CN118151488A - Colored photosensitive resin composition, pigment dispersion liquid, partition wall, organic electroluminescent element, image display device, and illumination - Google Patents

Colored photosensitive resin composition, pigment dispersion liquid, partition wall, organic electroluminescent element, image display device, and illumination Download PDF

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Publication number
CN118151488A
CN118151488A CN202410172111.4A CN202410172111A CN118151488A CN 118151488 A CN118151488 A CN 118151488A CN 202410172111 A CN202410172111 A CN 202410172111A CN 118151488 A CN118151488 A CN 118151488A
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group
mass
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resin composition
colored photosensitive
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小野由香子
泽井良尚
伊藤敦哉
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Mitsubishi Chemical Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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    • C—CHEMISTRY; METALLURGY
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    • C08F2/00—Processes of polymerisation
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    • C—CHEMISTRY; METALLURGY
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    • C08F2/00—Processes of polymerisation
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    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
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    • 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
    • C09B57/00—Other synthetic dyes of known constitution
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    • 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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    • 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
    • C09B67/0063—Preparation of organic pigments of organic pigments with only macromolecular substances
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    • 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
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/008—Preparations of disperse dyes or solvent dyes
    • C09B67/0082—Preparations of disperse dyes or solvent dyes in liquid form
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    • 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
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    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • 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
    • 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
    • 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
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
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    • 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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Abstract

The first object of the present invention is to provide a colored photosensitive resin composition which has a small amount of outgas after forming a cured product, is excellent in reliability, and has good adhesion of a fine pattern in a development step when producing the cured product. The colored photosensitive resin composition of the present invention according to the first aspect contains (a) a colorant containing (A1) an organic black pigment containing at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound, (B) a dispersant containing an acrylic dispersant, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator, and (C) the binder resin contains 75 mass% or more of (C1) an epoxy (meth) acrylate resin.

Description

Colored photosensitive resin composition, pigment dispersion liquid, partition wall, organic electroluminescent element, image display device, and illumination
The present application is a divisional application of application No. 201780070424.7, which is a coloring photosensitive resin composition, pigment dispersion, partition wall, organic electroluminescent element, image display device, and illumination, and has application No. 2017, 11, 29.
Technical Field
The present invention relates to a colored photosensitive resin composition, and further relates to a pigment dispersion liquid used in the colored photosensitive resin composition, a partition wall composed of the colored photosensitive resin composition, an organic electroluminescent element provided with the partition wall, an image display device, and illumination.
Background
A Liquid Crystal Display (LCD) utilizes the property that the arrangement of liquid crystal molecules is switched by the on/off action of a voltage applied to liquid crystal. On the other hand, each member constituting a cell of an LCD is often formed by a method using a photosensitive composition, typically photolithography. For this photosensitive composition, the application range of the photosensitive composition will tend to be further widened in the future because of the ease of forming a microstructure and the ease of processing a large-screen substrate.
In addition, along with simplification of the panel structure and the manufacturing process, a method of forming so-called columnar spacers by photolithography, which are used to keep the interval between 2 substrates in a liquid crystal panel constant, has been studied, and in recent years, colored spacers in which photo spacers and black matrices are integrated have been developed. However, such a colored spacer is required to have a volume resistivity equal to or higher than a certain value and a relative dielectric constant equal to or lower than a certain value in addition to a normal shape and compression characteristics so that a short circuit of a circuit is not caused even if the colored spacer is directly mounted on a TFT element.
As such a colored spacer, a colored spacer using a plurality of organic colored pigments as pigments and a colored spacer using an organic black pigment have been proposed. Patent document 1 describes a photosensitive coloring composition having excellent dispersibility, light-shielding properties, and a low relative dielectric constant by combining a specific organic black pigment and a dispersant.
On the other hand, an image display device including an organic electroluminescent element (also referred to as an organic electroluminescent element or an organic EL) is attracting attention as a Flat Panel Display (FPD) of the next generation because it is excellent in visibility, responsiveness, and the like, and is capable of achieving low power consumption, thin and light weight, and flexibility of a display main body.
The organic electroluminescent element has the following structure: an organic layer including a light-emitting layer or various functional layers is sandwiched between a pair of electrodes at least one of which has light transmittance. The image display device performs image display by driving a panel in which organic electroluminescent elements are arranged for each pixel.
Conventionally, such an organic electroluminescent device is manufactured by forming a partition wall (dam) on a substrate, and then laminating a light-emitting layer or various functional layers in a region surrounded by the partition wall.
In order to form a light-emitting layer or the like in a region surrounded by the partition walls, a vapor deposition method is used in which a material is sublimated in a vacuum state and attached to a substrate to form a film. In recent years, a method of forming a film by a wet process such as a casting method, a spin coating method, or an inkjet printing method has been attracting attention. In particular, the inkjet printing method is suitable as a method for forming an organic layer in a large-sized panel because it is possible to reduce film thickness unevenness even when a large area is formed, and it is possible to achieve high definition of a display by separate coating at the time of coating, reduction in the amount of material used, and improvement in yield.
As a method for easily forming the barrier ribs, a method of forming barrier ribs by photolithography using a photosensitive resin composition is known.
Prior art literature
Patent literature
Patent document 1: international publication No. 2015/046178
Disclosure of Invention
Problems to be solved by the invention
In recent years, it has been demanded to reduce the outgas generated from a cured product constituting an image display device or the like after the cured product is formed. In particular, in an organic electroluminescent device, it is strongly demanded to reduce outgas generated by a partition wall when the device emits light. This is because, in the organic electroluminescent element, if the amount of outgas generated from the cured product such as the partition wall is large, there is a possibility that the lifetime of the element is reduced.
On the other hand, in the image display device, it is necessary to miniaturize a cured product constituting the high-resolution model, and it is required that even a fine pattern is sufficiently adhered to a substrate or the like in a developing process.
The present inventors have studied and found that the photosensitive coloring composition described in patent document 1 has a large amount of outgas and has a problem in practical use.
In addition, patent document 1 does not describe or suggest the application of the spacer to the organic electroluminescent element, and the present inventors have found that the adhesion of the spacer to a pattern of a size required for a model of normal resolution is sufficient, but the adhesion of the pattern to a fine pattern required for a model of high resolution is insufficient when the application of the spacer to the organic electroluminescent element is studied.
The first object of the present invention is to provide a colored photosensitive resin composition which has a small amount of outgas after forming a cured product, is excellent in reliability, and has good adhesion of a fine pattern in a development step when producing the cured product.
The present invention also provides a partition wall formed using the colored photosensitive resin composition, an organic electroluminescent element provided with the partition wall, an image display device including the organic electroluminescent element, and illumination.
Further, the second object of the present invention is to provide a colored photosensitive resin composition for forming a partition wall of an organic electroluminescent element, which is excellent in reliability and has a small amount of outgas after forming a cured product.
The present invention also provides a partition wall formed using the colored photosensitive resin composition, an organic electroluminescent element provided with the partition wall, an image display device including the organic electroluminescent element, and illumination.
A third object of the present invention is to provide a pigment dispersion for constituting a photosensitive resin composition for solving the first object.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above problems can be solved by a colored photosensitive resin composition containing a specific organic black pigment and today containing a specific binder resin in an amount of not less than a specific amount, and have completed the present invention.
Namely, the gist of the present invention is as follows.
[1] A colored photosensitive resin composition comprising: (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator, wherein,
The (A) colorant comprises (A1) an organic black pigment, the (A1) organic black pigment contains at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound,
The (B) dispersant comprises an acrylic dispersant,
The binder resin (C) contains 75 mass% or more of (C1) an epoxy (meth) acrylate resin,
[ Chemical formula 1]
(In the formula (I), R a1 and R a6 each independently represent a hydrogen atom, CH 3、CF3, a fluorine atom or a chlorine atom;
R a2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9 and R a10 each independently represent a hydrogen atom, a halogen atom 、Ra11、COOH、COORa11、COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、OOCNRa11Ra12、NO2、NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12、N＝CH2、N＝CHRa11、N＝CRa11Ra12、SH、SRa11、SORa11、SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11 or SO 2NRa11Ra12;
And, at least one combination selected from the group consisting of R a2 and R a3、Ra3 and R a4、Ra4 and R a5、Ra7 and R a8、Ra8 and R a9, and R a9 and R a10 are optionally bonded directly to each other, or bonded to each other by bridging with an oxygen atom, a sulfur atom, NH, or NR a11;
R a11 and R a12 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. )
[2] The colored photosensitive resin composition according to the above [1], wherein the content of the (C1) epoxy (meth) acrylate resin in the (C) binder resin is 85 mass% or more.
[3] The colored photosensitive resin composition according to the above [1] or [2], wherein the (C1) epoxy (meth) acrylate resin comprises one or both of an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (III),
[ Chemical formula 2]
(In the formula (II), R 11 represents a hydrogen atom or a methyl group;
R 12 represents an optionally substituted 2-valent hydrocarbon group;
the benzene ring in formula (II) is optionally further substituted with any substituent;
* Indicating the bonding location. )
[ Chemical formula 3]
(In the formula (III), R 13 each independently represents a hydrogen atom or a methyl group;
r 14 represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R 15 and R 16 each independently represent an optionally substituted 2-valent aliphatic group;
m and n each independently represent an integer of 0 to 2;
* Indicating the bonding location. )
[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the acrylic dispersant is a nitrogen atom-containing acrylic dispersant.
[5] The colored photosensitive resin composition according to any one of [1] to [4], wherein the content of the colorant (A) is 60% by mass or less based on the total solid content of the colored photosensitive resin composition.
[6] The colored photosensitive resin composition according to any one of [1] to [5], wherein the (A) colorant further comprises one or both of (A2) an organic coloring pigment and (A3) carbon black.
[7] The colored photosensitive resin composition according to any one of [1] to [6], wherein the content of the organic black pigment (A1) in the colorant (A) is 10% by mass or more.
[8] The colored photosensitive resin composition according to any one of [1] to [7], which is used for forming a partition wall of an organic electroluminescent element.
[9] A colored photosensitive resin composition for forming a partition wall of an organic electroluminescent element, the colored photosensitive resin composition comprising: (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator, wherein,
The (A) colorant comprises (A1) an organic black pigment, the (A1) organic black pigment contains at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound,
The binder resin (C) contains 75 mass% or more of (C1) an epoxy (meth) acrylate resin,
[ Chemical formula 4]
(In the formula (I), R a1 and R a6 each independently represent a hydrogen atom, CH 3、CF3, a fluorine atom or a chlorine atom;
R a2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9 and R a10 each independently represent a hydrogen atom, a halogen atom 、Ra11、COOH、COORa11、COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、OOCNRa11Ra12、NO2、NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12、N＝CH2、N＝CHRa11、N＝CRa11Ra12、SH、SRa11、SORa11、SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11 or SO 2NRa11Ra12;
And, at least one combination selected from the group consisting of R a2 and R a3、Ra3 and R a4、Ra4 and R a5、Ra7 and R a8、Ra8 and R a9, and R a9 and R a10 are optionally bonded directly to each other, or bonded to each other by bridging with an oxygen atom, a sulfur atom, NH, or NR a11;
R a11 and R a12 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. )
[10] The colored photosensitive resin composition according to the above [9], wherein the content of the (C1) epoxy (meth) acrylate resin in the (C) binder resin is 85 mass% or more.
