質量部と、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ＢＹＫＣｈｅｍｉｅ社製）の５．２質量部と、ＰＧＭＥＡの８３．１質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合および分散した。その後さらに、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、Ｇｒｅｅｎ顔料分散液を得た。 Green pigment dispersion C. I. Pigment Green 36, 6.4 parts by mass, C.I. I. A mixed solution of 5.3 parts by mass of Pigment Yellow 150, 5.2 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA was added to a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours according to 3 mm diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a green pigment dispersion.
・Ｂｌｕｅ顔料分散液
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６の９．７質量部と、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３の２．４質量部と、分散剤（Ｄｉｓｐｅｒｂｙｋ－１６１、ＢＹＫＣｈｅｍｉｅ社製）の５．５質量部と、ＰＧＭＥＡの８２．４質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合および分散した。その後さらに、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、Ｂｌｕｅ顔料分散液を得た。 Blue pigment dispersion C.I. I. Pigment Blue 15: 6, 9.7 parts by mass, C.I. I. A mixed solution consisting of 2.4 parts by mass of Pigment Violet 23, 5.5 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by mass of PGMEA is a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours according to 3 mm diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a blue pigment dispersion.
・ＩＲ顔料分散液
　近赤外線吸収色素Ｋ２の６．２５質量部と、顔料誘導体Ｋ４の１．２５質量部と、分散剤Ｃ３の６質量部と、ＰＧＭＥＡの８６．５質量部とからなる混合液を、ビーズミル（ジルコニアビーズ０．３ｍｍ径）により３時間混合および分散した。その後さらに、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、ＩＲ顔料分散液を得た。 -IR pigment dispersion liquid mixed liquid consisting of 6.25 parts by mass of near infrared absorbing dye K2, 1.25 parts by mass of pigment derivative K4, 6 parts by mass of dispersant C3, and 86.5 parts by mass of PGMEA Were mixed and dispersed for 3 hours with a bead mill (zirconia beads 0.3 mm in diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain an IR pigment dispersion.
１１０：固体撮像素子、１１１：近赤外線カットフィルタ、１１２：カラーフィルタ、１１４：赤外線透過フィルタ、１１５：マイクロレンズ、１１６：平坦化層
 

  110: solid-state imaging device, 111: near infrared cut filter, 112: color filter, 114: infrared transmission filter, 115: microlens, 116: flattening layer

Claims (14)

