WO2017099019A1 - 感放射線性樹脂組成物、硬化膜、パターン形成方法、固体撮像素子および画像表示装置 - Google Patents
感放射線性樹脂組成物、硬化膜、パターン形成方法、固体撮像素子および画像表示装置 Download PDFInfo
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- WO2017099019A1 WO2017099019A1 PCT/JP2016/085914 JP2016085914W WO2017099019A1 WO 2017099019 A1 WO2017099019 A1 WO 2017099019A1 JP 2016085914 W JP2016085914 W JP 2016085914W WO 2017099019 A1 WO2017099019 A1 WO 2017099019A1
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- the present invention relates to a radiation-sensitive resin composition, a cured film, a pattern forming method, a solid-state imaging device, and an image display device.
- a cured film is produced using a radiation-sensitive resin composition containing a resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and an organic solvent.
- Patent Document 1 discloses a compound (A) having an ethylenically unsaturated double bond, a pigment (B), a pigment dispersant (C), a photopolymerization initiator (D), and water solubility.
- a coloring composition comprising a solvent (E) containing more than 7.0% by weight of the solvent (S) at 25% by weight or more of the total solvent weight, wherein the water content of the coloring composition is the total weight of the coloring composition
- An invention relating to a coloring composition having a reference of 0.3 to 2.0% by weight is described.
- Paragraph 0007 of the same document describes that the coloring composition described in the document has a high sensitivity and a high development speed because it contains an appropriate amount of water.
- Patent Document 2 describes an invention relating to a colored composition containing a triarylmethane dye, a solvent, and a resin, wherein the water content of the colored composition is 1060 ppm to 11000 ppm. Yes. According to paragraph 0007 of the same document, it is described that the luminance and heat resistance of a pixel can be improved by adjusting the water content to the above-described range.
- Patent Document 3 describes an invention relating to a colored composition containing at least an alkali-soluble resin, an organic solvent-soluble dye, a photosensitive compound, and a solvent and having a water content of 1.0% by mass or less. Yes. In paragraph 0012 of the same document, it is described that, by setting the water content in the coloring composition within the above-mentioned range, peeling of a micropattern after development and occurrence of a biting shape between the pattern and the substrate can be suppressed. .
- the radiation-sensitive resin composition may be used to produce a cured film using the prepared composition, or to be used after storing the prepared radiation-sensitive resin composition for a long period of time. . According to the study by the present inventors, it has been found that when the radiation-sensitive resin composition is stored for a long period of time, the sensitivity may increase or decrease compared to immediately after production.
- the pattern size may vary when exposure is performed under the same conditions to produce a pattern. For this reason, when there is a variation in sensitivity, it may be time-consuming to set exposure conditions according to the radiation-sensitive resin composition to be used. Moreover, since the exposure amount at the time of pattern formation will increase when the sensitivity of a radiation sensitive resin composition is low, time may be required for pattern formation and a running cost may be increased.
- an object of the present invention is to provide a radiation-sensitive resin composition, a cured film, a pattern formation method, a solid-state imaging device, and an image display device that have good sensitivity and excellent sensitivity over time. .
- the present inventors have found that the above object can be achieved by using a radiation-sensitive resin composition described later, and have completed the present invention. That is, the present invention is as follows.
- a radiation-sensitive resin composition containing a resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, an organic solvent, and water,
- the photopolymerization initiator includes an oxime ester compound having at least one group selected from a branched alkyl group and a cyclic alkyl group,
- a radiation sensitive resin composition having a water content of 0.1 to 2% by mass relative to the mass of the radiation sensitive resin composition.
- ⁇ 2> The radiation-sensitive resin composition according to ⁇ 1>, wherein the resin includes an alkali-soluble resin.
- the polymerizable compound is a polyfunctional (meth) acrylate compound having an ethylenically unsaturated bond equivalent of 3.0 to 12.0 mmol / g. object.
- ⁇ 4> The oxime ester compound according to any one of ⁇ 1> to ⁇ 3>, wherein the oxime ester compound has at least one group selected from a branched alkyl group having 7 or more carbon atoms and a cyclic alkyl group having 7 or more carbon atoms. Radiation sensitive resin composition.
- ⁇ 5> The radiation-sensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the oxime ester compound has a carbazole structure.
- ⁇ 6> The radiation-sensitive resin composition according to ⁇ 5>, wherein the carbazole structure has a structure in which a ring is further condensed to a benzene ring of a carbazole part.
- ⁇ 7> The radiation-sensitive resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the oxime ester compound is an oxime ester compound containing a fluorine atom.
- oxime ester compound is a compound represented by the formula (1);
- Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent, and R 1 to R 3 each independently represents an alkyl group or an aryl group.
- R 1 to R 3 is a branched alkyl group or a cyclic alkyl group
- Ar 1 and Ar 2 is a branched alkyl group or a cyclic alkyl group
- Organic solvents are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, butyl acetate, ethyl-3-ethoxypropionate, propylene glycol monoethyl ether acetate, xylene, ethylbenzene, methyl isobutyl ketone, 2-butanol
- the radiation-sensitive resin composition according to any one of ⁇ 1> to ⁇ 8>, which is at least one selected from dipropylene glycol monomethyl ether.
- ⁇ 10> The radiation-sensitive resin composition according to any one of ⁇ 1> to ⁇ 9>, further comprising at least one selected from a chromatic colorant and inorganic particles.
- ⁇ 11> The radiation-sensitive resin composition according to any one of ⁇ 1> to ⁇ 10>, further comprising a phthalimide compound.
- ⁇ 12> The radiation-sensitive resin composition according to any one of ⁇ 1> to ⁇ 11>, further comprising an ultraviolet absorber.
- ⁇ 13> The radiation-sensitive resin composition according to any one of ⁇ 1> to ⁇ 12>, further comprising a thermosetting compound.
- the compound other than the oxime ester compound is at least one selected from an oxime ester compound having no branched alkyl group and a cyclic alkyl group, an alkylphenone compound, and an acylphosphine compound, according to ⁇ 14>.
- Radiation sensitive resin composition. ⁇ 16> A cured film using the radiation-sensitive resin composition according to any one of ⁇ 1> to ⁇ 15>.
- ⁇ 17> The cured film according to ⁇ 16>, wherein the transmittance of light having a wavelength of 365 nm is 15% or less.
- a step of forming a radiation-sensitive resin composition layer on a support using the radiation-sensitive resin composition according to any one of ⁇ 1> to ⁇ 15>, and a radiation-sensitive resin composition layer A pattern forming method including a step of exposing in a pattern and a step of developing and removing an unexposed portion to form a pattern.
- a solid-state imaging device having the cured film according to ⁇ 16> or ⁇ 17>.
- ⁇ 20> An image display device having the cured film according to ⁇ 16> or ⁇ 17>.
- the notation which does not describe substitution and unsubstituted includes group (atomic group) which has a substituent with group (atomic group) which does not have a substituent.
- 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).
- light means actinic rays or radiation.
- Actinic light or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
- exposure is not limited to exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, X-rays, EUV light, etc., but also particle beams such as electron beams and ion beams. Include drawing in exposure.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the total solid content refers to the total mass of components obtained by removing the solvent from all components of the composition.
- “(meth) acrylate” represents both and / or acrylate and methacrylate
- “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”.
- Allyl represents both and / or allyl and methallyl
- “(meth) acryloyl” represents both and / or acryloyl and methacryloyl.
- the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
- a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by a gel permeation chromatography (GPC) measurement.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column.
- 0.0 mm ID (inner diameter) ⁇ 15.0 cm) can be obtained by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
- the radiation sensitive resin composition of the present invention is a radiation sensitive resin composition comprising a resin, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, an organic solvent, and water,
- the polymerization initiator includes an oxime ester compound having at least one group selected from a branched alkyl group and a cyclic alkyl group, and the water content is 0.1 to 2 with respect to the mass of the radiation-sensitive resin composition. % By mass.
- the radiation-sensitive resin composition is also referred to as a resin composition.
- the sensitivity is good and the sensitivity is stable over time. That is, when the resin composition of the present invention contains 0.1 to 2% by mass of water, the sensitivity is good, and further, the sensitivity over time can be suppressed from increasing or decreasing. If the water content is equal to or higher than the lower limit value described above, the sensitivity is good. In addition, when the water content is equal to or less than the above-described upper limit value, the sensitivity stability over time is good. On the other hand, when water is contained in the radiation-sensitive resin composition, the initial sensitivity is good, but the sensitivity over time tends to decrease. The reason is presumed that the photopolymerization initiator is decomposed by water.
- water content shall be 2 mass% or less, and at least chosen from a branched alkyl group and a cyclic alkyl group as a photoinitiator. It has been found that a decrease in sensitivity can be suppressed by using an oxime ester compound having one type of group (hereinafter also referred to as oxime ester compound A).
- oxime ester compound A is less susceptible to water decomposition because the nucleophilic attack of water on the oxime ester moiety is inhibited by at least one group selected from a branched alkyl group and a cyclic alkyl group I guess.
- the sensitivity is good, and the increase or decrease in sensitivity over time is achieved. It is presumed that a suppressed resin composition with excellent sensitivity over time could be obtained.
- the resin composition of the present invention has a water content of 0.1 to 2.0% by mass.
- the lower limit is preferably 0.11% by mass or more, and more preferably 0.12% by mass or more.
- the upper limit is preferably 1.7% by mass or less, and more preferably 1.5% by mass or less.
- the resin composition of the present invention preferably contains 20 to 7000 parts by mass of water with respect to 100 parts by mass of the oxime ester compound having at least one group selected from a branched alkyl group and a cyclic alkyl group. More preferably, it contains 25 to 1500 parts by mass of water, and more preferably 30 to 1000 parts by mass of water.
- the resin composition of the present invention preferably contains 4 to 500 parts by mass of water, more preferably 5 to 450 parts by mass of water with respect to 100 parts by mass of the photopolymerization initiator. More preferably, the content is 10 to 300 parts by mass.
- the water content in the resin composition is a value measured by the Karl Fischer method.
- the Karl Fischer method uses a Karl Fischer reagent (comprising a solvent such as iodine, sulfur dioxide, base, and alcohol) that selectively and quantitatively reacts with water to determine the water content in the composition. It is a method of measuring. This method includes a coulometric titration method and a volumetric titration method, but either method may be used.
- the transmittance at a wavelength of 365 nm of the film is preferably 15% or less, more preferably 10% or less, 7% or less is more preferable.
- Resin compositions used for the production of a film having such a spectrum tend to have low sensitivity because of low i-line transmittance.
- the resin composition of the present invention is particularly suitable for the production of a resin composition for producing a film having a low transmittance at a wavelength of 365 nm because excellent sensitivity can be obtained by adopting the above-described configuration.
- the resin composition of the present invention is particularly suitable as a resin composition for i-line exposure.
- the resin composition of the present invention contains a polymerizable compound having an ethylenically unsaturated bond.
- the polymerizable compound having an ethylenically unsaturated bond include compounds having a group having an ethylenically unsaturated bond.
- the group having an ethylenically unsaturated bond include a vinyl group, a styryl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.
- the polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more, and even more preferably three or more.
- the upper limit is preferably 15 or less, and more preferably 6 or less.
- the ethylenically unsaturated bond equivalent of the polymerizable compound is preferably 3.0 to 12.0 mmol / g.
- the ethylenically unsaturated bond equivalent (double bond equivalent) is defined by the valence of the ethylenically unsaturated bond relative to the molecular weight of the compound.
- the polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a multimer thereof. Monomers are preferred.
- the molecular weight of the polymerizable compound is preferably 100 to 3000.
- the upper limit is preferably 2000 or less, and more preferably 1500 or less.
- the lower limit is preferably 150 or more, and more preferably 250 or more.
- the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
- the polymerizable compound is preferably a polyfunctional (meth) acrylate compound having an ethylenically unsaturated bond equivalent of 3.0 to 12.0 mmol / g.
- polymerizable compound examples include paragraph numbers 0095 to 0108 in JP2009-288705A, paragraph number 0227 in JP2013-29760A, and paragraph numbers 0254 to 0257 in JP2008-292970A. And the contents of which are incorporated herein.
- Polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.) , Dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are bonded via ethylene glycol and propylene glycol residues (for example, commercially available from Sar
- oligomer types can also be used.
- KAYARAD RP-1040 and DPCA-20 can also be used.
- NK ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.
- Shin-Nakamura Chemical Co., Ltd. can also be used.
- the polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
- an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
- examples of commercially available products include M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. Aronix TO-2349 (Toagosei Co., Ltd.) can also be used.
- the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
- the polymerizable compound is also preferably a compound having a caprolactone structure.
- examples of the polymerizable compound having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.
- a polymerizable compound having an alkyleneoxy group can also be used.
- the polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 3 to 4 having 4 to 20 ethyleneoxy groups.
- a hexafunctional (meth) acrylate compound is more preferable.
- Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, and six pentyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy groups.
- the following compounds can also be used as the polymerizable compound.
- Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Is also preferable.
- urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
- the content of the polymerizable compound is preferably 0.1 to 50% by mass with respect to the total solid content of the resin composition.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less.
- One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.
- the resin composition of the present invention contains a photopolymerization initiator.
- the photopolymerization initiator includes an oxime ester compound (oxime ester compound A) having at least one group selected from a branched alkyl group and a cyclic alkyl group.
- (Oxime ester compound A) 3 or more are preferable, as for carbon number of the branched alkyl group which the oxime ester compound A has, 5 or more are more preferable, and 7 or more are further more preferable.
- the upper limit is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
- the upper limit is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
- the oxime ester compound A preferably has a carbazole structure. According to this aspect, it is easy to obtain a resin composition excellent in sensitivity. Furthermore, the sensitivity over time is also good.
- the carbazole structure preferably has a structure in which a ring is further condensed to the benzene ring of the carbazole part.
- the benzene ring in the carbazole part preferably has an aromatic ring condensed, more preferably a benzene ring condensed to form a naphthalene ring. Examples of such a structure include the following structures, and (CB-1) is preferable.
- R represents a hydrogen atom or a substituent.
- the oxime ester compound A is preferably an oxime ester compound containing a fluorine atom. According to this aspect, it is easy to obtain a resin composition excellent in sensitivity. Furthermore, the sensitivity over time is also good.
- the oxime ester compound containing a fluorine atom preferably has a group containing a fluorine atom.
- the group containing a fluorine atom is preferably an alkyl group having a fluorine atom (hereinafter also referred to as a fluorine-containing alkyl group) and / or a group containing an alkyl group having a fluorine atom (hereinafter also referred to as a fluorine-containing group).
- fluorine-containing group examples include —OR X11 , —SR X11 , —COR X11 , —COOR X11 , —OCOR X11 , —NR X11 R X12 , —NHCOR X11 , —CONR X11 R X12 , —NHCONR X11 R X12 , —NHCOOR At least one group selected from X11 , —SO 2 R X11 , —SO 2 OR X11 and —NHSO 2 R X11 is preferred.
- R X11 represents a fluorine-containing alkyl group
- R X12 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group, or a heterocyclic group.
- the fluorine-containing group is more preferably —OR X11 .
- the alkyl group and fluorine-containing alkyl group preferably have 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4.
- the alkyl group and the fluorine-containing alkyl group may be linear, branched or cyclic, but are preferably linear or branched.
- the fluorine-containing alkyl group preferably has a fluorine atom substitution rate of 40 to 100%, more preferably 50 to 100%, and still more preferably 60 to 100%.
- the substitution rate of a fluorine atom means the ratio (%) of the number substituted by the fluorine atom among the number of all the hydrogen atoms which an alkyl group has.
- the carbon number of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
- the aryl group may be a single ring or a condensed ring.
- the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
- the heterocyclic group may be a single ring or a condensed ring.
- the number of condensation is preferably 2 to 8, more preferably 2 to 6, still more preferably 3 to 5, and particularly preferably 3 to 4.
- the number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and more preferably 3 to 20.
- the number of heteroatoms constituting the heterocyclic group is preferably 1 to 3.
- the hetero atom constituting the heterocyclic group is preferably a nitrogen atom, oxygen atom or sulfur atom, more preferably a nitrogen atom.
- the group containing a fluorine atom is preferably a fluorine-containing alkyl group and / or —OR X11 .
- the group containing a fluorine atom preferably has a terminal structure represented by the formula (1) or (2). * In the formula represents a connecting hand. * -CHF 2 (1) * -CF 3 (2)
- the total number of fluorine atoms in the compound is preferably 3 or more, more preferably 4 to 10.
- the oxime ester compound is preferably a compound represented by the formula (1).
- Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent
- R 1 to R 3 each independently represents an alkyl group or an aryl group.
- at least one of R 1 to R 3 is a branched alkyl group or a cyclic alkyl group, or at least one of R 1 to R 3 , Ar 1 and Ar 2 is a branched alkyl group or a cyclic alkyl group
- Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring that may have a substituent.
- the aromatic hydrocarbon ring may be a single ring or a condensed ring.
- the number of carbon atoms constituting the ring of the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10.
- the aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring.
- Ar 1 and Ar 2 is a benzene ring and the other is a naphthalene ring.
- Ar 1 is more preferably a benzene ring.
- Ar 2 is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring.
- Ar 1 and Ar 2 may have, an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, —OR X1 , —SR X1 , —COR X1 , —COOR X1 , —OCOR X1 , —NR X1 R X2 , —NHCOR X1 , —CONR X1 R X2 , —NHCONR X1 R X2 , —NHCOOR X1 , —SO 2 R X1 , —SO 2 OR X1 , —NHSO 2 R X1, etc. Can be mentioned.
- R X1 and R X2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
- the number of carbon atoms of the alkyl group as a substituent and the alkyl group represented by R X1 and R X2 is preferably 1-30.
- the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
- part or all of the hydrogen atoms may be substituted with a halogen atom (preferably a fluorine atom).
- part or all of the hydrogen atoms may be substituted with the above substituents.
- the number of carbon atoms of the aryl group as a substituent and the aryl group represented by R X1 and R X2 is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
- the aryl group may be a single ring or a condensed ring.
- part or all of the hydrogen atoms may be substituted with the above substituents.
- the heterocyclic group as a substituent and the heterocyclic group represented by R X1 and R X2 are preferably 5-membered or 6-membered rings.
- the heterocyclic group may be a single ring or a condensed ring.
- the number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and more preferably 3 to 12.
- the number of heteroatoms constituting the heterocyclic group is preferably 1 to 3.
- the hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In the heterocyclic group, part or all of the hydrogen atoms may be substituted with the above substituents.
- the aromatic hydrocarbon ring represented by Ar 1 is preferably unsubstituted.
- the aromatic hydrocarbon ring represented by Ar 2 may be unsubstituted or may have a substituent. It preferably has a substituent.
- —COR X1 is preferable.
- R X1 is preferably an alkyl group, an aryl group or a heterocyclic group, more preferably an aryl group.
- the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.
- R 1 to R 3 each independently represents an alkyl group or an aryl group.
- R 1 is preferably an alkyl group or an aryl group.
- R 2 and R 3 are preferably each independently an alkyl group.
- the alkyl group preferably has 1 to 30 carbon atoms.
- the alkyl group may be linear, branched or cyclic.
- the alkyl group may be unsubstituted or may have a substituent.
- the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- the aryl group may be a single ring or a condensed ring. Further, it may be unsubstituted or may have a substituent.
- R 1 to R 3 is a branched alkyl group or a cyclic alkyl group, or at least one of R 1 to R 3 , Ar 1 and Ar 2 is a branched alkyl group or a cyclic group.
- the branched alkyl group preferably has 3 or more carbon atoms, more preferably 5 or more, and still more preferably 7 or more.
- the upper limit is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
- the number of carbon atoms in the cyclic alkyl group is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more.
- R 3 is preferably a branched alkyl group or a cyclic alkyl group, and R 3 is more preferably a branched alkyl group.
- R 1 is also preferably an aryl group having a group containing a fluorine atom.
- the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- the aryl group may be a single ring or a condensed ring.
- Examples of the group containing a fluorine atom include the above-described alkyl group having a fluorine atom (fluorine-containing alkyl group) and a group containing an alkyl group having a fluorine atom (fluorine-containing group). The preferable range is also the same.
- the fluorine-containing alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
- the fluorine-containing alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
- the fluorine-containing alkyl group preferably has a fluorine atom substitution rate of 40 to 100%, more preferably 50 to 100%, and still more preferably 60 to 100%.
- the oxime ester compound A is preferably a compound having a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably a compound having an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably those having high absorbance at 365 nm and 405 nm.
- the molar extinction coefficient of the oxime ester compound A at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, from the viewpoint of sensitivity. Particularly preferred is 200,000.
- a known method can be used. For example, in a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure.
- oxime ester compound A examples include the following compounds.
- the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, more preferably 0.5% to 30% by mass, based on the total solid content of the resin composition.
- the content is preferably 1 to 20% by mass.
- a photoinitiator contains 0.01 mass% or more of oxime ester compounds A, and it is more preferable that 0.02 mass% or more is included.
- the upper limit may be 100% by mass or less, and may be 10% by mass or less.
- the content of the oxime ester compound A is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass with respect to the total solid content of the resin composition.
- the content is preferably 1 to 20% by mass. By setting it as this range, it can be set as the resin composition which was excellent in the sensitivity and excellent in the temporal stability of the sensitivity.
- the resin composition of the present invention may contain only one type of oxime ester compound A or two or more types. When two or more types are included, the total amount is preferably within the above range.
- the resin composition of the present invention can contain a photopolymerization initiator (another photopolymerization initiator) other than the oxime ester compound described above, and preferably further contains another photopolymerization initiator. By further containing another photopolymerization initiator, it is easy to produce a cured film having good sensitivity and adhesion.
- photopolymerization initiators include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds (for example, acylphosphine oxide, etc.), hexaarylbiphenyls.
- halogenated hydrocarbon derivatives for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.
- acylphosphine compounds for example, acylphosphine oxide, etc.
- hexaarylbiphenyls examples include imidazole, oxime compounds (for example, oxime ester compounds having no branched alkyl group and cyclic alkyl group), organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenones.
- trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds (preferably branched alkyl groups and cyclic alkyl groups) Oxime ester compound having no group), triarylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyloxadiazole compound, 3 -At least one compound selected from aryl-substituted coumarin compounds is preferred, oxime ester compounds having no branched alkyl group and no cyclic alkyl group, Particularly preferred are at least one compound selected from a kiluphenone compound and an acylphosphine compound.
- hydroxyacetophenone compounds As other photopolymerization initiators, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
- hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a light source of 365 nm or 405 nm can also be used.
- acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
- photopolymerization initiators are preferably oxime compounds.
- oxime compounds include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
- oxime compounds examples include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A Nos. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
- IRGACURE-OXE01 manufactured by BASF
- IRGACURE-OXE02 manufactured by BASF
- TRONLY TR-PBG-304 TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arcles 30 (Made by ADEKA) can also be used.
- IRGACURE-OXE01 and IRGACURE-OXE02 are preferable.
- 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 the carbazole ring, and those described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety
- compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye site ketoxime compounds described in International Publication No. WO2009 / 131189, and triazine skeleton and oxime skeleton are the same A compound described in US Pat. No.
- the oxime compound is preferably a compound represented by the following formula (OX-1).
- the oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
- R and B each independently represent a monovalent substituent
- A represents a divalent organic group
- Ar represents an aryl group.
- the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
- the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
- these groups may have one or more substituents.
- the substituent mentioned above may be further substituted by another substituent.
- the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
- the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- an oxime compound having a fluorene ring can be used as another photopolymerization initiator.
- Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A No. 2014-137466. This content is incorporated herein.
- an oxime compound having a fluorine atom can be used as another photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom include a compound described in JP2010-262028A, a compound (C-3) described in JP2013-164471A, and the like. These contents are incorporated herein.
- an oxime compound having a nitro group can be used as another photopolymerization initiator.
- oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, ADEKA Acruz NCI-831 (made by ADEKA) is mentioned.
- oxime compounds that are 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 a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably a compound having an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably a compound having high absorbance at 365 nm and 405 nm.
- the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200,000 from the viewpoint of sensitivity. 000 is particularly preferred.
- a known method can be used. Specifically, for example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is used and an ethyl acetate solvent is used. It is preferable to measure at a concentration of 0.01 g / L. You may use a photoinitiator in combination of 2 or more type as needed.
- the content of the other photopolymerization initiator is preferably 100 to 1300 parts by mass, more preferably 330 to 1000 parts by mass with respect to 100 parts by mass of the oxime ester compound A.
- the content of the other photopolymerization initiator is within the above range, effects such as sensitivity adjustment and improved adhesion and rectangular pattern can be obtained.
- it can also be set as the composition which does not contain other photoinitiators substantially. “Containing substantially no other photopolymerization initiator” means that the content of the other photopolymerization initiator is preferably 1% by mass or less, more preferably 0.1% by mass or less, based on the mass of the total photopolymerization initiator. Is more preferable, and it is still more preferable not to contain.
- the resin composition of the present invention preferably contains a thermosetting compound.
- a thermosetting compound By containing a thermosetting compound, the effect of improving the curability of the film after post-baking and improving various resistances such as solvent resistance can be expected.
- the thermosetting compound means a compound that is cured by heating.
- thermosetting compound for example, a compound having a thermosetting functional group can be used.
- the thermosetting compound may be a low molecular compound (for example, a molecular weight of less than 1000) or a high molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more). Either is acceptable.
- the thermosetting compound is preferably a polymer compound, more preferably a compound having a molecular weight (weight average molecular weight) of 1,000 to 100,000.
- thermosetting compound examples include an epoxy group-containing compound (epoxy compound), an oxetanyl group-containing compound (oxetanyl compound), a methylol group-containing compound (methylol compound), and an alkoxymethyl group-containing compound (alkoxymethyl compound). And a compound having an oxetanyl group (block isocyanate compound).
- the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
- the number of epoxy groups is preferably 2 to 100 per molecule.
- the upper limit may be 10 or less, and may be 5 or less.
- the epoxy compound may be a low molecular compound (for example, a molecular weight of less than 1000) or a high molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more).
- the epoxy compound is preferably an epoxy resin.
- the weight average molecular weight of the epoxy resin is preferably 1000 to 10,000.
- the lower limit is preferably 1500 or more, and more preferably 2000 or more.
- the upper limit is preferably 9000 or less, and more preferably 8000 or less.
- the epoxy resin is preferably a compound having substantially no molecular weight distribution.
- substantially having no molecular weight distribution means that the dispersity of the compound (weight average molecular weight (Mw) / number average molecular weight (Mn)) is 1.0 to 1.5. Is preferable, and 1.0 to 1.3 is more preferable.
- the epoxy compound is preferably a compound having an aromatic ring and / or an aliphatic ring, and more preferably a compound having an aliphatic ring.
- the epoxy group is preferably bonded to the aromatic ring and / or the aliphatic ring via a single bond or a linking group.
- the linking group include an alkylene group, an arylene group, —O—, —NR ′ — (R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. And a group containing at least one selected from —SO 2 —, —CO—, —O—, and —S—.
- the epoxy group is preferably directly bonded (single bond) to the aliphatic ring.
- the epoxy group is preferably bonded to the aromatic ring via a linking group.
- the linking group is preferably an alkylene group or a group comprising a combination of an alkylene group and —O—.
- the epoxy group compound a compound having a structure in which two or more aromatic rings are connected by a hydrocarbon group may be used.
- the hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. It is preferable that the epoxy group is connected via the connecting group.
- examples of the epoxy compound include compounds represented by the following formula (EP1).
- R EP1 to R EP3 each represent a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure, and may have a substituent. Also good. R EP1 and R EP2 and R EP2 and R EP3 may be bonded to each other to form a ring structure.
- QEP represents a single bond or an nEP- valent organic group.
- R EP1 ⁇ R EP3 combines with Q EP may form a ring structure.
- nEP represents an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 6. However, n EP is 2 when Q EP is a single bond.
- R EP1 to R EP3 and Q EP can be referred to the descriptions in paragraph numbers 0087 to 0088 of Japanese Patent Application Laid-Open No. 2014-089408, the contents of which are incorporated herein.
- Specific examples of the compound represented by the formula (EP1) include a compound described in paragraph 0090 of JP-A-2014-089408, the contents of which are incorporated herein.
- epoxy compound bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin, or the like can be used.
- Epoxy compounds are described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraphs 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A. Compounds can also be used. These contents are incorporated herein. A commercially available product may be used as the epoxy compound.
- jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1051, EPICLON1051, EPICLON1051 As mentioned above, DIC Corporation) etc. are mentioned.
- Examples of the bisphenol F type epoxy resin include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, made by DIC Corporation), LCE-21, RE-602S. (Nippon Kayaku Co., Ltd.) and the like.
- phenol novolac type epoxy resins jER152, jER154, jER157S70, jER157S65 (Mitsubishi Chemical Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation), etc. Is mentioned.
- Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), and the like.
- Aliphatic epoxy resins include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), and the like.
- ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation), JER1031S (manufactured by Mitsubishi Chemical Corporation), and the like.
- the oxetanyl compound is preferably a compound having two or more oxetanyl groups in one molecule.
- the number of oxetanyl groups is preferably 2 to 100 per molecule.
- the upper limit may be 10 or less, and may be 5 or less.
- the compound having two or more oxetanyl groups in one molecule include Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, manufactured by Toagosei Co., Ltd.), ETERNACOLL (registered trademark) OXMA, ETERNACOLL (registered trademark) OXBP (manufactured by Ube Industries, Ltd.) can be used.
- alkoxymethyl compounds, methylol compounds examples include compounds in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom or a carbon atom that forms an aromatic ring.
- Compounds having an alkoxymethyl group or a methylol group bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxymethyl Urea urea, methylolated urea and the like are preferable.
- the descriptions in paragraphs 0134 to 0147 of JP-A-2004-295116 and paragraphs 0095 to 0126 of JP-A-2014-089408 can be referred to, and the contents thereof are incorporated in this specification.
- Preferable structures of the compound in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include compounds represented by the following formulas (8-1) to (8-4).
- Examples of the compound in which an alkoxymethyl group or a methylol group is bonded to a carbon atom forming an aromatic ring include those represented by the following general formulas (4) and (5).
- X represents a single bond or a monovalent to tetravalent organic group
- R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group
- n is an integer of 1 to 4.
- p and q are each independently an integer of 0 to 4.
- two Y's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and may contain an oxygen atom or a fluorine atom
- R 13 to R 16 are each independently a hydrogen atom.
- m and n are each independently an integer of 1 to 3
- p and q are each independently an integer of 0 to 4.
- Examples of commercially available products of alkoxymethyl compounds and methylol compounds include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174. , UFR65, 300 (Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -032, -706, -708, -40, -31, -270, -280, -290, -750LM, Nicarak MS- 11, Nicalac MW-30HM, -100LM, -390 (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.
- Block isocyanate compound Although there is no restriction
- the blocked isocyanate group in this invention is a group which can produce
- the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
- the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 to 260 ° C.
- the skeleton of the blocked isocyanate compound is not particularly limited, and may be an aliphatic, alicyclic or aromatic polyisocyanate.
- the description in paragraph 0144 of JP2014-238438A can be referred to, and the contents thereof are incorporated in the present specification.
- Examples of the matrix structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
- Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide compound. Can do.
- a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
- description in paragraph 0146 of JP2014-238438A can be referred to, and the contents thereof are incorporated in the present specification.
- the blocked isocyanate compound is available as a commercial product.
- Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Death Module BL1100, BL1265 MPA / X , BL3575 / 1, BL3272MPA,
- the content of the thermosetting compound is preferably 0 to 10% by mass with respect to the total solid content of the resin composition of the present invention.
- the lower limit is preferably 1% by mass or more.
- the upper limit is preferably 5% by mass or less, and more preferably 3% by mass or less.
- the resin composition of this invention can also be set as the composition which does not contain a thermosetting compound substantially.
- the phrase “not containing a thermosetting compound substantially” means that, for example, the content of the thermosetting compound is preferably 1% by mass or less based on the total solid content of the resin composition of the present invention. 0.5 mass% or less is more preferable, 0.1 mass% or less is more preferable, and it is still more preferable not to contain.
- the resin composition of the present invention contains a resin.
- the resin is blended, for example, for the purpose of dispersing the pigment in the composition or the purpose of the binder.
- the resin mainly used for dispersing the pigment in the composition is also referred to as a dispersant.
- the resin is a material different from the radical polymerizable compound and the thermosetting compound.
- the weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000.
- the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
- the lower limit is preferably 3,000 or more, and more preferably 5,000 or more.
- the resin content is preferably 1 to 90% by mass of the total solid content of the resin composition.
- the lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.
- the upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.
- the resin composition of the present invention may contain only one type of resin or two or more types of resins. When two or more types are included, the total amount is preferably within the above range.