[11] The colored photosensitive resin composition according to the above [9] or [10], wherein the (C1) epoxy (meth) acrylate resin comprises one or both of an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (III),
[ Chemical formula 5]
(In the formula (II), R 11 represents a hydrogen atom or a methyl group;
R 12 represents an optionally substituted 2-valent hydrocarbon group;
the benzene ring in formula (II) is optionally further substituted with any substituent;
* Indicating the bonding location. )
[ Chemical formula 6]
(In the formula (III), R 13 each independently represents a hydrogen atom or a methyl group;
r 14 represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R 15 and R 16 each independently represent an optionally substituted 2-valent aliphatic group;
m and n each independently represent an integer of 0 to 2;
* Indicating the bonding location. )
[12] The colored photosensitive resin composition according to any one of [9] to [11], wherein the content of the colorant (A) is 60 mass% or less with respect to the total solid content of the colored photosensitive resin composition.
[13] The colored photosensitive resin composition according to any one of the above [9] to [12], wherein the (A) colorant further comprises one or both of (A2) an organic coloring pigment and (A3) carbon black.
[14] The colored photosensitive resin composition according to any one of [9] to [13], wherein the content of the organic black pigment (A1) in the colorant (A) is 10 mass% or more.
[15] A partition wall comprising the colored photosensitive resin composition according to any one of the above [1] to [14 ].
[16] An organic electroluminescent device comprising the partition wall according to [15 ].
[17] An image display device comprising the organic electroluminescent element described in [16] above.
[18] An illumination device comprising the organic electroluminescent element as described in [16] above.
[19] A pigment dispersion comprising: a colorant, a dispersant and a binder resin, wherein,
The (A) colorant comprises (A1) an organic black pigment, the (A1) organic black pigment contains at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound,
The (B) dispersant comprises an acrylic dispersant,
The (C) binder resin comprises (C1) an epoxy (meth) acrylate resin,
[ Chemical formula 7]
(In the formula (I), R a1 and R a6 each independently represent a hydrogen atom, CH 3、CF3, a fluorine atom or a chlorine atom;
R a2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9 and R a10 each independently represent a hydrogen atom, a halogen atom 、R11、COOH、COORa11、COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、OOCNRa11Ra12、NO2、NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12、N＝CH2、N＝CHRa11、N＝CRa11Ra12、SH、SRa11、SORa11、SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11 or SO 2NRa11Ra12;
And, at least one combination selected from the group consisting of R a2 and R a3、Ra3 and R a4、Ra4 and R a5、Ra7 and R a8、Ra8 and R a9, and R a9 and R a10 are optionally bonded directly to each other, or bonded to each other by bridging with an oxygen atom, a sulfur atom, NH, or NR a11;
R a11 and R a12 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. )
[20] The pigment dispersion according to [19], wherein the content of the dispersant (B) is 10 parts by mass or more based on 100 parts by mass of the colorant (A).
[21] The pigment dispersion according to the above [19] or [20], wherein the (C1) epoxy (meth) acrylate resin comprises one or both of an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (III),
[ Chemical formula 8]
(In the formula (II), R 11 represents a hydrogen atom or a methyl group;
R 12 represents an optionally substituted 2-valent hydrocarbon group;
the benzene ring in formula (II) is optionally further substituted with any substituent;
* Indicating the bonding location. )
[ Chemical formula 9]
(In the formula (III), R 13 each independently represents a hydrogen atom or a methyl group;
r 14 represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R 15 and R 16 each independently represent an optionally substituted 2-valent aliphatic group;
m and n each independently represent an integer of 0 to 2;
* Indicating the bonding location. )
[22] The pigment dispersion liquid according to any one of the above [19] to [21], wherein the acrylic dispersant is an acrylic dispersant containing a nitrogen atom.
[23] The pigment dispersion liquid according to any one of the above [19] to [22], which is used for producing a colored photosensitive resin composition.
ADVANTAGEOUS EFFECTS OF INVENTION
According to one aspect of the present invention, a colored photosensitive resin composition having a small amount of outgas after formation of a cured product, excellent reliability, and good adhesion of a fine pattern in a development step at the time of producing the cured product can be provided. In addition, the cured product formed from the colored photosensitive resin composition of the present invention has a small amount of outgas during use, and has a small reduction in lifetime and excellent reliability as a light-emitting element.
In addition, according to another aspect of the present invention, there can be provided a colored photosensitive resin composition for forming a partition wall of an organic electroluminescent element, which has a small amount of outgas after forming a cured product and is excellent in reliability. In addition, the cured product formed from the colored photosensitive resin composition of the present invention has a small amount of outgas during use, and has a small reduction in lifetime and excellent reliability as a light-emitting element.
Further, the pigment dispersion liquid of the present invention can provide the colored photosensitive resin composition.
Detailed Description
The present invention will be described in detail below. The following description is an example of the embodiment of the present invention, and the present invention is not limited to these examples within a range not exceeding the gist of the present invention.
In the present invention, "meth" acrylic acid "means" acrylic acid and/or methacrylic acid ", and" all solid components "means all components except a solvent in the colored photosensitive resin composition or pigment dispersion. In the present invention, the numerical range indicated by "to" indicates a range including the numerical values described before and after "to" as the lower limit value and the upper limit value.
In the present invention, the meaning of "(co) polymer" includes both single polymer (homopolymer) and copolymer (copolymer), and the meaning of "(acid anhydride", "… acid (anhydride)" includes both acid and anhydride thereof.
In the present invention, the partition wall material means a dam material, a wall material, and similarly, the partition wall means a dam, a wall, and a wall. The partition wall is a member for dividing a functional layer (organic layer) in an active-drive organic electroluminescent element, and is used for forming a pixel or the like composed of the functional layer and the partition wall by applying a material for constituting the functional layer on the divided region (pixel region) by vapor deposition, ink jet, or the like and drying the material.
In the present invention, the weight average molecular weight refers to a polystyrene-equivalent weight average molecular weight (Mw) based on GPC (gel permeation chromatography).
In the present invention, reliability means reliability in driving an organic electroluminescent element, and in particular, image display device means reliability, and illumination means light emission reliability.
The colored photosensitive resin composition according to the first aspect of the present invention is for solving the first problem, wherein the (a) colorant comprises (A1) an organic black pigment, the (A1) organic black pigment contains at least one selected from the group consisting of a compound represented by the general formula (I) described later, a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound, the (B) dispersant comprises an acrylic dispersant, and the (C) binder resin comprises 75 mass% or more of (C1) epoxy (meth) acrylate resin.
The colored photosensitive resin composition according to the second aspect of the present invention is a colored photosensitive resin composition for forming a partition wall of an organic electroluminescent element, wherein the (a) colorant comprises (A1) an organic black pigment, and the (A1) organic black pigment contains at least one selected from the group consisting of a compound represented by the general formula (I) described later, a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound, and the (C) binder resin contains 75 mass% or more of (C1) epoxy (meth) acrylate resin.
The pigment dispersion according to the third aspect of the present invention is the pigment dispersion for solving the third problem, wherein the (a) colorant comprises (A1) an organic black pigment, the (A1) organic black pigment contains at least one selected from the group consisting of a compound represented by the general formula (I) described later, a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound, the (B) dispersant comprises an acrylic dispersant, and the (C) binder resin comprises a (C1) epoxy (meth) acrylate resin.
Hereinafter, unless otherwise specified, "the colored photosensitive resin composition of the present invention" refers to both the colored photosensitive resin composition of the first embodiment and the colored photosensitive resin composition of the second embodiment.
[1] Components and compositions of colored photosensitive resin composition
The components and the compositions constituting the colored photosensitive resin composition of the present invention will be described.
The colored photosensitive resin composition of the present invention (hereinafter, may be simply referred to as "photosensitive resin composition") contains (a) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator, and further usually contains a solvent.
[1-1] (A) colorant
The (a) colorant in the colored photosensitive resin composition and the pigment dispersion of the present invention contains (A1) an organic black pigment (hereinafter, sometimes referred to as "(A1) an organic black pigment"), and the (A1) organic black pigment contains at least one selected from the group consisting of a compound represented by the following general formula (I) (hereinafter, sometimes referred to as "compound (I)"), a geometric isomer of the above-mentioned compound, a salt of the above-mentioned compound, and a salt of the geometric isomer of the above-mentioned compound.
Thus, by including (A1) the organic black pigment, it is considered that high resistance, low dielectric constant and high light shielding rate can be achieved. Further, since a cured product having a color tone closer to black can be obtained, it is possible to use the cured product as a colorant for forming a partition wall of an organic electroluminescent element having a large area ratio in an image display region of an image display device. In addition, the use of the (A1) organic black pigment is excellent in dispersibility and preservability, and in the colored photosensitive resin composition containing the (A1) organic black pigment, the pattern adaptability upon development is also excellent.
[ Chemical formula 10]
In the formula (I), R a1 and R a6 each independently represent a hydrogen atom, CH 3、CF3, a fluorine atom or a chlorine atom;
R a2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9 and R a10 each independently represent a hydrogen atom, a halogen atom 、Ra11、COOH、COORa11、COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、OOCNRa11Ra12、NO2、NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12、N＝CH2、N＝CHRa11、N＝CRa11Ra12、SH、SRa11、SORa11、SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11 or SO 2NRa11Ra12;
And, at least one combination selected from the group consisting of R a2 and R a3、Ra3 and R a4、Ra4 and R a5、Ra7 and R a8、Ra8 and R a9, and R a9 and R a10 are optionally bonded directly to each other, or bonded to each other by bridging with an oxygen atom, a sulfur atom, NH, or NR 11;
R a11 and R a12 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
The geometric isomer of the compound represented by the general formula (I) has the following core structure (wherein, substituents in the structural formula are omitted), and the trans-trans isomer may be the most stable.
[ Chemical formula 11]
In the case where the compound represented by the general formula (I) is anionic, it is preferably a salt obtained by compensating the charge of any known suitable cation, for example, a metal, organic, inorganic or metal-organic cation, specifically, a quaternary ammonium or organic metal complex such as a tertiary amine such as an alkali metal, alkaline earth metal, transition metal, primary amine, secondary amine, trialkylamine, or tetraalkylammonium. In the case where the geometric isomer of the compound represented by the general formula (I) is anionic, the same salt is preferable.
The substituents of the general formula (I) are preferably as follows, since they tend to have an increased shielding rate. This is because the following substituents are not considered to be absorbed and do not affect the hue of the pigment.
R a2、Ra4、Ra5、Ra7、Ra9 and R a10 are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
R a3 and R a8 are each independently preferably a hydrogen atom, NO 2、OCH3、OC2H5, a bromine atom, a chlorine atom 、CH3、C2H5、N(CH3)2、N(CH3)(C2H5)、N(C2H5)2、α- naphthyl group, a beta-naphthyl group, SO 3 H or SO 3 -, more preferably a hydrogen atom or SO 3 H.
R 1 and R 6 are each independently preferably a hydrogen atom, CH 3 or CF 3, more preferably a hydrogen atom.
