WO2021111950A1 - 着色組成物、硬化膜、構造体、カラーフィルタおよび表示装置 - Google Patents
着色組成物、硬化膜、構造体、カラーフィルタおよび表示装置 Download PDFInfo
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- WO2021111950A1 WO2021111950A1 PCT/JP2020/043853 JP2020043853W WO2021111950A1 WO 2021111950 A1 WO2021111950 A1 WO 2021111950A1 JP 2020043853 W JP2020043853 W JP 2020043853W WO 2021111950 A1 WO2021111950 A1 WO 2021111950A1
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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
- G03F7/004—Photosensitive materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
- C09B45/22—Monoazo compounds containing other metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/10—Obtaining compounds having halogen atoms directly bound to the phthalocyanine skeleton
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
Definitions
- the present invention relates to a coloring composition. More specifically, the present invention relates to a coloring composition used for forming green pixels of a color filter and the like. The present invention also relates to a cured film, a structure, a color filter and a display device using the coloring composition.
- color filters are generally used to colorize display images. Further, in a color filter, an attempt is made to adjust the spectroscopy by using a plurality of pigments in combination.
- the coloring composition for forming green pixels of the color filter contains a green coloring agent as a coloring agent.
- a coloring composition containing a colorant containing Color Index Pigment Green 7 and Color Index Pigment Yellow 150, a polymerizable compound, and a photopolymerization initiator is used in green. It is described that the pixels are formed.
- the viscosity of a coloring composition using a coloring agent containing a pigment tends to increase with time, and further improvement in storage stability is desired.
- the color filter it is desired that the color separation property is high and the light resistance is excellent. These characteristics have been demanded at a higher level in recent years.
- the present invention provides: ⁇ 1> A coloring composition containing a colorant, a polymerizable compound, and a photopolymerization initiator.
- the colorant includes a green colorant containing 1% by mass or more of Color Index Pigment Green 7 and a yellow colorant containing Color Index Pigment Yellow 150, and a green colorant other than Color Index Pigment Green 7 and a color index.
- the coloring composition exists in a wavelength range in which the absorbance at 0.2 is 550 nm or more and 600 nm or less, where 1 is the absorbance for light having a wavelength of 450 nm.
- Coloring composition ⁇ 2> The coloring composition according to ⁇ 1>, wherein the coloring composition has a minimum absorbance in a wavelength range of 495 nm or more and less than 550 nm among the absorbances for light having a wavelength of 400 to 700 nm.
- the coloring composition exists in each of a wavelength range in which the absorbance at 0.2 is 470 nm or more and 490 nm or less and a wavelength range in which 550 nm or more and 600 nm or less, when the absorbance for light having a wavelength of 450 nm is 1.
- ⁇ 4> The coloring composition according to any one of ⁇ 1> to ⁇ 3>, wherein the total amount of the color index pigment green 7 and the color index pigment yellow 150 in the colorant is 80% by mass or more.
- ⁇ 5> The coloring composition according to any one of ⁇ 1> to ⁇ 4>, wherein the green colorant other than the color index pigment green 7 contains the color index pigment green 36.
- ⁇ 6> The coloring composition according to any one of ⁇ 1> to ⁇ 5>, wherein the yellow coloring agent is substantially only Color Index Pigment Yellow 150.
- the yellow coloring agent is substantially only Color Index Pigment Yellow 150.
- the green colorant is substantially only Color Index Pigment Green 7.
- ⁇ 8> The coloring composition according to any one of ⁇ 1> to ⁇ 7>, which contains 50 to 240 parts by mass of Color Index Pigment Yellow 150 with respect to 100 parts by mass of Color Index Pigment Green 7.
- ⁇ 9> The coloring composition according to any one of ⁇ 1> to ⁇ 8>, wherein the content of the coloring agent in the total solid content of the coloring composition is 20% by mass or more.
- ⁇ 10> The coloring composition according to any one of ⁇ 1> to ⁇ 9>, wherein the polymerizable compound contains a polymerizable compound having three or more ethylenically unsaturated bond-containing groups.
- the polymerizable compound contains a polymerizable compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group.
- the photopolymerization initiator contains an oxime compound.
- ⁇ 13> The coloring composition according to any one of ⁇ 1> to ⁇ 12>, wherein the photopolymerization initiator contains an oxime compound and a hydroxyalkylphenone compound.
- ⁇ 14> The coloring composition according to any one of ⁇ 1> to ⁇ 13>, which is a coloring composition for forming green pixels of a color filter.
- ⁇ 15> The coloring composition according to any one of ⁇ 1> to ⁇ 14>, which is a coloring composition for a display device.
- ⁇ 16> The coloring composition according to any one of ⁇ 1> to ⁇ 15>, which is used for forming a cured film at a temperature of 150 ° C. or lower throughout the entire process.
- ⁇ 17> A cured film obtained by using the coloring composition according to any one of ⁇ 1> to ⁇ 16>.
- ⁇ 18> A structure having a green pixel, a red pixel, and a blue pixel, and the green pixel is obtained by using the coloring composition according to any one of ⁇ 1> to ⁇ 16>.
- ,Structure. ⁇ 19> The color filter having the cured film according to ⁇ 17>.
- ⁇ 20> A display device having the cured film according to ⁇ 17>.
- the present invention it is possible to provide a coloring composition capable of forming a cured film having good storage stability and excellent light resistance and color separation from other colors.
- the present invention can also provide a cured film, a structure, a color filter and a display device using the coloring composition.
- the notation not describing substitution and non-substitution includes a group having no substituent (atomic group) as well as a group having a substituent (atomic group).
- 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).
- the term "exposure” as used herein includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam.
- the emission line spectrum of a mercury lamp far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation
- the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
- the total solid content means the total mass of all the components of the composition excluding the solvent.
- “(meth) acrylate” represents both acrylate and methacrylate, or either
- “(meth) acrylic” represents both acrylic and methacrylic, or either.
- Allyl represents both allyl and methacrylic, or either, and" (meth) acryloyl “represents both acryloyl and methacrylic, or either.
- process is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
- weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values measured by gel permeation chromatography (GPC).
- the coloring composition of the present invention is a coloring composition containing a coloring agent, a polymerizable compound, and a photopolymerization initiator.
- the colorant includes a green colorant containing 1% by mass or more of Color Index Pigment Green 7 and a yellow colorant containing Color Index Pigment Yellow 150, and a green colorant other than Color Index Pigment Green 7 and a color index.
- the coloring composition is characterized in that the wavelength at which the absorbance is 0.2 exists in the wavelength range of 550 nm or more and 600 nm or less when the absorbance with respect to light having a wavelength of 450 nm is 1.
- the coloring composition of the present invention contains a green colorant containing 1% by mass or more of the color index pigment green 7 as a colorant and a yellow colorant containing the color index pigment yellow 150, and is other than the color index pigment green 7.
- the absorbance A ⁇ at a certain wavelength ⁇ is defined by the following equation (Ab1).
- a ⁇ -log (T ⁇ / 100) ...
- a ⁇ is the absorbance at the wavelength ⁇ , and T ⁇ is the transmittance (%) at the wavelength ⁇ .
- the absorbance value may be a value measured in a solution state or a value of a cured film formed by using a coloring composition.
- a coloring composition is applied onto a glass substrate by a method such as spin coating, dried at 100 ° C. for 2 minutes using a hot plate or the like, and then the light illuminance is 20 mW / cm 2 . It is preferable to perform i-line exposure under the condition of an exposure amount of 1 J / cm 2 , and then measure using a film (cured film) obtained by heating on a hot plate at 100 ° C. for 20 minutes and allowing to cool to room temperature. ..
- the absorbance can be measured using a conventionally known spectrophotometer.
- the coloring composition of the present invention exists in a wavelength range in which the absorbance at 0.2 is 550 nm or more and 600 nm or less, where 1 is the absorbance for light having a wavelength of 450 nm.
- the coloring composition of the present invention exists in each of a wavelength range in which the absorbance at 0.2 is 470 nm or more and 490 nm or less and a wavelength range in which 550 nm or more and 600 nm or less, respectively, when the absorbance with respect to light having a wavelength of 450 nm is 1. Is preferable.
- the wavelength on the short wavelength side (hereinafter, also referred to as wavelength ⁇ 1) at which the absorbance is 0.2 is preferably present in the wavelength range of 473 nm or more and 487 nm or less from the viewpoint of color separation, and is a wavelength of 475 nm or more and 485 nm or less. It is more preferably present in the range, and even more preferably in the wavelength range of 478 nm or more and 482 nm or less.
- the wavelength on the long wavelength side (hereinafter, also referred to as wavelength ⁇ 2) at which the absorbance is 0.2 preferably exists in the wavelength range of 555 nm or more and 595 nm or less from the viewpoint of color separation, and is a wavelength of 560 nm or more and 590 nm or less. It is more preferably present in the range, and even more preferably in the wavelength range of 565 nm or more and 585 nm or less.
- the wavelength difference ( ⁇ 2- ⁇ 1) between the wavelength ⁇ 2 and the wavelength ⁇ 1 is preferably 60 to 115 nm, more preferably 70 to 105 nm, and even more preferably 75 to 100 nm from the viewpoint of color separation.
- the colored composition of the present invention preferably has the minimum absorbance in the wavelength range of 495 nm or more and less than 550 nm, and has the absorbance in the wavelength range of 500 nm or more and 535 nm or less, among the absorbances for light having a wavelength of 400 to 700 nm. It is more preferable to have a minimum value, and it is further preferable to have a minimum value of absorbance in the wavelength range of 505 nm or more and 525 nm or less.
- the wavelength showing the minimum value of the absorbance is also referred to as wavelength ⁇ min.
- the wavelength difference between the wavelength ⁇ min and the wavelength ⁇ 1 (wavelength ⁇ min- ⁇ 1) is preferably 15 to 60 nm, more preferably 20 to 50 nm, and further preferably 25 to 40 nm from the viewpoint of color separation. preferable.
- the wavelength difference between the wavelength ⁇ 2 and the wavelength ⁇ min (wavelength ⁇ 2-wavelength ⁇ min) is preferably 30 to 70 nm, more preferably 40 to 60 nm, and 45 to 55 nm from the viewpoint of color separation. Is even more preferable.
- the maximum value of the transmittance for light having a wavelength of 495 nm or more and less than 550 nm in the thickness direction of the film is 65% or more. It is preferably 70% or more, more preferably 75% or more.
- the average transmittance of the film for light having a wavelength of 495 nm or more and less than 550 nm is preferably 60% or more, more preferably 65% or more, and further preferably 70% or more.
- the transmittance of the film with respect to light having a wavelength of 450 nm is preferably 10% or less, more preferably 5% or less, and further preferably 2% or less.
- the average transmittance of the film with respect to light having a wavelength of 400 nm or more and 450 nm or less is preferably 10% or less, more preferably 5% or less, and further preferably 1% or less.
- the average transmittance of the film for light having a wavelength of 550 nm or more and 600 nm or less is preferably 60% or less, more preferably 50% or less, and further preferably 40% or less.
- the coloring composition of the present invention can be preferably used as a coloring composition for forming pixels of a color filter, and more preferably as a coloring composition for forming green pixels of a color filter.
- the coloring composition of the present invention can be preferably used as a coloring composition for a display device. More specifically, it can be preferably used as a coloring composition for forming pixels of a color filter for a display device, and more preferably as a coloring composition for forming green pixels of a color filter for a display device.
- the type of display device is not particularly limited, and examples thereof include a display device having an organic semiconductor element as a light source, such as an organic electroluminescence display device.
- the coloring composition of the present invention can also be used as a coloring composition for a solid-state image sensor. More specifically, it can be preferably used as a coloring composition for forming pixels of a color filter for a solid-state image sensor, and more preferably as a coloring composition for forming green pixels of a color filter for a solid-state image sensor.
- the coloring composition of the present invention is used for forming a cured film at a temperature of 150 ° C. or lower (preferably a temperature of 120 ° C. or lower) throughout the entire process.
- forming a cured film at a temperature of 150 ° C. or lower throughout the entire process means that all the steps of forming a cured film using the coloring composition are performed at a temperature of 150 ° C. or lower.
- the thickness of the cured film and pixels formed by the coloring composition of the present invention is preferably 0.5 to 3.0 ⁇ m.
- the lower limit is preferably 0.8 ⁇ m or more, more preferably 1.0 ⁇ m or more, and even more preferably 1.1 ⁇ m or more.
- the upper limit is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, and even more preferably 1.8 ⁇ m or less.
- the line width (pattern size) of the pixels formed by the coloring composition of the present invention is preferably 2.0 to 10.0 ⁇ m.
- the upper limit is preferably 7.5 ⁇ m or less, more preferably 5.0 ⁇ m or less, still more preferably 4.0 ⁇ m or less.
- the lower limit is preferably 2.25 ⁇ m or more, more preferably 2.5 ⁇ m or more, and even more preferably 2.75 ⁇ m or more.
- the coloring composition of the present invention contains a coloring agent.
- the colorant used in the coloring composition of the present invention includes a green colorant and a yellow colorant.
- the green colorant and the yellow colorant may be either an inorganic pigment or an organic pigment.
- an inorganic pigment or a material in which a part of the organic-inorganic pigment is replaced with an organic chromophore can be used. Hue design can be facilitated by replacing inorganic pigments and organic-inorganic pigments with organic chromophores.
- green colorant used in the coloring composition of the present invention examples include Color Index (CI) Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine type) and 65 (phthalocyanine type). System), 66 (phthalocyanine system) and the like.
- CI Color Index
- zinc halide has an average number of halogen atoms in one molecule of 10 to 14, a bromine atom number of 8 to 12, and a chlorine atom number of 2 to 5 on average.
- Phthalocyanine pigments can also be mentioned. Specific examples include the compounds described in WO 2015/118720.
- examples of the green colorant include the compound described in Chinese Patent Application No.
- phthalocyanine compound having a phosphoric acid ester described in International Publication No. 2012/10395 as a ligand and Japanese Patent Application Laid-Open No. 2019-008014.
- the phthalocyanine compound described in JP-A-2018-180023, the phthalocyanine compound described in JP-A-2019-038958, and the like can also be mentioned.
- the green colorant used in the present invention is C.I. I. Those containing 1% by mass or more of Pigment Green 7 are used. C. in the green colorant. I. The content of Pigment Green 7 is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4% by mass or more. The green colorant is C.I. I. A green colorant other than Pigment Green 7 may be further contained. C. I. Examples of green colorants other than Pigment Green 7 include C.I. I. Pigment Green 36 and Pigment Green 58 are preferable, and C.I. I. Pigment Green 36 is more preferred.
- Preferred embodiments of the green colorant used in the present invention include the following aspects G1 and G2, and the following aspect G1 is preferable from the viewpoint of color separability.
- Aspect G1 The green colorant is substantially C.I. I. A mode in which only Pigment Green 7 is used.
- the green colorant is substantially C.I. I.
- the case where only Pigment Green 7 is used means that C.I. I. It means that the content of Pigment Green 7 is 99.5% by mass or more, and preferably 99.9% by mass or more.
- the green colorant of the above aspect G2 is substantially C.I. I. Pigment Green 7 and C.I. I. It is preferably composed of Pigment Green 36.
- the green colorant is substantially C.I. I. Pigment Green 7 and C.I. I. When it is composed of Pigment Green 36, C.I. I. Pigment Green 7 and C.I. I. It means that the total content with Pigment Green 36 is 99.5% by mass or more, and preferably 99.9% by mass or more.
- the content of green colorants other than Pigment Green 7 is determined by C.I. I. It is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and further preferably 5 to 25 parts by mass with respect to 100 parts by mass of Pigment Green 7.
- the content of Pigment Green 36 is C.I. I. It is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and further preferably 5 to 25 parts by mass with respect to 100 parts by mass of Pigment Green 7.
- Examples of the yellow colorant used in the coloring composition of the present invention include C.I. 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, 180,181,182,185,187,188,193,194,199,213,214,215,228,231,232 (methine type),
- Examples of the yellow colorant include the compounds described in JP-A-2017-201003, the compounds described in JP-A-2017-197719, and paragraph numbers 0011 to 0062 and 0137-0276 of JP-A-2017-171912.
- quinophthalone compounds described in JP2013-032486 Compounds, quinophthalone compounds described in JP2012-226110, quinophthalone compounds described in JP2008-074987, and quinophthalone compounds described in JP2008-081565.
- a compound represented by the following formula (QP2) can also be mentioned.
- X 1 to X 16 independently represent a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms.
- Specific examples of the compound represented by the formula (QP1) include the compounds described in paragraph No. 0016 of Japanese Patent No. 6443711.
- Y 1 ⁇ Y 3 represents a halogen atom independently.
- n and m represent integers of 0 to 6, and p represents an integer of 0 to 5.
- N + m is 1 or more.
- Specific examples of the compound represented by the formula (QP2) include the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
- a nickel azobarbiturate complex having the following structure can also be used as the yellow colorant.
- the yellow colorant used in the present invention is C.I.
- I. Includes Pigment Yellow 150.
- the content of Pigment Yellow 150 is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more.
- Preferred embodiments of the yellow colorant used in the present invention include the following aspects Y1 and Y2, and the following embodiment Y1 is preferable from the viewpoint of light resistance.
- Aspect Y1 The yellow colorant is substantially C.I. I. A mode in which only Pigment Yellow 150 is used.
- the yellow colorant is substantially C.I. I.
- the case where only Pigment Yellow 150 is used means that C.I. I. It means that the content of Pigment Yellow 150 is 99.5% by mass or more, and preferably 99.9% by mass or more.
- yellow colorant other than Pigment Yellow 150 examples include C.I. I. Pigment Yellow 129, Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 185 and the like, and C.I. I. Pigment Yellow 129 and Pigment Yellow 138 are preferable.
- the content of the yellow colorant other than Pigment Yellow 150 is determined by C.I. I. It is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and further preferably 10 to 25 parts by mass with respect to 100 parts by mass of Pigment Yellow 150.
- the colorant used in the coloring composition of the present invention is C.I. I. Green colorants other than Pigment Green 7 and C.I. I.
- the mass ratio with Pigment Yellow 150 is within the above range, the storage stability of the coloring composition is good, and by using this coloring composition, a cured film having excellent light resistance can be formed.
- C.I. I. Examples of green colorants other than Pigment Green 7 include C.I. I. Pigment Green 36 is preferred.
- the colorant used in the coloring composition of the present invention is C.I. I.
- Pigment Yellow 150 is preferably contained in an amount of 50 to 240 parts by mass.
- the upper limit is preferably 200 parts by mass or less, and more preferably 150 parts by mass or less.
- the lower limit is preferably 80 parts by mass or more, and more preferably 100 parts by mass or more.
- C. I. Pigment Green 7 and C.I. I. When the ratio with Pigment Yellow 150 is in the above range, better storage stability can be easily obtained.
- the colorant used in the coloring composition of the present invention preferably contains 50 to 240 parts by mass of the yellow colorant with respect to 100 parts by mass of the green colorant.
- the upper limit is preferably 200 parts by mass or less, and more preferably 150 parts by mass or less.
- the lower limit is preferably 80 parts by mass or more, and more preferably 100 parts by mass or more.
- the total content of the green colorant and the yellow colorant in the total amount of the colorant used in the coloring composition of the present invention is preferably 50 to 100% by mass, preferably 75 to 100% by mass. More preferably, it is more preferably 90 to 100% by mass.
- the colorant used in the coloring composition of the present invention may contain a colorant other than the green colorant and the yellow colorant (hereinafter, also referred to as another colorant).
- the content of the other colorant in the colorant is preferably 50% by mass or less, more preferably 25% by mass or less, further preferably 10% by mass or less, and from the viewpoint of color separability. It is particularly preferable that it contains substantially no other colorant.
- the content of the other colorant in the colorant is less than 0.5% by mass. It is preferably less than 0.1% by mass, and more preferably does not contain other colorants.
- colorants examples include chromatic colorants such as red colorants, blue colorants, purple colorants, and orange colorants.
- the other colorant may be a pigment or a dye. Pigments and dyes may be used in combination. Examples of the pigment include those shown below.
- an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraph numbers 0047 of JP2011-157478A.
- red colorant a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, and a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of Patent No. 6248838.