- the resin composition of the present invention preferably contains an alkali-soluble resin as the resin. By containing an alkali-soluble resin, developability and pattern formability are improved.
- the alkali-soluble resin can also be used as a dispersant or a binder.
- the alkali-soluble resin is a material different from the radical polymerizable compound and the thermosetting compound.
- the molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably 5000 to 100,000.
- the number average molecular weight (Mn) is preferably 1000 to 20,000.
- the alkali-soluble resin may be a linear organic polymer, and has at least one alkali-soluble polymer in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having groups to promote.
- the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance.
- Acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.
- Examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and a carboxyl group is preferable. Only one type of acid group may be used, or two or more types may be used.
- a known radical polymerization method can be applied.
- Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and experimental conditions It is also possible to determine.
- the alkali-soluble resin a polymer having a carboxyl group in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, and a partial esterification are used.
- examples include maleic acid copolymers, alkali-soluble phenol resins such as novolak resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers having a hydroxyl group added with an acid anhydride.
- a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
- examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
- 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,
- vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfury
- N-substituted maleimide monomers described in JP-A-10-300922 can also be used. Examples thereof include N-phenylmaleimide and N-cyclohexylmaleimide. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.
- Alkali-soluble resins include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate / Multi-component copolymers composed of (meth) acrylic acid / other monomers can be preferably used.
- an alkali-soluble resin having a polymerizable group may be used as the alkali-soluble resin.
- the polymerizable group include a (meth) allyl group and a (meth) acryloyl group.
- the alkali-soluble resin having a polymerizable group an alkali-soluble resin having a polymerizable group in the side chain is useful.
- the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer.
- Diamond Shamrock Co., Ltd. Biscote R-264, KS resist 106 (any) Also manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (both manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Corporation), Acryl RD-F8 (Japan) Catalyst).
- Cyclomer P series for example, ACA230AA
- Plaxel CF200 series both manufactured by Daicel Corporation
- Ebecryl 3800 manufactured by Daicel UCB Corporation
- Acryl RD-F8 Japan Catalyst
- the alkali-soluble resin is a monomer containing a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). It is also preferable to include a polymer obtained by polymerizing the components.
- R 1 and R 2 each independently represents 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 2010-168539 A can be referred to.
- ether dimer for example, paragraph 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used. The structure derived from the ether dimer may be copolymerized with other monomers.
- the alkali-soluble resin may contain a structural 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 represents a hydrogen atom or a benzene ring that may contain a benzene ring.
- n represents an integer of 1 to 15.
- the alkylene group of R 2 preferably has 2 to 3 carbon atoms.
- the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R 3 may contain a benzene ring.
- Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
- alkali-soluble resin examples include the following resins.
- the acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g.
- the lower limit is more preferably 50 mgKOH / g or more, and still more preferably 70 mgKOH / g or more.
- the upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and still more preferably 120 mgKOH / g or less.
- the content of the alkali-soluble resin is preferably 1 to 90% by mass with respect to the total solid content of the resin composition.
- the lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.
- the upper limit is preferably 70% by mass or less, and more preferably 60% by mass or less.
- the resin composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
- the resin composition of the present invention can contain a dispersant as a resin.
- the dispersant include polymer dispersants [for example, resins having amine groups (polyamideamine and salts thereof), oligoimine resins, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, Modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate] and the like.
- the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
- a resin having an acid value of 60 mgKOH / g or more (more preferably, an acid value of 60 mgKOH / g or more and 300 mgKOH / g or less) can also be suitably exemplified.
- Examples of the terminal-modified polymer include a polymer having a phosphate group at the end described in JP-A-3-112992 and JP-T-2003-533455, and JP-A-2002-273191. Examples thereof include a polymer having a sulfonic acid group at the terminal and a polymer having a partial skeleton of organic dye or a heterocyclic ring described in JP-A-9-77994. In addition, polymers having two or more pigment surface anchor sites (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) introduced at the polymer ends described in JP-A-2007-277514 are also available. It is preferable because of excellent dispersion stability.
- graft polymer examples include reaction products of poly (lower alkyleneimine) and polyester described in JP-A-54-37082, JP-A-8-507960, JP-A-2009-258668, and the like. Copolymers of polyallylamine and polyester reaction products described in JP-A-9-169821, etc., macromonomers described in JP-A-10-339949, JP-A-2004-37986, etc., and monomers containing nitrogen atoms Polymers, graft type polymers having a partial skeleton of organic dye or a heterocyclic ring described in JP-A No.
- block polymers As the block polymer, block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.
- a graft copolymer containing a repeating unit represented by any one of the following formulas (1) to (4) can also be used.
- W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH
- X 1 , X 2 , X 3 , X 4 , and X 5 each independently represents a hydrogen atom or a monovalent organic group
- Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group
- Z 1 , Z 2 , Z 3 , and Z 4 each independently represents a monovalent organic group
- R 3 represents an alkylene group
- R 4 represents a hydrogen atom or a monovalent organic group
- n, m, p, and q each independently represents 1 to Represents an integer of 500
- j and k each independently represent an integer of 2 to 8
- a plurality of R 3 may be the same or different from each other.
- may, in the formula (4), when q is 2 ⁇ 500, X 5 and R 4 existing in plural numbers may be different
- W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
- X 1 , X 2 , X 3 , X 4 , and X 5 are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably each independently a hydrogen atom or a methyl group, A methyl group is particularly preferred.
- Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
- the structure of the monovalent organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 is not particularly limited.
- an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group examples thereof include an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group.
- the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms.
- a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable.
- the alkyl group contained in the alkoxy group may be linear, branched or cyclic.
- n, m, p, and q are each independently an integer of 1 to 500.
- j and k each independently represent an integer of 2 to 8.
- J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
- R 3 represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms.
- p is 2 to 500, a plurality of R 3 may be the same or different.
- R 4 represents a hydrogen atom or a monovalent organic group.
- the monovalent organic group is not particularly limited in terms of structure.
- R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group.
- R 4 is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferable, and 1 to 20 carbon atoms is preferable.
- linear alkyl groups having 1 to 6 carbon atoms are particularly preferable.
- q is 2 to 500
- a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
- an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain can be used.
- the oligoimine-based dispersant has a repeating unit having a partial structure X having a functional group of pKa14 or less and a side chain containing a side chain Y having 40 to 10,000 atoms, and has a main chain and a side chain.
- a resin having at least one basic nitrogen atom is preferred.
- the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
- oligoimine-based dispersant the description in paragraphs 0102 to 0174 of JP 2012-255128 A can be referred to, and the above contents are incorporated in this specification.
- resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.
- the dispersant is also available as a commercial product.
- examples of such a dispersant include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110, 111 (containing an acid group) manufactured by BYK Chemie.
- Copolymer 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ", manufactured by EFKA “EFKA 4047, 4050-4165 (polyurethane), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester) ), 6745 (phthalocyanine derivatives) , 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co., Ltd.,“ Floren TG-710 (urethane oligomer), Polyflow No.
- dispersants may be used alone or in combination of two or more.
- the alkali-soluble resin described above can also be used.
- Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain.
- the acid cellulose derivative include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable.
- An alkali-soluble resin containing is also preferred.
- the content of the dispersing agent is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, and still more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the pigment.
- the resin composition of the present invention may contain a pigment derivative.
- the pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group.
- a pigment derivative having an acidic group or a basic group is preferable from the viewpoint of dispersibility and dispersion stability of the pigment.
- Organic pigments for constituting the pigment derivative include pyrrolopyrrole pigment, diketopyrrolopyrrole pigment, quinacridone pigment, anthraquinone pigment, dianthraquinone pigment, benzoisoindole pigment, thiazineindigo pigment, azo pigment, quinophthalone pigment, phthalocyanine pigment , Naphthalocyanine pigments, dioxazine pigments, perylene pigments, perinone pigments, benzimidazolone pigments, benzothiazole pigments, benzimidazole pigments and benzoxazole pigments.
- a sulfonic acid group a carboxylic acid group, and its salt
- a carboxylic acid group and a sulfonic acid group are more preferable
- a sulfonic acid group is especially preferable.
- the basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
- the description in paragraphs 0111 to 0175 of JP-A-2015-063593 can be referred to, the contents of which are incorporated herein.
- the content of the pigment derivative is preferably 1 to 30% by mass, and more preferably 3 to 20% by mass with respect to the mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
- the resin composition of the present invention can contain a chromatic colorant.
- the chromatic colorant means a colorant other than the white colorant and the black colorant.
- the chromatic colorant is preferably a colorant having an absorption maximum in a wavelength range of 400 nm or more and less than 650 nm.
- the chromatic colorant may be a pigment or a dye.
- the pigment preferably has an average particle diameter (r) of preferably 20 nm ⁇ r ⁇ 300 nm, more preferably 25 nm ⁇ r ⁇ 250 nm, and particularly preferably 30 nm ⁇ r ⁇ 200 nm.
- the “average particle size” here means the average particle size of secondary particles in which primary particles of the pigment are aggregated.
- the particle size distribution of the secondary particles of the pigment that can be used (hereinafter also simply referred to as “particle size distribution”) is such that the secondary particles falling into (average particle size ⁇ 100) nm are 70% by mass or more of the whole, Preferably it is 80 mass% or more.
- the particle size distribution of the secondary particles can be measured using the scattering intensity distribution.
- TEM transmission electron microscope
- the pigment is preferably an organic pigment, and examples thereof include the following. However, the present invention is not limited to these. 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, 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
- 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, 22
- Specific examples include the compounds described in WO2015 / 118720. Further, as the yellow colorant, quinophthalone compounds described in paragraphs 0011 to 0034 of JP2013-54339A, quinophthalone compounds described in paragraphs 0013 to 0058 of JP2014-26228A, and the like can also be used. Moreover, the aluminum phthalocyanine compound which has a phosphorus atom can also be used as a blue pigment. Specific examples include compounds described in paragraphs 0022 to 0030 of JP2012-247491A and paragraph 0047 of JP2011-157478A. These organic pigments can be used alone or in various combinations.
- the organic pigment is preferably at least one selected from a green pigment and a yellow pigment, and more preferably a combination of a green pigment and a yellow pigment.
- the green pigment is C.I. I. Pigment Green 7, 36, 58, 59 is preferred.
- the above-described zinc halide phthalocyanine pigment is also preferable.
- the yellow pigment is C.I. I.
- at least one selected from Pigment Yellow 139, 150, and 185 is used.
- the quinophthalone pigment described above is also preferable.
- the dye is not particularly limited, and a known dye can be used.
- Chemical structures include pyrazole azo, anilino azo, triaryl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene, phthalocyanine, benzopyran, indigo, and pyromethene dyes can be used.
- a thiazole compound described in JP2012-158649A, an azo compound described in JP2011-184493A, and an azo compound described in JP2011-145540A can also be preferably used.
- an acid dye and / or a derivative thereof may be suitably used.
- direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.
- acid dye examples include the following dyes and derivatives of these dyes.
- acid alizarin violet N acid blue 1,7,9,15,18,23,25,27,29,40-45,62,70,74,80,83,86,87,90,92,103,112,113,120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1, acid chroma violet K, acid Fuchsin; acid green 1,3,5,9,16,25,27,50, acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95, acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150,
- azo, xanthene and phthalocyanine acid dyes are also preferred.
- I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.
- the dye triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo
- a colorant selected from anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone pyromethene is preferable.
- the chromatic colorant may be a dye multimer.
- the dye multimer is preferably a dye used by being dissolved in a solvent. However, the dye multimer may form particles, and when the dye multimer is particles, the dye multimer is usually dispersed in a solvent. Used.
- the particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples thereof include compounds and production methods described in JP-A-2015-214682.
- the dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but can be 100 or less.
- the dye structures in one molecule may be the same dye structure or different dye structures. In the present invention, different dye structures include not only dye structures having different dye skeletons but also dye structures having the same dye skeleton and different types of substituents bonded to the dye skeleton. And
- the weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50000.
- the lower limit is more preferably 3000 or more, and further preferably 6000 or more.
- the upper limit is more preferably 30000 or less, and still more preferably 20000 or less.
- the dye structure possessed by the dye multimer may be a structure derived from a dye compound having absorption in the visible region (preferably in the wavelength range of 400 to 700 nm, more preferably in the range of 400 to 650 nm). It may be a structure derived from a dye compound having an absorption at (preferably a compound having a maximum absorption wavelength in the range of 700 to 1200 nm).
- triarylmethane dye structure for example, triarylmethane dye structure, xanthene dye structure, anthraquinone dye structure, cyanine dye structure, squarylium dye structure, quinophthalone dye structure, phthalocyanine dye structure, subphthalocyanine dye structure, azo dye structure, pyrazolotriazole dye structure, dipyrromethene dye structure , Isoindoline dye structure, thiazole dye structure, benzimidazolone dye structure, perinone dye structure, pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, diimonium dye structure, naphthalocyanine dye structure, rylene dye structure, dibenzofuranone dye structure , Merocyanine dye structure, croconium dye structure, oxonol dye structure, and the like.
- a dye structure derived from the thiazole compound described in JP2012-158649A, a dye structure derived from the azo compound described in JP2011-184493A, and the azo compound described in JP2011-145540A can also be preferably used.
- the dye multimer comprises at least one of the repeating unit represented by the formula (A), the repeating unit represented by the formula (B), and the repeating unit represented by the formula (C), Or it is preferable to represent with a formula (D).
- X 1 represents the main chain of the repeating unit
- L 1 represents a single bond or a divalent linking group
- D 1 represents a dye structure.
- X 2 represents the main chain of the repeating unit
- L 2 represents a single bond or a divalent linking group
- D 2 represents a dye structure having a group capable of ionic bonding or coordination bonding with Y 2.
- Y 2 represents a group capable of ionic bonding or coordination bonding with D 2 .
- L 3 represents a single bond or a divalent linking group
- D 3 represents a dye structure
- m represents 0 or 1.
- L 4 represents an (n + k) -valent linking group
- L 41 and L 42 each independently represent a single bond or a divalent linking group
- D 4 represents a dye structure
- P 4 represents a substituent
- n represents 2 to 15
- k represents 0 to 13
- n + k represents 2 to 15.
- the plurality of D 4 may be different from each other or the same.
- the plurality of P 4 may be different from each other or the same.
- Examples of the (n + k) -valent linking group represented by L 4 include the linking groups described in paragraph Nos. 0071 to 0072 of JP2008-222950A and the linkage described in paragraph No. 0176 of JP2013-029760A.
- Examples of the substituent represented by P 4 include an acid group and a curable group.
- Examples of the curable group include a radical polymerizable group such as a group having an ethylenically unsaturated bond, an epoxy group, an oxazoline group, and a methylol group.
- Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- Examples of the acid group include a carboxyl group, a sulfonic acid group and a phosphoric acid group.
- the substituent represented by P 4 may be a monovalent polymer chain having a repeating unit.
- the monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound.
- the dye structure represented by D 4 may be a structure in which one or more arbitrary atoms of the dye compound are removed, and a part of the dye compound may be bonded to L 4 . Further, it may be a polymer chain containing a repeating unit having a dye structure (a structure in which one or more arbitrary atoms of the dye compound are removed) in the main chain or the side chain.
- the polymer chain is not particularly defined as long as it contains a dye structure, but is one kind selected from (meth) acrylic resins, styrene resins, and (meth) acrylic / styrene resins.
- the repeating unit of the polymer chain is not particularly defined, and examples thereof include a repeating unit represented by the formula (A) and a repeating unit represented by the formula (C).
- the total number of repeating units having a dye structure in all repeating units constituting the polymer chain is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and further preferably 20 to 40 mol%. preferable.
- n and k in one pigment multimer (D) are integers, in the present invention, the pigment multimer may include a plurality of compounds having different n and k in formula (D). Good. Therefore, the average value of n and k in Compound A may not be an integer.
- the dye multimer represented by the formula (D) preferably has a structure represented by the formula (D-1).
- L 4 represents an (n + k) -valent linking group.
- n represents 2 to 15, and k represents 0 to 13.
- D 4 represents a dye structure
- P 4 represents a substituent.
- B 41 and B 42 are each independently a single bond, —O—, —S—, —CO—, —NR—, —O 2 C—, —CO 2 —, —NROC—, or —CONR—.
- R represents a hydrogen atom, an alkyl group or an aryl group.
- C 41 and C 42 each independently represents a single bond or a divalent linking group.
- S represents a sulfur atom.
- n is 2 or more, the plurality of D 4 may be different from each other or the same.
- k is 2 or more, the plurality of P 4 may be different from each other or the same.