Preferably at least one combination selected from the group consisting of R 1 and R 6、R2 and R 7、R3 and R 8、R4 and R 9, and R 5 and R 10 is the same, more preferably R 1 is the same as R 6, R 2 is the same as R 7, R 3 is the same as R 8, R 4 is the same as R 9, and R 5 is the same as R 10.
Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, 2-pentyl, 3-pentyl, 2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1, 3-tetramethylbutyl, 2-ethylhexyl, nonyl, decyl, undecyl and dodecyl.
Cycloalkyl having 3 to 12 carbon atoms is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, limonyl (thujyl), norbornyl, bornyl, carenyl,Alkyl, pinanyl, 1-adamantyl or 2-adamantyl.
Alkenyl having 2 to 12 carbon atoms is, for example, vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1, 3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-propen-1-yl1-Buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1, 4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl.
Cycloalkenyl having 3 to 12 carbon atoms is, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2, 4-cyclohexadien-1-yl, 1-pairAlkenyl-8-yl, 4 (10) -limonen-10-yl, 2-norbornen-1-yl, 2, 5-norbornadien-1-yl, 7-dimethyl-2, 4-norcaren-3-yl or campyl.
Alkynyl having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1, 4-glutaronin-3-yl, 1, 3-glutaronin-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1, 3-hexyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl or 1-dodecen-12-yl.
The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The organic black pigment (A1) is preferably at least one selected from the group consisting of a compound represented by the following general formula (I-1) (hereinafter, sometimes referred to as "compound (I-1)") and geometric isomers of the compound.
[ Chemical formula 12]
Specific examples of such an organic Black pigment include an organic Black pigment having a trade name of Irgaphor (registered trademark) Black S0100 CF (manufactured by BASF corporation).
The organic black pigment is preferably dispersed in a dispersant or a solvent by a method described later. Further, if the sulfonic acid derivative (sulfonic acid substituent) of the above-mentioned compound (1) or the sulfonic acid derivative of the geometric isomer of the compound (I), particularly the sulfonic acid derivative of the above-mentioned compound (I-1) or the sulfonic acid derivative of the geometric isomer of the above-mentioned compound (I-1) is present at the time of dispersion, dispersibility and preservation may be improved.
The colorant (A) used in the present invention may contain other colorants in addition to the above-mentioned (A1) organic black pigment. As the other colorant, a pigment is preferably used, and the pigment may be an organic pigment or an inorganic pigment, and from the viewpoint of high impedance and low dielectric constant, an organic pigment is more preferably used, and in particular, an organic coloring pigment (hereinafter, may be referred to as an "(A2) organic coloring pigment") is more preferably used.
The chemical structure of these pigments is not particularly limited, and azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, and di-can be usedOrganic pigments such as oxazine, indanthrene and perylene. Hereinafter, specific examples of the organic pigment that can be used are shown by the pigment numbers. The terms "c.i. pigment red 2" and the like listed below refer to pigment index numbers (c.i.).
As the red pigment, there may be mentioned: among them, c.i. pigment red 1、2、3、4、5、6、7、8、9、12、14、15、16、17、21、22、23、31、32、37、38、41、47、48、48:1、48:2、48:3、48:4、49、49:1、49:2、50:1、52:1、52:2、53、53:1、53:2、53:3、57、57:1、57:2、58:4、60、63、63:1、63:2、64、64:1、68、69、81、81:1、81:2、81:3、81:4、83、88、90:1、101、101:1、104、108、108:1、109、112、113、114、122、123、144、146、147、149、151、166、168、169、170、172、173、174、175、176、177、178、179、181、184、185、187、188、190、193、194、200、202、206、207、208、209、210、214、216、220、221、224、230、231、232、233、235、236、237、238、239、242、243、245、247、249、250、251、253、254、255、256、257、258、259、260、262、263、264、265、266、267、268、269、270、271、272、273、274、275、276. may be preferably c.i. pigment red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, and c.i. pigment red 177, 209, 224, 254 may be more preferably used.
In terms of dispersibility and light-shielding properties, c.i. pigment red 177, 254, 272 are preferably used, and in the case of curing the colored photosensitive resin composition of the present invention with ultraviolet light, a red pigment having low ultraviolet light absorptivity is preferably used as the red pigment, and from the above standpoint, c.i. pigment red 254, 272 are more preferably used.
As Orange (Orange) pigments, there may be mentioned: among them, c.i. pigment orange 1、2、5、13、16、17、19、20、21、22、23、24、34、36、38、39、43、46、48、49、61、62、64、65、67、68、69、70、71、72、73、74、75、77、78、79. is preferably used in terms of dispersibility and light-shielding properties, and c.i. pigment orange 13, 43, 64, and 72 is preferably used as an orange pigment in the case of curing the colored photosensitive resin composition of the present invention by ultraviolet rays, and c.i. pigment orange 64 and 72 are more preferably used in terms of the above-mentioned properties, and c.i. pigment orange 64 is particularly preferred.
As the blue pigment, there may be mentioned: among these, c.i. pigment blue 1、1:2、9、14、15、15:1、15:2、15:3、15:4、15:6、16、17、19、25、27、28、29、33、35、36、56、56:1、60、61、61:1、62、63、66、67、68、71、72、73、74、75、76、78、79. may be preferably c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and more preferably c.i. pigment blue 15:6.
In terms of dispersibility and light-shielding properties, c.i. pigment blue 15:6, 16, and 60 are preferably used, and in the case of curing the colored photosensitive resin composition of the present invention with ultraviolet light, a blue pigment having low ultraviolet light absorptivity is preferably used as the blue pigment, and from the above viewpoint, c.i. pigment blue 60 is more preferably used.
As the violet pigment, there may be mentioned: c.i. pigment violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among them, c.i. pigment violet 19, 23 are preferably used, and c.i. pigment violet 23 is more preferably used, from the viewpoint of light shielding properties.
In terms of dispersibility and light-shielding properties, c.i. pigment violet 23 and c.i. pigment violet 29 are preferably used, and in the case of curing the colored photosensitive resin composition of the present invention with ultraviolet light, a violet pigment having low ultraviolet absorptivity is preferably used as the violet pigment, and from the above viewpoint, c.i. pigment violet 29 is more preferably used.
Examples of usable organic coloring pigments other than red pigment, orange pigment, blue pigment and violet pigment include green pigment and yellow pigment.
As the green pigment, there may be mentioned: c.i. pigment green 1,2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58. Among them, c.i. pigment green 7, 36 are preferable.
As the yellow pigment, there may be mentioned: among them, c.i. pigment yellow 1、1:1、2、3、4、5、6、9、10、12、13、14、16、17、24、31、32、34、35、35:1、36、36:1、37、37:1、40、41、42、43、48、53、55、61、62、62:1、63、65、73、74、75、81、83、87、93、94、95、97、100、101、104、105、108、109、110、111、116、117、119、120、126、127、127:1、128、129、133、134、136、138、139、142、147、148、150、151、153、154、155、157、158、159、160、161、162、163、164、165、166、167、168、169、170、172、173、174、175、176、180、181、182、183、184、185、188、189、190、191、191:1、192、193、194、195、196、197、198、199、200、202、203、204、205、206、207、208. may be preferably c.i. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably c.i. pigment yellow 83, 138, 139, 150, 180.
Among these pigments, a combination of at least one selected from red pigments and orange pigments and at least one selected from blue pigments and violet pigments is preferably used. In this way, a combination of specific pigments tends to realize high light-shielding properties.
Among the above, from the viewpoints of light-shielding property and color tone, it is preferable to contain at least one or more of the following pigments.
Red pigment: c.i. pigment red 177, 254, 272
Orange pigment: c.i. pigment orange 43, 64, 72
Blue pigment: c.i. pigment blue 15: 6. 60 (60)
Violet pigment: c.i. pigment violet 23, 29
The combination of colors is not particularly limited, and examples thereof include, from the viewpoint of light shielding properties: a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment and a violet pigment, and the like.
Further, as other colorants, other black colorants may be used in addition to the above-mentioned organic coloring pigments.
Among the black colorants, other organic black pigments than those represented by the above general formula (I) may be used from the viewpoints of light-blocking properties and color tone. Examples of the other organic black pigment include nigrosine, perylene black, and triamcinolone black.
In addition, in the present invention, an inorganic black pigment may be used. As the inorganic black pigment, there may be mentioned: carbon black, acetylene black, lamp black, bone carbon, graphite, iron black, titanium black, and the like. Among these, carbon black (hereinafter, sometimes referred to as "(A3) carbon black") can be preferably used from the viewpoints of light-shielding properties and image characteristics. Examples of the carbon black include the following carbon blacks.
Mitsubishi chemical Co., ltd ：MA7、MA8、MA11、MA77、MA100、MA100R、MA100S、MA220、MA230、MA600、MCF88、#5、#10、#20、#25、#30、#32、#33、#40、#44、#45、#47、#50、#52、#55、#650、#750、#850、#900、#950、#960、#970、#980、#990、#1000、#2200、#2300、#2350、#2400、#2600、#2650、#3030、#3050、#3150、#3250、#3400、#3600、#3750、#3950、#4000、#4010、OIL7B、OIL9B、OIL11B、OIL30B、OIL31B
Degussa Co., ltd.): printex (registered trademark, the same as follows) )3、Printex3OP、Printex30、Printex30OP、Printex40、Printex45、Printex55、Printex60、Printex75、Printex80、Printex85、Printex90、Printex A、Printex L、Printex G、Printex P、Printex U、Printex V、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100、SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、Color Black FW2V、Color Black FW18、Color Black FW200、Color Black S160、Color Black S170
Cabot Corp: monaroch (registered trademark, hereinafter the same )120、Monarch280、Monarch460、Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、Monarch1400、Monarch4630、REGAL( registered trademark, hereinafter the same )99、REGAL99R、REGAL415、REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BLACK PEARLS480、PEARLS130、VULCAN( registered trademark, hereinafter the same) XC72R, ELFTEX (registered trademark) -8
Birror, inc.: RAVEN (registered trademark, the same applies hereinafter )11、RAVEN14、RAVEN15、RAVEN16、RAVEN22RAVEN30、RAVEN35、RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、RAVEN2000、RAVEN2500U、RAVEN3500、RAVEN5000、RAVEN5250、RAVEN5750、RAVEN7000
Carbon black obtained by coating with a resin may be used as the carbon black. When the carbon black obtained by coating with a resin is used, the adhesion to a glass substrate and the volume resistance value are improved. As the carbon black obtained by coating with a resin, for example, carbon black described in japanese unexamined patent publication No. 09-71733 and the like can be preferably used. From the viewpoints of volume resistance and dielectric constant, it is preferable to use a resin-coated carbon black.
The total content of Na and Ca is preferably 100ppm or less as carbon black to be subjected to the coating treatment with the resin. Carbon black generally contains ash in percentage levels, and the composition of the ash is Na, ca, K, mg, al, fe, and the like mixed from raw oil, fuel oil (or gas), reaction end water and granulation water, furnace materials of a reaction furnace, and the like at the time of production. In general, na and Ca are contained in an amount of several hundred ppm or more, respectively, and by reducing Na and Ca, penetration into a transparent electrode (ITO) and other electrodes can be suppressed, and electrical short-circuiting tends to be prevented.