- Diketopyrrolopyrrole compound described in WO2012 / 102399 Diketopyrrolopyrrole compound described in WO2012 / 117965, naphtholazo compound described in JP2012-229344, patent No. 6516119.
- the red colorant described in Japanese Patent No. 6525101, the red colorant described in Japanese Patent No. 6525101, and the like can also be used.
- red colorant a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used. You can also.
- dyes there are no particular restrictions on the dye, and known dyes can be used.
- pyrazole azo system anilino azo system, triarylmethane system, anthraquinone system, anthrapyridone system, benzylidene system, oxonol system, pyrazolotriazole azo system, pyridone azo system, cyanine system, phenothiazine system, pyrrolopyrazole azomethine system, xanthene system
- phthalocyanine-based benzopyran-based, indigo-based, and pyrromethene-based dyes.
- 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 may be 100 or less.
- the plurality of dye structures contained in one molecule may have the same dye structure or different dye structures.
- the weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000.
- the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
- the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
- Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, International Publication No. 2016/031442, and the like. Compounds can also be used.
- the content of the colorant in the total solid content of the coloring composition is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more.
- the upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.
- the coloring composition of the present invention contains a polymerizable compound.
- the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group.
- the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the polymerizable compound is preferably a compound that can be polymerized by radicals (radical polymerizable compound).
- the polymerizable compound may be in any chemical form such as a monomer, a prepolymer, or an oligomer, but a monomer is preferable.
- 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, more preferably 250 or more.
- the lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and further preferably 5 mmol / g or more.
- the upper limit is preferably 12 mmol / g or less, more preferably 10 mmol / g or less, and even more preferably 8 mmol / g or less.
- the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, and more preferably a compound containing 4 or more ethylenically unsaturated bond-containing groups. According to this aspect, the curability of the coloring composition by exposure is good.
- the upper limit of the ethylenically unsaturated bond-containing group is preferably 15 or less, more preferably 10 or less, and further preferably 6 or less, from the viewpoint of stability over time of the coloring composition.
- the polymerizable compound is preferably a trifunctional or higher functional (meth) acrylate compound, more preferably a 3 to 15 functional (meth) acrylate compound, and a 3 to 10 functional (meth) acrylate compound. It is more preferable to have a (meth) acrylate compound having 3 to 6 functions, and it is particularly preferable to use a (meth) acrylate compound.
- the polymerizable compound is also preferably a compound containing an ethylenically unsaturated bond-containing group and an alkyleneoxy group. Since such a polymerizable compound has high flexibility and the ethylenically unsaturated bond-containing group easily moves, the polymerizable compounds easily react with each other at the time of exposure, and a cured film having excellent adhesion to a support or the like (a cured film). Pixels) can be formed. Further, when a hydroxyalkylphenone compound is used as the photopolymerization initiator, the polymerizable compound and the photopolymerization initiator are close to each other to generate radicals in the vicinity of the polymerizable compound to make the polymerizable compound more effective. It is presumed that the reaction can be carried out, and it is easy to form a cured film (pixel) having better adhesion, light resistance, and solvent resistance.
- the number of alkyleneoxy groups contained in one molecule of the polymerizable compound is preferably 3 or more, and more preferably 4 or more.
- the upper limit is preferably 20 or less from the viewpoint of the stability of the coloring composition over time.
- the SP value (Solubility Parameter) of the compound containing an ethylenically unsaturated bond-containing group and an alkyleneoxy group is preferably 9.0 to 11.0 from the viewpoint of compatibility with other components in the coloring composition. ..
- the upper limit is preferably 10.75 or less, and more preferably 10.5 or less.
- the lower limit is preferably 9.25 or more, and more preferably 9.5 or more.
- the SP value used is a calculated value based on the Fedors method.
- Examples of the compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group include a compound represented by the following formula (M-1). Equation (M-1) In the formula, A 1 represents an ethylenically unsaturated bond-containing group, L 1 represents a single bond or a divalent linking group, R 1 represents an alkylene group, m represents an integer of 1 to 30, and n. Represents an integer of 3 or more, and L 2 represents an n-valent linking group.
- Examples of the ethylenically unsaturated bond-containing group represented by A 1 include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.
- Examples of the divalent linking group represented by L 1 include an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, and a group in which two or more of these are combined. ..
- the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 15 carbon atoms.
- the alkylene group may be linear, branched or cyclic.
- the arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- the carbon number of the alkylene group represented by R 1 is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, particularly preferably 2 or 3, and most preferably 2.
- the alkylene group represented by R 1 is preferably linear or branched, and more preferably linear. Specific examples of the alkylene group represented by R 1 include an ethylene group, a linear or branched propylene group, and the ethylene group is preferable.
- M represents an integer of 1 to 30, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably 1 to 5.
- N represents an integer of 3 or more, and an integer of 4 or more is preferable.
- the upper limit of n is preferably an integer of 15 or less, more preferably an integer of 10 or less, and even more preferably an integer of 6 or less.
- the n-valent linking group represented by L 2 includes an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group and a group consisting of a combination thereof, and an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a complex. Examples thereof include a group formed by combining at least one selected from ring groups and at least one selected from -O-, -CO-, -COO-, -OCO- and -NH-.
- the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.
- the aliphatic hydrocarbon group may be linear, branched or cyclic, and linear or branched is preferable.
- the number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10.
- the heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group.
- the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
- Examples of the heteroatom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom.
- the number of heteroatoms constituting the heterocyclic group is preferably 1 to 3.
- the heterocyclic group may be a monocyclic ring or a condensed ring.
- the n-valent linking group represented by L 2 is also preferably a group derived from a polyfunctional alcohol.
- Equation (M-2) a compound represented by the following formula (M-2) is more preferable.
- R 2 represents a hydrogen atom or a methyl group
- R 1 represents an alkylene group
- m represents an integer of 1 to 30
- n represents an integer of 3 or more
- L 2 represents an n-valent linking group.
- R 1, L 2, m, n of formula (M-2) is R 1, L 2, m, synonymous with n in formula (M-1), and preferred ranges are also the same.
- Examples of commercially available compounds having an ethylenically unsaturated bond-containing group and an alkyleneoxy group include KAYARAD T-1420 (T) and RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).
- dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku) NK ester A-DPH-12E manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues.
- Examples of the polymerizable compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and isocyanurate ethyleneoxy-modified tri (meth).
- Trifunctional (meth) acrylate compounds such as acrylate and pentaerythritol trimethylolpropane (meth) acrylate can also be used.
- Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305.
- M-303, M-452, M-450 manufactured by Toa Synthetic Co., Ltd.
- NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT manufactured by Shin Nakamura Chemical Industry Co., Ltd.
- KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.
- the polymerizable compound it is also preferable to use a polymerizable compound having an acid group.
- a polymerizable compound having an acid group By using a polymerizable compound having an acid group, the colored composition layer in the unexposed portion can be easily removed during development, and the generation of development residue can be suppressed.
- the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferable.
- the polymerizable compound having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate.
- Examples of commercially available products of the polymerizable compound having an acid group include Aronix M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
- the preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g.
- the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developing solution is good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling.
- polymerizable compound it is also preferable to use a compound having a caprolactone structure.
- Polymerizable compounds 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, and DPCA-120.
- the polymerizable compound it is also preferable to use a compound that does not substantially contain an environmentally regulated substance such as toluene.
- an environmentally regulated substance such as toluene.
- commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
- Examples of the polymerizable compound include urethane acrylates as described in JP-A-48-041708, JP-A-51-0371993, JP-A-02-032293, and JP-A-02-016765.
- Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
- a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238.
- the polymerizable compounds are UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, and LINK-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.
- the content of the polymerizable compound is preferably 5 to 35% by mass in the total solid content of the coloring composition.
- the upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less.
- the lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
- the coloring composition of the present invention contains a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- the photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole compounds, oxime derivatives and the like.
- halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
- acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole compounds, oxime derivatives and the like.
- examples thereof include oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ether compounds, aminoalkylphenone compounds, hydroxyalkylphenone compounds, and phenylglycilate compounds.
- the photopolymerization initiator used in the present invention preferably contains an oxime compound, and more preferably contains an oxime compound and a hydroxyalkylphenone compound.
- phenylglycolate compound examples include phenylglycoxylic acid methyl ester and the like.
- examples of commercially available products include Omnirad MBF (manufactured by IGM Resins BV) and Irgacure MBF (manufactured by BASF).
- acylphosphine compound examples include the acylphosphine compound described in Japanese Patent No. 4225898. Specific examples include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.
- examples of commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
- aminoalkylphenone compound examples include the aminoalkylphenone compound described in JP-A No. 10-291969.
- Commercially available products of aminoalkylphenone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins BV), Irgacure 907, Irgacure 369, Irgare 369, Irgar BASF) and the like.
- hydroxyalkylphenone compound examples include compounds represented by the following formula (V). Equation (V) In the formula, Rv 1 represents a substituent, Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent, and Rv 2 and Rv 3 may be bonded to each other to form a ring. m represents an integer from 0 to 5.
- Examples of the substituent represented by Rv 1 include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms).
- the alkyl group and the alkoxy group are preferably linear or branched, and more preferably linear.
- the alkyl group and alkoxy group represented by Rv 1 may be unsubstituted or may have a substituent.
- Examples of the substituent include a hydroxy group and a group having a hydroxyalkylphenone structure.
- Examples of the group having a hydroxyalkylphenone structure include a benzene ring to which Rv 1 is bonded in the formula (V) or a group having a structure in which one hydrogen atom is removed from Rv 1.
- Rv 2 and Rv 3 independently represent a hydrogen atom or a substituent.
- an alkyl group preferably an alkyl group having 1 to 10 carbon atoms
- Rv 2 and Rv 3 may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms).
- the alkyl group is preferably linear or branched, more preferably linear.
- hydroxyalkylphenone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, IGM Resins BV), Irgacare 184, Irgacare 1173, Irgacure 1173, Irgacure 1173, Irgacure. (Made) and so on.
- Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, and the compounds described in JP-A-2006-342166.
- oxime compound examples include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminovtan-2-one, 2-acetoxyimiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropane-1-one.
- an oxime compound having a fluorene ring can also be used.
- Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466.
- an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
- Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
- an oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
- the oxime compound containing a fluorine atom is preferably a compound represented by the formula (OX-1).
- Ar 1 and Ar 2 each independently represent an aromatic hydrocarbon ring which may have a substituent, and R 1 is an aryl group having a group containing a fluorine atom.
- R 2 and R 3 independently represent an alkyl group or an aryl group, respectively.
- the aromatic hydrocarbon ring represented by Ar 1 and Ar 2 of the formula (OX-1) may be a monocyclic 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.
- Ar 1 is preferably a benzene ring.
- Ar 2 is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring.
- the substituents that Ar 1 and Ar 2 may have include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR X1 , -SR X1 , -COR X1 , and -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.
- RX1 and RX2 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 alkyl group as a substituent and the alkyl group represented by RX1 and RX2 preferably have 1 to 30 carbon atoms.
- the alkyl group may be linear, branched or cyclic, but linear or branched is preferred.
- Alkyl groups may have some or all of hydrogen atoms substituted with halogen atoms (preferably fluorine atoms).
- a part or all of hydrogen atoms may be substituted with the above-mentioned substituent.
- the aryl group as a substituent and the aryl group represented by RX1 and RX2 have a preferably 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- the aryl group may be a monocyclic ring or a fused ring.
- a part or all of hydrogen atoms may be substituted with the above-mentioned substituent.
- the heterocyclic group as a substituent and the heterocyclic group represented by RX1 and RX2 are preferably a 5-membered ring or a 6-membered ring.
- the heterocyclic group may be a monocyclic 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 even 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. Further, in the heterocyclic group, a part or all of a hydrogen atom may be substituted with the above-mentioned substituent.
- the aromatic hydrocarbon ring represented by Ar 1 is preferably an unsubstituted aromatic hydrocarbon ring.
- the aromatic hydrocarbon ring represented by Ar 2 preferably has a substituent.
- -COR X1 is preferable.
- RX1 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 of the formula (OX-1) represents 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 even more preferably 6 to 10 carbon atoms.
- 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 a group containing an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorine-containing group).
- the fluorine-containing groups include -OR F1 , -SR F1 , -COR F1 , -COOR F1 , -OCOR F1 , -NR F1 R F2 , -NHCOR F1 , -CONR F1 R F2 , -NHCONR F1 R F2 , and -NHCOOR.
- At least one group selected from F1, -SO 2 R F1 , -SO 2 OR F1 and -NHSO 2 R F1 is preferred.
- R F1 represents a fluorinated alkyl group
- R F2 represents a hydrogen atom, an alkyl group, fluorinated alkyl group, an aryl group or a heterocyclic group.
- the fluorine-containing group is preferably ⁇ OR F1.
- R F1 and a fluorine-containing alkyl group R F2 represents, as well as the number of carbon atoms in the alkyl group represented by R F2 is preferably from 1 to 20, more preferably 1 to 15, more preferably from 1 to 10, particularly preferably from 1 to 4 ..
- the fluorine-containing alkyl group and the alkyl group may be linear, branched or cyclic, but linear or branched is preferable.
- the substitution rate of the fluorine atom is preferably 40 to 100%, more preferably 50 to 100%, and even more preferably 60 to 100%.
- the substitution rate of fluorine atoms means the ratio (%) of the number of fluorine atoms substituted to the total number of hydrogen atoms of the alkyl group.
- the number of carbon atoms of the aryl group R F2 represents preferably 6 to 20, more preferably 6 to 15, more preferably 6 to 10.
- Heterocyclic group R F2 represents a 5-membered ring or 6-membered ring.
- the heterocyclic group may be a monocyclic ring or a condensed ring.
- the number of condensations is preferably 2 to 8, more preferably 2 to 6, further 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 even 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, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom.
- 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)
- R 2 of the formula (OX-1) represents an alkyl group or an aryl group, and an alkyl group is preferable.
- the alkyl group and the aryl group may be unsubstituted or have a substituent. Examples of the substituent include the substituents described in the above-mentioned Substituents Ar 1 and Ar 2 may have.
- the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 4.
- the alkyl group may be linear, branched or cyclic, but linear or branched is preferred.
- the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- R 3 of the formula (OX-1) represents an alkyl group or an aryl group, and an alkyl group is preferable.
- the alkyl group and the aryl group may be unsubstituted or have a substituent. Examples of the substituent include the substituents described as the substituents that Ar 1 and Ar 2 may have.
- the number of carbon atoms of the alkyl group represented by R 3 is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10.
- the alkyl group may be linear, branched or cyclic, but linear or branched is preferred.
- the aryl group represented by R 3 preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like.
- an oxime compound having a nitro group can be used as the photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation).
- an oxime compound having a benzofuran skeleton can also be used.
- Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
- an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
- Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
- the photopolymerization initiator A1 having an extinction coefficient of 1.0 ⁇ 10 3 mL / gcm or more in methanol at a wavelength of 365 nm and the extinction coefficient of 365 nm in methanol are 1. It is also preferable to use in combination with the photopolymerization initiator A2 having an extinction coefficient of 0 ⁇ 10 2 mL / gcm or less and a wavelength of 254 nm of 1.0 ⁇ 10 3 mL / gcm or more.
- the coloring composition is easily cured sufficiently by exposure, and the flatness is good in a low temperature process (for example, a process at a temperature of 150 ° C. or lower, preferably 120 ° C. or lower throughout the whole process). Moreover, it is possible to form pixels having excellent characteristics such as light resistance and solvent resistance.
- a low temperature process for example, a process at a temperature of 150 ° C. or lower, preferably 120 ° C. or lower throughout the whole process.
- the extinction coefficient of the photopolymerization initiator at the above wavelength is a value measured as follows. That is, it was calculated by dissolving the photopolymerization initiator in methanol to prepare a measurement solution, and measuring the absorbance of the above-mentioned measurement solution. Specifically, the above-mentioned measurement solution was placed in a glass cell having a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrum meter (Cary5000) manufactured by Agilent Technologies. The absorbance coefficient (mL / gcm) at 254 nm was calculated. In the above formula, ⁇ represents the extinction coefficient (mL / gcm), A represents the absorbance, c represents the concentration of the photopolymerization initiator (g / mL), and l represents the optical path length (cm).
- the absorption coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 365 nm is 1.0 ⁇ 10 3 mL / gcm or more, preferably 1.0 ⁇ 10 4 mL / gcm or more, preferably 1.1 ⁇ . It is more preferably 10 4 mL / g cm or more, further preferably 1.2 ⁇ 10 4 to 1.0 ⁇ 10 5 mL / g cm, and 1.3 ⁇ 10 4 to 5.0 ⁇ 10 4 mL. It is even more preferably / gcm, and particularly preferably 1.5 ⁇ 10 4 to 3.0 ⁇ 10 4 mL / gcm.
- the extinction coefficient of light of the photopolymerization initiator A1 in methanol at a wavelength of 254 nm is preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 5 mL / gcm, preferably 1.5 ⁇ 10 4 to 1.5. It is more preferably 9.5 ⁇ 10 4 mL / gcm, and even more preferably 3.0 ⁇ 10 4 to 8.0 ⁇ 10 4 mL / gcm.
- an oxime compound, an aminoalkylphenone compound, and an acylphosphine compound are preferable, an oxime compound and an acylphosphine compound are more preferable, an oxime compound is further preferable, and compatibility with other components contained in the composition.
- the oxime compound contains a fluorine atom.
- the oxime compound containing a fluorine atom the compound represented by the above formula (OX-1) is preferable.
- photopolymerization initiator A1 examples include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (commercially available products include, for example, Irgacure OXE01, BASF). , Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (commercially available products include, for example, Irgacure OXE02, BASF), (C-13), (C-14), (C-17) and the like shown in the above-mentioned specific examples of the oxime compound can be mentioned.
- the extinction coefficient of light of the photopolymerization initiator A2 in methanol at a wavelength of 365 nm is 1.0 ⁇ 10 2 mL / gcm or less, preferably 10 to 1.0 ⁇ 10 2 mL / gcm, 20 More preferably, it is ⁇ 1.0 ⁇ 10 2 mL / gcm.
- the difference between the absorption coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator A1 and the absorption coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator A2 is 9.0 ⁇ 10 2 mL.
- the absorption coefficient of light of the photopolymerization initiator A2 at a wavelength of 254 nm in methanol is 1.0 ⁇ 10 3 mL / gcm or more, and 1.0 ⁇ 10 3 to 1.0 ⁇ 10 6 mL / gcm. It is preferably 5.0 ⁇ 10 3 to 1.0 ⁇ 10 5 mL / g cm.
- a hydroxyalkylphenone compound, a phenylglioxylate compound, an aminoalkylphenone compound, and an acylphosphine compound are preferable, a hydroxyalkylphenone compound and a phenylglioxylate compound are more preferable, and a hydroxyalkylphenone compound is further preferable.
- the hydroxyalkylphenone compound the compound represented by the above-mentioned formula (V) is preferable.
- photopolymerization initiator A2 examples include 1-hydroxy-cyclohexyl-phenyl-ketone and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-. For example, on.
- a combination in which the photopolymerization initiator A1 is an oxime compound and the photopolymerization initiator A2 is a hydroxyalkylphenone compound is preferable, and the photopolymerization initiator A1 is used.
- a combination of an oxime compound in which the photopolymerization initiator A2 is a compound represented by the above formula (V) is more preferable, the photopolymerization initiator A1 is an oxime compound containing a fluorine atom, and the photopolymerization initiator A2 is A combination of compounds represented by the above formula (V) is particularly preferable.
- the content of the photopolymerization initiator is preferably 3 to 25% by mass in the total solid content of the coloring composition.
- the lower limit is preferably 5% by mass or more, more preferably 7.5% by mass or more, further preferably 8% by mass or more, further preferably 9% by mass or more, and 10% by mass. % Or more is particularly preferable.
- the upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and further preferably 15% by mass or less.
- the photopolymerization initiator may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount thereof is within the above range.
- the content M of the polymerizable compound in the total solid content of the coloring composition and the content I of the photopolymerization initiator in the total solid content of the coloring composition on a mass% basis.
- the ratio (M / I) to and to is preferably 20 or less.
- the upper limit of the ratio is preferably 10 or less, more preferably 5 or less, further preferably 3 or less, and particularly preferably 2 or less.