- n + k represents 2-15.
- L 4, D 4 and P 4 of formula (D-1) has the same meaning as L 4, D 4 and P 4 of the formula (D).
- B 41 and B 42 in the formula (D-1) are each independently a single bond, —O—, —S—, —CO—, —NR—, —O 2 C—, —CO 2 —, —NROC. —
- —CONR— represents a single bond, —O—, —CO—, —O 2 C—, —CO 2 —, —NROC— or —CONR—, preferably a single bond, —O— , —CO—, —O 2 C— or —CO 2 — is more preferred.
- R represents a hydrogen atom, an alkyl group or an aryl group.
- C 41 and C 42 in the formula (D-1) each independently represent a single bond or a divalent linking group.
- the divalent linking group is preferably an alkylene group, an arylene group, or a group obtained by combining these.
- the alkylene group preferably has 1 to 30 carbon atoms, and more preferably 1 to 10 carbon atoms.
- the alkylene group may be linear, branched or cyclic.
- the number of carbon atoms in the arylene group is preferably 6 to 30, and more preferably 6 to 12.
- dye multimer compounds described in JP2011-213925A, JP2013-041097A, JP2015-028144A, JP2015-030742A, and the like can also be used.
- the content of the chromatic colorant is preferably 0 to 70% by mass with respect to the total solid content of the resin composition.
- the upper limit is more preferably 65% by mass or less, and still more preferably 60% by mass or less.
- the lower limit can be set to 1% by mass or more, for example.
- the resin composition of the present invention may contain inorganic particles.
- the inorganic particles include black pigments and transparent particles.
- Specific examples of the inorganic particles include titanium oxide, titanium oxynitride, silicon oxide, cesium tungsten oxide, indium tin oxide, vanadium oxynitride, carbon black, titanium black, aluminum oxide, and zirconium oxide.
- the inorganic particles are preferably black pigments, for example.
- the composition containing a black pigment often has low sensitivity. However, according to the present invention, even a resin composition containing a black pigment can obtain excellent sensitivity, so the effect of the present invention is remarkable. Is obtained.
- the black pigment is not particularly limited, and known ones can be used. Examples thereof include carbon black, titanium black (titanium oxynitride, etc.), graphite, vanadium oxynitride, and the like. Carbon black, titanium black, and vanadium oxynitride are preferable, and titanium black is particularly preferable. Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and treatment with a water-repellent substance as disclosed in JP-A-2007-302836 is also possible. Is possible.
- Titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small. Specifically, the average primary particle size is preferably in the range of 10 nm to 45 nm.
- the particle diameter that is, the particle diameter is a diameter of a circle having an area equal to the projected area of the outer surface of the particle. The projected area of the particles can be obtained by measuring the area obtained by photographing with an electron micrograph and correcting the photographing magnification.
- the specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is used in order that the water repellency after the surface treatment of titanium black with a water repellent becomes a predetermined performance. It is preferably 5 m 2 / g or more and 150 m 2 / g or less, and more preferably 20 m 2 / g or more and 120 m 2 / g or less.
- Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.
- Titanium black can also be used as a dispersion.
- examples thereof include a dispersion containing titanium black particles and silica particles and having a content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersion adjusted to a range of 0.20 to 0.50.
- the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification.
- Transparent particles examples include titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), zirconium oxide (ZrO 2 ), silicon oxide (SiO 2 ), tin oxide (SnO 2 ), and the like.
- ITO indium tin oxide
- ITO is an inorganic compound of indium oxide (In 2 O 3 ) and tin oxide (SnO 2 ), as the transparent particles.
- antimony tin oxide ATO
- zinc oxide ZnO
- Al-doped zinc oxide Al-doped ZnO
- fluorine-doped tin dioxide F-doped SnO 2
- niobium-doped titanium dioxide Nb-doped TiO 2
- cesium tungsten oxide etc. It is also preferable to use.
- Silver (Ag) particles, gold (Au) particles, copper (Cu) particles, and nickel (Ni) particles can also be used.
- the description of paragraphs 0025 to 0029 of International Publication No. WO2014 / 142259 can be referred to for cesium tungsten oxide, the contents of which are incorporated herein.
- the transparent particles preferably have an average particle size of 1 to 200 nm, more preferably 10 to 100 nm.
- the average particle diameter of the transparent particles can be determined from the photograph obtained by observing the dispersed particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom to obtain the average particle size (usually, 300 or more particles are measured in order to obtain the average particle size).
- the primary particle diameter of the transparent particles is preferably 1 to 100 nm, and more preferably 1 to 60 nm.
- the refractive index of the transparent particles is preferably 1.6 to 2.8, more preferably 1.7 to 2.7, and most preferably 1.8 to 2.7.
- the specific surface area of the transparent particles is preferably 10 to 2000 m 2 / g, more preferably 20 to 1800 m 2 / g, and most preferably 40 to 1500 m 2 / g.
- the transparent particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as they satisfy a predetermined particle size.
- the shape is most preferably a spherical shape, but may be a bead shape, a shape having a major axis / minor axis ratio of 1 or more, or an indefinite shape.
- commercially available particles can be preferably used. For example, Ishihara Sangyo Co., Ltd.
- TTO series TTO-51 (A), TTO-51 (C), etc.
- TTO-S V series (TTO-S-1, TTO-S-2, TTO-V-3) Etc.
- MT series MT-01, MT-05, etc.
- Examples of commercially available dispersions containing cesium tungsten oxide include YMF-02A, YMS-01A-2, and YMF-10A-1 manufactured by Sumitomo Metal Mining Co., Ltd.
- the content of inorganic particles is preferably 0 to 70% by mass with respect to the total solid content of the resin composition.
- the upper limit is more preferably 65% by mass or less, and still more preferably 60% by mass or less.
- the lower limit can be set to 1% by mass or more, for example.
- the resin composition of the present invention preferably contains a phthalimide compound.
- a green pigment in particular, a halogenated zinc phthalocyanine pigment
- a cured film in which the occurrence of needle-like foreign matters and the like is suppressed can be produced by including a phthalimide compound.
- the phthalimide compound is preferably a compound represented by the following general formula (PI).
- a 1 to A 4 each independently represents a hydrogen atom, a halogen atom, or an alkyl group.
- the halogen atom include a chlorine atom, a bromine atom, and a fluorine atom, and a chlorine atom or a fluorine atom is preferable.
- the alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
- the alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
- At least one of A 1 to A 4 is preferably selected from a chlorine atom and a bromine atom, and more preferably a bromine atom.
- all of the A 1 ⁇ A 4 is a chlorine atom and, more preferably selected from a bromine atom, all of A 1 ⁇ A 4 is more preferably a bromine atom.
- the content of the phthalimide compound is preferably 0.001 to 5% by mass with respect to the total solid content in the resin composition.
- the lower limit is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.15% by mass or more.
- the upper limit is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.9% by mass or less, and particularly preferably 0.8% by mass or less.
- the phthalimide compound may be one type or two or more types. When 2 or more types are included, the total is preferably within the above range.
- the resin composition of the present invention contains an organic solvent.
- the organic solvent is basically not particularly limited as long as the solubility of each component and the applicability of the composition are satisfied, but it is preferably selected in consideration of the applicability and safety of the composition.
- organic solvents include the following.
- esters include 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, alkyloxyalkyl acetate (Eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
- organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
- Organic solvents are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, butyl acetate, ethyl-3-ethoxypropionate, propylene glycol monoethyl ether acetate, xylene, ethylbenzene, methyl isobutyl ketone, 2-butanol, dipropylene
- the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
- the content of the organic solvent is preferably such that the total solid content of the resin composition is 25 to 80% by mass.
- the lower limit is preferably 30% by mass or more, and more preferably 35% by mass or more.
- the upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less.
- the resin composition of the present invention may contain a curing accelerator for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature.
- the curing accelerator include polyfunctional thiol compounds (polyfunctional mercapto compounds) having two or more mercapto groups in the molecule.
- the polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
- the polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (T1).
- T1 In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.
- the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
- Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable. These polyfunctional thiol compounds can be used alone or in combination.
- Curing accelerators include methylol compounds (for example, compounds exemplified as a crosslinking agent in paragraph 0246 of JP-A-2015-34963), amines, phosphonium salts, amidine salts, amide compounds (above, for example, special No. 2013-41165, curing agent described in paragraph 0186), base generator (for example, ionic compound described in JP-A-2014-55114), cyanate compound (for example, JP-A-2012-150180) A compound described in paragraph 0071), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP2011-255304A), an onium salt compound (for example, paragraph 0216 in JP2015-34963A).
- Compounds exemplified as acid generators, JP2009 Compounds described in JP-180949 can also be used.
- the content of the curing accelerator is preferably 0.3 to 8.9% by mass with respect to the total solid content of the resin composition, 0.8 to 6 More preferably, 4% by mass.
- the resin composition of the present invention may contain a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the crosslinkable compound during production or storage of the composition.
- Polymerization inhibitors include hydroquinone, para-methoxyphenol, di-tert-butyl-para-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.) and the like. Of these, para-methoxyphenol is preferred.
- the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the resin composition.
- the resin composition of the present invention may contain various surfactants from the viewpoint of further improving applicability.
- various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
- liquid properties (particularly fluidity) when prepared as a coating solution can be further improved, and uniformity of coating thickness and liquid-saving properties can be further improved. it can. That is, in the case of forming a film using a coating liquid to which a resin composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid is reduced, and the wettability to the coated surface is reduced. Is improved, and the coating property to the coated surface is improved. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
- the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
- fluorosurfactant examples include MegaFuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc.
- the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
- the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
- the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant.
- nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Rusperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), etc. Also, NCW-101, NCW-1001, NCW-1002, manufactured by Wako Pure Chemical Industries, Ltd.
- cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
- phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
- organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
- (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
- W001 manufactured by Yusho Co., Ltd.
- anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Kasei Co., Ltd.), and the like.
- silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.
- the content of the surfactant is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on the total solid content of the resin composition of the present invention.
- the resin composition of the present invention may contain an ultraviolet absorber.
- Compositions containing ultraviolet absorbers tend to have reduced i-line transmittance. For this reason, when a resin composition containing an ultraviolet absorber is exposed with i-rays, the sensitivity may be low.
- even a resin composition containing an ultraviolet absorber has excellent sensitivity. Therefore, the effect of the present invention is remarkably obtained.
- UV absorber examples include salicylate UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, substituted acrylonitrile UV absorbers, and triazine UV absorbers.
- a commercial item can also be used for a ultraviolet absorber.
- UV503 (Daito Chemical Co., Ltd.), TINUVIN477 (made by BASF Corporation) etc. are mentioned, for example.
- the content of the ultraviolet absorber is preferably 0.01 to 10% by mass and more preferably 0.01 to 5% by mass with respect to the total solid content of the resin composition of the present invention.
- the resin composition of the present invention may contain a silane coupling agent for the purpose of improving substrate adhesion.
- a silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule.
- a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
- the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction.
- Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
- the number of carbon atoms is preferably 6 or less, and more preferably 4 or less.
- an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
- the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (except for a silicon atom to which a hydrolyzable group is bonded). However, it does not include an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, or a branched alkyl group having 3 or more carbon atoms. desirable.
- the silane coupling agent is a compound different from the polymerizable compound and the thermosetting compound described above. That is, a compound having a hydrolyzable group and other functional group in the molecule is a silane coupling agent.
- the silane coupling agent preferably has a group represented by the following formula (Z). * Represents a bonding position.
- R z1 represents an alkyl group
- R z2 represents a hydrolyzable group
- m represents an integer of 1 to 3.
- the alkyl group represented by R z1 preferably has 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.
- the definition of the hydrolyzable group represented by R z2 is as described above.
- the silane coupling agent preferably has a curable functional group.
- the curable functional group includes (meth) acryloyloxy group, epoxy group, oxetanyl group, isocyanate group, hydroxyl group, amino group, carboxyl group, thiol group, alkoxysilyl group, methylol group, vinyl group, (meth) acrylamide.
- the curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.
- the molecular weight of the silane coupling agent is not particularly limited, and is preferably from 100 to 1,000 from the viewpoint of handleability, preferably from 270 or more, and more preferably from 270 to 1000, from the viewpoint of more excellent effects of the present invention.
- silane coupling agent is a silane coupling agent X represented by the formula (W).
- Formula (W) R z3 -Lz-Si (R z1) 3-m (R z2) m
- R z1 represents an alkyl group
- R z2 represents a hydrolyzable group
- R z3 represents a curable functional group
- Lz represents a single bond or a divalent linking group
- m is an integer of 1 to 3.
- the definition of the alkyl group represented by R z1 is as described above.
- the definition of the hydrolyzable group represented by R z2 is as described above.
- Lz represents a single bond or a divalent linking group.
- Examples of the divalent linking group include an alkylene group, an arylene group, —NR 12 —, —CONR 12 —, —CO—, —CO 2 —, —SO 2 NR 12 —, —O—, —S—, —SO. 2- or a combination thereof.
- the alkylene group preferably has 1 to 20 carbon atoms.
- the alkylene group may be linear or branched.
- the alkylene group and the arylene group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group.
- Lz is at least one selected from the group consisting of an alkylene group having 2 to 10 carbon atoms and an arylene group having 6 to 12 carbon atoms, or these groups and —NR 12 —, —CONR 12 —, —CO—. , —CO 2 —, —SO 2 NR 12 —, —O—, —S—, and a group consisting of a combination with at least one group selected from the group consisting of —SO 2 — are preferred.
- a group consisting of ⁇ 10 alkylene groups, —CO 2 —, —O—, —CO—, —CONR 12 —, or a combination of these groups is more preferred.
- R 12 represents a hydrogen atom or a methyl group.
- m represents 1 to 3, preferably 2 to 3, and more preferably 3.
- N- ⁇ -aminoethyl- ⁇ -aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-trimethoxy Silane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-trimethoxysilane (Trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name KBM-602 manufactured by Shin
- a preferred embodiment of the silane coupling agent includes a silane coupling agent Y having at least a silicon atom, a nitrogen atom, and a curable functional group in the molecule, and having a hydrolyzable group bonded to the silicon atom. It is done.
- the silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different.
- Atoms and substituents that can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an aryl group, a silyl group Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like.
- substituents further include amino groups, halogen atoms, sulfonamide groups, which can be substituted with silyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, alkyl groups and / or aryl groups, It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, a salt thereof, a sulfo group, or a salt thereof.
- at least one hydrolyzable group is bonded to the silicon atom.
- the definition of the hydrolyzable group is as described above.
- the silane coupling agent Y may contain a group represented by the formula (Z).
- the silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably has at least one organic group.
- the amino group structure may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.
- examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof.
- substituents may further have a substituent
- substituents that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide.
- the nitrogen atom is couple
- Preferred examples of the organic linking group include the above-described nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.
- the definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above. It is sufficient that at least one curable functional group is contained in one molecule of the silane coupling agent Y, but it is possible to adopt an embodiment having two or more curable functional groups, and from the viewpoint of sensitivity and stability. Is preferably 2 to 20, more preferably 4 to 15, and most preferably 6 to 10 curable functional groups in the molecule.
- Examples of the silane coupling agent Y include compounds represented by the following formula (Y).
- R y1 represents an alkyl group
- R y2 represents a hydrolyzable group
- R y3 represents a curable functional group
- LN represents a (n + 1) -valent linking group having a nitrogen atom
- m represents an integer of 1 to 3
- n represents an integer of 1 or more.
- R y1 , R y2 , R y3 and m in the formula (Y) are synonymous with R z1 , R z2 , R z3 and m in the formula (W), and preferred ranges are also the same.
- N in the formula (Y) represents an integer of 1 or more.
- the upper limit is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
- the lower limit is preferably 2 or more, more preferably 4 or more, and still more preferably 6 or more.
- n can be 1.
- LN in the formula (Y) represents a group having a nitrogen atom.
- the group having a nitrogen atom is at least one selected from the following formulas (LN-1) to (LN-4), or the following formulas (LN-1) to (LN-4), an alkylene group, an arylene group, And a group consisting of a combination with at least one selected from —CO—, —CO 2 —, —O—, —S— and —SO 2 —.
- the alkylene group may be linear or branched.
- the alkylene group and the arylene group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group.
- * represents a connecting hand.
- silane coupling agent Y examples include the following compounds.
- Et represents an ethyl group.
- compounds described in paragraph Nos. 0018 to 0036 of JP-A-2009-288703 can be mentioned, the contents of which are incorporated herein.
- the molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but include the above-described ranges (preferably 270 or more).