As a method for reducing the content of ash containing Na and Ca, a method of strictly selecting a substance having a very small content of Na and Ca as a raw oil, fuel oil (or gas), and reaction end water in the production of carbon black, and a method of extremely reducing the amount of alkali substance added for adjusting the structure can be adopted. As other methods, there are mentioned methods of washing carbon black produced from a furnace with water, hydrochloric acid or the like to dissolve and remove Na and Ca.
Specifically, carbon black is mixed and dispersed in water, hydrochloric acid or hydrogen peroxide water, and then a solvent which is hardly soluble in water is added, and at this time, the carbon black is transferred to the solvent side, and almost all Na and Ca existing in the carbon black are dissolved in water or acid and removed while being completely separated from the water. In order to reduce the total amount of Na and Ca to 100ppm or less, although the method can be realized only by a carbon black production process in which raw materials are strictly selected alone or by a method of dissolving in water or acid alone, it is easier to make the total amount of Na and Ca 100ppm or less by combining both methods.
The resin-coated carbon black is preferably so-called acid carbon black having a pH of 6 or less. The dispersion diameter (agglomerate size ) in water is preferably small, and coating with fine units can be performed. More preferably, the carbon black has an average particle diameter of 40nm or less and a dibutyl phthalate (DBP) absorption of 140ml/100g or less. In the above range, a coating film having good light shielding properties tends to be obtained. The average particle diameter is an equivalent circle diameter obtained by particle image analysis in which several views are taken at several tens of thousands of magnifications by observation with an electron microscope, and about 2000 to 3000 carbon black particles in the obtained photograph are measured by an image processing apparatus.
The method for producing the resin-coated carbon black is not particularly limited, and for example, after the blending amount of the carbon black and the resin is appropriately adjusted, the following method can be employed:
1. Mixing resin with solvent such as cyclohexanone, toluene, xylene, etc., heating and dissolving to obtain resin solution, mixing carbon black and water to obtain suspension, mixing the resin solution and the suspension, stirring to separate carbon black from water, removing water, heating and mixing to obtain composition, shaping the obtained composition into sheet, pulverizing, and drying;
2. Mixing and stirring the resin solution and the suspension prepared in the same way, granulating the carbon black and the resin, separating the obtained granules, heating, and removing the residual solvent and water;
3. Dissolving carboxylic acids such as maleic acid and fumaric acid in a solvent, adding carbon black, mixing, drying, removing the solvent to obtain carbon black with carboxylic acid, adding resin, and dry-mixing;
4. Preparing a suspension by stirring a monomer component containing a reactive group constituting a resin to be coated with water at a high speed, polymerizing, cooling, obtaining a resin containing a reactive group from the polymer suspension, adding carbon black thereto, kneading, reacting the carbon black with the reactive group (grafting the carbon black), cooling, and pulverizing; etc.
The type of the resin to be subjected to the coating treatment is not particularly limited, and is usually a synthetic resin, and a resin further having a benzene nucleus in the structure is preferable in view of dispersibility and dispersion stability, because of its higher function as an amphoteric surfactant.
Specific synthetic resins include thermosetting resins such as phenol resins, melamine resins, xylene resins, diallyl phthalate resins, polyethylene terephthalate resins, and alkylbenzene resins, and thermoplastic resins such as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfone, poly-p-phenylene terephthalamide, polyamide imide, polyimide, polyaminobismaleimide, polyethersulfone polyphenylsulfone, polyarylate, and polyetheretherketone. The amount of the coating resin is preferably 1 to 30% by mass relative to the total amount of the carbon black and the coating resin. When the amount of the coating resin is not less than the lower limit, carbon black tends to be sufficiently coated. On the other hand, when the amount of the coating resin is not more than the upper limit, adhesion between the resins is prevented, and dispersibility tends to be good.
The carbon black thus obtained by coating with a resin can be used as a light-shielding material for forming a partition wall or a colored spacer by a usual method, and an organic light-emitting element or a color filter having the partition wall or the colored spacer as a constituent element can be produced by a usual method. If such carbon black is used, a high light shielding rate and low cost tend to be achieved. Further, by coating the surface of carbon black with a resin, a light shielding material such as a partition wall or a colored spacer having high resistance and low dielectric constant can be produced.
In addition, as other colorants, dyes may be used in addition to the above-mentioned organic coloring pigments and black colorants. As dyes that can be used as colorants, there may be mentioned: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like.
Examples of azo dyes include: c.i. acid yellow 11, c.i. acid orange 7, c.i. acid red 37, c.i. acid red 180, c.i. acid blue 29, c.i. direct red 28, c.i. direct red 83, c.i. direct yellow 12, c.i. direct orange 26, c.i. direct green 28, c.i. direct green 59, c.i. reactive yellow 2, c.i. reactive red 17, c.i. reactive red 120, c.i. reactive black 5, c.i. disperse orange 5, c.i. disperse red 58, c.i. disperse blue 165, c.i. basic blue 41, c.i. basic red 18, c.i. intermediate red 7, c.i. intermediate yellow 5, c.i. intermediate black 7, and the like.
Examples of the anthraquinone dye include: c.i. vat blue 4, c.i. acid blue 40, c.i. acid green 25, c.i. active blue 19, c.i. active blue 49, c.i. disperse red 60, c.i. disperse blue 56, c.i. disperse blue 60, etc.
Examples of the phthalocyanine dye include c.i. vat blue 5, examples of the quinone imine dye include c.i. basic blue 3 and c.i. basic blue 9, examples of the quinoline dye include c.i. solvent yellow 33, c.i. acid yellow 3 and c.i. disperse yellow 64, and examples of the nitro dye include c.i. acid yellow 1, c.i. acid orange 3 and c.i. disperse yellow 42.
The pigments (A1) such as organic black pigment, organic coloring pigment and black colorant (A2) are preferably dispersed and used in such a manner that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. Wherein the reference of the average particle diameter is the number of pigment particles.
The average particle diameter of the pigment is a value obtained from the particle diameter of the pigment measured by Dynamic Light Scattering (DLS). The particle size measurement is performed on a sufficiently diluted colored photosensitive resin composition (usually diluted to a pigment content of about 0.005 to 0.2 mass%, but if the concentration is recommended depending on the measuring instrument), and the measurement is performed at 25 ℃.
[1-2] (B) dispersant
The colored photosensitive resin composition and pigment dispersion liquid of the present invention contain (B) a dispersant because it is important to finely disperse (a) a colorant and stabilize the dispersion state thereof to ensure stability of quality.
In the colored photosensitive resin composition according to the first aspect of the present invention and the pigment dispersion liquid according to the third aspect of the present invention, the (B) dispersant includes an acrylic dispersant. Since the acrylic dispersant has a soft main skeleton with a linear molecular structure, it is considered that the coloring agent is uniformly dispersed in the colored photosensitive resin composition and the pigment dispersion by adsorbing a plurality of adsorbing groups to the coloring agent. By uniformly disposing the colorant in the coating film, the coating film becomes a dense film, and it is considered that by uniformly disposing the colorant as a component insoluble in the alkali developer in the coating film, penetration of the developer into the coating film during the development treatment is suppressed, and the pattern adhesion becomes good, particularly even in a fine pattern, and the adhesion becomes good.
Further, as the acrylic dispersant, a polymer dispersant having a functional group is preferable. Further, from the viewpoint of dispersion stability, it is preferable to contain a carboxyl group; a phosphate group; a sulfonic acid group; or salt groups thereof; and an acrylic dispersant containing a nitrogen atom, among which an acrylic dispersant containing a nitrogen atom is preferable. Further, from the viewpoint of being able to disperse with a small amount of dispersant when dispersing a colorant such as a pigment, it is particularly preferable to have a primary amino group, a secondary amino group, or a tertiary amino group; a quaternary ammonium salt group; and a polymer dispersant having a basic functional group such as a nitrogen-containing heterocyclic group derived from pyridine, pyrimidine, pyrazine or the like. These functional groups function as adsorption groups that adsorb to the colorant.
Examples of commercially available acrylic dispersants include DISPERBYK-2000, DISPERBYK-2001, BYK-LPN21116, BYK-LPN6919 and the like (all of which are manufactured by BYK-Chemie Co., ltd.).
As the acrylic dispersant containing a nitrogen atom, a random copolymer, a graft copolymer, or a block copolymer of a monomer having a functional group (the functional group described above is a functional group contained in the polymer dispersant) and containing an unsaturated group and a monomer having no functional group but containing an unsaturated group is preferably used. These copolymers can be produced by a known method.
Examples of the unsaturated group-containing monomer having a functional group include unsaturated monomers having a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and acrylic acid dimer; specific examples of the unsaturated monomer having a tertiary amino group and a quaternary ammonium salt group include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, and their quaternary compounds. They may be used singly or in combination of 2 or more.
Examples of the monomer having no functional group but containing an unsaturated group include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and derivatives thereof, N-substituted maleimides such as α -methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate, and polymethyl (meth) acrylate macromonomers, polystyrene macromonomers, poly (meth) acrylate 2-hydroxyethyl macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone and the like. They may be used singly or in combination of 2 or more. The side chains of these monomers act as solvent affinity moieties that are compatible with the solvent.
From the viewpoint of dispersibility, the acrylic dispersant is preferably an ase:Sub>A-B or B-ase:Sub>A-B block copolymer composed of an ase:Sub>A block having ase:Sub>A functional group and ase:Sub>A B block having no functional group. In this case, the a block may contain a partial structure derived from the unsaturated group-containing monomer, in addition to the partial structure derived from the functional group-containing monomer, and these structures may be contained in any form of random copolymerization or block copolymerization in the a block. The content of the partial structure containing no functional group in the a block is usually 80% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less, and most preferably 0% by mass.
From the viewpoint of dispersibility, the B block is preferably composed of only partial structures derived from the above-mentioned monomer having no functional group but containing an unsaturated group, and 1B block may contain partial structures derived from 2 or more monomers, and these structures may be contained in the B block in any form of random copolymerization or block copolymerization.
The A-B or B-A-B block copolymer can be produced, for example, by the living polymerization method shown below.
Living polymerization methods include anionic living polymerization, cationic living polymerization, and radical living polymerization, wherein the polymerization-active species of the anionic living polymerization are anions, which are represented, for example, by the following synthetic routes.
[ Chemical formula 13]
In the above synthetic route, ar 1 is a 1-valent organic group, ar 2 is a 1-valent organic group different from Ar 1, M is a metal atom, and s and t are integers of 1 or more, respectively.
The polymerization-active species of the radical living polymerization method are radicals, and are represented, for example, by the following synthetic routes.
[ Chemical formula 14]
In the above synthetic route, ar 1 is a 1-valent organic group, ar 2 is a 1-valent organic group different from Ar 1, j and k are integers of 1 or more, R a is a hydrogen atom or a 1-valent organic group, and R b is a hydrogen atom or a 1-valent organic group, different from R a.
For the synthesis of the acrylic dispersant, known methods described in Japanese patent application laid-open No. 9-62002, no. 、P.Lutz,P.Masson et al,Polym.Bull.12,79(1984),B.C.Anderson,G.D.Andrews et al,Macromolecules,14,1601(1981),K.Hatada,K.Ute,et al,Polym.J.17,977(1985),18,1037(1986),, haoya, massa Medicata Fermentata, 36,366 (1987), tokugaku Ming-Can, ganod Man, polymer paper, 46, 189 (1989), M.Kuroki, T.Aida, J.Am.Chem.Sic,109,4737 (1987), xiang Tianzhuo, mirabilitum, organic synthetic chemistry, 43,300 (1985), D.Y.Sogoh, W.R.Hertler et al, macromolecules,20,1473 (1987) and the like can be used.