- the lower limit of the ratio is preferably 0.1 or more, and more preferably 0.5 or more.
- the content of the oxime compound is preferably 3 to 25% by mass in the total solid content of the coloring composition.
- the lower limit is preferably 5% by mass or more, more preferably 7.5% by mass or more, further preferably 8% by mass or more, further preferably 9% by mass or more, and 10% by mass. % Or more is particularly preferable.
- the upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and further preferably 15% by mass or less.
- the oxime compound may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount thereof is within the above range.
- the content M of the polymerizable compound in the total solid content of the coloring composition and the content IO of the oxime compound in the total solid content of the coloring composition on a mass% basis.
- the ratio (M / IO ) of is preferably 20 or less.
- the upper limit of the ratio is preferably 10 or less, more preferably 5 or less, further preferably 3 or less, and particularly preferably 2 or less.
- the lower limit of the ratio is preferably 0.1 or more, and more preferably 0.5 or more.
- the content of the photopolymerization initiator A1 is 3 to 25% by mass in the total solid content of the coloring composition. Is preferable.
- the lower limit is preferably 5% by mass or more, more preferably 7.5% by mass or more, further preferably 8% by mass or more, further preferably 9% by mass or more, and 10% by mass. % Or more is particularly preferable.
- the upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and further preferably 15% by mass or less.
- the ratio with and (M / I A1 ) is preferably 20 or less.
- the upper limit of the ratio is preferably 10 or less, more preferably 5 or less, further preferably 3 or less, and particularly preferably 2 or less.
- the lower limit of the ratio is preferably 0.1 or more, and more preferably 0.5 or more.
- the content of the photopolymerization initiator A2 is 0.1 to 10.0 in the total solid content of the coloring composition. It is preferably by mass%.
- the lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and further preferably 1.5% by mass or more.
- the upper limit is preferably 9.0% by mass or less, more preferably 8.0% by mass or less, and further preferably 7.0% by mass or less.
- the coloring composition of the present invention comprises 100 parts by mass of the photopolymerization initiator A1.
- the upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less.
- the lower limit is preferably 60 parts by mass or more, and more preferably 70 parts by mass or more. According to this aspect, a cured film having excellent properties such as solvent resistance can be formed in a low temperature process (for example, a process at a temperature of 150 ° C.
- the total amount of each satisfies the above requirements.
- the photopolymerization initiator A1 and the photopolymerization initiator in the total solid content of the coloring composition are used to initiate photopolymerization.
- the total content with the agent A2 is preferably 3.1 to 25% by mass.
- the lower limit is preferably 4% by mass or more, preferably 5% by mass or more, more preferably 7.5% by mass or more, further preferably 8% by mass or more, and 9% by mass. The above is more preferable, and 10% by mass or more is particularly preferable.
- the upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and further preferably 15% by mass or less.
- the coloring composition of the present invention may contain a photopolymerization initiator other than the photopolymerization initiator A1 and the photopolymerization initiator A2 (hereinafter, also referred to as other photopolymerization initiator) as the photopolymerization initiator. It is preferable that the other photopolymerization initiator is substantially not contained. When the content of the other photopolymerization initiator is substantially not contained, the content of the other photopolymerization initiator is 1 part by mass with respect to 100 parts by mass of the total of the photopolymerization initiator A1 and the photopolymerization initiator A2. It means that it is less than or equal to 0.5 parts by mass or less, more preferably 0.1 part by mass or less, and further preferably not containing another photopolymerization initiator.
- the coloring composition of the present invention preferably contains a resin.
- the resin is blended, for example, for the purpose of dispersing pigments (CI Pigment Green 7, CI Pigment Yellow 150, etc.) in a coloring composition or for a binder.
- the resin mainly used for dispersing the pigment in the coloring composition is also referred to as a dispersant.
- a dispersant such an application of the resin is an example, and the resin can be used for purposes other than such an application.
- the weight average molecular weight (Mw) of the resin is preferably 2000 to 2000000.
- the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
- the lower limit is preferably 3000 or more, more preferably 4000 or more, and even more preferably 5000 or more.
- the resin examples include (meth) acrylic resin, (meth) acrylamide resin, epoxy resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene.
- examples thereof include ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin.
- the resins described in paragraphs 0041 to 0060 of JP-A-2017-206689, the resins described in paragraphs 0022 to 0071 of JP-A-2018-010856, and the resins described in JP-A-2017-057256 The resin described in JP-A-2017-032685, the resin described in JP-A-2017-075248, the resin described in JP-A-2017-066240, the resin described in JP-A-2000-081701, the Japanese Patent Application Laid-Open No. 2000-081701
- the resin described in JP-A-1998-1233311, the resin described in JP-A-11-160523, and the resin described in JP-A-2017-173787 can also be used.
- the resin used in the present invention may have an acid group.
- the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. These acid groups may be only one kind or two or more kinds.
- the resin having an acid group preferably contains a repeating unit having an acid group in the side chain.
- the resin having an acid group can also be used as an alkali-soluble resin or a dispersant.
- the acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g.
- the lower limit is more preferably 50 mgKOH / g or more, and even 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 most preferably 120 mgKOH / g or less.
- the resin having an acid group may have a repeating unit derived from a maleimide compound.
- the maleimide compound include N-alkylmaleimide and N-arylmaleimide.
- the repeating unit derived from the maleimide compound include a repeating unit represented by the formula (C-mi).
- Rmi represents an alkyl group or an aryl group.
- the alkyl group preferably has 1 to 20 carbon atoms.
- the alkyl group may be linear, branched or cyclic.
- the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- Rmi is preferably an aryl group.
- the resin having an acid group is a repeating compound derived from a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer"). It is also preferable that the resin contains a unit.
- R 1 and R 2 each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
- the description in JP-A-2010-168539 can be referred to, and the contents thereof are incorporated in the present specification.
- paragraph number 0317 of JP2013-209760A can be referred to, and the content thereof is incorporated in the present specification.
- Examples of the resin containing the repeating unit derived from the ether dimer include a resin having the following structure.
- Me represents a methyl group.
- the resin used in the present invention may have a polymerizable group.
- the polymerizable group include ethylenically unsaturated bond-containing groups such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- Commercially available products of resins having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, Diamond Shamlock Co., Ltd.), Viscort R-264, KS.
- Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel CF200 series (all manufactured by Daicel Co., Ltd.), Ebeclyl3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure Examples thereof include RD-F8 (manufactured by Nippon Catalyst Co., Ltd.) and DP-1305 (manufactured by Fuji Fine Chemicals Co., Ltd.).
- a resin having an epoxy group can also be used.
- the resin having an epoxy group include a resin having a repeating unit represented by the formula (E-1).
- X 1E represents the main chain of the repeating unit and L 1E represents a single bond or a divalent linking group.
- the main chain of the repeating unit represented by X 1E is not particularly limited. There is no particular limitation as long as it is a linking group formed from a known polymerizable monomer.
- poly (meth) acrylic linking groups polyalkyleneimine-based linking groups, polyester-based linking groups, polyurethane-based linking groups, polyurea-based linking groups, polyamide-based linking groups, polyether-based linking groups, polystyrene-based linking groups, etc.
- the poly (meth) acrylic-based linking group and the polystyrene-based linking group are preferable, and the poly (meth) acrylic-based linking group is more preferable.
- an alkylene group preferably an alkylene group having 1 to 12 carbon atoms
- an arylene group preferably an arylene group having 6 to 20 carbon atoms
- examples thereof include -NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, -OCO-, -S-, and groups composed of a combination of two or more of these.
- the alkylene group may be linear, branched, or cyclic, and is preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
- the resin having an epoxy group also preferably has a repeating unit having a cyclic alkyl group.
- the bulkiness of the cyclic alkyl group can be expected to have the effect of making the resin rigid and improving the solvent resistance of the cured film.
- the cyclic alkyl group include a dicyclopentanyl group and a cyclohexyl group, and a dicyclopentanyl group is preferable because it is bulkier and the solvent resistance of the cured film is further improved.
- the repeating unit having a cyclic alkyl group include a repeating unit represented by the formula (E-2).
- X 2E represents the main chain of the repeating unit
- L 2E represents a single bond or a divalent linking group
- Z 2E represents a cyclic alkyl group.
- the main chain of the repeating unit represented by X 2E of the formula (E-2) include the structure described as the main chain of the repeating unit represented by X 1E of the formula (E-2).
- the divalent linking group represented by L 2E of the formula (E-2) include a group having the structure described as the divalent linking group represented by L 2E of the formula (E-1).
- the cyclic alkyl group represented by Z 2E include the above-mentioned groups, and a dicyclopentanyl group is preferable.
- the resin having an epoxy group further contains a repeating unit derived from an aromatic vinyl compound (preferably a styrene compound).
- the resin used in the present invention preferably contains a resin b1 containing a repeating unit derived from the compound represented by the formula (I).
- a resin b1 containing a repeating unit derived from the compound represented by the formula (I) By using the resin b1, the curability at a low temperature is excellent, and a sufficiently cured cured film can be formed even by heating at a relatively low temperature. Furthermore, it is easy to form a cured film having excellent spectral characteristics.
- X 1 represents O or NH, and is preferably O.
- R 1 represents a hydrogen atom or a methyl group.
- L 1 represents a divalent linking group.
- Divalent linking groups include hydrocarbon groups, heterocyclic groups, -NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, -OCO-, -S- and these. A group consisting of a combination of two or more of the above can be mentioned.
- the hydrocarbon group include an alkyl group and an aryl group.
- the heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group.
- the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
- heteroatom constituting the heterocyclic group examples include a nitrogen atom, an oxygen atom, and a sulfur atom.
- the number of heteroatoms constituting the heterocyclic group is preferably 1 to 3.
- the heterocyclic group may be a monocyclic ring or a condensed ring.
- the hydrocarbon group and the heterocyclic group may have a substituent.
- the substituent examples include an alkyl group, an aryl group, a hydroxy group, a halogen atom and the like.
- R 10 represents a substituent.
- Examples of the substituent represented by R 10 include the substituent T shown below, which is preferably a hydrocarbon group, and more preferably an alkyl group which may have an aryl group as a substituent.
- m represents an integer of 0 to 2, preferably 0 or 1, more preferably 0.
- p represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, further preferably 0 to 2, even more preferably 0 or 1, and particularly preferably 1.
- the substituent T includes a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group, -ORt 1 , -CORt 1 , -COORt 1 , -OCORt 1 , -NRt 1 Rt 2 , -NHCORt 1 , and-.
- Rt 1 and Rt 2 independently represent a hydrogen atom, a hydrocarbon group or a heterocyclic group, respectively.
- Rt 1 and Rt 2 may be combined to form a ring.
- Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 8.
- the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably branched.
- the alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.
- the alkenyl group may be linear, branched or cyclic, preferably linear or branched.
- the alkynyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 25 carbon atoms.
- the alkynyl group may be linear, branched or cyclic, preferably linear or branched.
- the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
- the heterocyclic group may be a monocyclic ring or a condensed ring.
- the heterocyclic group is preferably a single ring or a condensed ring having 2 to 4 condensation numbers.
- the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3.
- the hetero atom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- the number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
- the hydrocarbon group and the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituent described as the above-mentioned Substituent T.
- the compound represented by the formula (I) is preferably a compound represented by the following formula (I-1).
- X 1 represents O or NH, and is preferably O.
- R 1 represents a hydrogen atom or a methyl group.
- R 2, R 3 and R 11 each independently represents a hydrocarbon group.
- the hydrocarbon group represented by R 2 and R 3 is preferably an alkylene group or an arylene group, and more preferably an alkylene group.
- the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms.
- the hydrocarbon group represented by R 11 is preferably an alkyl group which may have an aryl group as a substituent, and more preferably an alkyl group having an aryl group as a substituent.
- the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.
- the carbon number of the alkyl group means the carbon number of the alkyl moiety.
- R 12 represents a substituent. Examples of the substituent represented by R 12 include the above-mentioned substituent T.
- n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.
- m represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
- p1 represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, further preferably 0 to 2, even more preferably 0 to 1, and particularly preferably 0.
- q1 represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1.
- the compound represented by the formula (I) is preferably a compound represented by the following formula (III).
- R 1 represents a hydrogen atom or a methyl group
- R 21 and R 22 each independently represent an alkylene group
- n represents an integer of 0 to 15.
- the alkylene group represented by R 21 and R 22 preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms.
- n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.
- Examples of the compound represented by the formula (I) include ethylene oxide of paracumylphenol or propylene oxide-modified (meth) acrylate.
- Examples of commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
- the ratio of the repeating unit derived from the compound represented by the formula (I) (preferably the formula (III)) to all the repeating units is preferably 1 to 99 mol%.
- the lower limit is more preferably 3 mol% or more, further preferably 5 mol% or more.
- the upper limit is more preferably 95 mol% or less, further preferably 90 mol% or less.
- the resin b1 may further contain a repeating unit other than the repeating unit derived from the compound represented by the formula (I).
- the resin b1 can contain a repeating unit derived from (meth) acrylate, and preferably contains a repeating unit derived from alkyl (meth) acrylate.
- the number of carbon atoms in the alkyl moiety of the alkyl (meth) acrylate is preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6.
- Preferred specific examples of the alkyl (meth) acrylate include n-butyl (meth) acrylate and the like. It is also preferable that the resin b1 contains a repeating unit having an acid group.
- the resin used in the present invention preferably contains a resin having a repeating unit containing a blocked isocyanate group (hereinafter, also referred to as resin BI). According to this aspect, more excellent low temperature curability can be obtained, and a sufficiently cured cured film can be formed even by heating at a relatively low temperature.
- resin BI a resin having a repeating unit containing a blocked isocyanate group
- the blocked isocyanate group contained in the resin BI is preferably a group capable of generating an isocyanate group by heat, and more preferably a group capable of generating an isocyanate group by heat of 70 to 150 ° C. preferable.
- the blocked isocyanate group include a group having a structure in which the isocyanate group is chemically protected by a blocking agent.
- the blocked isocyanate group is a group having a structure in which the isocyanate group is protected by a compound called a blocking agent, and although it does not show reactivity as an isocyanate group at room temperature (for example, 10 to 30 ° C.), it is heated or the like. It is a group having a structure in which an isocyanate group is generated by desorbing a blocking agent from a blocked isocyanate group.
- the blocked isocyanate group contained in the resin BI is more preferably a group capable of generating an isocyanate group by heat at 70 to 150 ° C. That is, the isocyanate formation temperature (desorption temperature of the blocking agent) of the blocked isocyanate group is preferably 70 to 150 ° C.
- the lower limit of the isocyanate formation temperature is preferably 75 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of storage stability.
- the upper limit of the isocyanate formation temperature is preferably 130 ° C. or lower, and more preferably 120 ° C. or lower, from the viewpoint of curability.
- Examples of the blocking agent that protects the isocyanate group of the blocked isocyanate group 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. From the viewpoint of easiness of the deprotection reaction, an oxime compound, a lactam compound, an active methylene compound and a pyrazole compound are preferable, an oxime compound, an active methylene compound and a pyrazole compound are more preferable, and an oxime compound is further preferable.
- Examples of the oxime compound include acetoxime, formaldoxime, cyclohexaneoxime, methylethylketone oxime, cyclohexanone oxime, and benzophenone oxime.
- Examples of the lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
- Examples of the phenol compound include phenol, naphthol, cresol, xylenol, halogen-substituted phenol and the like.
- Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
- Examples of the amine compound include primary amines and secondary amines.
- the amine compound may be any of aromatic amines, aliphatic amines and alicyclic amines, and specific examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
- Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate.
- Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
- Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
- imidazole compound examples include imidazole, 1-methylimidazole, 1-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole.
- imide compound examples include maleimide, succinimide, phthalimide, and derivatives thereof.
- the molecular weight of the blocking agent is preferably 50 to 200, more preferably 50 to 160, and even more preferably 50 to 120.
- the molecular weight of the blocking agent is 50 or more, desorption of the blocking agent at room temperature can be suppressed, and the storage stability of the coloring composition can be improved.
- the molecular weight of the blocking agent is 200 or less, it is easy to remove the blocking agent by heat treatment at a low temperature (for example, 150 ° C. or less) to allow the curing reaction to proceed, and it is easy to form a sufficiently cured cured film. Therefore, it is easy to form a cured film in which color transfer with other colors is suppressed.
- methylethylketone oxime, cyclohexanone oxime, acetoxime, diethyl malonate, ethyl acetoacetate, ⁇ -caprolactam, ⁇ -butyrolactam and pyrazole are preferable, methylethylketone oxime, acetoxime, diethyl malonate and pyrazole are more preferable, and methylethylketone oxime is preferable. More preferred.
- Examples of the repeating unit containing a blocked isocyanate group include a repeating unit represented by the following formula (Bi-1).
- X 1 represents the main chain of the repeating unit
- L 1 represents a single bond or a divalent linking group
- Z 1 represents a blocked isocyanate group.
- the main chain of the repeating unit represented by X 1 is not particularly limited. There is no particular limitation as long as it is a linking group formed from a known polymerizable monomer.
- poly (meth) acrylic linking groups polyalkyleneimine-based linking groups, polyester-based linking groups, polyurethane-based linking groups, polyurea-based linking groups, polyamide-based linking groups, polyether-based linking groups, polystyrene-based linking groups, etc.
- the poly (meth) acrylic-based linking group and the polystyrene-based linking group are preferable, and the poly (meth) acrylic-based linking group is more preferable.
- the divalent linking group represented by L 1 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), and an arylene group. Examples thereof include -NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, -OCO-, -S-, and groups composed of a combination of two or more of these.
- the alkylene group may be linear, branched, or cyclic, and is preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
- Z 1 represents a blocked isocyanate group.
- the content of the repeating unit containing the blocked isocyanate group is preferably 45% by mass or more, more preferably 50% by mass or more, and 55% by mass or more in all the repeating units of the resin BI. Is even more preferable.
- the upper limit can be 100% by mass, 95% by mass or less, or 85% by mass or less.
- the coloring composition of the present invention can contain a resin as a dispersant.
- the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
- the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
- the acidic dispersant (acidic resin) a resin in which the amount of acid groups accounts for 70 mol% or more is preferable, and substantially, when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%.
- a resin consisting only of an acid group is more preferable.
- the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
- the acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g.
- the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups.
- a resin in which the amount of basic groups exceeds 50 mol% is preferable when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%.
- the basic group contained in the basic dispersant is preferably an amino group.
- dispersant examples include polymer dispersants [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth). Acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine, alkanol amine and the like. Polymer dispersants can be further classified into linear polymers, terminally modified polymers, graft-type polymers, and block-type polymers based on their structures.
- polymer dispersants for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth). Acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alky
- the polymer dispersant acts to prevent reaggregation by adsorbing on the surface of particles such as pigments. Therefore, end-modified polymers, graft-type polymers, and block-type polymers having anchor sites on the surface of particles such as pigments can be mentioned as preferable structures. Further, the dispersant described in paragraphs 0028 to 0124 of JP2011-070156 and the dispersant described in JP2007-277514 are also preferably used.
- a graft copolymer can also be used as the dispersant.
- the description in paragraphs 0131 to 0160 of JP2012-137564A can be referred to, and the contents thereof are incorporated in the present specification.
- an oligoimine-based copolymer containing a nitrogen atom in at least one of the main chain and the side chain can be used as the dispersant.
- the description in paragraphs 0102 to 0174 of JP2012-255128A can be referred to, and this content is incorporated in the present specification.
- Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series manufactured by Big Chemie (for example, Disperbyk-111, 2001, etc.) and the Solsparse series manufactured by Nippon Lubrizol Co., Ltd. For example, Solsparse 20000, 76500, etc.), Ajinomoto Fine Techno Co., Ltd.'s Ajispar series and the like can be mentioned. Further, the product described in paragraph number 0129 of JP2012-137564A and the product described in paragraph number 0235 of JP2017-194662 can also be used as a dispersant.
- the content of the resin is preferably 5 to 50% by mass based on the total solid content of the coloring composition.
- the upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.
- the lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
- the content of the resin is preferably 25 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound.
- the upper limit is preferably 250 parts by mass or less, more preferably 150 parts by mass or less.