- the content of the silane coupling agent is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 8% by mass, and more preferably from 1.0 to 6%, based on the total solid content in the resin composition of the present invention. More preferred is mass%.
- a silane coupling agent may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.
- additives for example, fillers, adhesion promoters, antioxidants, anti-aggregation agents, and the like can be blended with the resin composition of the present invention as necessary.
- additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
- the antioxidant for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph No. 2011-90147 paragraph), a thioether compound, or the like can be used.
- the resin composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph 0081 of the publication.
- the resin composition may contain metal elements, but from the viewpoint of suppressing the occurrence of defects, the content of Group 2 elements (calcium, magnesium, etc.) in the resin composition is 50 ppm or less. It is preferable to control to 0.01 to 10 ppm.
- the total amount of the inorganic metal salt in the resin composition is preferably 100 ppm or less, and more preferably controlled to 0.5 to 50 ppm.
- the resin composition of the present invention can be prepared by mixing the aforementioned components.
- each component may be blended at once, or may be blended sequentially after each component is dissolved and dispersed in a solvent.
- the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
- any filter can be used without particular limitation as long as it has been conventionally used for filtration.
- fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight)
- PP polypropylene
- polypropylene including high density polypropylene
- nylon are preferable.
- the pore size of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, more preferably about 0.05 to 0.5 ⁇ m. By setting it within this range, it becomes possible to reliably remove fine foreign matters that hinder the preparation of a uniform composition and the formation of a smooth film in the subsequent steps. Further, it is also preferable to use a fiber-shaped filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like. , TPR005, etc.) and SHPX type series (SHPX003 etc.) filter cartridges can be used.
- the filtering by the first filter may be performed only once or may be performed twice or more.
- the pore diameter here can refer to the nominal value of the filter manufacturer.
- a commercially available filter for example, selected from various filters provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nihon Microlith Co., Ltd.) can do.
- the second filter a filter formed of the same material as the first filter described above can be used.
- the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.
- the resin composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface shape (flatness, etc.) and the film thickness.
- the value of the viscosity can be appropriately selected according to need. For example, it can be 0.3 mPa ⁇ s to 50 mPa ⁇ s, preferably 0.5 mPa ⁇ s to 20 mPa ⁇ s at 25 ° C.
- As a measuring method for example, Toki Sangyo Viscometer RE85L (rotor: 1 ° 34 ′ ⁇ R24, measuring range 0.6 to 1200 mPa ⁇ s) is used, and the temperature is adjusted to 25 ° C. be able to.
- the cured film of the present invention is formed using the above-described resin composition of the present invention.
- the cured film of the present invention can be used in various devices such as a solid-state imaging device such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor) and an image display device.
- the cured film of the present invention can be used for color filters, light shielding films, transparent films, and the like.
- a cured film suitable for a color filter or the like can be manufactured by using a resin composition containing a chromatic colorant.
- the cured film suitable for the light shielding film etc. can be manufactured by using the resin composition containing a black pigment.
- the cured film suitable for a transparent film (transparent pixel) etc. can be manufactured by using the resinous composition which does not contain any of a chromatic colorant and a black pigment.
- the cured film of the present invention may have a pattern or may be a film (flat film) having no pattern.
- the film thickness of the cured film of the present invention can be appropriately adjusted according to the purpose.
- the film thickness is preferably 0.3 to 10 ⁇ m.
- the lower limit can be 0.4 ⁇ m or more, and can also be 0.5 ⁇ m or more.
- the upper limit is more preferably 7 ⁇ m or less, further preferably 5 ⁇ m or less, and particularly preferably 3 ⁇ m or less.
- the transmittance of light having a wavelength of 365 nm is preferably 15% or less, more preferably 10% or less, and further preferably 7% or less.
- the voltage holding ratio of the liquid crystal display element provided with the cured film is preferably 70% or more, and more preferably 90% or more.
- Known means for obtaining a high voltage holding ratio can be appropriately incorporated. Typical examples include the use of high-purity materials (for example, reduction of ionic impurities) and control of the amount of acidic functional groups in the composition. Is mentioned.
- the voltage holding ratio can be measured, for example, by the method described in paragraph 0243 of JP2011-008004A and paragraphs 0123 to 0129 of JP2012-224847A.
- the pattern forming method of the present invention includes a step of forming a radiation sensitive resin composition layer on a support using the radiation sensitive resin composition of the present invention, and exposing the radiation sensitive resin composition layer in a pattern. And a step of developing and removing the unexposed portion to form a pattern.
- each step will be described.
- the process of forming a radiation sensitive resin composition layer >> In the step of forming the radiation sensitive resin composition layer, the radiation sensitive resin composition layer is formed on the support using the radiation sensitive resin composition.
- a solid-state image sensor substrate in which a solid-state image sensor (light receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.
- the pattern in the present invention may be formed on the solid-state image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface).
- an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface.
- various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be used.
- the radiation sensitive resin composition layer formed on the support may be dried (prebaked). When a pattern is formed by a low temperature process, pre-baking may not be performed.
- the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.
- the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher.
- the prebake time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Drying can be performed with a hot plate, oven, or the like.
- Exposure process the radiation sensitive resin composition layer is exposed in a pattern (exposure process).
- pattern exposure can be performed by exposing the radiation-sensitive resin composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
- radiation (light) that can be used for exposure ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line).
- Irradiation dose (exposure dose) for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
- the oxygen concentration at the time of exposure can be appropriately selected.
- the exposure illuminance can be set as appropriate, and can usually be selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , 35000 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 thickness of the cured film is preferably 2.0 ⁇ m or less, more preferably 1.0 ⁇ m or less, and even more preferably 0.7 ⁇ m or less.
- the lower limit can be, for example, 0.1 ⁇ m or more, and can also be 0.2 ⁇ m or more.
- the unexposed portion is developed and removed to form a pattern.
- the development removal of the unexposed portion can be performed using a developer.
- the radiation sensitive resin composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains.
- the developer an organic alkali developer that does not damage the underlying solid-state imaging device or circuit is desirable.
- the temperature of the developer is preferably 20 to 30 ° C., for example.
- the development time is preferably 20 to 180 seconds.
- the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
- alkaline agent used in the developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide.
- organic alkaline compounds such as dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene.
- an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used.
- 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 inorganic alkali for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like are preferable.
- a surfactant may be used for the developer. Examples of the surfactant include the surfactant described in the above-described curable composition, and a nonionic surfactant is preferable.
- clean (rinse) with a pure water after image development.
- Post-baking is a heat treatment after development for 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.
- the post-bake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower. Preferably, 100 ° C. or lower is more preferable, and 90 ° C. or lower is particularly preferable.
- the lower limit can be, for example, 50 ° C. or higher.
- the film after development can be performed continuously or batch-wise using heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so as to satisfy the above conditions. it can. Further, when a pattern is formed by a low temperature process, post baking is not necessary.
- the solid-state imaging device of the present invention has the cured film of the present invention.
- the configuration of the solid-state imaging device of the present invention is a configuration provided with the cured film of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .
- a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support.
- a configuration having a light condensing means for example, a microlens, etc., the same applies hereinafter
- a structure having the light condensing means on the color filter Etc for example, a microlens, etc., the same applies hereinafter
- the cured film of this invention can be used for image display apparatuses, such as a liquid crystal display device and an organic electroluminescent display apparatus.
- the image display device provided with the cured film of the present invention can display a high-quality image having a good color tone and excellent display characteristics.
- display devices and details of each display device refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year).
- the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”.
- the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
- the cured film of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device.
- the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
- the present invention provides a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), and a STN (Super-Twist Nematic).
- IPS In Plane Switching
- MVA Multi-domain Vertical Alignment
- STN Super-Twist Nematic
- the color filter of the present invention can also be used for a COA (Color-filter On Array) system.
- COA Color-filter On Array
- a mixed solution having the following composition was mixed for 2 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.)).
- a dispersion was prepared.
- YMS-01A-2 manufactured by Sumitomo Metal Mining Co., Ltd. was used.
- ⁇ Preparation of radiation-sensitive resin composition The materials shown in the table below were mixed and stirred at the ratio (mass%) shown in the table below, and after adjusting the water content to the values (mass%) shown in the table below, a nylon filter having a pore diameter of 0.45 ⁇ m (Nippon Pole) A radiation sensitive resin composition was prepared by filtration through DFA4201NXEY. The water content in the composition was measured by the Karl Fischer method.
- A-1 Acryl RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)
- A-2 Acrybase FF-426 (manufactured by Fujikura Kasei Co., Ltd.)
- B-1 NK Ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- B-2 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
- B-3 The following structure
- B-5 The following structure
- UV absorber UV-503 (Daito Chemical Co., Ltd.)
- E-2 TINUVIN477 (manufactured by BASF)
- thermosetting compound F-1 EHPE3150 (manufactured by Daicel Corporation)
- CT-4000 manufactured by FUJIFILM Electronics Materials Co., Ltd.
- the radiation-sensitive resin composition obtained above was applied onto the undercoat layer of the silicon wafer substrate with the undercoat layer prepared above to form a coating film.
- the heat processing (prebaking) was performed for 120 second using a 100 degreeC hotplate so that the dry film thickness of this coating film might be set to the film thickness as described in the following table
- i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
- exposure was performed at a wavelength of 365 nm through a mask having a pattern and with an exposure amount described in Table 3.
- a mask having a 0.9 ⁇ m ⁇ 0.9 ⁇ m Bayer pattern was used.
- Examples 5 to 8 a mask having a Bayer pattern of 1.1 ⁇ m ⁇ 1.1 ⁇ m was used.
- a mask having a hole pattern with a diameter of 100 ⁇ m was used.
- a mask having a Bayer pattern of 10 ⁇ m ⁇ 10 ⁇ m was used.
- a mask having a Bayer pattern of 0.8 ⁇ m ⁇ 0.8 ⁇ m was used.
- Examples 15 and 16 a mask having an island pattern of 1.0 ⁇ m ⁇ 1.0 ⁇ m was used.
- the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.).
- CD-1030 manufactured by FUJIFILM Electronics Materials Co., Ltd.
- the paddle development was performed 4 times to maintain the paddle state for 30 seconds to form a pattern.
- the substrate on which the pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is showered from an ejection nozzle above the rotation center. And then rinsed (23 seconds ⁇ 2 times), spin-dried, and post-baked on a hot plate at 200 ° C. for 300 seconds to obtain a pattern.
- the width of the pattern portion is in the range of 95% to 105% of the pattern size of the mask used.
- the radiation sensitive resin composition was put in a sealed container and stored in an environment of 10 ° C. for 3 to 9 months. Using the radiation-sensitive resin composition after storage, a pattern was formed under the same conditions as the initial sensitivity evaluation. About the obtained pattern, it expanded by 20,000 times using the scanning electron microscope (SEM), the width
- SEM scanning electron microscope
- A The pattern width of the pattern using the radiation-sensitive resin composition after storage for 9 months is in the range of 90% to 110% of the pattern width of the pattern produced using the radiation-sensitive resin composition immediately after production. It is.
- B The pattern width of the pattern using the radiation-sensitive resin composition after storage for 9 months is less than 90% of the pattern width of the pattern manufactured using the radiation-sensitive resin composition immediately after manufacture, or The change rate of the pattern width of the pattern using the radiation-sensitive resin composition after storage for 6 months is over 110%, but the pattern width of the pattern manufactured using the radiation-sensitive resin composition immediately after production is ⁇ It is in the range of 10% to + 10%.
- C The pattern width of the pattern using the radiation-sensitive resin composition after storage for 6 months is less than 90% of the pattern width of the pattern produced using the radiation-sensitive resin composition immediately after production, or Over 110%.
- a radiation-sensitive resin composition is applied onto a glass substrate, pre-baked (100 ° C. for 120 seconds), 500 mj / cm 2 exposure (entire exposure without a mask), and post-baking (200 ° C. for 300 seconds) to form a flat film ( Film without pattern) was produced.
- the obtained flat film was measured with a multi-channel spectrometer MCPD-3000 manufactured by Otsuka Electronics Co., Ltd., with a spectral transmittance of 350 nm to 800 nm in 5 nm steps, and a transmittance of light having a wavelength of 365 nm was measured.
- Examples 1 to 16 in which an oxime ester compound having at least one group selected from a branched alkyl group and a cyclic alkyl group as a photopolymerization initiator and another photopolymerization initiator are used in combination are described as photopolymerization initiators.
- Example 17 in which only the oxime ester compound having at least one group selected from a branched alkyl group and a cyclic alkyl group was used the developability was good and the pattern shape was excellent.
- Comparative Example 1 containing no water, the pattern width increased over time, sensitization was observed over time, and the sensitivity stability over time was inferior. Furthermore, the development speed of Comparative Example 1 was slower than that of the Example.
- Comparative Examples 2 to 7 using a photopolymerization initiator that does not contain an oxime ester compound having at least one group selected from a branched alkyl group and a cyclic alkyl group Comparative Examples 2 to 6 have initial sensitivity. It was inferior. In Comparative Example 7, the initial sensitivity was good, but the pattern width became smaller over time, the sensitivity decreased over time, and the stability over time of the sensitivity was inferior.