As described above, the acrylic dispersant that can be used in the present invention may be an ase:Sub>A-B block copolymer or ase:Sub>A B-ase:Sub>A-B block copolymer, and the ase:Sub>A block/B block ratio constituting the copolymer is not particularly limited, but is preferably 1/99 to 80/20 (mass ratio), more preferably 5/95 to 60/40 (mass ratio), and if the ratio falls within this range, there is ase:Sub>A tendency that the balance between dispersibility and storage stability can be ensured.
In addition, in 1g can be used in the invention of the A-B block copolymer, B-A-B block copolymer, quaternary ammonium salt group amount is usually preferably 0.1-10 mmol, by making the range, can ensure good dispersion tendency.
On the other hand, such an acrylic dispersant may contain an amino group. The amine value of the acrylic dispersant is usually about 1 to 130mgKOH/g, preferably 10mgKOH/g or more, more preferably 30mgKOH/g or more, still more preferably 50mgKOH/g or more, particularly preferably 60mgKOH/g or more, and further preferably 120mgKOH/g or less, more preferably 100mgKOH/g or less, still more preferably 90mgKOH/g or less, particularly preferably 80mgKOH/g or less. When the content is equal to or higher than the lower limit, dispersibility tends to be good, and when the content is equal to or lower than the upper limit, storage stability after dispersion tends to be good. The combination of the upper limit and the lower limit is preferably 10to 120mgKOH/g, more preferably 30 to 100mgKOH/g, still more preferably 50 to 90mgKOH/g, particularly preferably 60 to 80mgKOH/g.
The amine value of the acrylic dispersant was expressed by the KOH mass corresponding to the alkali content of 1g of the solid component excluding the solvent in the dispersant sample, and was measured by the following method.
0.5 To 1.5g of the dispersant sample was precisely weighed in a 100mL beaker, dissolved in 50mL of acetic acid, and the solution was subjected to neutralization titration with 0.1mol/L of HClO 4 acetic acid solution using an automatic titration apparatus equipped with a pH electrode, and the inflection point of the titration pH curve was used as the titration end point, and the amine value was determined according to the following formula.
Amine value [ mgKOH/g ] = (561 XV)/(W X S)
[ Wherein, W: the dispersant sample weights [ g ], V: titration amounts [ mL ], S: the solid content concentration [ mass%) of the dispersant sample is shown. ]
The weight average molecular weight (Mw) of the acrylic dispersant is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more, further preferably 4000 or more, particularly preferably 5000 or more, and is preferably 50000 or less, more preferably 20000 or less, further preferably 15000 or less. When the viscosity is equal to or higher than the lower limit, dispersibility tends to be excellent, and when the viscosity is equal to or lower than the upper limit, viscosity change tends to be less likely to occur. The combination of the upper limit and the lower limit is preferably 1000 to 50000, more preferably 3000 to 20000, further preferably 4000 to 15000, particularly preferably 5000 to 15000.
In the case where the acrylic dispersant has a quaternary ammonium salt group as a functional group, the chemical structure of the repeating unit containing the quaternary ammonium salt group is not particularly limited, but from the viewpoint of dispersibility, it is preferable that the acrylic dispersant has a repeating unit represented by the following formula (V) (hereinafter, sometimes referred to as "repeating unit (V)").
[ Chemical formula 15]
In the above formula (V), R 31～R33 is each independently a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an aralkyl group optionally having a substituent, and 2 or more of R 31～R33 may be bonded to each other to form a cyclic structure;
R 34 is a hydrogen atom or a methyl group;
X is a 2-valent linking group;
Y - is a counter anion.
The number of carbon atoms of the alkyl group optionally having a substituent in R 31～R33 of the above formula (V) is not particularly limited, and is usually 1 or more, and preferably 10 or less, more preferably 6 or less, further preferably 4 or less, and particularly preferably 2 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, and among these, methyl, ethyl, propyl, butyl, pentyl, or hexyl groups are preferable, methyl, ethyl, propyl, or butyl groups are more preferable, and methyl or ethyl groups are still more preferable. The form may be any of linear and branched. In addition, the compound may further contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
The number of carbon atoms of the aryl group optionally having a substituent in R 31～R33 of the above formula (V) is not particularly limited, and is usually 6 or more, preferably 16 or less, more preferably 12 or less. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthracenyl, and the like, and among these, phenyl, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl is preferable, and phenyl, methylphenyl, or ethylphenyl is more preferable.
The number of carbon atoms of the aralkyl group optionally having a substituent in R 31～R33 of the above formula (V) is not particularly limited, and is usually 7 or more, preferably 16 or less, and more preferably 12 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group, and among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, and a phenylbutylene group are preferable, and a phenylmethylene group and a phenylethylene group are more preferable.
Among these, from the standpoint of dispersibility, it is preferable that R 31～R33 are each independently an alkyl group or an aralkyl group, specifically, it is preferable that R 31 and R 33 are each independently a methyl group or an ethyl group, and R 32 is a phenylmethylene group or a phenylethylene group, more preferably, R 31 and R 33 are methyl groups, and R 32 is a phenylmethylene group.
In the case where the polymer dispersant has a tertiary amine as a functional group, it is preferable that the polymer dispersant has a repeating unit represented by the following formula (VI) (hereinafter, sometimes referred to as "repeating unit (VI)") from the viewpoint of dispersibility.
[ Chemical formula 16]
In the above formula (VI), R 35 and R 36 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted aralkyl group, and R 35 and R 36 may be bonded to each other to form a cyclic structure;
r 37 is a hydrogen atom or a methyl group;
z is a 2-valent linking group.
As the alkyl group optionally having a substituent in R 35 and R 36 of the above formula (VI), those exemplified as R 31～R33 of the above formula (V) can be preferably used.
Similarly, as the aryl group optionally having a substituent in R 35 and R 36 of the above formula (VI), those exemplified as R 31～R33 of the above formula (V) can be preferably used. As the aralkyl group optionally having a substituent in R 35 and R 36 of the above formula (VI), those exemplified as R 31～R33 of the above formula (V) can be preferably used.
Among these, from the viewpoint of dispersibility, R 35 and R 36 are each independently preferably an alkyl group optionally having a substituent, more preferably a methyl group or an ethyl group.
Examples of the substituent optionally contained in the alkyl group, aralkyl group or aryl group in R 31～R33 of the above formula (V) and R 35 and R 36 of the above formula (VI) include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group.
In the above formulae (V) and (VI), examples of the 2-valent linking groups X and Z include: alkylene of 1 to 10 carbon atoms, arylene of 6 to 12 carbon atoms, -CONH-R 43 -group, -COOR 44 -group [ wherein R 43 and R 44 are single bonds, alkylene of 1 to 10 carbon atoms or ether group (alkyloxyalkyl) of 2 to 10 carbon atoms ], etc., preferably-COO-R 44 -group, more preferably-COO-C 2H4 -group.
In the above formula (V), Y - as a counter anion is Cl-、Br-、I-、ClO4 -、BF4 -、CH3COO-、PF6 - or the like.
The content of the repeating unit represented by the formula (V) is not particularly limited, but is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, and is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, particularly preferably 30 mol% or more, with respect to the total of the content of the repeating unit represented by the formula (V) and the content of the repeating unit represented by the formula (VI) from the viewpoint of dispersibility. The combination of the upper limit and the lower limit is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 20 to 40 mol%, particularly preferably 30 to 35 mol%.
The content of the repeating unit represented by the formula (V) in the total repeating units of the dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, particularly preferably 10 mol% or more, and is preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, particularly preferably 15 mol% or less, from the viewpoint of dispersibility. The combination of the upper limit and the lower limit is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, even more preferably 8 to 20 mol%, particularly preferably 10 to 15 mol%.
The content of the repeating unit represented by the formula (VI) is not particularly limited, but is preferably 100 mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less, particularly preferably 70 mol% or less, and further preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, particularly preferably 60 mol% or more, with respect to the total of the content of the repeating unit represented by the formula (V) and the content of the repeating unit represented by the formula (VI) from the viewpoint of dispersibility. The combination of the upper limit and the lower limit is preferably 10 to 100 mol%, more preferably 30 to 90 mol%, still more preferably 50 to 80 mol%, particularly preferably 60 to 70 mol%.
The content of the repeating unit represented by the formula (VI) in the total repeating units of the dispersant is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, particularly preferably 20 mol% or more, and is preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, particularly preferably 25 mol% or less, from the viewpoint of dispersibility. The combination of the upper limit and the lower limit is preferably 5 to 600 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 30 mol%, particularly preferably 20 to 25 mol%.
In addition, from the viewpoint of improving compatibility with an adhesive component such as a solvent and improving dispersion stability, the acrylic dispersant preferably has a repeating unit represented by the following formula (VII) (hereinafter, sometimes referred to as "repeating unit (VII)").
[ Chemical formula 17]
In the above formula (VII), R 40 is ethylene or propylene;
r 41 is optionally substituted alkyl;
R 42 is a hydrogen atom or a methyl group;
n is an integer of 1 to 20.
The number of carbon atoms of the alkyl group optionally having a substituent in R 41 of the above formula (VII) is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less, and further preferably 4 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like, and among these, methyl, ethyl, propyl, butyl, pentyl, or hexyl is preferable, and methyl, ethyl, propyl, or butyl is more preferable. The form may be any of linear and branched. In addition, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be contained.
In addition, n in the above formula (VII) is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, from the viewpoints of compatibility with and dispersibility in an adhesive component such as a solvent. The combination of the upper limit and the lower limit is preferably an integer of 1 to 10, more preferably an integer of 2 to 5.
The content of the repeating unit represented by the formula (VII) in the total repeating units of the dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less. In the case of the above range, compatibility with an adhesive component such as a solvent and dispersion stability tend to be simultaneously achieved. The combination of the upper limit and the lower limit is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol%.
In addition, from the viewpoint of improving the compatibility of the dispersant with an adhesive component such as a solvent and improving the dispersion stability, the acrylic dispersant preferably has a repeating unit represented by the following general formula (VIII) (hereinafter, sometimes referred to as "repeating unit (VIII)").
[ Chemical formula 18]
In the above formula (VIII), R 38 is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group;
r 39 is a hydrogen atom or a methyl group.
The number of carbon atoms of the alkyl group optionally having a substituent in R 3 of the above formula (VIII) is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and further preferably 10 or less, more preferably 8 or less. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and 2-ethylhexyl groups, and among these, methyl, ethyl, propyl, butyl, pentyl, hexyl, and 2-ethylhexyl groups are preferable, and methyl, ethyl, propyl, butyl, and 2-ethylhexyl groups are more preferable. The form may be any of linear and branched. In addition, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be contained.
The number of carbon atoms of the aryl group optionally having a substituent in R 38 of the above formula (VIII) is not particularly limited, but is usually 6 or more, and is preferably 16 or less, more preferably 12 or less, and further preferably 8 or less. Specific examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthracenyl, and the like, and among these, phenyl, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl is preferable, and phenyl, methylphenyl, or ethylphenyl is more preferable.