- the lower limit is preferably 50 parts by mass or more, and more preferably 75 parts by mass or more.
- the content of the above-mentioned resin b1 in the total amount of the resin contained in the coloring composition of the present invention is preferably 0.1 to 100% by mass, and more preferably 5 to 100% by mass.
- the upper limit can be 90% by mass or less, 80% by mass or less, or 70% by mass or less.
- the content of the resin b1 described above is preferably 5 to 50% by mass in the total solid content of the coloring composition.
- the upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.
- the lower limit is preferably 10% by mass or more, and more preferably 12.5% by mass or more.
- the content of the above-mentioned resin BI in the total amount of the resin contained in the coloring composition of the present invention is preferably 0.1 to 100% by mass, and more preferably 5 to 100% by mass.
- the upper limit can be 90% by mass or less, 80% by mass or less, or 70% by mass or less.
- the content of the resin BI described above is preferably 5 to 50% by mass in the total solid content of the coloring composition.
- the upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.
- the lower limit is preferably 10% by mass or more, and more preferably 12.5% by mass or more.
- the coloring composition of the present invention preferably contains a compound containing a frill group (hereinafter, also referred to as a frill group-containing compound).
- a frill group-containing compound a compound containing an ethylenically unsaturated bond-containing group
- the frill group contained in the frill group-containing compound and the ethylenically unsaturated bond-containing group contained in the above-mentioned polymerizable compound are composed of ethylene-. Since a bond is formed by the Alder reaction even at a low temperature of 150 ° C. or lower, it is excellent in low temperature curing.
- the structure of the frill group-containing compound is not particularly limited as long as it contains a frill group (a group obtained by removing one hydrogen atom from furan).
- a frill group a group obtained by removing one hydrogen atom from furan.
- the compounds described in paragraphs 0049 to 0089 of JP-A-2017-194662 can be used.
- Examples of the frill group-containing compound include JP-A-2000-233581, JP-A-1994-271558, JP-A-1994-293830, JP-A-1996-239421, and JP-A-1998-508655.
- the frill group-containing compound may be a monomer or a polymer.
- a polymer is preferable because it is easy to improve the durability of the obtained film.
- the weight average molecular weight is preferably 2000 to 70,000.
- the upper limit is preferably 60,000 or less, more preferably 50,000 or less.
- the lower limit is preferably 3000 or more, more preferably 4000 or more, and even more preferably 5000 or more.
- the molecular weight is preferably less than 2000, more preferably 1800 or less, and even more preferably 1500 or less.
- the lower limit is preferably 100 or more, more preferably 150 or more, and even more preferably 175 or more.
- the polymer-type frill group-containing compound is also a component corresponding to the resin in the coloring composition of the present invention.
- the frill group-containing compound having a polymerizable group is also a component corresponding to the polymerizable compound in the coloring composition of the present invention.
- Examples of the monomer-type frill group-containing compound include a compound represented by the following formula (fur-1).
- Rf 1 represents a hydrogen atom or a methyl group
- Rf 2 represents a divalent linking group.
- an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and two or more of these are combined.
- the group is mentioned.
- the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 15 carbon atoms.
- the alkylene group may be linear, branched or cyclic.
- the arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- the alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxy group and the like.
- the frill group-containing monomer is preferably a compound represented by the following formula (fur-1-1).
- Rf 1 represents a hydrogen atom or a methyl group
- Rf 11 represents -O- or -NH-
- Rf 12 represents a single bond or a divalent linking group.
- the divalent linking group represented by Rf 12 an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two or more of these are combined.
- the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 15 carbon atoms.
- the alkylene group may be linear, branched or cyclic.
- the arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
- the alkylene group and the arylene group may have a substituent. Examples of the substituent include a hydroxy group and the like.
- frill group-containing monomer examples include compounds having the following structures.
- Rf 1 represents a hydrogen atom or a methyl group.
- the polymer-type frill group-containing compound (hereinafter, also referred to as a frill group-containing polymer) is preferably a resin containing a repeating unit containing a frill group, and is a repeating compound derived from the compound represented by the above formula (fur-1). More preferably, it is a resin containing a unit.
- the ratio of the repeating unit containing a frill group to all the repeating units is preferably 30 to 70% by mass.
- the lower limit is preferably 35% by mass or more, more preferably 40% by mass or more.
- the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
- the concentration of the frill group in the frill group-containing polymer is preferably 0.5 to 6.0 mmol, more preferably 1.0 to 4.0 mmol per 1 g of the frill group-containing polymer.
- concentration of the frill group is 0.5 mmol or more, preferably 1.0 mmol or more, it is easy to form an excellent cured film due to solvent resistance and the like.
- concentration of the frill group is 6.0 mmol or less, preferably 4.0 mmol or less, the stability over time of the coloring composition is good.
- the frill group-containing polymer may contain a repeating unit having an acid group and / or a repeating unit having a polymerizable group, in addition to the repeating unit having a frill group.
- the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
- the polymerizable group include ethylenically unsaturated bond-containing groups such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the acid value of the frill group-containing polymer is preferably 10 to 200 mgKOH / g, more preferably 40 to 130 mgKOH / g.
- the proportion of the repeating unit having an acid group is preferably 2 to 25% by mass based on all the repeating units of the frill group-containing polymer.
- the lower limit is preferably 4% by mass or more, and more preferably 5% by mass or more.
- the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
- the ratio of the repeating unit having a polymerizable group is preferably 20 to 60% by mass based on all the repeating units of the frill group-containing polymer.
- the lower limit is preferably 25% by mass or more, more preferably 30% by mass or more.
- the upper limit is preferably 55% by mass or less, more preferably 50% by mass or less.
- the frill group-containing polymer can be produced by the method described in paragraphs 0052 to 0101 of JP-A-2017-194662.
- the content of the frill group-containing compound is preferably 0.1 to 70% by mass based on the total solid content of the coloring composition.
- the lower limit is preferably 2.5% by mass or more, more preferably 5.0% by mass or more, and further preferably 7.5% by mass or more.
- the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.
- the content of the frill group-containing polymer in the resin contained in the coloring composition is preferably 0.1 to 100% by mass.
- the lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.
- the upper limit is preferably 90% by mass or less, and more preferably 80% by mass or less.
- the content of the frill group-containing polymer is the same as that of the resin b1. It is preferably 10 to 200 parts by mass with respect to 100 parts by mass.
- the upper limit is preferably 175 parts by mass or less, and preferably 150 parts by mass or less.
- the lower limit is preferably 25 parts by mass or more, and preferably 150 parts by mass or more.
- the coloring composition of the present invention can further contain a compound having an epoxy group.
- a compound having two or more epoxy groups in one molecule is preferable. It is preferable to have 2 to 100 epoxy groups in one molecule.
- the upper limit may be, for example, 10 or less, or 5 or less.
- the compound having an epoxy group may be either a low molecular weight compound (for example, a molecular weight of less than 1000) or a polymer compound (for example, a molecular weight of 1000 or more, in the case of a polymer, a weight average molecular weight of 1000 or more). ..
- the molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
- the upper limit of the molecular weight (in the case of a polymer, the weight average molecular weight) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1500 or less.
- Examples of the compound having an epoxy group include paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP2014-043556, and paragraph numbers 0085 to 0092 of JP2014-089408.
- the described compound, the compound described in JP-A-2017-179172, can also be used, and the contents thereof are incorporated in the present specification.
- the content of the compound having an epoxy group is preferably 0.1 to 40% by mass based on the total solid content of the coloring 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 30% by mass or less, further preferably 20% by mass or less.
- the compound having an epoxy group may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount thereof is within the above range.
- the coloring composition of the present invention preferably contains a solvent.
- the solvent include organic solvents.
- the solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the coloring composition.
- the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents and the like.
- paragraph No. 0223 of WO 2015/166779 can be referred to, the contents of which are incorporated herein by reference.
- an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used.
- organic solvent examples include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N , N-Dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol and the like.
- aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may need to be reduced for environmental reasons (for example, 50 mass ppm (parts per) with respect to the total amount of the organic solvent. Million) or less, 10 mass ppm or less, or 1 mass ppm or less).
- a solvent having a low metal content it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, a solvent at the mass ppt (parts per fraction) level may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).
- Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
- the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
- the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
- the solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
- the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
- the content of the solvent in the coloring composition is preferably 60 to 95% by mass.
- the upper limit is preferably 90% by mass or less, more preferably 87.5% by mass or less, and further preferably 85% by mass or less.
- the lower limit is preferably 65% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more.
- the solvent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount thereof is within the above range.
- the coloring composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulation.
- substantially free of the environmentally regulated substance means that the content of the environmentally regulated substance in the coloring composition is 50 mass ppm or less, and preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
- environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
- Examples of the method for reducing the environmentally regulated substance include a method of heating or depressurizing the inside of the system to raise the boiling point of the environmentally regulated substance to the boiling point or higher and distilling off the environmentally regulated substance from the system to reduce the amount of the environmentally regulated substance. Further, when distilling off a small amount of an environmentally regulated substance, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to improve efficiency.
- a polymerization inhibitor or the like is added and distilled under reduced pressure in order to prevent the radical polymerization reaction from proceeding and cross-linking between molecules during distillation under reduced pressure. You may.
- distillation methods are performed at the stage of the raw material, the stage of the product obtained by reacting the raw material (for example, the resin solution after polymerization or the polyfunctional monomer solution), or the stage of the coloring composition prepared by mixing these compounds. It is also possible at the stage of.
- the coloring composition of the present invention can contain a pigment derivative.
- the pigment derivative include compounds having a structure in which a part of the chromophore is replaced with an acid group, a basic group or a phthalimide methyl group.
- the chromogens constituting the pigment derivative include quinoline skeleton, benzoimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthracinone skeleton, quinacridone skeleton, dioxazine skeleton, perinone skeleton, perylene skeleton, thioindigo skeleton, and iso.
- Examples thereof include indolin skeleton, isoindolinone skeleton, quinophthalone skeleton, slene skeleton, metal complex skeleton, and quinoline skeleton, benzoimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, quinophthalone skeleton, isoindrin skeleton and phthalocyanine skeleton are preferable. , Azo skeleton and benzoimidazolone skeleton are more preferred.
- As the acid group contained in the pigment derivative a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable.
- an amino group is preferable, and a tertiary amino group is more preferable.
- Specific examples of the pigment derivative include Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 01-2170777, Japanese Patent Application Laid-Open No. 03-009961, and Japanese Patent Application Laid-Open No. 03-026767.
- the content of the pigment derivative is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the pigment.
- the lower limit of this range is more preferably 0.25 parts by mass or more, further preferably 0.5 parts by mass or more, particularly preferably 0.75 parts by mass or more, and 1 part by mass or more. It is more preferable to have.
- the upper limit of this range is more preferably 25 parts by mass or less, further preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less.
- a curing accelerator may be added for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature.
- the curing accelerator include polyfunctional thiol 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 compound, and more preferably a compound represented by the formula (T1). Equation (T1) (In formula (T1), n represents an integer of 2 to 4, and L represents a linking group of 2 to 4 valences.)
- 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.
- the curing accelerator is a methylol-based compound (for example, a compound exemplified as a cross-linking agent in paragraph No. 0246 of JP-A-2015-034963), amines, phosphonium salt, amidin salt, amide compound (for example, above, for example.
- an alkoxysilane compound for example, an alkoxysilane compound having an epoxy group described in JP-A-2011-253504
- an onium salt compound for example, JP-A-2015-034963.
- a compound exemplified as an acid generator in paragraph No. 0216, a compound described in JP-A-2009-180949) and the like can also be used.
- the content of the curing accelerator is preferably 0.3 to 8.9% by mass, preferably 0.8 to 6.4% by mass, based on the total solid content of the coloring composition. More preferably by mass.
- the coloring composition of the present invention can contain a silane coupling agent.
- a silane coupling agent a silane compound having at least two kinds of functional groups having different reactivity in one molecule is preferable.
- the silane coupling agent includes at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group.
- silane coupling agent examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-602), N-2- (aminoethyl) -3.
- the description in paragraphs 0155 to 0158 of JP2013-254847A can be referred to, and this content is incorporated in the present specification.
- the content of the silane coupling agent is preferably 0.001 to 20% by mass, preferably 0.01 to 10% by mass, based on the total solid content of the coloring composition. Is more preferable, and 0.1% by mass to 5% by mass is particularly preferable.
- the coloring composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types of silane coupling agent. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
- the coloring composition of the present invention can contain a polymerization inhibitor.
- the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, quaternary-thiobis (3-methyl-6-t-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.).
- the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the coloring composition.
- the coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types of polymerization inhibitors. When two or more types are contained, it is preferable that the total amount thereof is within the above range.
- the coloring composition of the present invention can contain an ultraviolet absorber.
- an ultraviolet absorber a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indol compound, a triazine compound and the like can be used.
- paragraph numbers 0052 to 0072 of JP2012-208374A paragraph numbers 0317 to 0334 of JP2013-066814, and paragraphs 0061 to 0080 of JP2016-162946.
- Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.).
- Examples of the benzotriazole compound include the MYUA series made by Miyoshi Oil & Fat Co., Ltd. (The Chemical Daily, February 1, 2016).
- the ultraviolet absorber the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used.
- the coloring composition of the present invention contains an ultraviolet absorber
- the content of the ultraviolet absorber is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the coloring composition. It is preferable, and 0.1 to 3% by mass is particularly preferable.
- the ultraviolet absorber only one kind may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.
- the coloring composition of the present invention can contain a surfactant.
- a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.
- the surfactant the surfactant described in paragraph Nos. 0238 to 0245 of International Publication No. 2015/166779 is mentioned, and the content thereof is incorporated in the present specification.
- the surfactant is preferably a fluorine-based surfactant.
- the liquid characteristics particularly, fluidity
- the liquid saving property can be further improved. It is also possible to form a film having a small thickness unevenness.
- the fluorine content in the fluorine-based surfactant 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 property, and has good solubility in a coloring composition.
- fluorine-based surfactant examples include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Application Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of the corresponding International Publication No. 2014/017669) and the like, JP-A-2011- The surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 132503 and the surfactants described in JP-A-2020-0083634 are mentioned, and the contents thereof are incorporated in the present specification.
- fluorine-based surfactants include, for example, Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS.
- the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
- fluorine-based surfactants include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
- fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
- a fluorine-based surfactant include the fluorine-based surfactants described in JP-A-2016-216602, the contents of which are incorporated in the present specification.
- the fluorine-based surfactant a block polymer can also be used.
- 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 groups and propyleneoxy groups) (meth).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
- the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.
- the weight average molecular weight of the above compounds is preferably 3000 to 50000, for example 14000.
- % indicating the ratio of the repeating unit is mol%.
- a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used.
- the compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation, RS-72-K and the like can be mentioned.
- the fluorine-based surfactant the compounds described in paragraphs 0015 to 0158 of JP2015-117327A can also be used.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc.
- Examples of the silicon-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, (Shinetsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all manufactured by Big Chemie) and the like.
- the content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005 to 3.0% by mass.
- the surfactant may be only one kind or two or more kinds. In the case of two or more types, the total amount is preferably in the above range.
- additives such as fillers, adhesion promoters, antioxidants, anti-aggregation agents and the like can be added to the coloring composition of the present invention, if necessary.
- additives include the additives described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated in the present specification.
- the antioxidant for example, a phenol compound, a phosphorus-based compound (for example, the compound described in paragraph No. 0042 of JP-A-2011-090147), a thioether compound and the like can be used.
- ADEKA stub series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-" manufactured by ADEKA Corporation. 330, etc.).
- the antioxidant the polyfunctional hindered amine antioxidant described in International Publication No. 2017/006600, the antioxidant described in International Publication No. 2017/1604024, paragraph Nos. 0023 to Japanese Patent No. 6268967.
- the antioxidant described in 0048 can also be used. Only one type of antioxidant may be used, or two or more types may be used.
- the coloring composition of the present invention may contain a latent antioxidant, if necessary.
- the latent antioxidant is a compound whose site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst.
- a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned.
- Specific examples of the latent antioxidant include the compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
- Examples of commercially available products include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like.
- the coloring composition of the present invention includes a sensitizer and a light stabilizer described in paragraph No.
- JP-A-2004-295116 a thermal polymerization inhibitor described in paragraph No. 1981 of JP-A-2004, JP-A-2018-.
- the storage stabilizer described in paragraph No. 0242 of Japanese Patent Application Laid-Open No. 091940 can be contained.
- the container for the colored composition of the present invention is not particularly limited, and a known container can be used.
- a storage container a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin and a bottle in which 6 types of resin are composed of 7 layers are used for the purpose of suppressing impurities from being mixed into raw materials and coloring compositions. It is also preferable to use. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
- the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, improving the storage stability of the composition, and suppressing deterioration of the components.
- the coloring composition of the present invention can be produced by mixing the above-mentioned components.
- all the components may be simultaneously dissolved and / or dispersed in a solvent to produce the coloring composition, or each component may be appropriately used as two or more solutions or dispersions, if necessary. Then, these may be mixed at the time of use (at the time of application) to produce a coloring composition.
- a process of dispersing particles such as pigments may be included.
- the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like.
- Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like.
- the process and disperser for dispersing pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial. Practical application The process and disperser described in Paragraph No.
- JP-A-2015-157893 "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used.
- the particles may be miniaturized in the salt milling step.
- the materials, equipment, processing conditions, etc. used in the salt milling step for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.
- any filter that has been conventionally used for filtration or the like can be used without particular limitation.
- fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight).
- PTFE polytetrafluoroethylene
- nylon eg, nylon-6, nylon-6,6)
- polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight).
- PP polypropylene
- the pore size of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m. If the pore size of the filter is within the above range, fine foreign matter can be removed more reliably.
- the nominal value of the filter manufacturer can be referred to.
- various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can be used.
- fibrous filter medium examples include polypropylene fiber, nylon fiber, glass fiber and the like.
- examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd.
- filters for example, a first filter and a second filter
- the filtration with each filter may be performed only once or twice or more.
- filters having different pore diameters may be combined within the above-mentioned range.
- the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration may be performed with the second filter.
- the cured film of the present invention is a film obtained by curing the above-mentioned coloring composition of the present invention.
- the cured film of the present invention can be used as a color filter or the like. Specifically, it can be preferably used as a colored layer (pixel) of a color filter, and more preferably used as a green pixel.
- the film thickness of the cured film of the present invention can be appropriately adjusted depending on the intended purpose, but is preferably 0.5 to 3.0 ⁇ m.
- the lower limit is preferably 0.8 ⁇ m or more, more preferably 1.0 ⁇ m or more, and even more preferably 1.1 ⁇ m or more.
- the upper limit is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, and even more preferably 1.8 ⁇ m or less.
- the maximum value of the transmittance for light having a wavelength of 495 nm or more and less than 550 nm is preferably 65% or more, more preferably 70% or more, still more preferably 75% or more. ..
- the average transmittance for light having a wavelength of 495 nm or more and less than 550 nm is preferably 60% or more, more preferably 65% or more, and further preferably 70% or more.
- the transmittance for light having a wavelength of 450 nm is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less.
- the average transmittance for light having a wavelength of 400 nm or more and 450 nm or less is preferably 10% or less, more preferably 5% or less, and further preferably 1% or less.
- the average transmittance for light having a wavelength of 550 nm or more and 600 nm or less is preferably 60% or less, more preferably 50% or less, and further preferably 40% or less.
- the color filter of the present invention has the cured film of the present invention described above.
- the cured film of the present invention is preferably provided as a colored pixel of a color filter, more preferably as a green pixel.
- the color filter of the present invention can be used for a solid-state image sensor or a display device.
- the color filter of the present invention preferably has colored pixels of other hues in addition to the pixels of the cured film of the present invention.
- colored pixels having other hues include blue pixels, red pixels, yellow pixels, magenta pixels, and cyan pixels.
- a preferred embodiment of the color filter of the present invention includes an embodiment having a green pixel, a red pixel, and a blue pixel composed of the cured film of the present invention.
- the color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
- the partition wall preferably has a lower refractive index than each colored pixel.
- the partition wall may be formed by the configuration described in US Patent Application Publication No. 2018/0040656.