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Abstract
Description
<1> 樹脂と、エチレン性不飽和結合を有する重合性化合物と、光重合開始剤と、有機溶剤と、水を含む感放射線性樹脂組成物であって、
光重合開始剤は、分岐アルキル基および環状アルキル基から選ばれる少なくとも1種類の基を有するオキシムエステル化合物を含み、
水の含有量が、感放射線性樹脂組成物の質量に対して0.1~2質量%である、感放射線性樹脂組成物。
<2> 樹脂は、アルカリ可溶性樹脂を含む、<1>に記載の感放射線性樹脂組成物。
<3> 重合性化合物は、エチレン性不飽和結合当量が3.0~12.0mmol/gの多官能(メタ)アクリレート化合物である、<1>または<2>に記載の感放射線性樹脂組成物。
<4> オキシムエステル化合物は、炭素数7以上の分岐アルキル基および、炭素数7以上の環状アルキル基から選ばれる少なくとも1種類の基を有する、<1>~<3>のいずれかに記載の感放射線性樹脂組成物。
<5> オキシムエステル化合物は、カルバゾール構造を有する、<1>~<4>のいずれかに記載の感放射線性樹脂組成物。
<6> カルバゾール構造は、カルバゾール部のベンゼン環に、更に環が縮合した構造を有する、<5>に記載の感放射線性樹脂組成物。
<7> オキシムエステル化合物は、フッ素原子を含むオキシムエステル化合物である、<1>~<6>のいずれかに記載の感放射線性樹脂組成物。
<8> オキシムエステル化合物は、式(1)で表される化合物である、<1>~<7>のいずれかに記載の感放射線性樹脂組成物;
<9> 有機溶剤は、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メチルエーテル、シクロヘキサノン、酢酸ブチル、エチル-3-エトキシプロピオネート、プロピレングリコールモノエチルエーテルアセテート、キシレン、エチルベンゼン、メチルイソブチルケトン、2-ブタノール、ジプロピレングリコールモノメチルエーテルから選ばれる少なくとも1種以上である、<1>~<8>のいずれかに記載の感放射線性樹脂組成物。
<10> 更に、有彩色着色剤および無機粒子から選ばれる少なくとも1種を含む、<1>~<9>のいずれかに記載の感放射線性樹脂組成物。
<11> 更に、フタルイミド化合物を含む、<1>~<10>のいずれかに記載の感放射線性樹脂組成物。
<12> 更に、紫外線吸収剤を含む、<1>~<11>のいずれかに記載の感放射線性樹脂組成物。
<13> 更に、熱硬化性化合物を含む、<1>~<12>のいずれかに記載の感放射線性樹脂組成物。
<14> 光重合開始剤は、更に、オキシムエステル化合物以外の化合物を含む、<1>~<13>のいずれかに記載の感放射線性樹脂組成物。
<15> オキシムエステル化合物以外の化合物は、分岐アルキル基および環状アルキル基を有さないオキシムエステル化合物、アルキルフェノン化合物、および、アシルホスフィン化合物から選ばれる少なくとも1種である、<14>に記載の感放射線性樹脂組成物。
<16> <1>~<15>のいずれかに記載の感放射線性樹脂組成物を用いた硬化膜。
<17> 波長365nmの光の透過率が15%以下である、<16>に記載の硬化膜。
<18> <1>~<15>のいずれかに記載の感放射線性樹脂組成物を用いて支持体上に感放射線性樹脂組成物層を形成する工程と、感放射線性樹脂組成物層をパターン状に露光する工程と、未露光部を現像除去してパターンを形成する工程とを含むパターン形成方法。
<19> <16>または<17>に記載の硬化膜を有する固体撮像素子。
<20> <16>または<17>に記載の硬化膜を有する画像表示装置。
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)を包含する。
本明細書において光とは、活性光線または放射線を意味する。また、「活性光線」または「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等を意味する。
本明細書において「露光」とは、特に断らない限り、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、X線、EUV光などによる露光のみならず、電子線、イオンビーム等の粒子線による描画も露光に含める。
本明細書において「~」を用いて表される数値範囲は、「~」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範囲を意味する。
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、「(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)アリル」は、アリルおよびメタリルの双方、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「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。
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)測定による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、重量平均分子量(Mw)及び数平均分子量(Mn)は、例えば、HLC-8220(東ソー(株)製)を用い、カラムとしてTSKgel Super AWM―H(東ソー(株)製、6.0mmID(内径)×15.0cm)を、溶離液として10mmol/L リチウムブロミドNMP(N-メチルピロリジノン)溶液を用いることによって求めることができる。
本発明の感放射線性樹脂組成物は、樹脂と、エチレン性不飽和結合を有する重合性化合物と、光重合開始剤と、有機溶剤と、水を含む感放射線性樹脂組成物であって、光重合開始剤は、分岐アルキル基および環状アルキル基から選ばれる少なくとも1種類の基を有するオキシムエステル化合物を含み、水の含有量が、感放射線性樹脂組成物の質量に対して0.1~2質量%である。以下、感放射線性樹脂組成物を、樹脂組成物ともいう。
一方、感放射線性樹脂組成物に水を含有させると、初期の感度は良好であるものの、経時における感度が低下し易い。この理由は、光重合開始剤が水によって分解されるためであると推測する。
本発明者らが水を含む感放射線性樹脂組成物について詳細に検討したところ、水の含有量を2質量%以下とし、かつ、光重合開始剤として分岐アルキル基および環状アルキル基から選ばれる少なくとも1種類の基を有するオキシムエステル化合物(以下、オキシムエステル化合物Aともいう)を用いることで、感度の低下を抑制できることを見出した。オキシムエステル化合物Aは、分岐アルキル基および環状アルキル基から選ばれる少なくとも1種類の基により、オキシムエステル部位への水分の求核攻撃が阻害されるという理由により、水による分解が生じにくくなったものと推測する。
このため、上述したオキシムエステル化合物Aを用い、かつ、樹脂組成物の水の含有量を0.1~2質量%とすることにより、感度が良好で、かつ、経時における感度の増加や低下が抑制された、感度の経時安定性に優れた樹脂組成物とすることができたと推測する。
また、本発明の樹脂組成物は、分岐アルキル基および環状アルキル基から選ばれる少なくとも1種類の基を有するオキシムエステル化合物の100質量部に対し、水を20~7000質量部含有することが好ましく、水を25~1500質量部含有することがより好ましく、水を30~1000質量部含有することがさらに好ましい。
また、本発明の樹脂組成物は、光重合開始剤の100質量部に対し、水を4~500質量部含有することが好ましく、水を5~450質量部含有することがより好ましく、水を10~300質量部含有することがさらに好ましい。
なお、本発明において、樹脂組成物中の水の含有量は、カールフィッシャー法により測定した値である。カールフィッシャー法とは、水と選択的に、且つ定量的に反応するカールフィッシャー試薬(ヨウ素、二酸化硫黄、塩基、及びアルコール等の溶剤より構成)を用いて、組成物中の水の含有量を測定する方法である。この方法には、電量滴定法と容量滴定法があるが、どちらの方法を用いても構わない。
本発明の樹脂組成物は、エチレン性不飽和結合を有する重合性化合物を含有する。エチレン性不飽和結合を有する重合性化合物としては、エチレン性不飽和結合を有する基を有する化合物などが挙げられる。エチレン性不飽和結合を有する基としては、ビニル基、スチリル基、(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い。重合性化合物は、エチレン性不飽和結合を有する基を1個以上有する化合物が好ましく、2個以上有する化合物がより好ましく、3個以上有することがさらに好ましい。上限は、たとえば、15個以下が好ましく、6個以下がより好ましい。
なお、本発明においてエチレン性不飽和結合当量(二重結合当量)は、化合物の分子量に対するエチレン性不飽和結合の価数で定義される。
カプロラクトン構造を有する重合性化合物は、例えば、日本化薬(株)からKAYARAD DPCAシリーズとして市販されており、DPCA-20、DPCA-30、DPCA-60、DPCA-120等が挙げられる。
市販品としては、ウレタンオリゴマーUAS-10、UAB-140(山陽国策パルプ社製)、UA-7200(新中村化学工業(株)製)、DPHA-40H(日本化薬社製)、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。
本発明の樹脂組成物は、光重合開始剤を含有する。光重合開始剤は、分岐アルキル基および環状アルキル基から選ばれる少なくとも1種類の基を有するオキシムエステル化合物(オキシムエステル化合物A)を含む。
オキシムエステル化合物Aが有する分岐アルキル基の炭素数は、3以上が好ましく、5以上がより好ましく、7以上がさらに好ましい。上限は、30以下が好ましく、20以下がより好ましく、15以下がさらに好ましい。
含フッ素アルキル基は、フッ素原子の置換率が、40~100%であることが好ましく、50~100%であることがより好ましく、60~100%であることがさらに好ましい。なお、フッ素原子の置換率とは、アルキル基が有する全水素原子の数のうち、フッ素原子に置換されている数の比率(%)をいう。
*-CHF2 (1)
*-CF3 (2)
ハロゲン原子は、フッ素原子、塩素原子、臭素原子、ヨウ素原子などが挙げられ、フッ素原子が好ましい。
置換基としてのアルキル基、ならびに、RX1およびRX2が表すアルキル基の炭素数は、1~30が好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。アルキル基は、水素原子の一部または全部がハロゲン原子(好ましくは、フッ素原子)で置換されていてもよい。また、アルキル基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。
置換基としてのアリール基、ならびに、RX1およびRX2が表すアリール基の炭素数は、6~20が好ましく、6~15がより好ましく、6~10が更に好ましい。アリール基は、単環であってもよく、縮合環であってもよい。また、アリール基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。
置換基としてのヘテロ環基、ならびに、RX1およびRX2が表すヘテロ環基は、5員環または6員環が好ましい。ヘテロ環基は、単環であってもよく、縮合環であってもよい。ヘテロ環基を構成する炭素原子の数は3~30が好ましく、3~18がより好ましく、3~12がより好ましい。ヘテロ環基を構成するヘテロ原子の数は1~3が好ましい。ヘテロ環基を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。また、ヘテロ環基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。
アルキル基の炭素数は、1~30が好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよい。アルキル基は、無置換であってもよく、置換基を有していてもよい。
アリール基の炭素数は、6~20が好ましく、6~15がより好ましく、6~10が更に好ましい。アリール基は、単環であってもよく、縮合環であってもよい。また、無置換であってもよく、置換基を有していてもよい。
式(1)において、R3が、分岐アルキル基もしくは環状アルキル基であることが好ましく、R3が、分岐アルキル基であることがより好ましい。
オキシムエステル化合物Aの365nm又は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、公知の方法を用いることができるが、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。
本発明の樹脂組成物において、オキシムエステル化合物Aの含有量は、樹脂組成物の全固形分に対し0.1~50質量%が好ましく、より好ましくは0.5~30質量%であり、さらに好ましくは1~20質量%である。この範囲とすることで、感度が良好で、かつ、感度の経時安定性に優れた樹脂組成物とすることができる。
本発明の樹脂組成物は、オキシムエステル化合物Aを、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の樹脂組成物は、上述したオキシムエステル化合物以外の光重合開始剤(他の光重合開始剤)を含有することができ、他の光重合開始剤をさらに含むことが好ましい。他の光重合開始剤をさらに含有することで、感度や密着性などが良好な硬化膜を製造しやすい。
市販品ではIRGACURE-OXE01(BASF社製)、IRGACURE-OXE02(BASF社製)も好適に用いられる。また、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(ADEKA社製)も用いることができる。なかでも、IRGACURE-OXE01、IRGACURE-OXE02が好ましい。
一般式(OX-1)中、Rで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
一価の非金属原子団としては、アルキル基、アリール基、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、複素環基、アルキルチオカルボニル基、アリールチオカルボニル基等が挙げられる。また、これらの基は、1以上の置換基を有していてもよい。また、前述した置換基は、さらに他の置換基で置換されていてもよい。
置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基またはアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、アリール基等が挙げられる。
一般式(OX-1)中、Bで表される一価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
一般式(OX-1)中、Aで表される二価の有機基としては、炭素数1~12のアルキレン基、アルキニレン基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
光重合開始剤は、必要に応じて2種以上を組み合わせて使用しても良い。
また、他の光重合開始剤を実質的に含有しない組成とすることもできる。他の光重合開始剤を実質的に含有しないとは、他の光重合開始剤の含有量が、全光重合開始剤の質量に対して、1質量%以下が好ましく、0.1質量%以下がより好ましく、含有しないことが一層好ましい。
本発明の樹脂組成物は、熱硬化性化合物を含有することも好ましい。熱硬化性化合物を含有することで、ポストベーク後の膜の硬化性を向上させ、耐溶剤性など各種耐性を向上できるという効果が期待できる。本発明において、熱硬化性化合物とは、加熱により硬化する化合物を意味する。
エポキシ化合物は、1分子内にエポキシ基を2つ以上有する化合物が好ましい。エポキシ基の数は、1分子内に2~100個が好ましい。上限は、例えば、10個以下とすることもでき、5個以下とすることもできる。
REP1~REP3、QEPの詳細について、特開2014-089408号公報の段落番号0087~0088の記載を参酌でき、この内容は本明細書に組み込まれる。式(EP1)で表される化合物の具体例としては、特開2014-089408号公報の段落0090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。
オキセタニル化合物は、1分子内にオキセタニル基を2つ以上有する化合物が好ましい。オキセタニル基の数は、1分子内に2~100個が好ましい。上限は、例えば、10個以下とすることもでき、5個以下とすることもできる。
1分子内に2個以上のオキセタニル基を有する化合物の具体例としては、アロンオキセタンOXT-121、OXT-221、OX-SQ、PNOX(以上、東亞合成(株)製)、ETERNACOLL(登録商標) OXMA、ETERNACOLL(登録商標) OXBP(宇部興産(株)製)を用いることができる。
アルコキシメチル化合物およびメチロール化合物としては、アルコキシメチル基またはメチロール基が、窒素原子または芳香族環を形成する炭素原子に結合している化合物が挙げられる。
ブロックイソシアネート化合物は、特に制限はないが、硬化性の観点から、1分子内に2以上のブロックイソシアネート基を有する化合物であることが好ましい。なお、本発明におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。また、ブロックイソシアネート基は、90~260℃の熱によりイソシアネート基を生成することが可能な基であることが好ましい。
本発明の樹脂組成物は、熱硬化性化合物を実質的に含有しない組成とすることもできる。なお、本発明において、熱硬化性化合物を実質的に含有しないとは、例えば、熱硬化性化合物の含有量が、本発明の樹脂組成物の全固形分に対し1質量%以下が好ましく、0.5質量%以下がより好ましく、0.1質量%以下がさらに好ましく、含有しないことが一層好ましい。
本発明の樹脂組成物は、樹脂を含む。樹脂は、例えば、顔料を組成物中で分散させる用途、バインダーの用途で配合される。なお、主に顔料を組成物中で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使用することもできる。なお、本発明において、樹脂は、ラジカル重合性化合物および熱硬化性化合物とは異なる材料である。
本発明の樹脂組成物は、樹脂としてアルカリ可溶性樹脂を含有することが好ましい。アルカリ可溶性樹脂を含有することにより、現像性およびパターン形成性が向上する。なお、アルカリ可溶性樹脂は、分散剤やバインダーとして用いることもできる。また、アルカリ可溶性樹脂は、ラジカル重合性化合物および熱硬化性化合物とは異なる材料である。
アルカリ可溶性樹脂としては、線状有機高分子重合体であってもよく、分子(好ましくは、アクリル系共重合体、スチレン系共重合体を主鎖とする分子)中に少なくとも1つのアルカリ可溶性を促進する基を有するアルカリ可溶性樹脂の中から適宜選択することができる。
本発明の樹脂組成物は、樹脂として分散剤を含有することができる。分散剤としては、高分子分散剤〔例えば、アミン基を有する樹脂(ポリアミドアミンとその塩など)、オリゴイミン系樹脂、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ(メタ)アクリレート、(メタ)アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕等を挙げることができる。高分子分散剤は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、ブロック型高分子に分類することができる。また、高分子分散剤としては、酸価が60mgKOH/g以上(より好ましくは、酸価60mgKOH/g以上、300mgKOH/g以下)の樹脂も好適に挙げることができる。
本発明の樹脂組成物は、顔料誘導体を含有してもよい。顔料誘導体は、有機顔料の一部分を、酸性基、塩基性基又はフタルイミドメチル基で置換した構造を有する化合物が好ましい。顔料誘導体としては、顔料の分散性及び分散安定性の観点から、酸性基又は塩基性基を有する顔料誘導体が好ましい。
また、顔料誘導体が有する酸性基としては、スルホン酸基、カルボン酸基及びその塩が好ましく、カルボン酸基及びスルホン酸基がさらに好ましく、スルホン酸基が特に好ましい。顔料誘導体が有する塩基性基としては、アミノ基が好ましく、特に三級アミノ基が好ましい。
顔料誘導体の具体例としては、特開2015-063593号公報の段落0111~0175の記載を参酌でき、この内容は本明細書に組み込まれる。