  1. 　下記式（Ｉ）で表されるアゾ化合物およびその互変異性構造のアゾ化合物から選ばれる少なくとも１種のアニオンと、２種以上の金属イオンと、メラミン化合物とを含む金属アゾ顔料と、
    　前記金属アゾ顔料以外の色材であって、波長４００～７００ｎｍの範囲に吸収極大を有する色材と、
    　エチレン性不飽和結合基を有する化合物、および、環状エーテル基を有する化合物から選ばれる少なくとも１種の化合物と、を含む組成物であり、
    　前記組成物の波長４００～６００ｎｍの範囲における吸光度の最小値Ａと、波長１０００～１３００ｎｍの範囲における吸光度の最大値Ｂとの比であるＡ／Ｂが４．５以上である、組成物；
    Figure JPOXMLDOC01-appb-C000001
     　式中、Ｒ１およびＲ２はそれぞれ独立して、ＯＨまたはＮＲ５Ｒ６であり、
    　Ｒ３およびＲ４はそれぞれ独立して、＝Ｏまたは＝ＮＲ７であり、
    　Ｒ５～Ｒ７はそれぞれ独立して、水素原子またはアルキル基である。     A metal azo pigment comprising at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomeric structure, two or more metal ions, and a melamine compound;
    A coloring material other than the metal azo pigment and having an absorption maximum in a wavelength range of 400 to 700 nm;
    A composition comprising a compound having an ethylenically unsaturated bonding group, and at least one compound selected from a compound having a cyclic ether group,
    A composition wherein A / B, which is a ratio of the minimum value A of the absorbance in the wavelength range of 400 to 600 nm to the maximum value B of the absorbance in the range of wavelength 1000 to 1300 nm, is 4.5 or more;
    Figure JPOXMLDOC01-appb-C000001
     In the formula, R 1 and R 2 are each independently OH or NR 5 R 6 ,
    R 3 and R 4 are each independently = O or NRNR 7 ,
    R 5 to R 7 are each independently a hydrogen atom or an alkyl group.
  2. 　前記金属アゾ顔料は、前記アニオンと、Ｚｎ２＋およびＣｕ２＋を少なくとも含む金属イオンと、前記メラミン化合物とを含む、請求項１に記載の組成物。 The composition according to claim 1, wherein the metal azo pigment comprises the anion, a metal ion containing at least Zn 2+ and Cu 2+ , and the melamine compound.
  3. 　前記金属アゾ顔料中の全金属イオンの１モルを基準として、Ｚｎ２＋およびＣｕ２＋を合計で９５～１００モル％含有する、請求項２に記載の組成物。 The composition according to claim 2, which comprises a total of 95 to 100 mol% of Zn 2+ and Cu 2+ based on 1 mol of total metal ions in the metal azo pigment.
  4. 　前記金属アゾ顔料中のＺｎ２＋とＣｕ２＋とのモル比が、Ｚｎ２＋：Ｃｕ２＋＝１９９：１～１：１５である、請求項２または３に記載の組成物。 The composition according to claim 2 or 3, wherein the molar ratio of Zn 2+ to Cu 2+ in the metal azo pigment is Zn 2+ : Cu 2+ = 199: 1 to 1:15.
  5. 　前記金属アゾ顔料における前記メラミン化合物が、下記式（ＩＩ）で表される化合物である、請求項１～４のいずれか１項に記載の組成物；
    Figure JPOXMLDOC01-appb-C000002
     　式中Ｒ１１～Ｒ１３は、それぞれ独立して水素原子またはアルキル基である。     The composition according to any one of claims 1 to 4, wherein the melamine compound in the metal azo pigment is a compound represented by the following formula (II);
    Figure JPOXMLDOC01-appb-C000002
     In the formula, R 11 to R 13 each independently represent a hydrogen atom or an alkyl group.
  6. 　前記波長４００～７００ｎｍの範囲に吸収極大を有する色材は、青色着色剤および紫色着色剤から選ばれる少なくとも１種を含む、請求項１～５のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 5, wherein the colorant having an absorption maximum in the wavelength range of 400 to 700 nm comprises at least one selected from a blue colorant and a violet colorant.
  7. 　更に、近赤外線吸収色素を含む、請求項１～６のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 6, further comprising a near infrared absorbing dye.
  8. 　前記近赤外線吸収色素は波長８００～９００ｎｍの範囲に吸収極大を有する、請求項７に記載の組成物。 The composition according to claim 7, wherein the near infrared absorbing dye has an absorption maximum in the wavelength range of 800 to 900 nm.
  9. 　前記近赤外線吸収色素はピロロピロール化合物、シアニン化合物、スクアリリウム化合物、フタロシアニン化合物、ナフタロシアニン化合物、および、クロコニウム化合物から選ばれる少なくとも１種である、請求項７または８に記載の組成物。 The composition according to claim 7 or 8, wherein the near infrared absorbing dye is at least one selected from pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, and croconium compounds.
  10. 　赤外線透過フィルタ用である、請求項１～９のいずれか１項に組成物。 The composition according to any one of claims 1 to 9, which is for an infrared transmission filter.
  11. 　請求項１～１０のいずれか１項に記載の組成物を用いて得られる膜。 A film obtained using the composition according to any one of claims 1 to 10.
  12. 　請求項１１に記載の膜を有する赤外線透過フィルタ。 The infrared rays permeable filter which has a film | membrane of Claim 11.
  13. 　請求項１１に記載の膜を有する固体撮像素子。 A solid-state imaging device comprising the film according to claim 11.
  14. 　請求項１１に記載の膜を有する光センサ。
     

          An optical sensor comprising the film according to claim 11.


PCT/JP2018/039289 2017-11-29 2018-10-23 Composition, film, infrared transmission filter, solid state imaging device, and optical sensor WO2019107015A1 (en)

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