The number of carbon atoms of the aralkyl group optionally having a substituent in R 38 of the above formula (VIII) is not particularly limited, but is usually 7 or more, and is preferably 16 or less, more preferably 12 or less, and further preferably 10 or less. Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group, and among these, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.
Among these, R 38 is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group or a phenylmethyl group, from the viewpoints of solvent compatibility and dispersion stability.
Examples of the substituent optionally contained in the alkyl group in R 38 include a halogen atom and an alkoxy group. Examples of the substituent optionally included in the aryl group or the aralkyl group include a chain alkyl group, a halogen atom, an alkoxy group, and the like. The chain alkyl group represented by R 38 includes both a straight chain alkyl group and a branched alkyl group.
From the standpoint of dispersibility, the content of the repeating unit represented by the formula (VIII) in the total repeating units of the dispersant (in the case where the repeating unit represented by the formula (VIII) is contained in an amount of 2 or more kinds, the total content thereof) is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, and still more preferably 80 mol% or less, still more preferably 70 mol% or less. The combination of the upper limit and the lower limit is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, and even more preferably 50 to 70 mol%.
The acrylic dispersant may have a repeating unit (V), a repeating unit (VI), a repeating unit (VII), and a repeating unit other than the repeating unit (VIII). Examples of such repeating units include styrene monomers derived from styrene, α -methylstyrene and the like; (meth) acryl chloride-based monomers such as (meth) acryl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, butenyl glycidyl ether; repeating units of monomers such as N-methacryloyl morpholine.
From the viewpoint of further improving dispersibility, the acrylic dispersant is preferably a block copolymer having an a block having a repeating unit (V) and a repeating unit (VI) and a B block having no repeating unit (V) and repeating unit (VI). The block copolymer is preferably an A-B block copolymer or ase:Sub>A B-A-B block copolymer. By introducing quaternary ammonium salt groups and tertiary amino groups into the a block, the dispersing ability of the dispersant tends to be remarkably improved. The B block preferably has a repeating unit (VII), and more preferably has a repeating unit (VIII).
The A block may contain the repeating unit (V) and the repeating unit (VI) in any form of random copolymerization or block copolymerization. In addition, the repeating units (V) and (VI) may be contained in at least 2 kinds of the a blocks, respectively, in which case the repeating units may be contained in any form of random copolymerization or block copolymerization in the a blocks.
The a block may contain a repeating unit other than the repeating unit (V) and the repeating unit (VI), and examples of such repeating units include repeating units derived from the (meth) acrylic acid ester monomer described above. The content of the repeating units other than the repeating unit (V) and the repeating unit (VI) in the a block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably the a block does not contain the repeating units.
The B block may contain repeating units other than the repeating units (VII) and (VIII), and examples of such repeating units include styrene monomers derived from styrene, α -methylstyrene and the like; (meth) acryl chloride-based monomers such as (meth) acryl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, butenyl glycidyl ether; repeating units of monomers such as N-methacryloyl morpholine. The content of the repeating unit (VII) and the repeating unit other than the repeating unit (VIII) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably the B block does not contain the repeating unit.
These acrylic dispersants may be used singly or in combination of 2 or more.
In addition to the acrylic dispersant described above, the (B) dispersant may contain other polymer dispersants shown below in the colored photosensitive resin composition according to the first aspect of the present invention and the pigment dispersion according to the third aspect of the present invention.
Examples of the other polymer dispersant include: urethane dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants formed from a monomer having an amino group and a macromonomer, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like.
Specific examples of such a dispersant include EFKA (registered trademark, manufactured by BASF corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie corporation), disparlon (registered trademark, manufactured by Nanj chemical Co., ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol corporation), KP (manufactured by Xinyue chemical Co., ltd.), polyflow (manufactured by Kyowa chemical Co., ltd.), ajisper (manufactured by registered trademark, manufactured by Weisu Co., ltd.).
The weight average molecular weight (Mw) of the other polymer dispersant is usually 700 or more, preferably 1000 or more, and is usually 100000 or less, preferably 50000 or less.
Among other polymer dispersants, from the viewpoint of pigment dispersibility, urethane-based polymer dispersants are preferred.
Among the urethane-based polymer dispersants, a polymer dispersant having a basic functional group and having a polyester bond and/or a polyether bond is preferable from the viewpoints of dispersibility and storage stability.
Examples of the urethane polymer dispersant include DISPERBYK160 to 167 and 182 series.
Specific examples of the preferable chemical structure of the urethane-based polymer dispersant include a dispersion resin having a weight average molecular weight of 1000 to 200000, which is obtained by reacting a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10000 and having 1 or 2 hydroxyl groups in the molecule, and a compound having an active hydrogen and a tertiary amino group in the same molecule. By treating the dispersion resin with a quaternary agent such as benzyl chloride, all or a part of the tertiary amino groups can be converted into quaternary ammonium salt groups.
Examples of the polyisocyanate compound include: aromatic diisocyanates such as p-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, 4' -diphenylmethane diisocyanate, naphthalene-1, 5-diisocyanate, tolidine diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), ω ' -diisocyanate dimethylcyclohexane, aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate, α, α, α ', α ' -tetramethylxylylene diisocyanate, lysine ester triisocyanate, undecane-1, 6, 11-triisocyanate, triisocyanate such as1, 8-diisocyanate-4-isocyanatomethyl octane, hexamethylene-1, 3, 6-triisocyanate, dicyclohexyl triisocyanate, triphenylmethane triisocyanate, thiophosphoric acid triisocyanate, and trimers, hydrogenated products, adducts thereof, and the like. As the polyisocyanate, preferred are trimers of organic diisocyanate, and most preferred are trimers of toluene diisocyanate and trimers of isophorone diisocyanate. They may be used alone or in combination of 2 or more.
The method for producing the trimer of isocyanate includes the following methods: the above polyisocyanates are partially trimerized with isocyanate groups using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc., and the trimerization is terminated by adding a catalyst poison, and then unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the target polyisocyanate containing the trimerization isocyanate groups.
Examples of the compound having a number average molecular weight of 300 to 10000 and having 1 or 2 hydroxyl groups in the same molecule include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, and the like, and a compound obtained by oxidizing one terminal hydroxyl group of the compound with an alkyl group having 1 to 25 carbon atoms, and a mixture of 2 or more of them.
Polyether diols include polyether glycol, polyether ester glycol, and mixtures of 2 or more thereof. Examples of the polyether glycol include those obtained by homo-or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene glycol propylene glycol, polyoxybutylene glycol, polyoxyhexylene glycol, polyoxyoctylene glycol, and mixtures of 2 or more thereof. Examples of the polyether ester diol include a diol having an ether group or a mixture of the diol and a dicarboxylic acid or an anhydride thereof, or a polyester diol having an alkylene oxide, such as poly (polyoxybutylene) adipate.
The polyether glycol is most preferably polyethylene glycol, polypropylene glycol, or polybutylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
As the polyester diol, there may be mentioned: aliphatic diols such as succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc. and diols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 2-methyl-1, 3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-methyl-2, 4-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2, 5-dimethyl-2, 5-hexanediol, 1, 8-octanediol, 2-methyl-1, 8-octanediol, 1, 9-nonanediol, etc., bis (hydroxymethyl) cyclohexane diol, dihydroxybenzene ethanol, bis (hydroxyethoxy) benzene alcohol, etc. are polycondensed to give aromatic diols such as N-diethanol, etc., for example, polyethylene adipate, polybutylene adipate, 1, 6-hexanediol adipate, polyethylene glycol propylene adipate and the like, or polylactone diol or polylactone monohydric alcohol obtained by using the above-mentioned diol or monohydric alcohol having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone diol, polymethyl valerolactone and their mixture of 2 kinds or more. As the polyester diol, polycaprolactone diol or polycaprolactone obtained by using an alcohol having 1 to 25 carbon atoms as an initiator is most preferable.
The polycarbonate diol includes poly (1, 6-hexanediol) ester, poly (3-methyl-1, 5-pentanediol) ester, and the polyolefin diol includes polybutadiene diol, hydrogenated polyisoprene diol, and the like.
They may be used alone or in combination of 2 or more.
The number average molecular weight of the compound having 1 or 2 hydroxyl groups in the same molecule is usually 300 to 10000, preferably 500 to 6000, more preferably 1000 to 4000.
The compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described.
Examples of the active hydrogen atom, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, include a hydrogen atom in a functional group such as a hydroxyl group, an amino group or a mercapto group, and among these, a hydrogen atom of an amino group, particularly a primary amino group, is preferable.
The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, a heterocyclic structure, more specifically an imidazole ring or a triazole ring, and the like.
Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1, 3-propanediamine, N-diethyl-1, 3-propanediamine, N-dipropyl-1, 3-propanediamine, N-dibutyl-1, 3-propanediamine, N, N-dimethylethylenediamine, N-diethylethylenediamine, N-dipropylethylenediamine, N-dibutylethylenediamine, N, N-dimethyl-1, 4-butanediamine, N-diethyl-1, 4-butanediamine, N-dipropyl-1, 4-butanediamine, N-dibutyl-1, 4-butanediamine, and the like.
In addition, examples of the nitrogen-containing heterocycle in the case where the tertiary amino group has a nitrogen-containing heterocycle structure include: pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, and benzoNitrogen-containing 5-membered heterocyclic rings such as an azole ring, benzothiazole ring, and benzothiadiazole ring, and nitrogen-containing 6-membered heterocyclic rings such as a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an acridine ring, and an isoquinoline ring. Of these nitrogen-containing heterocycles, an imidazole ring or a triazole ring is preferable.
Specific examples of the compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, and 1- (2-aminoethyl) imidazole. In addition, if these compounds having a triazole ring and an amino group are specifically exemplified, 3-amino-1, 2, 4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1, 2, 4-triazole, 4-amino-4H-1, 2, 4-triazole-3, 5-diol, 3-amino-5-phenyl-1H-1, 3, 4-triazole, 5-amino-1, 4-diphenyl-1, 2, 3-triazole, 3-amino-1-benzyl-1H-2, 4-triazole, and the like can be cited. Among them, N-dimethyl-1, 3-propanediamine, N-diethyl-1, 3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1, 2, 4-triazole are preferable.
They may be used singly or in combination of 2 or more.
The preferable blending ratio of the raw materials in the production of the urethane polymer dispersant is as follows: the compound having a number average molecular weight of 300 to 10000, which has 1 or 2 hydroxyl groups in the same molecule, is 10 to 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass, relative to 100 parts by mass of the polyisocyanate compound.
The urethane polymer dispersant can be produced by a known method for producing polyurethane resins. As the solvent used in the production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, etc. are generally used; esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc.; hydrocarbons such as benzene, toluene, xylene, hexane, etc.; partial alcohols such as diacetone alcohol, isopropyl alcohol, sec-butyl alcohol, tert-butyl alcohol, and the like, and chloro compounds such as methylene chloride, chloroform, and the like; ethers such as tetrahydrofuran and diethyl ether; polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, and the like. They may be used singly or in combination of 2 or more.