- the red pixels that are preferably used in combination with the pixels of the cured film of the present invention preferably contain a red colorant.
- the content of the red colorant in the colorant contained in the red pixel is preferably 30% by mass or more, and more preferably 40% by mass or more.
- the upper limit of the content of the red colorant in the colorant contained in the red pixel may be 100% by mass, 99% by mass or less, 95% by mass or less, or 90% by mass. It may be less than or equal to%.
- the red pixel preferably contains 40% by mass or more of the red colorant, more preferably 50% by mass or more, and further preferably 60% by mass or more.
- the upper limit of the content of the red colorant is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.
- the red colorant include C.I. 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, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291 Red pigments such as 294 (xanthene type, Organ
- the red pixel preferably contains a yellow colorant in addition to the red colorant.
- the content of the yellow colorant is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, and 10 to 40 parts by mass with respect to 100 parts by mass of the red colorant. More preferred.
- Examples of the yellow colorant include C.I. I.
- the maximum value of the transmittance of the red pixel with respect to light having a wavelength of 400 to 550 nm is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less.
- the average transmittance for light having a wavelength of 400 to 550 nm is preferably 3% or less, more preferably 1% or less, and even more preferably 0.5% or less.
- the minimum value of the transmittance for light having a wavelength of 600 to 700 nm is preferably 10% or more, more preferably 25% or more, and further preferably 40% or more.
- the average transmittance for light having a wavelength of 600 to 700 nm is preferably 80% or more, more preferably 90% or more, and further preferably 95% or more.
- the blue pixels that are preferably used in combination with the pixels of the cured film of the present invention preferably contain a blue colorant.
- the content of the blue colorant in the colorant contained in the blue pixel is preferably 40% by mass or more, and more preferably 60% by mass or more.
- the blue pixel preferably contains 20% by mass or more of the blue colorant, more preferably 25% by mass or more, and further preferably 30% by mass or more.
- the upper limit of the content of the blue colorant is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less. Examples of the blue colorant include C.I. I.
- Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,29,60,64,66,79,80,87 (monoazo system)
- blue pigments such as 88 (methine-based)
- C.I. I. Pigment Blue 15: 6 is preferred.
- the blue pixel contains at least one selected from a purple colorant and a red colorant in addition to the blue colorant.
- the content of the purple colorant is preferably 10 to 90 parts by mass, more preferably 20 to 75 parts by mass, and preferably 30 to 60 parts by mass with respect to 100 parts by mass of the blue colorant. More preferred.
- Examples of the purple colorant and the red colorant include C.I. I. Pigment Violet 1,19,23,27,32,37,42,60 (triarylmethane type), 61 (xanthene type) and other purple pigments, xanthene compounds and the like can be mentioned.
- Examples of the xanthene compound include salt-forming compounds obtained by reacting a resin having a cationic group in the side chain with a xanthene-based acid dye described in paragraphs 0025 to 0077 of JP-A-2016-180834. ..
- the maximum value of the transmittance of the blue pixel with respect to light having a wavelength of 400 to 500 nm is preferably 50% or more, more preferably 60% or more, and further preferably 70% or more.
- the average transmittance for light having a wavelength of 400 to 500 nm is preferably 40% or more, more preferably 50% or more, and even more preferably 60% or more.
- the minimum value of the transmittance for light having a wavelength of 550 to 700 nm is preferably 30% or less, more preferably 20% or less, and further preferably 10% or less.
- the average transmittance for light having a wavelength of 550 to 700 nm is preferably 25% or less, more preferably 10% or less, and even more preferably 5% or less.
- the structure of the present invention has green pixels, red pixels, and blue pixels obtained by using the coloring composition of the present invention described above.
- the green pixel preferably has the spectral characteristics described in the section of the cured film of the present invention described above.
- the red pixel and the blue pixel preferably have the spectral characteristics described in the above-mentioned color filter section.
- ⁇ Pixel formation method> A method of forming pixels will be described.
- green pixels By using the coloring composition of the present invention, for example, green pixels can be formed.
- the pixel forming method includes a step of applying a coloring composition on a support to form a coloring composition layer, a step of exposing the coloring composition layer in a pattern, and developing a coloring composition layer after exposure. It is preferable to include the steps to be performed. Pixels are preferably formed at a temperature of 150 ° C. or lower throughout the entire process. In the present invention, “performing at a temperature of 150 ° C. or lower throughout the entire process” means that all the steps of forming pixels using the coloring composition are performed at a temperature of 150 ° C. or lower. When a step of further heating is provided after developing the colored composition layer after exposure, it means that this heating step is also performed at a temperature of 150 ° C. or lower.
- each step will be described in detail.
- the coloring composition is applied onto the support to form the coloring composition layer.
- the support include a glass substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamide-imide substrate, a polyimide substrate, and the like.
- An organic light emitting layer may be formed on these substrates.
- an undercoat layer may be provided on the substrate in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface.
- the undercoat layer can also be formed by using, for example, a composition obtained by removing a colorant from the above-mentioned coloring composition of the present invention.
- the surface contact angle of the undercoat layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the undercoat layer is within the above range, the coating property of the resin composition is good.
- the surface contact angle of the undercoat layer can be adjusted by, for example, adding a surfactant.
- a known method can be used as a method for applying the coloring composition.
- a dropping method drop casting
- a slit coating method for example, a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395).
- Methods described in the publication Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc.
- Various printing methods; transfer method using a mold or the like; nano-imprint method and the like can be mentioned.
- the method of application to inkjet is not particularly limited, and is, for example, the method shown in "Expandable and usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). (Page 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, regarding the method of applying the coloring composition, the description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents are incorporated in the present specification.
- the colored composition layer formed on the support may be dried (prebaked).
- the prebaking temperature is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, further preferably 60 ° C. or lower, and particularly preferably 50 ° C. or lower.
- the lower limit can be, for example, 40 ° C. or higher.
- the prebaking time is preferably 10 to 3600 seconds. Pre-baking can be performed on a hot plate, an oven, or the like.
- the colored composition layer is exposed in a pattern (exposure step).
- the colored composition layer can be exposed in a pattern by exposing the colored composition layer through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. As a result, the exposed portion can be cured.
- Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also be used.
- the pulse exposure is an exposure method of a method of repeatedly irradiating and pausing light in a cycle of a short time (for example, a millisecond level or less).
- the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less.
- the lower limit of the pulse width is not particularly limited, but may be 1 femtosecond (fs) or more, and may be 10 femtoseconds or more.
- the frequency is preferably 1 kHz or higher, more preferably 2 kHz or higher, and even more preferably 4 kHz or higher.
- the upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and further preferably 10 kHz or less.
- Maximum instantaneous intensity is preferably at 50000000W / m 2 or more, more preferably 100000000W / m 2 or more, more preferably 200000000W / m 2 or more.
- the upper limit of the maximum instantaneous intensity is preferably at 1000000000W / m 2 or less, more preferably 800000000W / m 2 or less, further preferably 500000000W / m 2 or less.
- the pulse width is the time during which light is irradiated in the pulse period.
- the frequency is the number of pulse cycles per second.
- the maximum instantaneous illuminance is the average illuminance within the time during which the light is irradiated in the pulse period.
- the pulse cycle is a cycle in which light irradiation and pause in pulse exposure are one cycle.
- the irradiation amount (exposure amount) is preferably 0.03 to 2.5 J / cm 2, for example.
- the lower limit is preferably at 0.05 J / cm 2 or more, more preferably 0.2 J / cm 2 or more, still more preferably 0.5 J / cm 2 or more, 0.8 J / cm 2 The above is even more preferable, and 1.0 J / cm 2 or more is even more preferable.
- the upper limit is preferably 2.0 J / cm 2 or less, and more preferably 1.5 J / cm 2 or less.
- the exposure illuminance can be set as appropriate, and is preferably 50 mW / cm 2 to 10 W / cm 2, for example.
- the lower limit of the exposure intensity is preferably at 500 mW / cm 2 or more, more preferably 800 mW / cm 2 or more, more preferably 1000 mW / cm 2 or more.
- the upper limit of the exposure intensity is preferably 10 W / cm 2 or less, more preferably 7W / cm 2 or less, still more preferably 5W / cm 2 or less.
- the oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment) or in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, or 50% by volume) in which the oxygen concentration exceeds 21% by volume.
- Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illumination intensity 1W / cm 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 2W / cm 2.
- irradiate light preferably i-line
- irradiate light having a wavelength of more than 350 nm and 380 nm or less with an exposure amount of 1 J / cm 2 or more for exposure.
- the colored composition layer after exposure is developed. That is, the unexposed portion of the coloring composition layer is developed and removed to form a pattern (pixel).
- the unexposed portion of the coloring composition layer can be developed and removed using a developing solution.
- the colored composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains.
- the temperature of the developing solution is preferably, for example, 20 to 30 ° C.
- the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.
- Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used.
- the alkaline developer an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable.
- the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
- Ethyltrimethylammonium hydroxide Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, etc.
- examples thereof include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate.
- the alkaline agent a compound having a large molecular weight is preferable in terms of environment and safety.
- the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
- the developer may further contain a surfactant.
- the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable.
- the developer may be once produced as a concentrated solution and diluted to a concentration required for use from the viewpoint of convenience of transfer and storage.
- the dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development.
- the rinsing is performed by supplying the rinsing liquid to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support. At this time, when moving the nozzle from the central portion of the support to the peripheral portion, the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the central portion to the peripheral portion of the support.
- Additional exposure treatment and post-baking are post-development curing treatments to complete the curing.
- the heating temperature is preferably 150 ° C or lower.
- the upper limit of the heating temperature is more preferably 120 ° C. or lower, further preferably 100 ° C. or lower.
- the lower limit of the heating temperature is not particularly limited as long as it can accelerate the curing of the composition, but is more preferably 50 ° C. or higher, further preferably 75 ° C. or higher.
- the heating time is preferably 1 minute or longer, more preferably 5 minutes or longer, and even more preferably 10 minutes or longer.
- the upper limit is not particularly limited, but 20 minutes or less is preferable from the viewpoint of productivity.
- Post-baking is also preferably carried out in an atmosphere of an inert gas.
- thermal polymerization can proceed with very high efficiency without being hindered by oxygen, and even when pixels are manufactured at a temperature of 120 ° C. or lower throughout the entire process, flatness is achieved. It is possible to manufacture pixels having good properties such as solvent resistance.
- the inert gas include nitrogen gas, argon gas, helium gas and the like, and nitrogen gas is preferable.
- the oxygen concentration at the time of post-baking is preferably 100 ppm or less.
- the step of exposing the colored composition layer in a pattern involves light having a wavelength of more than 350 nm and 380 nm or less (preferably light having a wavelength of 355 to 370 nm) with respect to the colored composition layer. More preferably, it is exposed by irradiating with i-ray), and the additional exposure treatment (exposure after development) is performed with respect to the developed colored composition layer with light having a wavelength of 254 to 350 nm (preferably light having a wavelength of 254 nm). ) Is irradiated and exposed.
- the coloring composition layer can be appropriately cured by the first exposure (exposure before development), and the entire coloring composition layer is cured almost completely by the next exposure (exposure after development).
- the colored composition layer can be sufficiently cured even under low temperature conditions to form pixels having excellent properties such as solvent resistance, adhesion, and rectangularness.
- the coloring composition contains, as a photopolymerization initiator, a photopolymerization initiator A1 having an extinction coefficient of 1.0 ⁇ 10 3 mL / g cm or more at a wavelength of 365 nm in methanol.
- It contains a photopolymerization initiator A2 having an extinction coefficient of 1.0 ⁇ 10 2 mL / gcm or less at a wavelength of 365 nm in methanol and an extinction coefficient of 1.0 ⁇ 10 3 mL / gcm or more at a wavelength of 254 nm. Is preferably used.
- Exposure after development can be performed using, for example, an ultraviolet photoresist curing device.
- the ultraviolet photoresist curing apparatus may irradiate light having a wavelength of 254 to 350 nm and other light (for example, i-line).
- Irradiation amount of exposure after development is preferably 0.03 ⁇ 4.0J / cm 2, more preferably 0.05 ⁇ 3.5J / cm 2.
- the difference between the wavelength of light used in the exposure before development and the wavelength of light used in the exposure after development is preferably 200 nm or less, and more preferably 100 to 150 nm.
- the display device of the present invention has the cured film of the present invention described above.
- Examples of the display device include a liquid crystal display device and an organic electroluminescence display device.
- Examples of each display device see, for example, “Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", “Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd.)” (Issued in 1989) ”etc.
- liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)".
- the liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".
- the organic electroluminescence display device may have a light source composed of a white organic electroluminescent element.
- the white organic electroluminescence device preferably has a tandem structure.
- Japanese Patent Application Laid-Open No. 2003-045676 supervised by Akiyoshi Mikami, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association It is described on pages 326-328, 2008 and the like.
- the spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm-700 nm) are more preferable.
- the organic electroluminescence display device may have a lens on the color filter.
- the shape of the lens various shapes derived by the optical system design can be taken, and examples thereof include a convex shape and a concave shape. For example, it is easy to improve the light condensing property by making it a concave shape (concave lens).
- the lens may be in direct contact with the color filter, and another layer such as an adhesion layer or a flattening layer may be provided between the lens and the color filter.
- the lens can also be arranged and used in the manner described in International Publication No. 2018/135189.
- the coloring composition and the cured film of the present invention can also be used for a solid-state image sensor.
- the configuration of the solid-state image sensor is not particularly limited as long as it has the cured film of the present invention and functions as a solid-state image sensor, and examples thereof include the following configurations.
- a solid-state image sensor CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.
- a transfer electrode made of polysilicon or the like.
- the configuration is such that the cured film of the present invention is provided on the device protective film.
- a configuration having a condensing means for example, a microlens or the like; the same applies hereinafter
- a condensing means for example, a microlens or the like; the same applies hereinafter
- the cured film of the present invention may be embedded in a space partitioned by a partition wall, for example, in a grid pattern.
- the partition wall in this case preferably has a lower refractive index than the cured film of the present invention. Examples of an imaging apparatus having such a structure are described in JP2012-227478A, Japanese Patent Application Laid-Open No. 2014-179757, International Publication No.
- An image pickup device provided with a solid-state image sensor can be used not only for a digital camera and an electronic device having an image pickup function (mobile phone, etc.), but also for an in-vehicle camera and a surveillance camera.
- Pigment dispersion liquid PG1 ⁇ Preparation of pigment dispersion liquid> (Pigment dispersion liquid PG1) C. I. After mixing 10.40 parts by mass of Pigment Green 7, 2.60 parts by mass of Pigment Derivative 1, 6.5 parts by mass of Dispersant 1, and 80.50 parts by mass of propylene glycol monomethyl ether acetate, Using zirconia beads having a diameter of 1 mm, the pigment dispersion liquid P-G1 was prepared by dispersing with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours and then filtering with a filter having a pore size of 5 ⁇ m.
- Eiger mill Mini Model M-250MKII
- Pigment dispersion liquid PG2 (Pigment dispersion liquid PG2) C. I. After mixing 12.60 parts by mass of Pigment Green 36, 1.26 parts by mass of Pigment Derivative 1, 5.04 parts by mass of Dispersant 1, and 81.10 parts by mass of propylene glycol monomethyl ether acetate, Using zirconia beads having a diameter of 1 mm, the pigment dispersion liquid P-G2 was prepared by dispersing with an Eiger mill (“Mini model M-250MKII” manufactured by Eiger Japan) for 5 hours and then filtering with a filter having a pore size of 5 ⁇ m.
- Eiger mill Mini model M-250MKII
- Pigment dispersion liquid PG3 (Pigment dispersion liquid PG3) C. I. After mixing 12.60 parts by mass of Pigment Green 58, 1.26 parts by mass of Pigment Derivative 1, 5.04 parts by mass of Dispersant 1, and 81.10 parts by mass of propylene glycol monomethyl ether acetate, Using zirconia beads having a diameter of 1 mm, the pigment dispersion liquid P-G3 was prepared by dispersing with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours and then filtering with a filter having a pore size of 5 ⁇ m.
- Eiger mill Mini Model M-250MKII
- Pigment dispersion liquid P-Y1 C. I. After mixing 12.0 parts by mass of Pigment Yellow 150, 1.2 parts by mass of Pigment Derivative 2, 6.8 parts by mass of Dispersant 2, and 80.0 parts by mass of propylene glycol monomethyl ether acetate, Using zirconia beads having a diameter of 1 mm, the pigment dispersion liquid P-Y1 was prepared by dispersing with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours and then filtering with a filter having a pore size of 5 ⁇ m.
- Eiger mill Mini Model M-250MKII
- Pigment dispersion liquid P-Y2 After mixing 12.0 parts by mass of Pigment Yellow 185, 1.2 parts by mass of Pigment Derivative 2, 6.8 parts by mass of Dispersant 2, and 80.0 parts by mass of propylene glycol monomethyl ether acetate, Using zirconia beads having a diameter of 1 mm, the pigment dispersion liquid P-Y2 was prepared by dispersing with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours and then filtering with a filter having a pore size of 5 ⁇ m.
- Eiger mill Mini Model M-250MKII
- Pigment derivative 1 Compound with the following structure
- Pigment derivative 2 A compound having the following structure
- Dispersant 2 Resin with the following structure
- ⁇ Preparation of coloring composition The raw materials shown in the table below were mixed, stirred, and then filtered using a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare a colored composition.
- Initiator 1 Irgacure OXE01 (manufactured by BASF, a compound having the following structure, having an extinction coefficient in methanol at a wavelength of 365 nm is 6696 mL / gcm).
- Initiator 2 Omnirad 2959 (manufactured by IGM Resins B.V., compound having the following structure, extinction coefficient in methanol at a wavelength of 365 nm is 48.93 mL / gcm, and extinction coefficient at a wavelength of 254 nm is 3.0 ⁇ 10 4 mL / gcm.)
- Initiator 3 Irgacure OXE02 (manufactured by BASF, a compound having the following structure, an extinction coefficient in methanol at a wavelength of 365 nm is 7794 mL / gcm).
- Initiator 4 A compound having the following structure (the extinction coefficient of light at a wavelength of 365 nm in methanol is 18900 mL / gcm).
- Initiator 5 Omnirad 184 (manufactured by IGM Resins B.V., compound with the following structure, extinction coefficient in methanol at a wavelength of 365 nm is 88.64 mL / gcm, and extinction coefficient at a wavelength of 254 nm is 3.3 ⁇ 10 4 mL / gcm.)
- Initiator 6 Compound with the following structure
- M1 Compound with the following structure
- M2 Compound with the following structure
- M3 Trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd., Aronix M-309)
- M4 Trimethylolpropane PO-modified triacrylate (manufactured by Toagosei Co., Ltd., Aronix M-350)
- M5 Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., Aronix M-402)
- Resin C Solid content 40% by mass of propylene glycol monomethyl ether acetate solution of A10 (frill group-containing resin) of Example 31 of JP-A-2017-194662.
- Resin D Described in paragraph No. 0208 of JP-A-2019-153389.
- Acrylic resin solution 1 solid content 40% propylene glycol monomethyl ether acetate solution
- Resin G A resin having the following structure (a resin having a repeating unit containing a blocked isocyanate group and a repeating unit having a group in which an acid group is protected by a protecting group. The numerical value added to the main chain is a mass ratio.
- Mw . 7100
- PG7 refers to C.I. I. Pigment Green 7
- PG36 is C.I. I. Pigment Green 36
- PG58 is C.I. I. Pigment Green 58
- PY150 is C.I. I. Pigment Yellow 150.
- Thickening rate (%) [(viscosity (V2) -viscosity (V1)) / viscosity (V1)] x 100
- AA The thickening rate is less than 5%.
- Each coloring composition was applied onto a glass substrate using a spin coater so that the finished film thickness after drying was 2.0 ⁇ m, and dried on a hot plate at 100 ° C. for 2 minutes. Then, using an ultra-high pressure mercury lamp, i-line exposure was performed under the conditions of an exposure illuminance of 20 mW / cm 2 and an exposure amount of 1 J / cm 2. Then, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200 ° C., and the mixture was allowed to cool to form a cured film.
- the obtained cured film was measured for the absorbance of light in the wavelength range of 300 to 800 nm using an ultraviolet-visible near-infrared spectrophotometer (UV3600, manufactured by Shimadzu Corporation) using a reference as a glass substrate.