本発明の樹脂組成物は有彩色着色剤を含有することができる。本発明において、有彩色着色剤とは、白色着色剤および黒色着色剤以外の着色剤を意味する。有彩色着色剤は、波長400nm以上650nm未満の範囲に吸収極大を有する着色剤が好ましい。本発明において、有彩色着色剤は、顔料であってもよく、染料であってもよい。顔料は、平均粒径(r)が、好ましくは20nm≦r≦300nm、より好ましくは25nm≦r≦250nm、特に好ましくは30nm≦r≦200nmを満たすことが好ましい。ここでいう「平均粒径」とは、顔料の一次粒子が集合した二次粒子についての平均粒径を意味する。また、使用しうる顔料の二次粒子の粒径分布(以下、単に「粒径分布」ともいう。)は、(平均粒径±100)nmに入る二次粒子が全体の70質量%以上、好ましくは80質量%以上であることが好ましい。なお、二次粒子の粒径分布は、散乱強度分布を用いて測定することができる。なお、一次粒子の平均粒径は、走査型電子顕微鏡(SEM)あるいは透過型電子顕微鏡(TEM)で観察し、粒子が凝集していない部分で粒子サイズを100個計測し、平均値を算出することによって求めることができる。
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)。
また、緑色顔料として、分子中のハロゲン原子数が平均10~14個であり、臭素原子が平均8~12個であり、塩素原子が平均2~5個であるハロゲン化亜鉛フタロシアニン顔料を用いることも可能である。具体例としては、WO2015/118720公報に記載の化合物が挙げられる。
また、黄色着色剤として、特開2013-54339号公報の段落0011~0034に記載のキノフタロン化合物、特開2014-26228号公報の段落0013~0058に記載のキノフタロン化合物などを用いることもできる。
また、青色顔料として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開2012-247591号公報の段落0022~0030、特開2011-157478号公報の段落0047に記載の化合物などが挙げられる。
これら有機顔料は、単独若しくは種々組合せて用いることができる。
有機顔料は、緑色顔料および黄色顔料から選ばれる少なくとも1種が好ましく、緑色顔料と黄色顔料との組み合わせがより好ましい。緑色顔料は、C.I.Pigment Green 7,36,58,59から選ばれる少なくとも1種が好ましい。また、上述したハロゲン化亜鉛フタロシアニン顔料も好ましい。黄色顔料は、C.I.Pigment Yellow 139,150,185から選ばれる少なくとも1種が好ましい。また、上述したキノフタロン顔料も好ましい。
その他、直接染料、塩基性染料、媒染染料、酸性媒染染料、アゾイック染料、分散染料、油溶染料、食品染料、及び/又は、これらの誘導体等も有用に使用することができる。
acid alizarin violet N、
acid blue 1,7,9,15,18,23,25,27,29,40~45,62,70,74,80,83,86,87,90,92,103,112,113,120,129,138,147,158,171,182,192,243,324:1、
acid chrome violet K、
acid Fuchsin;acid green 1,3,5,9,16,25,27,50、
acid orange 6,7,8,10,12,50,51,52,56,63,74,95、
acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88,91,92,94,97,103,111,114,129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274、
acid violet 6B,7,9,17,19、
acid yellow 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184,243、
Food Yellow 3
なかでも、染料としては、トリアリールメタン系、アントラキノン系、アゾメチン系、ベンジリデン系、オキソノール系、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、ピラゾールアゾ系、アニリノアゾ系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、アンスラピリドン系ピロメテン系から選ばれる着色剤であることが好ましい。
L4が表す(n+k)価の連結基としては、特開2008-222950号公報の段落番号0071~0072に記載された連結基、特開2013-029760号公報の段落番号0176に記載された連結基などが挙げられる。
P4が表す置換基は、酸基、硬化性基等が挙げられる。硬化性基としては、エチレン性不飽和結合を有する基等のラジカル重合性基、エポキシ基、オキサゾリン基、メチロール基等が挙げられる。エチレン性不飽和結合を有する基としては、ビニル基、(メタ)アリル基、(メタ)アクリロイル基等が挙げられる。酸基としては、カルボキシル基、スルホン酸基、リン酸基等が挙げられる。P4が表す置換基は、繰り返し単位を有する1価のポリマー鎖であってもよい。繰り返し単位を有する1価のポリマー鎖は、ビニル化合物由来の繰り返し単位を有する1価のポリマー鎖が好ましい。
D4が表す色素構造は、色素化合物が有する任意の原子を1個以上取り除いた構造であって、色素化合物の一部がL4に結合してなるものであってもよい。また、主鎖または側鎖に色素構造(色素化合物が有する任意の原子を1個以上取り除いた構造)を有する繰り返し単位を含むポリマー鎖であってもよい。上記ポリマー鎖は、色素構造を含んでいれば特に定めるものではないが、(メタ)アクリル系樹脂、スチレン系樹脂、および、(メタ)アクリル/スチレン系樹脂から選ばれる1種であるであることが好ましい。ポリマー鎖の繰り返し単位としては、特に定めるものではないが、式(A)で表される繰り返し単位、式(C)で表される繰り返し単位などが挙げられる。また、ポリマー鎖を構成する全繰り返し単位中における、色素構造を有する繰り返し単位の合計は、5~60モル%であることが好ましく、10~50モル%がより好ましく、20~40モル%がさらに好ましい。
なお、1つの色素多量体(D)における、nおよびkは、それぞれ整数であるが、本発明においては、色素多量体は、式(D)におけるn、kが異なる化合物を複数含んでいてもよい。従って、化合物A中の、nおよびkの平均値は整数にならない場合がある。
式(D-1)のB41およびB42は、それぞれ独立に、単結合、-O-、-S-、-CO-、-NR-、-O2C-、-CO2-、-NROC-、または、-CONR-を表し、単結合、-O-、-CO-、-O2C-、-CO2-、-NROC-、または、-CONR-が好ましく、単結合、-O-、-CO-、-O2C-または-CO2-がより好ましい。Rは、水素原子、アルキル基またはアリール基を表す。
本発明の樹脂組成物は、無機粒子を含んでいても良い。無機粒子は、黒色顔料、透明粒子などが挙げられる。無機粒子の具体例としては、酸化チタン、酸窒化チタン、酸化ケイ素、セシウム酸化タングステン、酸化インジウムスズ、酸窒化バナジウム、カーボンブラック、チタンブラック、酸化アルミニウム、酸化ジルコニウムなどが挙げられる。無機粒子は、例えば黒色顔料が好ましい。黒色顔料を含む組成物は、感度が低いことが多いが、本発明によれば、黒色顔料を含む樹脂組成物であっても、優れた感度を得ることができるので、本発明の効果が顕著に得られる。
黒色顔料としては、特に限定されず、公知のものを用いることができる。カーボンブラック、チタンブラック(酸窒化チタンなど)、グラファイト、酸窒化バナジウム等が挙げられ、カーボンブラック、チタンブラック、酸窒化バナジウムが好ましく、チタンブラックが特に好ましい。チタンブラックとは、チタン原子を含有する黒色粒子である。好ましくは低次酸化チタンや酸窒化チタン等である。チタンブラック粒子は、分散性向上、凝集性抑制などの目的で必要に応じ、表面を修飾することが可能である。酸化珪素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム、又は、酸化ジルコニウムで被覆することが可能であり、また、特開2007-302836号公報に表されるような撥水性物質での処理も可能である。
透明粒子は、酸化チタン(TiO2)、酸化アルミニウム(Al2O3)、酸化ジルコニウム(ZrO2)、酸化ケイ素(SiO2)、酸化スズ(SnO2)等が挙げられる。また、透明粒子は、酸化インジウム(In2O3)と、酸化スズ(SnO2)の無機化合物である、酸化インジウムスズ(tin-doped indium oxide、ITO)を用いることも好ましい。また、酸化アンチモンスズ(ATO)、酸化亜鉛(ZnO)、Alドープ酸化亜鉛(AlドープZnO)、フッ素ドープ二酸化スズ(FドープSnO2)、ニオブドープ二酸化チタン(NbドープTiO2)、セシウム酸化タングステンなどを用いることも好ましい。また、銀(Ag)粒子、金(Au)粒子、銅(Cu)粒子、ニッケル(Ni)粒子を用いることもできる。セシウム酸化タングステンは、国際公開WO2014/142259号公報の段落0025~0029の記載を参酌でき、この内容は本明細書に組み込まれる。
本発明の樹脂組成物は、フタルイミド化合物を含有することが好ましい。特に、着色剤として、緑色顔料(なかでもハロゲン化亜鉛フタロシアニン顔料)を使用した場合、フタルイミド化合物を含有させることで、針状の異物などの発生が抑制された硬化膜を製造することができる。フタルイミド化合物は、下記一般式(PI)で表される化合物であることが好ましい。
ハロゲン原子としては、塩素原子、臭素原子、フッ素原子が挙げられ、塩素原子またはフッ素原子が好ましい。
アルキル基の炭素数は、1~10が好ましく、1~5がより好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましく、直鎖がより好ましい。
A1~A4の少なくとも一つは、塩素原子、および、臭素原子から選ばれることが好ましく、臭素原子であることがより好ましい。また、A1~A4の全てが、塩素原子、および、臭素原子から選ばれることがより好ましく、A1~A4の全てが、臭素原子であることがより好ましい。
本発明の樹脂組成物は、有機溶剤を含有する。有機溶剤は、各成分の溶解性や組成物の塗布性を満足すれば基本的には特に制限はないが、組成物の塗布性、安全性を考慮して選ばれることが好ましい。
本発明において、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。
本発明の樹脂組成物は、重合性化合物の反応を促進させたり、硬化温度を下げる目的で、硬化促進剤を添加してもよい。硬化促進剤としては、分子内に2個以上のメルカプト基を有する多官能チオール化合物(多官能メルカプト化合物)などが挙げられる。多官能チオール化合物は安定性、臭気、解像性、現像性、密着性等の改良を目的として添加してもよい。多官能チオール化合物は、2級のアルカンチオール類であることが好ましく、特に下記一般式(T1)で表される構造を有する化合物であることが好ましい。
一般式(T1)
本発明の樹脂組成物は、組成物の製造中又は保存中において、架橋性化合物の不要な熱重合を阻止するために、重合禁止剤を含有させてもよい。重合禁止剤としては、ハイドロキノン、パラ-メトキシフェノール、ジ-tert-ブチル-パラ-クレゾール、ピロガロール、tert-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-tert-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)等が挙げられる。中でも、パラ-メトキシフェノールが好ましい。重合禁止剤の含有量は、樹脂組成物の全固形分に対して、0.01~5質量%が好ましい。
本発明の樹脂組成物は、塗布性をより向上させる観点から、各種の界面活性剤を含有させてもよい。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の各種界面活性剤を使用できる。
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、を含む含フッ素高分子化合物も好ましく用いることができ、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。
また、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開2010-164965号公報0050~0090段落および0289~0295段落に記載された化合物、例えばDIC社製のメガファックRS-101、RS-102、RS-718K、RS-72-K等が挙げられる。
本発明の樹脂組成物は、紫外線吸収剤を含有してもよい。紫外線吸収剤を含む組成物は、i線の透過率が低下する傾向にある。このため、紫外線吸収剤を含む樹脂組成物をi線で露光する場合、感度が低い場合があるが、本発明によれば、紫外線吸収剤を含む樹脂組成物であっても、優れた感度を得ることができるので、本発明の効果が顕著に得られる。
紫外線吸収剤の含有量は、本発明の樹脂組成物の全固形分に対して、0.01~10質量%が好ましく、0.01~5質量%がより好ましい。
本発明の樹脂組成物は、基板密着性を向上させる目的で、シランカップリング剤を含有させてもよい。
シランカップリング剤とは、分子中に加水分解性基とそれ以外の官能基を有する化合物である。なお、アルコキシ基等の加水分解性基は、珪素原子に結合している。
加水分解性基とは、珪素原子に直結し、加水分解反応及び/又は縮合反応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、アルケニルオキシ基が挙げられる。加水分解性基が炭素原子を有する場合、その炭素数は6以下であることが好ましく、4以下であることがより好ましい。特に、炭素数4以下のアルコキシ基又は炭素数4以下のアルケニルオキシ基が好ましい。
また、シランカップリング剤は硬化膜の密着性を向上させるため、フッ素原子および珪素原子(ただし、加水分解性基が結合した珪素原子は除く)を含まないことが好ましく、フッ素原子、珪素原子(ただし、加水分解性基が結合した珪素原子は除く)、珪素原子で置換されたアルキレン基、炭素数8以上の直鎖アルキル基、及び、炭素数3以上の分鎖アルキル基は含まないことが望ましい。
なお、本発明において、シランカップリング剤は、上述した重合性化合物および熱硬化性化合物とは異なる化合物である。すなわち、分子中に加水分解性基とそれ以外の官能基を有する化合物はシランカップリング剤とする。
式(Z) *-Si(Rz1)3-m(Rz2)m
Rz1はアルキル基を表し、Rz2は加水分解性基を表し、mは1~3の整数を表す。Rz1が表すアルキル基の炭素数は、1~5が好ましく、1~3がより好ましい。Rz2が表す加水分解性基の定義は上述の通りである。
式(W) Rz3-Lz-Si(Rz1)3-m(Rz2)m
Rz1はアルキル基を表し、Rz2は加水分解性基を表し、Rz3は、硬化性官能基を表し、Lzは、単結合又は2価の連結基を表し、mは1~3の整数を表す。
Rz1が表すアルキル基の定義は上述の通りである。Rz2が表す加水分解性基の定義は上述の通りである。
Lzは、単結合又は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、アリーレン基、-NR12-、-CONR12-、-CO-、-CO2-、-SO2NR12-、-O-、-S-、-SO2-、又は、これらの組み合わせが挙げられる。
アルキレン基の炭素数は、1~20が好ましい。アルキレン基は、直鎖および分岐のいずれでもよい。アルキレン基およびアリーレン基は、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、ハロゲン原子、ヒドロキシル基が挙げられる。
Lzは、炭素数2~10のアルキレン基および炭素数6~12のアリーレン基からなる群から選択される少なくとも1種、又は、これらの基と-NR12-、-CONR12-、-CO-、-CO2-、-SO2NR12-、-O-、-S-、及び-SO2-からなる群から選択される少なくとも1種の基との組み合わせからなる基が好ましく、炭素数2~10のアルキレン基、-CO2-、-O-、-CO-、-CONR12-、又は、これらの基の組み合わせからなる基がより好ましい。ここで、上記R12は、水素原子又はメチル基を表す。
mは1~3を表し、2~3が好ましく、3がより好ましい。
シランカップリング剤Yは、分子内に少なくとも1つの珪素原子を有すればよく、珪素原子は、以下の原子、置換基と結合できる。それらは同じ原子、置換基であっても異なっていてもよい。結合しうる原子、置換基は、水素原子、ハロゲン原子、水酸基、炭素数1から20のアルキル基、アルケニル基、アルキニル基、アリール基、アルキル基及び/又はアリール基で置換可能なアミノ基、シリル基、炭素数1から20のアルコキシ基、アリーロキシ基などが挙げられる。これらの置換基はさらに、シリル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリーロキシ基、チオアルコキシ基、アルキル基及び/又はアリール基で置換可能なアミノ基、ハロゲン原子、スルホンアミド基、アルコキシカルボニル基、アミド基、ウレア基、アンモニウム基、アルキルアンモニウム基、カルボキシル基、又はその塩、スルホ基、又はその塩などで置換されていてもよい。
なお、珪素原子には少なくとも一つの加水分解性基が結合している。加水分解性基の定義は、上述の通りである。
シランカップリング剤Yには、式(Z)で表される基が含まれていてもよい。
また、窒素原子は、任意の有機連結基を介して硬化性官能基と結合していることが好ましい。好ましい有機連結基としては、上述の窒素原子及びそれに結合する有機基に導入可能な置換基を挙げることができる。
硬化性官能基はシランカップリング剤Yの一分子中に少なくとも一つ以上有していればよいが、硬化性官能基を2以上有する態様をとることも可能であり、感度、安定性の観点からは、硬化性官能基を2~20有することが好ましく、4~15有することがさらに好ましく、最も好ましくは分子内に硬化性官能基を6~10有する態様である。
式(Y) (Ry3)n-LN-Si(Ry1)3-m(Ry2)m
Ry1はアルキル基を表し、Ry2は加水分解性基を表し、Ry3は、硬化性官能基を表し、
LNは、窒素原子を有する(n+1)価の連結基を表し、
mは1~3の整数を表し、nは1以上の整数を表す。
式(Y)のRy1、Ry2、Ry3およびmは、式(W)のRz1、Rz2、Rz3およびmと同義であり、好ましい範囲も同様である。
式(Y)のnは、1以上の整数を表す。上限は、例えば、20以下が好ましく、15以下がより好ましく、10以下が更に好ましい。下限は、例えば、2以上が好ましく、4以上がより好ましく、6以上が更に好ましい。また、nは1とすることもできる。
式(Y)のLNは、窒素原子を有する基を表す。
窒素原子を有する基としては、下記式(LN-1)~(LN-4)から選ばれる少なくとも一種、または、下記式(LN-1)~(LN-4)と、アルキレン基、アリーレン基、-CO-、-CO2-、-O-、-S-および-SO2-から選ばれる少なくとも1種との組み合わせからなる基が挙げられる。アルキレン基は、直鎖および分岐のいずれでもよい。アルキレン基およびアリーレン基は、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、ハロゲン原子、ヒドロキシル基が挙げられる。
本発明の樹脂組成物には、必要に応じて、各種添加物、例えば、充填剤、密着促進剤、酸化防止剤、凝集防止剤等を配合することができる。これらの添加物としては、特開2004-295116号公報の段落0155~0156に記載のものを挙げることができ、これらの内容は本明細書に組み込まれる。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 0042段落に記載の化合物)、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。酸化防止剤は2種以上を混合して使用してもよい。本発明の樹脂組成物においては、特開2004-295116号公報の段落0078に記載の増感剤や光安定剤、同公報の段落0081に記載の熱重合防止剤を含有することができる。
本発明の樹脂組成物は、前述の成分を混合して調製できる。樹脂組成物の調製に際しては、各成分を一括配合してもよいし、各成分を溶剤に溶解・分散した後に逐次配合してもよい。また、配合する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解・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2つ以上の溶液・分散液としておいて、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。