In the above production, a urethane reaction catalyst is generally used. Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and tin octoate, iron-based catalysts such as iron acetylacetonate and iron chloride, tertiary amines such as triethylamine and triethylenediamine, and the like. They may be used singly or in combination of 2 or more.
The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule to be introduced is preferably an amount in which the amine value after the reaction is controlled to be in the range of 1 to 100mgKOH/g, more preferably in the range of 5 to 95 mgKOH/g. The amine value is a value corresponding to the acid value in mg of KOH, which is obtained by neutralizing and titrating a basic amino group with an acid. When the amine value is less than the above range, dispersibility tends to be lowered, and when exceeding the above range, developability tends to be lowered.
In the case where an isocyanate group remains in the polymer dispersant in the above reaction, if the isocyanate group is further broken by an alcohol or an amino compound, the stability of the product with time is preferably improved.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1000 to 200000, preferably 2000 to 100000, more preferably 3000 to 50000. When the content is not less than the above-mentioned lower limit, dispersibility and dispersion stability tend to be improved, and when the content is not more than the above-mentioned upper limit, solubility is improved, dispersibility is improved, and reaction control tends to be easy.
In addition, from the viewpoint of improving dispersion stability, the (B) dispersant is preferably used in combination with a pigment derivative described later.
On the other hand, the dispersant (B) in the colored photosensitive resin composition of the second embodiment of the present invention is not limited at all as long as it can disperse the colorant (a). Specifically, the acrylic dispersant may be the above-mentioned acrylic dispersant, or may be another polymer dispersant as mentioned above. Among these, from the viewpoint of dispersibility, an acrylic dispersant or a urethane polymer dispersant is preferably contained.
[1-3] (C) Binder resin
The colored photosensitive resin composition and pigment dispersion of the present invention contain (C) a binder resin. By containing the binder resin (C), a uniform film can be obtained. (C) The binder resin is not particularly limited as long as a uniform film can be obtained, and is preferably an alkali-soluble resin from the viewpoint of solubility in an alkali developer.
In the colored photosensitive resin composition and pigment dispersion of the present invention, (C) the binder resin is characterized by comprising (C1) an epoxy (meth) acrylate resin from the viewpoint of reducing outgas. (C1) The epoxy (meth) acrylate resin has a rigid skeleton, has high heat resistance, is not easily thermally decomposed, and has a rigid skeleton, and can form a film having high crosslinkability by adopting an arrangement structure at the time of curing, and therefore, it is considered that the amount of outgas generated after the formation of a cured product is reduced.
In addition, from the viewpoint of solubility to an alkali developer, the (C1) epoxy (meth) acrylate resin is preferably a resin containing a carboxyl group or a hydroxyl group.
(C1) The epoxy (meth) acrylate resin is preferably a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond to an epoxy resin and further reacting a polybasic acid or an acid anhydride thereof. Examples include: the resin is obtained by ring-opening addition of a carboxyl group of an acid having an ethylenically unsaturated bond to an epoxy group of an epoxy resin, thereby adding the ethylenically unsaturated bond to the epoxy compound via an ester bond (-COO-) and simultaneously adding one carboxyl group of a polybasic acid anhydride to a hydroxyl group generated at this time. In addition, when a polybasic acid anhydride is added, a resin obtained by adding a polyhydric alcohol at the same time can be mentioned.
The (C1) epoxy (meth) acrylate resin is also a resin obtained by further reacting a compound having a functional group capable of reacting with a carboxyl group of the resin obtained by the reaction.
Therefore, the epoxy (meth) acrylate resin has substantially no epoxy group in chemical structure and is not limited to "(meth) acrylate", but is named as usual since an epoxy compound (epoxy resin) is a raw material and "(meth) acrylate" is a typical example thereof.
The epoxy resin herein means a raw material compound which is also a resin formed by heat curing, and can be suitably selected from known epoxy resins.
The epoxy resin may be a compound obtained by reacting a phenolic compound with an epihalohydrin. The phenolic compound is preferably a compound having a phenolic hydroxyl group of 2 or 3 or more members, and may be a monomer or a polymer.
Specific examples include: bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, triphenol epoxy resin, polymerized epoxy resin of phenol and dicyclopentane, dihydroxyfluorene type epoxy resin, dihydroxyalkylene oxyfluorene type epoxy resin, diglycidyl etherate of 9, 9-bis (4 '-hydroxyphenyl) fluorene, diglycidyl etherate of 1, 1-bis (4' -hydroxyphenyl) adamantane, and the like, and those having an aromatic ring in the main chain can be preferably used as described above.
Among them, bisphenol a epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, epoxy of a polymer of phenol and dicyclopentadiene, epoxy of 9, 9-bis (4 '-hydroxyphenyl) fluorene, epoxy resin having adamantyl group (diglycidyl etherate), epoxy resin having adamantyl group, and the like are preferable, and epoxy of a polymer of phenol and dicyclopentadiene, epoxy of 9, 9-bis (4' -hydroxyphenyl) fluorene, epoxy resin having adamantyl group are more preferable, from the viewpoint of high strength of a cured film.
Among the acids having an ethylenically unsaturated bond, ethylenically unsaturated monocarboxylic acids are preferred. Examples of the acid having an ethylenically unsaturated bond include: (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, pentaerythritol tri (meth) acrylate succinic anhydride adduct, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adduct, reaction products of dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adduct, (meth) acrylic acid and epsilon-caprolactone, and the like. Among them, (meth) acrylic acid is preferable from the viewpoint of sensitivity.
Examples of the polybasic acid (anhydride) include: succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, anhydrides thereof, and the like. Among them, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride is preferable, succinic anhydride or tetrahydrophthalic anhydride is more preferable, and tetrahydrophthalic anhydride is still more preferable from the viewpoint of reducing degassing.
By using a polyol, the molecular weight of the (C1) epoxy (meth) acrylate resin tends to be increased, and a branch is introduced into the molecule, so that the balance between the molecular weight and the viscosity tends to be obtained. In addition, the rate of introduction of an acid group into a molecule tends to be increased, and a balance of sensitivity, adhesion, and the like tends to be easily obtained.
The polyhydric alcohol is preferably, for example, 1 or 2 or more polyhydric alcohols selected from trimethylolpropane, bis (trimethylol) propane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2, 3-glycerol.
(C1) The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, still more preferably 40mgKOH/g or more, still more preferably 60mgKOH/g or more, particularly preferably 80mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 180mgKOH/g or less, still more preferably 150mgKOH/g or less, still more preferably 130mgKOH/g or less, and particularly preferably 120mgKOH/g or less. When the lower limit value is not less than the upper limit value, development of the unexposed portion tends to be improved, and when the upper limit value is not more than the upper limit value, film reduction or the like tends to be suppressed. The combination of the upper limit and the lower limit is preferably 10 to 200mgKOH/g, more preferably 20 to 180mgKOH/g, still more preferably 40 to 150mgKOH/g, still more preferably 60 to 130mgKOH/g, particularly preferably 80 to 120mgKOH/g.
(C1) The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin is not particularly limited, and is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, more preferably 4000 or more, particularly preferably 5000 or more, and is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, more preferably 10000 or less, particularly preferably 8000 or less. When the lower limit value is not less than the upper limit value, film reduction or the like tends to be suppressed, and when the lower limit value is not more than the upper limit value, development of the unexposed portion tends to be improved. The combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 2000 to 20000, further preferably 3000 to 15000, further preferably 4000 to 10000, particularly preferably 5000 to 8000.
(C1) The epoxy (meth) acrylate resin can be synthesized by a conventionally known method. Specifically, the following method may be used: the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having an ethylenically unsaturated bond is added to carry out an addition reaction, and then a polybasic acid or an anhydride thereof is added to continue the reaction.
Among them, examples of the organic solvent used in the reaction include one or more than 2 organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, quaternary ammonium salts such as tetramethyl ammonium chloride, methyltriethyl ammonium chloride, tetraethyl ammonium chloride, tetrabutyl ammonium chloride and trimethylbenzyl ammonium chloride, phosphorus compounds such as triphenylphosphine, and triphenylEqualOne or more than 2 kinds of class and the like. The polymerization inhibitor may be one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, and the like.
The acid or ester compound having an ethylenically unsaturated bond may be used in an amount of usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to the epoxy group 1 chemical equivalent of the epoxy resin. The temperature at the time of the addition reaction may be usually 60 to 150℃and preferably 80 to 120 ℃. The amount of the polybasic acid (anhydride) used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, relative to the chemical equivalent of the hydroxyl group 1 generated by the addition reaction.
(C1) The chemical structure of the epoxy (meth) acrylate resin is not particularly limited, but from the viewpoint of reducing outgassing, an epoxy (meth) acrylate resin containing a repeating unit structure represented by the following general formula (II) and/or an epoxy (meth) acrylate resin containing a partial structure represented by the following general formula (III) is preferable. The epoxy (meth) acrylate resin has high sensitivity, and therefore has good patterning performance, and has a hydrophobic skeleton and a proper dissolution rate, and therefore has good substrate adhesion. Further, unlike an acrylic resin, it is considered that the occurrence of outgas can be suppressed because it has a rigid skeleton and is tightly crosslinked by adopting a structure of alignment at the time of curing.
In particular, the epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and/or the epoxy (meth) acrylate resin having a partial structure represented by the following general formula (III) have a rigid skeleton in a large volume at the central portion, and are formed in a form in which hydrophilic sites such as (meth) acryloyl groups are developed outside, and it is considered that the development property is improved.
[ Chemical formula 19]
In the formula (II), R 11 represents a hydrogen atom or a methyl group;
R 12 represents an optionally substituted 2-valent hydrocarbon group;
the benzene ring in formula (II) is optionally further substituted with any substituent;
* Indicating the bonding location.
[ Chemical formula 20]
In the formula (III), R 13 each independently represents a hydrogen atom or a methyl group;
r 14 represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R 15 and R 16 each independently represent an optionally substituted 2-valent aliphatic group;
m and n each independently represent an integer of 0 to 2;
* Indicating the bonding location.
[ (C1-1) epoxy (meth) acrylate resin ]
With this, an epoxy (meth) acrylate resin having a repeating unit structure represented by the above general formula (II) (hereinafter, simply referred to as "(C1-1) epoxy (meth) acrylate resin") will be described in detail.
[ Chemical formula 21]
In the formula (II), R 11 represents a hydrogen atom or a methyl group;
R 12 represents an optionally substituted 2-valent hydrocarbon group;
the benzene ring in formula (II) is optionally further substituted with any substituent;
* Indicating the bonding location.
(R12)
In the above formula (II), R 12 represents a 2-valent hydrocarbon group optionally having a substituent.
Examples of the 2-valent hydrocarbon group include a 2-valent aliphatic group, a 2-valent aromatic ring group, 1 or more 2-valent aliphatic groups, and 1 or more 2-valent aromatic ring groups.
Examples of the 2-valent aliphatic group include linear, branched, and cyclic groups. Of these, a linear group is preferable from the viewpoint of developing solubility, and a cyclic group is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, more preferably 10 or less. When the lower limit value is not less than the upper limit value, a strong film is easily obtained, surface roughness is less likely to occur, adhesion to a substrate tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film is easily suppressed, and resolution tends to be improved. The combination of the upper limit and the lower limit is preferably 1 to 20, more preferably 3 to 15, and still more preferably 6 to 10.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of rigidity of the skeleton.