- Wavelength 1, wavelength 2, and wavelength 3 were measured, respectively.
- Wavelength 1 Of the absorptivity for light with a wavelength of 400 to 700 nm, when the absorptivity for light with a wavelength of 450 nm is 1, the absorptivity is 0.2.
- Short wavelength Wavelength 2 Absorption for light with a wavelength of 400 to 700 nm. Of these, a long wavelength with an absorbance of 0.2 when the absorbance for light with a wavelength of 450 nm is 1.
- Wavelength 3 Wavelength with a minimum absorbance for light with a wavelength of 400 to 700 nm.
- Each coloring composition was applied onto a glass substrate using a spin coater so that the finished film thickness after drying was 2.0 ⁇ m, and dried on a hot plate at 100 ° C. for 2 minutes. Then, using an ultra-high pressure mercury lamp, i-line exposure was performed under the conditions of an exposure illuminance of 20 mW / cm 2 and an exposure amount of 1 J / cm 2. Then, heat treatment (post-baking) was performed for 300 seconds using a hot plate at 200 ° C., and the mixture was allowed to cool to form a cured film.
- the transmittance of light having a wavelength in the range of 400 to 700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd.
- an ultraviolet cut filter manufactured by AS ONE, KU-1000100
- a light resistance tester manufactured by Suga Test Instruments Co., Ltd., Xenon Weather Meter SX75
- a light resistance test was conducted by irradiating with light of 10,000 lux for 50 hours.
- the temperature inside the test device was set to 63 ° C.
- the relative humidity in the test device was set to 50%.
- the transmittance of the cured film was measured, the maximum value of the amount of change in the transmittance was obtained, and the light resistance was evaluated according to the following criteria.
- the transmittance was measured 5 times for each sample, and the average value of the results of 3 times excluding the maximum value and the minimum value was adopted.
- the maximum value of the amount of change in the transmittance means the amount of change in the cured film before and after the light resistance test at the wavelength where the amount of change in the transmittance in the wavelength range of 400 to 700 nm is the largest.
- AA The maximum value of the amount of change in transmittance is 3% or less.
- C The maximum value of the amount of change in transmittance exceeds 10%.
- the examples were superior in the evaluation of storage stability and light resistance to the comparative examples. Further, the cured film obtained by using the coloring composition of the example had a high transmittance of light in the vicinity of a wavelength of 500 nm, and was excellent in sensitivity as a green pixel.
- Example 35 Regarding the coloring composition of Example 1, instead of a hot plate at 200 ° C., an ultraviolet photoresist curing device (UMA-802-HC-552; manufactured by Ushio Electric Co., Ltd.) was used at an exposure amount of 3000 mJ / cm 2. A cured film was prepared in the same manner except that the film was exposed. The evaluation result of light resistance was the same as in Example 1.
- UVA-802-HC-552 manufactured by Ushio Electric Co., Ltd.
- Example 36 With respect to the coloring composition of Example 9, a cured film was prepared in the same manner except that heat treatment (post-baking) was performed for 20 minutes using a hot plate at 100 ° C. instead of a hot plate at 200 ° C.
- the evaluation result of light resistance was the same as in Example 9.
- Example 37 Regarding the coloring composition of Example 16, an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) was used instead of a hot plate at 200 ° C., except that exposure was performed at an exposure amount of 1500 mJ / cm 2. A cured film was prepared in the same manner. The evaluation result of light resistance was the same as in Example 16.
- Example 1000 A coloring composition for forming green pixels was applied onto a silicon wafer by a spin coating method so that the film thickness after film formation was 2.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at 1000 mJ / cm2 through a mask with a 2 ⁇ m square dot pattern. Then, paddle development was carried out at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and further washed with pure water.
- TMAH tetramethylammonium hydroxide
- the mixture was heated at 200 ° C. for 5 minutes to form a green coloring pattern (green pixels).
- the red pixel forming coloring composition 1 and the blue pixel forming coloring composition 1 are sequentially patterned to form a red coloring pattern (red pixel) and a blue coloring pattern (blue pixel), respectively, to form a structure.
- the coloring composition for forming green pixels the coloring composition of Example 1 was used.
- the coloring composition 1 for forming red pixels and the coloring composition 1 for forming blue pixels will be described later.
- the obtained structure was incorporated into an organic electroluminescence display device according to a known method. This organic electroluminescence display device had suitable image recognition ability.
- Example 1001 Except that the red pixel forming coloring composition 2 was used instead of the red pixel forming coloring composition 1 of Example 1000, and the blue pixel forming coloring composition 2 was used instead of the blue pixel forming coloring composition 1. Formed a structure in the same manner as in Example 1000. The coloring composition 2 for forming red pixels and the coloring composition 2 for forming blue pixels will be described later. The obtained structure was incorporated into an organic electroluminescence display device according to a known method. This organic electroluminescence display device had suitable image recognition ability.
- Coloring composition for forming blue pixels 1 The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 ⁇ m filter to prepare a coloring composition 1 for forming blue pixels.
- Coloring composition for forming blue pixels 2 The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 ⁇ m filter to prepare a coloring composition 1 for forming blue pixels.
- the pigment dispersion liquid DR-1 used was prepared by the following method. C. I. After mixing 11.0 parts by mass of Pigment Red 264, 21.5 parts by mass of the resin solution 11, 1 part by mass of a dispersant (EFKA4300 manufactured by BASF), and 66.5 parts by mass of PGMEA, Using zirconia beads having a diameter of 1 mm, the pigment dispersion liquid DR-1 was prepared by dispersing with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours and then filtering with a filter having a pore size of 5 ⁇ m.
- Eiger mill Mini Model M-250MKII
- the pigment dispersion liquid DY-1 As the pigment dispersion liquid DY-1, the one prepared by the following method was used. C. I. After mixing 23.5 parts by mass of Pigment Yellow 139, 7 parts by mass of the resin solution 11, 3 parts by mass of a dispersant (EFKA4300 manufactured by BASF), and 66.5 parts by mass of PGMEA, the diameter is 1 mm. After dispersing for 5 hours with an Eiger mill (“Mini model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using the zirconia beads of the above, the pigment dispersion liquid DY-1 was prepared by filtering with a filter having a pore size of 5 ⁇ m.
- the pigment dispersion liquid DB-1 As the pigment dispersion liquid DB-1, the one prepared by the following method was used. C. I. 11.0 parts by mass of Pigment Blue 15: 6, 21.5 parts by mass of the resin solution 11, 1 part by mass of the dispersant (EFKA4300 manufactured by BASF), and 66.5 parts by mass of PGMEA were mixed. Then, using zirconia beads having a diameter of 1 mm, the pigment dispersion liquid DB-1 was prepared by dispersing with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours and then filtering with a filter having a pore size of 5 ⁇ m.
- Eiger mill Mini Model M-250MKII manufactured by Eiger Japan Co., Ltd.
- the pigment dispersion liquid DV-1 As the pigment dispersion liquid DV-1, the one prepared by the following method was used. C. I. After mixing 11.0 parts by mass of Pigment Violet 23, 21.5 parts by mass of the resin solution 11, 1 part by mass of a dispersant (EFKA4300 manufactured by BASF), and 66.5 parts by mass of PGMEA, Using zirconia beads having a diameter of 1 mm, the pigment dispersion solution DV-1 was prepared by dispersing with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours and then filtering with a filter having a pore size of 5 ⁇ m.
- Eiger mill Mini Model M-250MKII manufactured by Eiger Japan Co., Ltd.
- a resin solution 11 prepared by the following method was used as the resin solution 11. 196 parts by mass of PGMEA was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen.
- a resin solution 12 prepared by the following method was used as the resin solution 12. 207 parts by mass of PGMEA was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. , 20 parts by mass of methacrylic acid, 20 parts by mass of paracumylphenol ethylene oxide-modified acrylate (manufactured by Toa Synthetic Co., Ltd., Aronix M110), 45 parts by mass of methyl methacrylate, 8.5 parts by mass of 2-hydroxyethyl methacrylate from the dropping tube.
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Abstract
Description
<1> 着色剤と、重合性化合物と、光重合開始剤とを含む着色組成物であって、
上記着色剤は、カラーインデックスピグメントグリーン7を1質量%以上含む緑色着色剤と、カラーインデックスピグメントイエロー150を含む黄色着色剤とを含み、かつ、カラーインデックスピグメントグリーン7以外の緑色着色剤とカラーインデックスピグメントイエロー150との質量比が、カラーインデックスピグメントグリーン7以外の緑色着色剤:カラーインデックスピグメントイエロー150=0:100~18:82であり、
上記着色組成物は、波長450nmの光に対する吸光度を1としたとき、吸光度が0.2となる波長が550nm以上600nm以下の波長範囲に存在する、
着色組成物。
<2> 上記着色組成物は、波長400~700nmの光に対する吸光度のうち、495nm以上550nm未満の波長範囲に吸光度の最小値を有する、<1>に記載の着色組成物。
<3> 上記着色組成物は、波長450nmの光に対する吸光度を1としたとき、吸光度が0.2となる波長が470nm以上490nm以下の波長範囲と、550nm以上600nm以下の波長範囲のそれぞれに存在する、<1>または<2>に記載の着色組成物。
<4> 上記着色剤中におけるカラーインデックスピグメントグリーン7とカラーインデックスピグメントイエロー150との合計量が80質量%以上である、<1>~<3>のいずれか1つに記載の着色組成物。
<5> 上記カラーインデックスピグメントグリーン7以外の緑色着色剤がカラーインデックスピグメントグリーン36を含む、<1>~<4>のいずれか1つに記載の着色組成物。
<6> 上記黄色着色剤は、実質的にカラーインデックスピグメントイエロー150のみである、<1>~<5>のいずれか1つに記載の着色組成物。
<7> 上記緑色着色剤は、実質的にカラーインデックスピグメントグリーン7のみである、<1>~<6>のいずれか1つに記載の着色組成物。
<8> カラーインデックスピグメントグリーン7の100質量部に対してカラーインデックスピグメントイエロー150を50~240質量部含有する、<1>~<7>のいずれか1つに記載の着色組成物。
<9> 上記着色組成物の全固形分中における上記着色剤の含有量が20質量%以上である、<1>~<8>のいずれか1つに記載の着色組成物。
<10> 上記重合性化合物は、エチレン性不飽和結合含有基を3個以上有する重合性化合物を含む、<1>~<9>のいずれか1つに記載の着色組成物。
<11> 上記重合性化合物は、エチレン性不飽和結合含有基とアルキレンオキシ基とをする重合性化合物を含む、<1>~<10>のいずれか1つに記載の着色組成物。
<12> 上記光重合開始剤は、オキシム化合物を含有する、<1>~<11>のいずれか1つに記載の着色組成物。
<13> 上記光重合開始剤は、オキシム化合物とヒドロキシアルキルフェノン化合物を含有する、<1>~<12>のいずれか1つに記載の着色組成物。
<14> カラーフィルタの緑色画素形成用の着色組成物である、<1>~<13>のいずれか1つに記載の着色組成物。
<15> 表示装置用の着色組成物である、<1>~<14>のいずれか1つに記載の着色組成物。
<16> 全工程を通じて150℃以下の温度で硬化膜を形成するために用いられる、<1>~<15>のいずれか1つに記載の着色組成物。
<17> <1>~<16>のいずれか1つに記載の着色組成物を用いて得られる硬化膜。
<18> 緑色画素と赤色画素と青色画素とを有する構造体であって、上記緑色画素は<1>~<16>のいずれか1つに記載の着色組成物を用いて得られるものである、構造体。
<19> <17>に記載の硬化膜を有するカラーフィルタ。
<20> <17>に記載の硬化膜を有する表示装置。
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)をも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、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、電子線等の活性光線または放射線が挙げられる。
本明細書において「~」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合計質量をいう。
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(Mw)および数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィ(GPC)により測定したポリスチレン換算値として定義される。
本発明の着色組成物は、着色剤と、重合性化合物と、光重合開始剤とを含む着色組成物であって、
上記着色剤は、カラーインデックスピグメントグリーン7を1質量%以上含む緑色着色剤と、カラーインデックスピグメントイエロー150を含む黄色着色剤とを含み、かつ、カラーインデックスピグメントグリーン7以外の緑色着色剤とカラーインデックスピグメントイエロー150との質量比が、カラーインデックスピグメントグリーン7以外の緑色着色剤:カラーインデックスピグメントイエロー150=0:100~18:82であり、
上記着色組成物は、波長450nmの光に対する吸光度を1としたとき、吸光度が0.2となる波長が550nm以上600nm以下の波長範囲に存在することを特徴とする。
そして、この着色組成物は、上述した所定の吸光度の特性を満たすことにより、赤色や青色などの他色との色分離性に優れた分光特性を有する緑色の画素などに適した硬化膜を形成することができる。
Aλ=-log(Tλ/100) ・・・(Ab1)
Aλは、波長λにおける吸光度であり、Tλは、波長λにおける透過率(%)である。
また、上記膜の495nm以上550nm未満の波長の光に対する平均透過率は60%以上であることが好ましく、65%以上であることがより好ましく、70%以上であることが更に好ましい。
また、上記膜の波長450nmの光に対する透過率は10%以下であることが好ましく、5%以下であることがより好ましく、2%以下であることが更に好ましい。
また、上記膜の400nm以上450nm以下の波長の光に対する平均透過率は10%以下であることが好ましく、5%以下であることがより好ましく、1%以下であることが更に好ましい。