フィルタの孔径は、0.01~7.0μm程度が適しており、好ましくは0.01~3.0μm程度、さらに好ましくは0.05~0.5μm程度である。この範囲とすることにより、後工程において均一な組成物の調製や、平滑な膜の形成などを阻害する微細な異物を確実に除去することが可能となる。また、ファイバ状のろ材を用いることも好ましく、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、具体的に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)のフィルタカートリッジを用いることができる。
また、上述した範囲内で異なる孔径の第1のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社(DFA4201NXEY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)又は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の中から選択することができる。
第2のフィルタは、上述した第1のフィルタと同様の材料等で形成されたものを使用することができる。
例えば、第1のフィルタでのフィルタリングは、分散液のみで行い、他の成分を混合した後で、第2のフィルタリングを行ってもよい。
次に、本発明の硬化膜について説明する。
本発明の硬化膜は、上述した本発明の樹脂組成物を用いてなるものである。本発明の硬化膜は、CCD(電荷結合素子)やCMOS(相補型金属酸化膜半導体)などの固体撮像素子や、画像表示装置などの各種装置に用いることができる。
次に、本発明のパターン形成方法について説明する。
本発明のパターン形成方法は、本発明の感放射線性樹脂組成物を用いて支持体上に感放射線性樹脂組成物層を形成する工程と、感放射線性樹脂組成物層をパターン状に露光する工程と、未露光部を現像除去してパターンを形成する工程とを含む。以下、各工程について説明する。
感放射線性樹脂組成物層を形成する工程では、感放射線性樹脂組成物を用いて、支持体上に感放射線性樹脂組成物層を形成する。
本発明におけるパターンは、固体撮像素子用基板の固体撮像素子形成面側(おもて面)に形成してもよいし、固体撮像素子非形成面側(裏面)に形成してもよい。
支持体上には、必要により、上部の層との密着改良、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。
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。プリベーク温度を150℃以下で行うことにより、例えば、イメージセンサの光電変換膜を有機素材で構成した場合において、これらの特性をより効果的に維持することができる。
プリベーク時間は、10秒~300秒が好ましく、40~250秒がより好ましく、80~220秒がさらに好ましい。乾燥は、ホットプレート、オーブン等で行うことができる。
次に、感放射線性樹脂組成物層を、パターン状に露光する(露光工程)。例えば、感放射線性樹脂組成物層に対し、ステッパー等の露光装置を用いて、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線等の紫外線が好ましく(特に好ましくはi線)用いられる。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、大気下で行う他に、例えば酸素濃度が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可能であり、通常1000W/m2~100000W/m2(例えば、5000W/m2、15000W/m2、35000W/m2)の範囲から選択することができる。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。
硬化膜の膜厚は2.0μm以下が好ましく、1.0μm以下がより好ましく、0.7μm以下がさらに好ましい。下限は、例えば0.1μm以上とすることができ、0.2μm以上とすることもできる。膜厚を、2.0μm以下とすることにより、高解像性、高密着性が得られ易い。
次に、未露光部を現像除去してパターンを形成する。未露光部の現像除去は、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感放射線性樹脂組成物層が現像液に溶出し、光硬化した部分だけが残る。
現像液としては、下地の固体撮像素子や回路などにダメージを起さない、有機アルカリ現像液が望ましい。
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、残渣除去性を向上するため、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。
また、現像液には無機アルカリを用いてもよい。無機アルカリとしては、例えば、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が好ましい。
また、現像液には、界面活性剤を用いてもよい。界面活性剤の例としては、上述した硬化性組成物で説明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。
なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、一般に現像後純水で洗浄(リンス)することが好ましい。
ポストベークにおいては、現像後の膜を、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。また、低温プロセスによりパターンを形成する場合は、ポストベークは行わなくてもよい。
本発明の固体撮像素子は、本発明の硬化膜を有する。本発明の固体撮像素子の構成としては、本発明の硬化膜が備えられた構成であり、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が、例えば、以下のような構成が挙げられる。
さらに、上記デバイス保護膜上であってカラーフィルタの下(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、カラーフィルタ上に集光手段を有する構成等であってもよい。
本発明の硬化膜は、液晶表示装置や有機エレクトロルミネッセンス表示装置などの、画像表示装置に用いることができる。本発明の硬化膜を備えた画像表示装置は、表示画像の色合いが良好で表示特性に優れた高画質画像を表示することができる。表示装置の定義や各表示装置の詳細については、例えば「電子ディスプレイデバイス(佐々木 昭夫著、(株)工業調査会 1990年発行)」、「ディスプレイデバイス(伊吹 順章著、産業図書(株)平成元年発行)」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術(内田 龍男編集、(株)工業調査会 1994年発行)」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。
下記組成の混合液を、0.3mm径のジルコニアビーズを使用して、ビーズミル(減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製))で、2時間、混合して、分散液を調製した。なお、分散液8は、YMS-01A-2(住友金属鉱山(株)製)を用いた。
緑色顔料(C.I.Pigment Green 58):9.8質量部
黄色顔料(C.I.Pigment Yellow 185):2.8質量部
樹脂1(下記構造、重量平均分子量=24,000):4.6質量部
酸化チタン(TiO2):23.0質量部
樹脂1:6.2質量部
プロピレングリコールモノメチルエーテルアセテート:70.8質量部
酸化アルミニウム(Al2O3):19.5質量部
樹脂(MB-517-42、富士ファインケミカルズ(株)製):5.3質量部
プロピレングリコールモノメチルエーテルアセテート 75.2質量部
酸化ジルコニウム(ZrO2):21.1質量部
樹脂1:5.7質量部
プロピレングリコールモノメチルエーテルアセテート:73.2質量部
酸化インジウムスズ(ITO):18.0質量部
樹脂1:4.9質量部
プロピレングリコールモノメチルエーテルアセテート:77.1質量部
チタンブラック:23.3質量部
樹脂2(下記構造、重量平均分子量=38900):7.6質量部
酢酸ブチル:27.6質量部
酸窒化バナジウム:21.5質量部
樹脂1:6.4質量部
プロピレングリコールモノメチルエーテルアセテート 72.1質量部
YMS-01A-2(住友金属鉱山(株)製、セシウム酸化タングステン分散液、セシウム酸化タングステン(CsWO3) 25質量%、樹脂 13.7質量%含有)
カーボンブラック:19.0質量部
樹脂(アクリベースFFS-6824、藤倉化成(株)製):8.4質量部
プロピレングリコールモノメチルエーテルアセテート:38.3質量部
シクロヘキサノン:16.4質量部
エチル-3-エトキシプロピオネート:17.9質量部
緑色顔料(C.I.Pigment Green 58):9.77質量部
黄色顔料(C.I.Pigment Yellow 185):2.8質量部
樹脂1:4.6質量部
テトラブロモフタルイミド:0.03質量部
プロピレングリコールモノメチルエーテルアセテート:82.8質量部
下記表に示す材料を、下記表に示す割合(質量%)で混合および攪拌し、水分量を下記表に示す値(質量%)に調整した後、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製、DFA4201NXEY)でろ過して、感放射線性樹脂組成物を調製した。なお、組成物中の水の含有量は、カールフィッシャー法で測定した。
A-1:アクリキュアーRD-F8((株)日本触媒製)
A-2:アクリベースFF-426(藤倉化成(株)製)
A-3:下記構造(重量平均分子量=12,000)
A-4:下記構造(重量平均分子量=41,000)
A-5:下記構造(重量平均分子量=11,000)
B-1:NKエステルA-TMMT(新中村化学社工業(社)製)
B-2:KAYARAD DPHA(日本化薬(株)製)
B-3:下記構造
B-5:下記構造
[分岐アルキル基および環状アルキル基から選ばれる少なくとも1種類の基を有するオキシムエステル化合物]
C-1:下記構造の化合物(分岐アルキル基を有するオキシムエステル化合物)
C-2:下記構造の化合物(環状アルキル基を有するオキシムエステル化合物)
C-3:下記構造の化合物(分岐アルキル基を有するオキシムエステル化合物)
C-4:IRGACURE-OXE02(BASF社製)
C-5:IRGACURE-OXE01(BASF社製)
C-6:IRGACURE-369(BASF社製)
C-7:IRGACURE-379(BASF社製)
C-8:IRGACURE-819(BASF社製)
C-9:下記化合物
D-1:プロピレングリコールモノメチルエーテルアセテート
D-2:シクロヘキサノン
E-1:UV-503(大東化学(株)製)
E-2:TINUVIN477(BASF社製)
F-1:EHPE3150(ダイセル(株)製)
(初期感度の評価)
直径8インチ(1インチ=25.4mm)のシリコンウエハをオーブン中で200℃のもと30分加熱処理した。次いで、このシリコンウエハ上に、下塗り用レジスト液(CT-4000、富士フイルムエレクトロニクスマテリアルズ(株)製)を乾燥膜厚が0.1μmになるように塗布し、さらに220℃のオーブン中で1時間加熱乾燥させて下塗り層を形成し、下塗り層付シリコンウエハ基板を得た。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して365nmの波長で、パターンを有するマスクを通して表3に記載の露光量で露光を行った。なお、実施例1~4、17、比較例1~7は、0.9μm×0.9μmのベイヤーパターンを有するマスクを用いた。また、実施例5~8は、1.1μm×1.1μmのベイヤーパターンを有するマスクを用いた。また、実施例9~10、12は、直径100μmのホールパターンを有するマスクを用いた。また、実施例11、13は、10μm×10μmのベイヤーパターンを有するマスクを用いた。また、実施例14は、0.8μm×0.8μmのベイヤーパターンを有するマスクを用いた。また、実施例15および16は、1.0μm×1.0μmのアイランドパターンを有するマスクを用いた。
その後、照射された塗布膜が形成されているシリコンウエハ基板をスピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、23℃の現像液(CD-1030、富士フイルムエレクトロニクスマテリアルズ(株)製)をノズルからシャワー状に供給し(15秒間)、30秒間パドル状態を維持する操作を4回行って、パドル現像を行い、パターンを形成した。
次に、パターンが形成された基板を、真空チャック方式で水平回転テーブルに固定し、回転装置によってシリコンウエハ基板を回転数50rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理(23秒×2回)を行ない、次いで、スピン乾燥し、次いで、200℃で300秒間、ホットプレートでポストベークを行い、パターンを得た。
A:パターン部の幅が、使用したマスクのパターンサイズの95%以上105%以下の範囲である。
B:パターン部の幅が、使用したマスクのパターンサイズの90%以上95%未満であるか、または、使用したマスクのパターンサイズの105%を超え110%未満である。
C:パターン部の幅が、使用したマスクのパターンサイズの90%未満であるか、または、使用したマスクのパターンサイズの110%を超える。
感放射線性樹脂組成物を、密閉した容器に入れ、10℃の環境下で、3~9ヶ月間保管した。保管後の感放射線性樹脂組成物を用いて、初期感度の評価と同じ条件で、パターンを形成した。
得られたパターンについて、走査型電子顕微鏡(SEM)を用い、20,000倍に拡大して、パターン部の幅を評価し、以下の基準で初期感度を評価した。また、初期状態よりもパターン幅が大きくなっていれば感度が増加したと判断し、小さくなっていれば感度が低下したと判断した。
なお、比較例2~6は、初期感度が劣るため、経時安定性の評価は行わなかった。
A:9ヵ月間保管後の感放射線性樹脂組成物を用いたパターンのパターン幅が、製造直後の感放射線性樹脂組成物を用いて製造したパターンのパターン幅の90%以上110%以下の範囲である。
B:9ヵ月間保管後の感放射線性樹脂組成物を用いたパターンのパターン幅が、製造直後の感放射線性樹脂組成物を用いて製造したパターンのパターン幅の90%を下回るか、または、110%を超えるが、6ヵ月間保管後の感放射線性樹脂組成物を用いたパターンのパターン幅の変化率が、製造直後の感放射線性樹脂組成物を用いて製造したパターンのパターン幅の-10%~+10%の範囲である。
C:6ヵ月間保管後の感放射線性樹脂組成物を用いたパターンのパターン幅が、製造直後の感放射線性樹脂組成物を用いて製造したパターンのパターン幅の90%を下回るか、または、110%を超える。
ガラス基板上に、感放射線性樹脂組成物を塗布し、プリベーク(100℃120秒)、500mj/cm2露光(マスク無しで全面露光)、ポストベーク(200℃300秒)を行い、平坦膜(パターンが無い膜)を製造した。得られた平坦膜について、大塚電子株式会社製マルチチャンネル分光器MCPD-3000で350nm~800nmの分光透過率を5nmステップで測定し、波長365nmの光の透過率を測定した。
これに対し、水を含まない比較例1は、経時でパターン幅が大きくなり、経時で増感が見られ、感度の経時安定性が劣っていた。さらには、比較例1は、現像速度も実施例に比べて遅かった。
また、分岐アルキル基および環状アルキル基から選ばれる少なくとも1種類の基を有するオキシムエステル化合物を含まない光重合開始剤を使用した比較例2~7のうち、比較例2~6は、初期感度が劣るものであった。
また、比較例7は、初期感度は良好であったが、経時でパターン幅が小さくなっており、経時で感度の低下が見られ、感度の経時安定性が劣っていた。
Claims (20)
- 樹脂と、エチレン性不飽和結合を有する重合性化合物と、光重合開始剤と、有機溶剤と、水を含む感放射線性樹脂組成物であって、
前記光重合開始剤は、分岐アルキル基および環状アルキル基から選ばれる少なくとも1種類の基を有するオキシムエステル化合物を含み、
水の含有量が、前記感放射線性樹脂組成物の質量に対して0.1~2質量%である、感放射線性樹脂組成物。 - 前記樹脂は、アルカリ可溶性樹脂を含む、請求項1に記載の感放射線性樹脂組成物。
- 前記重合性化合物は、エチレン性不飽和結合当量が3.0~12.0mmol/gの多官能(メタ)アクリレート化合物である、請求項1または2に記載の感放射線性樹脂組成物。
- 前記オキシムエステル化合物は、炭素数7以上の分岐アルキル基および、炭素数7以上の環状アルキル基から選ばれる少なくとも1種類の基を有する、請求項1~3のいずれか1項に記載の感放射線性樹脂組成物。
- 前記オキシムエステル化合物は、カルバゾール構造を有する、請求項1~4のいずれか1項に記載の感放射線性樹脂組成物。
- 前記カルバゾール構造は、カルバゾール部のベンゼン環に、更に環が縮合した構造を有する、請求項5に記載の感放射線性樹脂組成物。
- 前記オキシムエステル化合物は、フッ素原子を含むオキシムエステル化合物である、請求項1~6のいずれか1項に記載の感放射線性樹脂組成物。
- 前記有機溶剤は、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メチルエーテル、シクロヘキサノン、酢酸ブチル、エチル-3-エトキシプロピオネート、プロピレングリコールモノエチルエーテルアセテート、キシレン、エチルベンゼン、メチルイソブチルケトン、2-ブタノール、ジプロピレングリコールモノメチルエーテルから選ばれる少なくとも1種以上である、請求項1~8のいずれか1項に記載の感放射線性樹脂組成物。
- 更に、有彩色着色剤および無機粒子から選ばれる少なくとも1種を含む、請求項1~9のいずれか1項に記載の感放射線性樹脂組成物。
- 更に、フタルイミド化合物を含む、請求項1~10のいずれか1項に記載の感放射線性樹脂組成物。
- 更に、紫外線吸収剤を含む、請求項1~11のいずれか1項に記載の感放射線性樹脂組成物。
- 更に、熱硬化性化合物を含む、請求項1~12のいずれか1項に記載の感放射線性樹脂組成物。
- 前記光重合開始剤は、更に、前記オキシムエステル化合物以外の化合物を含む、請求項1~13のいずれか1項に記載の感放射線性樹脂組成物。
- 前記オキシムエステル化合物以外の化合物は、分岐アルキル基および環状アルキル基を有さないオキシムエステル化合物、アルキルフェノン化合物、および、アシルホスフィン化合物から選ばれる少なくとも1種である、請求項14に記載の感放射線性樹脂組成物。
- 請求項1~15のいずれか1項に記載の感放射線性樹脂組成物を用いた硬化膜。
- 波長365nmの光の透過率が15%以下である、請求項16に記載の硬化膜。
- 請求項1~15のいずれか1項に記載の感放射線性樹脂組成物を用いて支持体上に感放射線性樹脂組成物層を形成する工程と、感放射線性樹脂組成物層をパターン状に露光する工程と、未露光部を現像除去してパターンを形成する工程とを含むパターン形成方法。
- 請求項16または17に記載の硬化膜を有する固体撮像素子。
- 請求項16または17に記載の硬化膜を有する画像表示装置。
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JP6860500B2 (ja) | 2021-04-14 |
KR20180077238A (ko) | 2018-07-06 |
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JP2021152678A (ja) | 2021-09-30 |
TW202141184A (zh) | 2021-11-01 |
US10921708B2 (en) | 2021-02-16 |
CN114779576A (zh) | 2022-07-22 |
TWI761230B (zh) | 2022-04-11 |
US20180275514A1 (en) | 2018-09-27 |
CN108369377B (zh) | 2022-05-17 |
JP6906659B2 (ja) | 2021-07-21 |
US20210132496A1 (en) | 2021-05-06 |
TW201740187A (zh) | 2017-11-16 |
CN108369377A (zh) | 2018-08-03 |
TWI731895B (zh) | 2021-07-01 |
JPWO2017099019A1 (ja) | 2018-09-13 |
KR102236564B1 (ko) | 2021-04-06 |
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