また、上記膜の550nm以上600nm以下の波長の光に対する平均透過率は60%以下であることが好ましく、50%以下であることがより好ましく、40%以下であることが更に好ましい。
<<着色剤>>
本発明の着色組成物は着色剤を含有する。本発明の着色組成物に用いられる着色剤は、緑色着色剤と黄色着色剤とを含む。緑色着色剤と黄色着色剤は、無機顔料、有機顔料のいずれでもよい。また、顔料には、無機顔料または有機-無機顔料の一部を有機発色団で置換した材料を用いることもできる。無機顔料や有機-無機顔料を有機発色団で置換することで、色相設計をしやすくできる。
態様G2:緑色着色剤が、C.I.ピグメントグリーン7と、C.I.ピグメントグリーン7以外の緑色着色剤としてC.I.ピグメントグリーン36とを含む態様。
態様Y2:黄色着色剤が、C.I.ピグメントイエロー150と、C.I.ピグメントイエロー150以外の黄色着色剤を含む態様。
C.I.ピグメントレッド1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291,294(キサンテン系、Organo Ultramarine、Bluish Red),295(モノアゾ系),296(ジアゾ系),297(アミノケトン系)等(以上、赤色顔料)、
C.I.ピグメントバイオレット1,19,23,27,32,37,42,60(トリアリールメタン系),61(キサンテン系)等(以上、紫色顔料)、
C.I.ピグメントブルー1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,29,60,64,66,79,80,87(モノアゾ系),88(メチン系)等(以上、青色顔料)。
本発明の着色組成物は、重合性化合物を含有する。重合性化合物としては、エチレン性不飽和結合含有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含有基としては、ビニル基、(メタ)アリル基、(メタ)アクリロイル基などが挙げられる。重合性化合物はラジカルにより重合可能な化合物(ラジカル重合性化合物)であることが好ましい。
式(M-1)
式(M-2)
本発明の着色組成物は光重合開始剤を含有する。光重合開始剤としては、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する化合物が好ましい。光重合開始剤は、光ラジカル重合開始剤であることが好ましい。
式(V)
(OX-1)
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。
*-CHF2 (1)
*-CF3 (2)
また、光重合開始剤A1のメタノール中での波長254nmの光の吸光係数は、1.0×104~1.0×105mL/gcmであることが好ましく、1.5×104~9.5×104mL/gcmであることがより好ましく、3.0×104~8.0×104mL/gcmであることが更に好ましい。
本発明の着色組成物は樹脂を含むことが好ましい。樹脂は、例えば、顔料(C.I.ピグメントグリーン7、C.I.ピグメントイエロー150など)を着色組成物中で分散させる用途や、バインダーの用途で配合される。なお、主に顔料を着色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を目的として樹脂を使用することもできる。
R1は水素原子またはメチル基を表す。
L1は2価の連結基を表す。2価の連結基としては、炭化水素基、複素環基、-NH-、-SO-、-SO2-、-CO-、-O-、-COO-、-OCO-、-S-およびこれらの2以上を組み合わせてなる基が挙げられる。炭化水素基としては、アルキル基、アリール基などが挙げられる。複素環基は、非芳香族の複素環基であってもよく、芳香族複素環基であってもよい。複素環基は、5員環または6員環が好ましい。複素環基を構成するヘテロ原子の種類は窒素原子、酸素原子、硫黄原子などが挙げられる。複素環基を構成するヘテロ原子の数は1~3が好ましい。複素環基は、単環であってもよく、縮合環であってもよい。炭化水素基および複素環基は置換基を有していてもよい。置換基としては、アルキル基、アリール基、ヒドロキシ基、ハロゲン原子などが挙げられる。
R10は置換基を表す。R10が表す置換基としては、以下に示す置換基Tが挙げられ、炭化水素基であることが好ましく、アリール基を置換基として有していてもよいアルキル基であることがより好ましい。
mは0~2の整数を表し、0または1が好ましく、0がより好ましい。
pは0以上の整数を表し、0~4が好ましく、0~3がより好ましく、0~2が更に好ましく、0または1がより一層好ましく、1が特に好ましい。
置換基Tとしては、ハロゲン原子、シアノ基、ニトロ基、炭化水素基、複素環基、-ORt1、-CORt1、-COORt1、-OCORt1、-NRt1Rt2、-NHCORt1、-CONRt1Rt2、-NHCONRt1Rt2、-NHCOORt1、-SRt1、-SO2Rt1、-SO2ORt1、-NHSO2Rt1または-SO2NRt1Rt2が挙げられる。Rt1およびRt2は、それぞれ独立して水素原子、炭化水素基または複素環基を表す。Rt1とRt2が結合して環を形成してもよい。
炭化水素基としては、アルキル基、アルケニル基、アルキニル基、アリール基が挙げられる。アルキル基の炭素数は、1~30が好ましく、1~15がより好ましく、1~8が更に好ましい。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、分岐がより好ましい。
アルケニル基の炭素数は、2~30が好ましく、2~12がより好ましく、2~8が特に好ましい。アルケニル基は直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましい。
アルキニル基の炭素数は、2~30が好ましく、2~25がより好ましい。アルキニル基は直鎖、分岐、環状のいずれでもよく、直鎖または分岐が好ましい。
アリール基の炭素数は、6~30が好ましく、6~20がより好ましく、6~12が更に好ましい。
複素環基は、単環であってもよく、縮合環であってもよい。複素環基は、単環または縮合数が2~4の縮合環が好ましい。複素環基の環を構成するヘテロ原子の数は1~3が好ましい。複素環基の環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。複素環基の環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。
炭化水素基および複素環基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述した置換基Tとして説明した置換基が挙げられる。
R1は水素原子またはメチル基を表す。
R2、R3およびR11はそれぞれ独立して炭化水素基を表す。
R2およびR3が表す炭化水素基は、アルキレン基またはアリーレン基であることが好ましく、アルキレン基であることがより好ましい。アルキレン基の炭素数は1~10であることが好ましく、1~5であることがより好ましく、1~3であることが更に好ましく、2または3であることが特に好ましい。R11が表す炭化水素基は、アリール基を置換基として有していてもよいアルキル基であることが好ましく、アリール基を置換基として有するアルキル基であることがより好ましい。アルキル基の炭素数は、1~20が好ましく、1~10がより好ましく、1~5が更に好ましい。なお、アルキル基が置換基としてアリール基を有する場合におけるアルキル基の炭素数は、アルキル部位の炭素数のことを意味する。
R12は置換基を表す。R12が表す置換基としては、上述した置換基Tが挙げられる。
nは0~15の整数を表し、0~5の整数であることが好ましく、0~4の整数であることがより好ましく、0~3の整数であることが更に好ましい。
mは0~2の整数を表し、0または1であることが好ましく、0であることがより好ましい。
p1は0以上の整数を表し、0~4が好ましく、0~3がより好ましく、0~2が更に好ましく、0~1がより一層好ましく、0が特に好ましい。
q1は1以上の整数を表し、1~4が好ましく、1~3がより好ましく、1~2が更に好ましく、1が特に好ましい。
ラクタム化合物としては、ε-カプロラクタム、及び、γ-ブチロラクタム等が挙げられる。
フェノール化合物としては、フェノール、ナフトール、クレゾール、キシレノール、及び、ハロゲン置換フェノール等が挙げられる。
アルコール化合物としては、メタノール、エタノール、プロパノール、ブタノール、シクロヘキサノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、及び、乳酸アルキル等が挙げられる。
アミン化合物としては、第一級アミン及び第二級アミンが挙げられる。アミン化合物は、芳香族アミン、脂肪族アミン、脂環族アミンのいずれでもよく、アニリン、ジフェニルアミン、エチレンイミン、及び、ポリエチレンイミン等が具体例として挙げられる。
活性メチレン化合物としては、マロン酸ジエチル、マロン酸ジメチル、アセト酢酸エチル、及び、アセト酢酸メチル等が挙げられる。
ピラゾール化合物としては、ピラゾール、メチルピラゾール、及び、ジメチルピラゾール等が挙げられる。
メルカプタン化合物としては、アルキルメルカプタン、及び、アリールメルカプタン等が挙げられる。
イミダゾール化合物としては、イミダゾール、1-メチルイミダゾール、1-エチルイミダゾール、1,2-ジメチルイミダゾール、2-エチル-4-メチルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-ベンジル-2-フェニルイミダゾール等が挙げられる。
イミド化合物としては、マレイミド、コハク酸イミド、フタルイミド、およびそれらの誘導体等が挙げられる。
また、樹脂の含有量は重合性化合物の100質量部に対して25~500質量部であることが好ましい。上限は250質量部以下が好ましく、150質量部以下がより好ましい。下限は50質量部以上が好ましく、75質量部以上がより好ましい。
また、本発明の着色組成物に含まれる樹脂の全量中における上述した樹脂b1の含有量は、0.1~100質量%であることが好ましく、5~100質量%であることがより好ましい。上限は、90質量%以下とすることもでき、80質量%以下とすることもでき、70質量%以下とすることもできる。
また、上述した樹脂b1の含有量は、着色組成物の全固形分中5~50質量%であることが好ましい。上限は、40質量%以下であることが好ましく、30質量%以下であることがより好ましい。下限は、10質量%以上であることが好ましく、12.5質量%以上であることがより好ましい。
また、本発明の着色組成物に含まれる樹脂の全量中における上述した樹脂BIの含有量は、0.1~100質量%であることが好ましく、5~100質量%であることがより好ましい。上限は、90質量%以下とすることもでき、80質量%以下とすることもでき、70質量%以下とすることもできる。
また、上述した樹脂BIの含有量は、着色組成物の全固形分中5~50質量%であることが好ましい。上限は、40質量%以下であることが好ましく、30質量%以下であることがより好ましい。下限は、10質量%以上であることが好ましく、12.5質量%以上であることがより好ましい。
本発明の着色組成物は、フリル基を含む化合物(以下、フリル基含有化合物ともいう)を含有することが好ましい。この態様によれば、低温での硬化性に優れる。例えば、重合性化合物としてエチレン性不飽和結合含有基を含有する化合物を用いた場合、フリル基含有化合物が有するフリル基と、上記重合性化合物が有するエチレン性不飽和結合含有基とが、Diels-Alder反応により、150℃以下の低温でも結合を形成するため、低温硬化に優れる。
また、フリル基含有化合物としてフリル基含有ポリマーを用いた場合、着色組成物に含まれる樹脂中におけるフリル基含有ポリマーの含有量は、0.1~100質量%であることが好ましい。下限は、10質量%以上であることが好ましく、15質量%以上であることがより好ましい。上限は、90質量%以下であることが好ましく、80質量%以下であることがより好ましい。
また、本発明の着色組成物に用いられる樹脂が上述した樹脂b1を含み、かつ、フリル基含有化合物としてフリル基含有ポリマーを用いた場合には、フリル基含有ポリマーの含有量は、樹脂b1の100質量部に対して10~200質量部であることが好ましい。上限は、175質量部以下であることが好ましく、150質量部以下であることが好ましい。下限は、25質量部以上であることが好ましく、150質量部以上であることが好ましい。樹脂b1とフリル基含有ポリマーとを併用することにより、低温での硬化性に優れ、かつ、分光特性に優れた硬化膜を形成し易い。更に、両者の割合が上記範囲である場合には得られる膜の耐久性をより向上できるという効果も期待できる。
本発明の着色組成物は、更にエポキシ基を有する化合物を含有することができる。エポキシ基を有する化合物としては、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。エポキシ基は、1分子内に2~100個有することが好ましい。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。エポキシ基を有する化合物のエポキシ当量(=エポキシ基を有する化合物の分子量/エポキシ基の数)は、500g/eq以下であることが好ましく、100~400g/eqであることがより好ましく、100~300g/eqであることがさらに好ましい。エポキシ基を有する化合物は、低分子化合物(例えば、分子量1000未満)でもよいし、高分子化合物(macromolecule)(例えば、分子量1000以上、ポリマーの場合は、重量平均分子量が1000以上)のいずれでもよい。エポキシ基を有する化合物の分子量(ポリマーの場合は、重量平均分子量)は、200~100000が好ましく、500~50000がより好ましい。分子量(ポリマーの場合は、重量平均分子量)の上限は、3000以下が好ましく、2000以下がより好ましく、1500以下が更に好ましい。
本発明の着色組成物は、溶剤を含有することが好ましい。溶剤としては、有機溶剤が挙げられる。溶剤は、各成分の溶解性や着色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。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。これらの詳細については、国際公開第2015/166779号の段落番号0223を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤を好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、シクロヘキサノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、3-メトキシ-N,N-ジメチルプロパンアミド、3-ブトキシ-N,N-ジメチルプロパンアミド、プロピレングリコールジアセテート、3-メトキシブタノールなどが挙げられる。ただし溶剤としての芳香族炭化水素類(ベンゼン、トルエン、キシレン、エチルベンゼン等)は、環境面等の理由により低減したほうがよい場合がある(例えば、有機溶剤全量に対して、50質量ppm(parts per million)以下とすることもでき、10質量ppm以下とすることもでき、1質量ppm以下とすることもできる)。
本発明の着色組成物は、顔料誘導体を含有することができる。顔料誘導体としては、発色団の一部分を、酸基、塩基性基また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挙げられる。顔料誘導体を構成する発色団としては、キノリン骨格、ベンゾイミダゾロン骨格、ジケトピロロピロール骨格、アゾ骨格、フタロシアニン骨格、アンスラキノン骨格、キナクリドン骨格、ジオキサジン骨格、ペリノン骨格、ペリレン骨格、チオインジゴ骨格、イソインドリン骨格、イソインドリノン骨格、キノフタロン骨格、スレン骨格、金属錯体骨格等が挙げられ、キノリン骨格、ベンゾイミダゾロン骨格、ジケトピロロピロール骨格、アゾ骨格、キノフタロン骨格、イソインドリン骨格およびフタロシアニン骨格が好ましく、アゾ骨格およびベンゾイミダゾロン骨格がより好ましい。顔料誘導体が有する酸基としては、スルホ基、カルボキシル基が好ましく、スルホ基がより好ましい。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、三級アミノ基がより好ましい。顔料誘導体の具体例としては、特開昭56-118462号公報、特開昭63-264674号公報、特開平01-217077号公報、特開平03-009961号公報、特開平03-026767号公報、特開平03-153780号公報、特開平03-045662号公報、特開平04-285669号公報、特開平06-145546号公報、特開平06-212088号公報、特開平06-240158号公報、特開平10-030063号公報、特開平10-195326号公報、国際公開第2011/024896号の段落番号0086~0098、国際公開第2012/102399号の段落番号0063~0094、国際公開第2017/038252号の段落番号0082、特開2015-151530号公報の段落番号0171、特開2011-252065号公報の段落番号0162~0183、特開2003-081972号公報、特許第5299151号公報、特開2015-172732号公報、特開2014-199308号公報、特開2014-085562号公報、特開2014-035351号公報、特開2008-081565号公報、特開2019-109512号公報および特開2019-133154号公報に記載の化合物が挙げられる。
本発明の着色組成物は、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、式(T1)で表される化合物であることがより好ましい。
式(T1)
本発明の着色組成物は、シランカップリング剤を含有することできる。シランカップリング剤としては、一分子中に少なくとも2種の反応性の異なる官能基を有するシラン化合物が好ましい。シランカップリング剤は、ビニル基、エポキシ基、スチレン基、メタクリル基、アミノ基、イソシアヌレート基、ウレイド基、メルカプト基、スルフィド基、および、イソシアネート基から選ばれる少なくとも1種の基と、アルコキシ基とを有するシラン化合物が好ましい。シランカップリング剤の具体例としては、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン(信越化学工業(株)製、KBM-602)、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン(信越化学工業(株)製、KBM-603)、3-アミノプロピルトリメトキシシラン(信越化学工業(株)製、KBM-903)、3-アミノプロピルトリエトキシシラン(信越化学工業(株)製、KBE-903)、3-メタクリロキシプロピルトリメトキシシラン(信越化学工業(株)製、KBM-503)、3-グリシドキシプロピルトリメトキシシラン(信越化学工業(株)製、KBM-403)等が挙げられる。シランカップリング剤の詳細については、特開2013-254047号公報の段落番号0155~0158の記載を参酌でき、この内容は本明細書に組み込まれる。本発明の着色組成物がシランカップリング剤を含有する場合、シランカップリング剤の含有量は、着色組成物の全固形分中0.001~20質量%が好ましく、0.01~10質量%がより好ましく、0.1質量%~5質量%が特に好ましい。本発明の着色組成物は、シランカップリング剤を、1種のみを含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
本発明の着色組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-t-ブチル-p-クレゾール、ピロガロール、t-ブチルカテコール、ベンゾキノン、4,4’-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン塩(アンモニウム塩、第一セリウム塩等)等が挙げられる。本発明の着色組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、着色組成物の全固形分中0.0001~5質量%が好ましい。本発明の着色組成物は、重合禁止剤を、1種のみを含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
本発明の着色組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤は、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物などを用いることができる。これらの詳細については、特開2012-208374号公報の段落番号0052~0072、特開2013-068814号公報の段落番号0317~0334、特開2016-162946号公報の段落番号0061~0080の記載を参酌でき、これらの内容は本明細書に組み込まれる。紫外線吸収剤の市販品としては、例えば、UV-503(大東化学(株)製)などが挙げられる。また、ベンゾトリアゾール化合物としては、ミヨシ油脂製のMYUAシリーズ(化学工業日報、2016年2月1日)が挙げられる。また、紫外線吸収剤として特許第6268967号公報の段落番号0049~0059に記載の化合物も使用できる。本発明の着色組成物が紫外線吸収剤を含有する場合、紫外線吸収剤の含有量は、着色組成物の全固形分中0.1~10質量%が好ましく、0.1~5質量%がより好ましく、0.1~3質量%が特に好ましい。また、紫外線吸収剤は、1種のみを用いてもよく、2種以上を用いてもよい。2種以上を用いる場合は、合計量が上記範囲となることが好ましい。
本発明の着色組成物は、界面活性剤を含有することができる。界面活性剤としては、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、シリコン系界面活性剤などの各種界面活性剤を使用することができる。界面活性剤については、国際公開第2015/166779号の段落番号0238~0245に記載された界面活性剤が挙げられ、この内容は本明細書に組み込まれる。
本発明の着色組成物には、必要に応じて、各種添加剤、例えば、充填剤、密着促進剤、酸化防止剤、凝集防止剤等を配合することができる。これらの添加剤としては、特開2004-295116号公報の段落番号0155~0156に記載の添加剤を挙げることができ、この内容は本明細書に組み込まれる。また、酸化防止剤としては、例えばフェノール化合物、リン系化合物(例えば特開2011-090147号公報の段落番号0042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。また、酸化防止剤として、国際公開第2017/006600号に記載された多官能ヒンダードアミン酸化防止剤、国際公開第2017/164024号に記載された酸化防止剤、特許第6268967号公報の段落番号0023~0048に記載された酸化防止剤を用いることもできる。酸化防止剤は1種のみを用いてもよく、2種以上を用いてもよい。また、本発明の着色組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤の具体例としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられる。市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。また、本発明の着色組成物は、特開2004-295116号公報の段落番号0078に記載の増感剤や光安定剤、同公報の段落番号0081に記載の熱重合防止剤、特開2018-091940号公報の段落番号0242に記載の貯蔵安定化剤を含有することができる。
本発明の着色組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収容容器として、原材料や着色組成物中への不純物混入を抑制することを目的に、容器内壁を6種6層の樹脂で構成する多層ボトルや6種の樹脂を7層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開2015-123351号公報に記載の容器が挙げられる。また、容器内壁は、容器内壁からの金属溶出を防ぎ、組成物の保存安定性を高めたり、成分変質を抑制するなど目的で、ガラス製やステンレス製などにすることも好ましい。
本発明の着色組成物は、前述の成分を混合して製造できる。着色組成物の製造に際しては、全成分を同時に溶剤に溶解および/または分散して着色組成物を製造してもよいし、必要に応じて、各成分を適宜2つ以上の溶液または分散液としておいて、使用時(塗布時)にこれらを混合して着色組成物を製造してもよい。
本発明の硬化膜は、上述した本発明の着色組成物を硬化して得られた膜である。本発明の硬化膜は、カラーフィルタなどに用いることができる。具体的には、カラーフィルタの着色層(画素)として好ましく用いることができ、緑色画素としてより好ましく用いられる。本発明の硬化膜の膜厚は、目的に応じて適宜調整できるが、0.5~3.0μmであることが好ましい。下限は0.8μm以上が好ましく、1.0μm以上がより好ましく、1.1μm以上がさらに好ましい。上限は2.5μm以下が好ましく、2.0μm以下がより好ましく、1.8μm以下がさらに好ましい。
また、495nm以上550nm未満の波長の光に対する平均透過率は60%以上であることが好ましく、65%以上であることがより好ましく、70%以上であることが更に好ましい。
また、波長450nmの光に対する透過率は10%以下であることが好ましく、5%以下であることがより好ましく、2%以下であることが更に好ましい。
また、400nm以上450nm以下の波長の光に対する平均透過率は10%以下であることが好ましく、5%以下であることがより好ましく、1%以下であることが更に好ましい。
また、550nm以上600nm以下の波長の光に対する平均透過率は60%以下であることが好ましく、50%以下であることがより好ましく、40%以下であることが更に好ましい。
次に、本発明のカラーフィルタについて説明する。本発明のカラーフィルタは、上述した本発明の硬化膜を有する。好ましくは、カラーフィルタの着色画素として、より好ましくは緑色画素として、本発明の硬化膜を有する。本発明のカラーフィルタは、固体撮像素子や表示装置に用いることができる。
本発明の構造体は、上述した本発明の着色組成物を用いて得られる緑色画素と、赤色画素と、青色画素とを有する。
緑色画素は、上述した本発明の硬化膜の項で説明した分光特性を有することが好ましい。また、赤色画素および青色画素は、上述したカラーフィルタの項で説明した分光特性を有することが好ましい。
画素の形成方法について説明する。本発明の着色組成物を用いることで、例えば、緑色画素を形成することができる。
本発明の表示装置は、上述した本発明の硬化膜を有する。表示装置としては、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が挙げられる。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。
本発明の着色組成物および硬化膜は、固体撮像素子に用いることもできる。固体撮像素子の構成としては、本発明の硬化膜を有し、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。
(顔料分散液P-G1)
C.I.ピグメントグリーン7の10.40質量部と、顔料誘導体1の2.60質量部と、分散剤1の6.5質量部と、プロピレングリコールモノメチルエーテルアセテートの80.50質量部とを混合した後、直径1mmのジルコニアビーズを用いて、アイガーミル(アイガージャパン社製「ミニモデルM-250MKII」)で5時間分散した後、孔径5μmのフィルタで濾過して顔料分散液P-G1を調製した。
C.I.ピグメントグリーン36の12.60質量部と、顔料誘導体1の1.26質量部と、分散剤1の5.04質量部と、プロピレングリコールモノメチルエーテルアセテートの81.10質量部とを混合した後、直径1mmのジルコニアビーズを用いて、アイガーミル(アイガージャパン社製「ミニモデルM-250MKII」)で5時間分散した後、孔径5μmのフィルタで濾過して顔料分散液P-G2を調製した。
C.I.ピグメントグリーン58の12.60質量部と、顔料誘導体1の1.26質量部と、分散剤1の5.04質量部と、プロピレングリコールモノメチルエーテルアセテートの81.10質量部とを混合した後、直径1mmのジルコニアビーズを用いて、アイガーミル(アイガージャパン社製「ミニモデルM-250MKII」)で5時間分散した後、孔径5μmのフィルタで濾過して顔料分散液P-G3を調製した。
C.I.ピグメントイエロー150の12.0質量部と、顔料誘導体2の1.2質量部と、分散剤2の6.8質量部と、プロピレングリコールモノメチルエーテルアセテートの80.0質量部とを混合した後、直径1mmのジルコニアビーズを用いて、アイガーミル(アイガージャパン社製「ミニモデルM-250MKII」)で5時間分散した後、孔径5μmのフィルタで濾過して顔料分散液P-Y1を調製した。
C.I.ピグメントイエロー185の12.0質量部と、顔料誘導体2の1.2質量部と、分散剤2の6.8質量部と、プロピレングリコールモノメチルエーテルアセテートの80.0質量部とを混合した後、直径1mmのジルコニアビーズを用いて、アイガーミル(アイガージャパン社製「ミニモデルM-250MKII」)で5時間分散した後、孔径5μmのフィルタで濾過して顔料分散液P-Y2を調製した。
下記表に示す原料を混合し、撹拌した後、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)を用いてろ過して着色組成物を調製した。
(顔料分散液)
P-G1~P-G3、P-Y1、P-Y2:上述の顔料分散液P-G1~P-G3、P-Y1、P-Y2
開始剤1:Irgacure OXE01(BASF社製、下記構造の化合物、メタノール中での波長365nmにおける吸光係数が6969mL/gcmである。)
開始剤2:Omnirad 2959(IGM Resins B.V.社製、下記構造の化合物、メタノール中での波長365nmにおける吸光係数が48.93mL/gcmであり、波長254nmにおける吸光係数が3.0×104mL/gcmである。)
開始剤3:Irgacure OXE02(BASF社製、下記構造の化合物、メタノール中での波長365nmにおける吸光係数が7749mL/gcmである。)
開始剤4:下記構造の化合物(メタノール中での波長365nmの光の吸光係数が18900mL/gcmである。)
開始剤5:Omnirad 184(IGM Resins B.V.社製、下記構造の化合物、メタノール中での波長365nmにおける吸光係数が88.64mL/gcmであり、波長254nmにおける吸光係数が3.3×104mL/gcmである。)
開始剤6:下記構造の化合物
M1:下記構造の化合物
M4:トリメチロールプロパンPO変性トリアクリレート(東亞合成(株)製、アロニックス M-350)
M5:ジペンタエリスリトールヘキサアクリレート(東亞合成(株)製、アロニックス M-402)
樹脂A:下記構造の樹脂(Mw=11000、主鎖に付記した数値はモル比である。)の40質量%プロピレングリコールモノメチルエーテルアセテート溶液
樹脂D:特開2019-153389号公報の段落番号0208に記載のアクリル樹脂溶液1の固形分40%プロピレングリコールモノメチルエーテルアセテート溶液
樹脂E:下記構造の樹脂(ブロックイソシアネート基を含む繰り返し単位と、酸基が保護基で保護された基を有する繰り返し単位とを有する樹脂。主鎖に付記した数値は質量比である。Mw=7500)の40質量%プロピレングリコールモノメチルエーテルアセテート溶液
溶剤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
溶剤2:シクロヘキサノン
(保存安定性の評価)
上記で得られた製造直後の着色組成物の粘度(V1)を、東機産業(株)製「RE-85L」にて測定した。この着色組成物を23℃の温度条件のもとで14日間静置した後、粘度(V2)を測定した。下記式から増粘率を算出し、下記評価基準に従って保存安定性を評価した。着色組成物の粘度は23℃に温度調整を施した状態で測定した。評価基準は下記の通りとし、評価結果は下記表に記載した。
増粘率(%)=[(粘度(V2)-粘度(V1))/粘度(V1)]×100
AA:増粘率が5%未満である。
A:増粘率が5%以上10%未満である。
B:増粘率が10%以上20%未満である。
C:増粘率が20%以上である。
各着色組成物を、スピンコーターを用いて、乾燥後の仕上がり膜厚が2.0μmとなるようにガラス基板上に塗布し、100℃のホットプレート上で2分間乾燥させた。その後、超高圧水銀ランプを用いて、露光照度20mW/cm2、露光量1J/cm2の条件でi線露光を実施した。そして、200℃のホットプレートを用いて300秒間加熱処理(ポストベーク)を行い、放冷して、硬化膜を形成した。
得られた硬化膜について、紫外可視近赤外分光光度計(UV3600、(株)島津製作所製)を用い、レファレンスをガラス基板として、波長300~800nmの範囲の光の吸光度を測定し、以下の波長1、波長2、波長3をそれぞれ測定した。
波長1:波長400~700nmの波長の光に対する吸光度のうち、波長450nmの光に対する吸光度を1としたとき、吸光度が0.2となる短波長
波長2:波長400~700nmの波長の光に対する吸光度のうち、波長450nmの光に対する吸光度を1としたとき、吸光度が0.2となる長波長
波長3:波長400~700nmの波長の光に対する吸光度が最小となる波長
各着色組成物を、スピンコーターを用いて、乾燥後の仕上がり膜厚が2.0μmとなるようにガラス基板上に塗布し、100℃のホットプレート上で2分間乾燥させた。その後、超高圧水銀ランプを用いて、露光照度20mW/cm2、露光量1J/cm2の条件でi線露光を実施した。そして、200℃のホットプレートを用いて300秒間加熱処理(ポストベーク)を行い、放冷して、硬化膜を形成した。
得られた硬化膜について、大塚電子(株)製のMCPD-3000を用い、400~700nmの範囲の波長の光の透過率を測定した。
次に、上記の透過率を測定した硬化膜に紫外線カットフィルター(アズワン社製、KU-1000100)を装着し、耐光試験機(スガ試験機(株)製、Xenon Weather Meter SX75)を用いて10万ルクスの光を50時間かけて照射して、耐光性試験を行った。試験装置内の温度は63℃に設定した。試験装置内の相対湿度は50%とした。耐光性試験を行った後、硬化膜の透過率を測定し、透過率の変化量の最大値を求め、以下の基準にて耐光性を評価した。透過率の測定は、各試料につき5回行い、最大値と最小値を除いた3回の結果の平均値を採用した。また、透過率の変化量の最大値とは、耐光性試験前後の硬化膜の、波長400~700nmの範囲における透過率の変化量が最も大きい波長における変化量を意味する。
AA:透過率の変化量の最大値が3%以下。
A:透過率の変化量の最大値が3%を超えて、5%以下。
B:透過率の変化量の最大値が5%を超えて、10%以下。
C:透過率の変化量の最大値が10%を超えている。
実施例1の着色組成物に関し、200℃のホットプレートの代わりに、紫外線フォトレジスト硬化装置(UMA-802-HC-552;ウシオ電気株式会社製)を用いて、3000mJ/cm2の露光量で露光を行った以外は同様にして硬化膜を作製した。耐光性の評価結果は実施例1と同様であった。
実施例9の着色組成物に関し、200℃のホットプレートの代わりに、100℃のホットプレートを用いて20分間加熱処理(ポストベーク)を行った以外は同様にして硬化膜を作製した。耐光性の評価結果は実施例9と同様であった。
実施例16の着色組成物に関し、200℃のホットプレートの代わりに、i線ステッパー露光装置FPA-3000i5+(キヤノン(株)製)を用い、1500mJ/cm2の露光量で露光を行った以外は同様にして硬化膜を作製した。耐光性の評価結果は実施例16と同様であった。
シリコンウエハ上に、緑色画素形成用着色組成物を製膜後の膜厚が2.0μmになるようにスピンコート法で塗布した。次いで、ホットプレートを用いて、100℃で2分間加熱した。次いで、i線ステッパー露光装置FPA-3000i5+(キヤノン(株)製)を用い、1000mJ/cm2で2μm四方のドットパターンのマスクを介して露光した。次いで、水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液を用い、23℃で60秒間パドル現像を行った。その後、スピンシャワーにてリンスを行い、更に純水にて水洗した。次いで、ホットプレートを用いて、200℃で5分間加熱することで、緑色の着色パターン(緑色画素)を形成した。同様に赤色画素形成用着色組成物1、青色画素形成用着色組成物1を順次パターニングし、赤色の着色パターン(赤色画素)、青色の着色パターン(青色画素)をそれぞれ形成して構造体を形成した。緑色画素形成用着色組成物としては、実施例1の着色組成物を使用した。赤色画素形成用着色組成物1、青色画素形成用着色組成物1については後述する。
得られた構造体を公知の方法に従い有機エレクトロルミネッセンス表示装置に組み込んだ。この有機エレクトロルミネッセンス表示装置は好適な画像認識能を有していた。
実施例1000の赤色画素形成用着色組成物1の代わりに、赤色画素形成用着色組成物2を用い、青色画素形成用着色組成物1の代わりに、青色画素形成用着色物2を用いた以外は実施例1000と同様にして構造体を形成した。赤色画素形成用着色組成物2、青色画素形成用着色組成物2については後述する。得られた構造体を公知の方法に従い有機エレクトロルミネッセンス表示装置に組み込んだ。この有機エレクトロルミネッセンス表示装置は好適な画像認識能を有していた。
下記組成の混合物を均一になるように撹拌混合した後、1.0μmのフィルタで濾過し、赤色画素形成用着色組成物1を作製した。
顔料分散液DR-1 ・・・30.2質量部
顔料分散液DY-1 ・・・8.4質量部
樹脂溶液12 ・・・15.2質量部
重合性化合物(アロニックス M-402、東亞合成(株)製) ・・・0.7質量部
光重合開始剤(Irgacure OXE02、BASF社製) ・・・0.3質量部
PGMEA ・・・44.2質量部
下記組成の混合物を均一になるように撹拌混合した後、1.0μmのフィルタで濾過し、赤色画素形成用着色組成物2を作製した。
顔料分散液DR-1 ・・・30.2質量部
顔料分散液DY-1 ・・・8.4質量部
樹脂溶液13 ・・・15.2質量部
重合性化合物(アロニックス M-402、東亞合成(株)製) ・・・0.7質量部
光重合開始剤(Irgacure OXE02、BASF社製) ・・・0.3質量部
PGMEA ・・・44.2質量部
下記組成の混合物を均一になるように撹拌混合した後、1.0μmのフィルタで濾過し、青色画素形成用着色組成物1を作製した。
顔料分散液DB-1 ・・・10.4質量部
顔料分散液DV-1 ・・・6.1質量部
樹脂溶液12 ・・・24.2質量部
重合性化合物(アロニックス M-402、東亞合成(株)製) ・・・0.7質量部
光重合開始剤(Irgacure OXE02、BASF社製) ・・・0.3質量部
PGMEA ・・・44.2質量部
下記組成の混合物を均一になるように撹拌混合した後、1.0μmのフィルタで濾過し、青色画素形成用着色組成物1を作製した。
顔料分散液DB-1 ・・・10.4質量部
顔料分散液DV-1 ・・・6.1質量部
樹脂溶液13 ・・・24.2質量部
重合性化合物(アロニックス M-402、東亞合成(株)製) ・・・0.7質量部
光重合開始剤(Irgacure OXE02、BASF社製) ・・・0.3質量部
PGMEA ・・・44.2質量部
C.I.ピグメントレッド264の11.0質量部と、樹脂溶液11の21.5質量部と、分散剤(BASF社製、EFKA4300)の1質量部と、PGMEAの66.5質量部とを混合した後、直径1mmのジルコニアビーズを用いて、アイガーミル(アイガージャパン社製「ミニモデルM-250MKII」)で5時間分散した後、孔径5μmのフィルタで濾過して顔料分散液DR-1を調製した。
C.I.ピグメントイエロー139の23.5質量部と、樹脂溶液11の7質量部と、分散剤(BASF社製、EFKA4300)の3質量部と、PGMEAの66.5質量部とを混合した後、直径1mmのジルコニアビーズを用いて、アイガーミル(アイガージャパン社製「ミニモデルM-250MKII」)で5時間分散した後、孔径5μmのフィルタで濾過して顔料分散液DY-1を調製した。
C.I.ピグメントブルー15:6の11.0質量部と、樹脂溶液11の21.5質量部と、分散剤(BASF社製、EFKA4300)の1質量部と、PGMEAの66.5質量部とを混合した後、直径1mmのジルコニアビーズを用いて、アイガーミル(アイガージャパン社製「ミニモデルM-250MKII」)で5時間分散した後、孔径5μmのフィルタで濾過して顔料分散液DB-1を調製した。
C.I.ピグメントバイオレット23の11.0質量部と、樹脂溶液11の21.5質量部と、分散剤(BASF社製、EFKA4300)の1質量部と、PGMEAの66.5質量部とを混合した後、直径1mmのジルコニアビーズを用いて、アイガーミル(アイガージャパン社製「ミニモデルM-250MKII」)で5時間分散した後、孔径5μmのフィルタで濾過して顔料分散液DV-1を調製した。
セパラブル4口フラスコに温度計、冷却管、窒素ガス導入管、滴下管および撹拌装置を取り付けた反応容器にPGMEAの196質量部を仕込み、80℃に昇温し、反応容器内を窒素置換した後、滴下管より、n-ブチルメタクリレート37.2質量部、2-ヒドロキシエチルメタクリレート12.9質量部、メタクリル酸12.0質量部、パラクミルフェノールエチレンオキサイド変性アクリレート(東亞合成(株)製、アロニックスM110)20.7質量部、2,2’-アゾビスイソブチロニトリル1.1質量部の混合物を2時間かけて滴下した。滴下終了後、更に3時間反応を継続し、樹脂(Mw=30000)を得た。室温まで冷却した後、PGMEAで希釈して固形分濃度を20質量%に調整し、樹脂溶液11を調製した。
セパラブル4口フラスコに温度計、冷却管、窒素ガス導入管、滴下管および撹拌装置を取り付けた反応容器にPGMEAの207質量部を仕込み、80℃に昇温し、反応容器内を窒素置換した後、滴下管より、メタクリル酸20質量部、パラクミルフェノールエチレンオキサイド変性アクリレート(東亞合成(株)製、アロニックスM110)20質量部、メタクリル酸メチル45質量部、2-ヒドロキシエチルメタクリレート8.5質量部、及び2,2’-アゾビスイソブチロニトリル1.33質量部の混合物を2時間かけて滴下した。滴下終了後、更に3時間反応を継続した。次に得られた溶液全量に対して、窒素ガスを停止し乾燥空気を1時間注入しながら撹拌したのちに、室温まで冷却した後、2-メタクリロイルオキシエチルイソシアネート(昭和電工(株)製、カレンズMOI)6.5質量部、ラウリン酸ジブチル錫0.08質量部、シクロヘキサノン26質量部の混合物を70℃で3時間かけて滴下した。滴下終了後、更に1時間反応を継続し、樹脂(Mw=18000)を得た。室温まで冷却した後、PGMEAで希釈して固形分濃度を20質量%に調整し、樹脂溶液12を調製した。
セパラブル4口フラスコに温度計、冷却管、窒素ガス導入管、滴下管および撹拌装置を取り付けた反応容器にPGMEAの207質量部を仕込み、80℃に昇温し、反応容器内を窒素置換した後、滴下管より、スチレン20質量部、メタクリル酸グリシジル70質量部、メタクリル酸ジシクロペンタニル2質量部、メタクリル酸メチル15質量部、及び2,2’-アゾビスイソブチロニトリル1.33質量部の混合物を2時間かけて滴下した。滴下終了後、更に3時間反応を継続し、樹脂(Mw=11000)を得た。室温まで冷却した後、PGMEAで希釈して固形分濃度を40質量%に調整し、樹脂溶液13を調製した。
Claims (20)
- 着色剤と、重合性化合物と、光重合開始剤とを含む着色組成物であって、
前記着色剤は、カラーインデックスピグメントグリーン7を1質量%以上含む緑色着色剤と、カラーインデックスピグメントイエロー150を含む黄色着色剤とを含み、かつ、カラーインデックスピグメントグリーン7以外の緑色着色剤とカラーインデックスピグメントイエロー150との質量比が、カラーインデックスピグメントグリーン7以外の緑色着色剤:カラーインデックスピグメントイエロー150=0:100~18:82であり、
前記着色組成物は、波長450nmの光に対する吸光度を1としたとき、吸光度が0.2となる波長が550nm以上600nm以下の波長範囲に存在する、
着色組成物。 - 前記着色組成物は、波長400~700nmの光に対する吸光度のうち、495nm以上550nm未満の波長範囲に吸光度の最小値を有する、請求項1に記載の着色組成物。
- 前記着色組成物は、波長450nmの光に対する吸光度を1としたとき、吸光度が0.2となる波長が470nm以上490nm以下の波長範囲と、550nm以上600nm以下の波長範囲のそれぞれに存在する、請求項1または2に記載の着色組成物。
- 前記着色剤中におけるカラーインデックスピグメントグリーン7とカラーインデックスピグメントイエロー150との合計量が80質量%以上である、請求項1~3のいずれか1項に記載の着色組成物。
- 前記カラーインデックスピグメントグリーン7以外の緑色着色剤がカラーインデックスピグメントグリーン36を含む、請求項1~4のいずれか1項に記載の着色組成物。
- 前記黄色着色剤は、実質的にカラーインデックスピグメントイエロー150のみである、請求項1~5のいずれか1項に記載の着色組成物。
- 前記緑色着色剤は、実質的にカラーインデックスピグメントグリーン7のみである、請求項1~6のいずれか1項に記載の着色組成物。
- カラーインデックスピグメントグリーン7の100質量部に対してカラーインデックスピグメントイエロー150を50~240質量部含有する、請求項1~7のいずれか1項に記載の着色組成物。
- 前記着色組成物の全固形分中における前記着色剤の含有量が20質量%以上である、請求項1~8のいずれか1項に記載の着色組成物。
- 前記重合性化合物は、エチレン性不飽和結合含有基を3個以上有する重合性化合物を含む、請求項1~9のいずれか1項に記載の着色組成物。
- 前記重合性化合物は、エチレン性不飽和結合含有基とアルキレンオキシ基とをする重合性化合物を含む、請求項1~10のいずれか1項に記載の着色組成物。
- 前記光重合開始剤は、オキシム化合物を含有する、請求項1~11のいずれか1項に記載の着色組成物。
- 前記光重合開始剤は、オキシム化合物とヒドロキシアルキルフェノン化合物を含有する、請求項1~12のいずれか1項に記載の着色組成物。
- カラーフィルタの緑色画素形成用の着色組成物である、請求項1~13のいずれか1項に記載の着色組成物。
- 表示装置用の着色組成物である、請求項1~14のいずれか1項に記載の着色組成物。
- 全工程を通じて150℃以下の温度で硬化膜を形成するために用いられる、請求項1~15のいずれか1項に記載の着色組成物。
- 請求項1~16のいずれか1項に記載の着色組成物を用いて得られる硬化膜。
- 緑色画素と赤色画素と青色画素とを有する構造体であって、前記緑色画素は請求項1~16のいずれか1項に記載の着色組成物を用いて得られるものである、構造体。
- 請求項17に記載の硬化膜を有するカラーフィルタ。
- 請求項17に記載の硬化膜を有する表示装置。
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JP2021562595A JP7376609B2 (ja) | 2019-12-04 | 2020-11-25 | 着色組成物、硬化膜、構造体、カラーフィルタおよび表示装置 |
KR1020227017434A KR20220092908A (ko) | 2019-12-04 | 2020-11-25 | 착색 조성물, 경화막, 구조체, 컬러 필터 및 표시 장치 |
CN202080080366.8A CN114761873A (zh) | 2019-12-04 | 2020-11-25 | 着色组合物、固化膜、结构体、滤色器及显示装置 |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006301100A (ja) * | 2005-04-18 | 2006-11-02 | Fujifilm Electronic Materials Co Ltd | 光硬化性組成物およびそれを用いたカラーフィルタ |
JP2011117986A (ja) * | 2008-03-19 | 2011-06-16 | Jsr Corp | 緑色画素形成用感放射線性組成物、カラーフィルタおよびカラー液晶表示素子 |
JP2011141534A (ja) * | 2009-12-09 | 2011-07-21 | Fujifilm Corp | 着色感光性組成物、カラーフィルタの製造方法、カラーフィルタ、及び液晶表示装置 |
JP2018146630A (ja) * | 2017-03-01 | 2018-09-20 | 富士フイルム株式会社 | カラーフィルタの下地膜用組成物、積層体、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子および画像表示装置 |
WO2018173524A1 (ja) * | 2017-03-24 | 2018-09-27 | 富士フイルム株式会社 | 着色組成物、顔料分散液、顔料分散液の製造方法、硬化膜、カラーフィルタ、固体撮像素子および画像表示装置 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001249215A (ja) * | 2000-03-06 | 2001-09-14 | Fujifilm Arch Co Ltd | カラーフィルターおよびカラーフィルタ−用組成物 |
JP4258180B2 (ja) * | 2001-10-11 | 2009-04-30 | 東レ株式会社 | カラーフィルター及び液晶表示装置 |
JP2009204816A (ja) * | 2008-02-27 | 2009-09-10 | Fujifilm Corp | 着色硬化性組成物、カラーフィルタ、及び液晶表示装置 |
KR101422851B1 (ko) * | 2008-04-10 | 2014-08-14 | 동우 화인켐 주식회사 | 착색 감광성 수지 조성물, 컬러필터 및 이를 구비한 액정표시장치 |
KR101679421B1 (ko) * | 2009-11-18 | 2016-11-24 | 동우 화인켐 주식회사 | 착색 감광성 수지 조성물, 이를 포함하는 컬러 필터 및 액정 표시 장치 |
KR20120077833A (ko) * | 2010-12-31 | 2012-07-10 | 동우 화인켐 주식회사 | 착색감광성수지 조성물 |
JP5818728B2 (ja) * | 2012-03-23 | 2015-11-18 | 東洋インキScホールディングス株式会社 | 固体撮像素子用着色組成物及びカラーフィルタ |
JP6252001B2 (ja) | 2012-07-25 | 2017-12-27 | 東レ株式会社 | 着色剤組成物、カラーフィルター基板及び液晶表示装置 |
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- 2020-11-25 JP JP2021562595A patent/JP7376609B2/ja active Active
- 2020-11-25 KR KR1020227017434A patent/KR20220092908A/ko not_active Application Discontinuation
- 2020-11-25 CN CN202080080366.8A patent/CN114761873A/zh active Pending
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006301100A (ja) * | 2005-04-18 | 2006-11-02 | Fujifilm Electronic Materials Co Ltd | 光硬化性組成物およびそれを用いたカラーフィルタ |
JP2011117986A (ja) * | 2008-03-19 | 2011-06-16 | Jsr Corp | 緑色画素形成用感放射線性組成物、カラーフィルタおよびカラー液晶表示素子 |
JP2011141534A (ja) * | 2009-12-09 | 2011-07-21 | Fujifilm Corp | 着色感光性組成物、カラーフィルタの製造方法、カラーフィルタ、及び液晶表示装置 |
JP2018146630A (ja) * | 2017-03-01 | 2018-09-20 | 富士フイルム株式会社 | カラーフィルタの下地膜用組成物、積層体、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子および画像表示装置 |
WO2018173524A1 (ja) * | 2017-03-24 | 2018-09-27 | 富士フイルム株式会社 | 着色組成物、顔料分散液、顔料分散液の製造方法、硬化膜、カラーフィルタ、固体撮像素子および画像表示装置 |
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TW202128888A (zh) | 2021-08-01 |
JPWO2021111950A1 (ja) | 2021-06-10 |
CN114761873A (zh) | 2022-07-15 |
KR20220092908A (ko) | 2022-07-04 |
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