Specific examples of the 2-valent branched aliphatic group include isopropyl, sec-butyl, tert-butyl, and isopentyl.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 12 or less, preferably 10 or less. When the lower limit value is not less than the upper limit value, a strong film is formed and the substrate adhesion tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of the surface smoothness and sensitivity of the film tends to be suppressed, and the resolution tends to be improved. Specific examples of the 2-valent cyclic aliphatic group include: a group obtained by removing 2 hydrogen atoms from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, tricyclodecane ring, adamantane ring, cyclododecane ring, dicyclopentadiene, or the like. Among these groups, groups in which 2 hydrogen atoms are removed from the tricyclodecane ring or the adamantane ring are preferable from the viewpoint of rigidity of the skeleton.
Examples of the substituent optionally contained in the 2-valent aliphatic group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, no substitution is preferable.
The 2-valent aromatic ring group includes a 2-valent aromatic hydrocarbon ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, more preferably 10 or less. When the lower limit value is not less than the upper limit value, a strong film is easily obtained, surface roughness is less likely to occur, adhesion to a substrate tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film is easily suppressed, and resolution tends to be improved.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the 2-valent aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, and the like having 2 free valences,Ring, benzophenanthrene ring, acenaphthene ring, fluoranthene ring, fluorene ring, and the like.
The aromatic heterocycle in the 2-valent aromatic heterocycle group may be a single ring or a condensed ring. Examples of the 2-valent aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring having 2 free valences,Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisotropicAn azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring,A group of a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, or the like.
Among these, from the viewpoint of patterning characteristics, a benzene ring or naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.
Examples of the substituent optionally contained in the 2-valent aromatic ring group include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, and a glycidyl ether group. Among these, from the viewpoints of developing solubility and moisture absorption resistance, substitution is preferable.
Examples of the group formed by linking 1 or more aliphatic groups having 2 valences to 1 or more aromatic groups having 2 valences include groups formed by linking 1 or more aliphatic groups having 2 valences to 1 or more aromatic groups having 2 valences.
The number of the 2-valent aliphatic groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, a strong film is easily obtained, surface roughness is less likely to occur, adhesion to a substrate tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film is easily suppressed, and resolution tends to be improved.
The number of the 2-valent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, a strong film is easily obtained, surface roughness is less likely to occur, adhesion to a substrate tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film is easily suppressed, and resolution tends to be improved.
Specific examples of the group formed by linking 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups include groups represented by the following formulas (II-A) to (II-F). Among these groups, from the viewpoints of rigidity of the skeleton and hydrophobization of the film, a group represented by the following formula (II-a) is preferable, and in the formula, the bonding position is represented by a.
[ Chemical formula 22]
As described above, the benzene ring in formula (II) may be further substituted with an optional substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited, and may be 1 or 2 or more.
Among these, from the viewpoint of patterning characteristics, no substitution is preferable.
In addition, from the viewpoint of ease of synthesis, the repeating unit structure represented by the above formula (II) is preferably a repeating unit structure represented by the following formula (II-1).
[ Chemical formula 23]
In the formula (II-1), R 11 and R 12 have the same meaning as in the formula (II);
R X represents a hydrogen atom or a polyacid residue;
* Indicating the bonding position;
the benzene ring in the formula (II-1) may be further substituted with an optional substituent.
The polyacid residue is a 1-valent group obtained by removing 1 OH group from a polyacid or an anhydride thereof. Examples of the polybasic acid include one or more selected from the group consisting of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endo-methyltetrahydrophthalic acid, hexachloro norbornene diacid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable, and tetrahydrophthalic anhydride is still more preferable from the viewpoint of patterning characteristics.
The repeating unit structure represented by the above formula (II-1) contained in the 1-molecule (C1-1) epoxy (meth) acrylate resin may be one kind or 2 or more kinds, and for example, R X may be a hydrogen atom and R X may be a polyacid residue.
The number of repeating unit structures represented by the above formula (II) contained in the 1-molecule (C1-1) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less. When the lower limit is not less than the above-mentioned lower limit, a strong film tends to be easily obtained, and surface roughness tends not to be easily generated, and when the upper limit is not more than the above-mentioned upper limit, deterioration of surface smoothness and sensitivity of the film tends to be easily suppressed, and resolution tends to be improved.
The weight average molecular weight (Mw) of the (C1-1) epoxy (meth) acrylate resin in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is not particularly limited, and is preferably 1000 or more, more preferably 1500 or more, further preferably 2000 or more, particularly preferably 3000 or more, and is preferably 30000 or less, more preferably 20000 or less, further preferably 10000 or less, particularly preferably 8000 or less. When the ratio is equal to or higher than the lower limit, the residual film ratio of the colored photosensitive resin composition tends to be good, and when the ratio is equal to or lower than the upper limit, the resolution tends to be good. The combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 1500 to 20000, further preferably 2000 to 10000, particularly preferably 3000 to 8000.
The acid value of the (C1-1) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, still more preferably 40mgKOH/g or more, still more preferably 50mgKOH/g or more, particularly preferably 80mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 130mgKOH/g or less, particularly preferably 100mgKOH/g or less. When the ratio is equal to or higher than the lower limit, the developing solubility tends to be improved and the resolution tends to be good, and when the ratio is equal to or lower than the upper limit, the residual film ratio of the colored photosensitive resin composition tends to be good. The combination of the upper limit and the lower limit is preferably 10 to 200mgKOH/g, more preferably 20 to 150mgKOH/g, still more preferably 40 to 130mgKOH/g, still more preferably 50 to 100mgKOH/g, particularly preferably 80 to 100mgKOH/g.
Specific examples of the (C1-1) epoxy (meth) acrylate resin are shown below.
[ Chemical formula 24]
[ Chemical formula 25]
[ Chemical formula 26]
[ Chemical formula 27]
[ (C1-2) epoxy (meth) acrylate resin ]
Next, an epoxy (meth) acrylate resin having a partial structure represented by the above general formula (III) (hereinafter, simply referred to as "(C1-2) epoxy (meth) acrylate resin) will be described in detail.
[ Chemical formula 28]
In the formula (III), R 13 each independently represents a hydrogen atom or a methyl group;
r 14 represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R 15 and R 16 each independently represent an optionally substituted 2-valent aliphatic group;
m and n each independently represent an integer of 0 to 2;
* Indicating the bonding location.
(R14)
In the above general formula (III), R 14 represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.
The number of rings of the aliphatic cyclic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit is not less than the above-mentioned lower limit, a strong film tends to be easily obtained, and surface roughness tends not to be easily generated, and when the upper limit is not more than the above-mentioned upper limit, deterioration of surface smoothness and sensitivity of the film tends to be easily suppressed, and resolution tends to be improved. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 to 3.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the lower limit is not less than the above-mentioned lower limit, a strong film tends to be easily obtained, and surface roughness tends not to be easily generated, and when the upper limit is not more than the above-mentioned upper limit, deterioration of surface smoothness and sensitivity of the film tends to be easily suppressed, and resolution tends to be improved. The combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, particularly preferably 8 to 15.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornyl ring, adamantane ring, cyclododecane ring, and the like. Among these, an adamantane ring is preferable from the viewpoints of the residual film ratio and resolution of the colored photosensitive resin composition.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less, more preferably 4 or less. When the lower limit is not less than the above-mentioned lower limit, a strong film tends to be easily obtained, and surface roughness tends not to be easily generated, and when the upper limit is not more than the above-mentioned upper limit, deterioration of surface smoothness and sensitivity of the film tends to be easily suppressed, and resolution tends to be improved. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and still more preferably 3 to 4.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 15 or less. When the lower limit value is not less than the upper limit value, a strong film tends to be easily obtained, and surface roughness tends to be less likely to occur, and when the upper limit value is not more than the upper limit value, patterning characteristics tend to be good. The combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, still more preferably 10 to 15, and particularly preferably 12 to 15.
Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,Ring, benzophenanthrene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. Among these, a fluorene ring is preferable from the viewpoint of patterning characteristics.
The 2-valent hydrocarbon group of the 2-valent hydrocarbon groups having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include: a 2-valent aliphatic group, a 2-valent aromatic ring group, and a group formed by linking 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups.
Examples of the 2-valent aliphatic group include linear, branched, and cyclic groups. Of these, a linear group is preferable from the viewpoint of developing solubility, and a cyclic group is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and is preferably 25 or less, more preferably 20 or less, more preferably 15 or less. When the lower limit value is not less than the upper limit value, a strong film is easily obtained, surface roughness is less likely to occur, adhesion to a substrate tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film is easily suppressed, and resolution tends to be improved.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of rigidity of the skeleton.
Specific examples of the 2-valent branched aliphatic group include: the above-mentioned 2-valent linear aliphatic group has a structure such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like as a side chain.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, a strong film tends to be easily obtained, and adhesion to a substrate tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film tends to be easily suppressed, and resolution tends to be improved. Specific examples of the 2-valent cyclic aliphatic group include groups obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, from the viewpoint of rigidity of the skeleton, a group in which 2 hydrogen atoms are removed from the adamantane ring is preferable.
Examples of the substituent optionally contained in the 2-valent aliphatic group include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, no substitution is preferable.
The 2-valent aromatic ring group includes a 2-valent aromatic hydrocarbon ring group and a 2-valent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, more preferably 15 or less. When the lower limit value is not less than the upper limit value, a strong film is easily obtained, surface roughness is less likely to occur, adhesion to a substrate tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film is easily suppressed, and resolution tends to be improved.
The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the 2-valent aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, and the like having 2 free valences,Ring, benzophenanthrene ring, acenaphthene ring, fluoranthene ring, fluorene ring, and the like.
The aromatic heterocycle in the 2-valent aromatic heterocycle group may be a single ring or a condensed ring. Examples of the 2-valent aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring having 2 free valences,Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisotropicAn azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring,A group of a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, or the like. Among these, from the viewpoint of patterning characteristics, a benzene ring or naphthalene ring having 2 free valences is preferable, and a fluorene ring having 2 free valences is more preferable.
A substituent optionally contained in the 2-valent aromatic ring group, such as a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, from the viewpoint of developing solubility, unsubstituted ones are preferable.
Examples of the group formed by linking 1 or more aliphatic groups having 2 valences to 1 or more aromatic groups having 2 valences include groups formed by linking 1 or more aliphatic groups having 2 valences to 1 or more aromatic groups having 2 valences.
The number of the 2-valent aliphatic groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, a strong film is easily obtained, surface roughness is less likely to occur, adhesion to a substrate tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film is easily suppressed, and resolution tends to be improved.
The number of the 2-valent aromatic ring groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 10 or less, preferably 5 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, a strong film is easily obtained, surface roughness is less likely to occur, adhesion to a substrate tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film is easily suppressed, and resolution tends to be improved.
Specific examples of the group formed by linking 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic ring groups include the groups represented by the above formulas (II-A) to (II-F). Among these groups, the group represented by the above formula (II-C) or the group represented by the above formula (II-D) is preferable from the viewpoints of rigidity of the skeleton and hydrophobization of the film.
The bonding method of the cyclic hydrocarbon group as the side chain is not particularly limited, and examples thereof include: the side chain is substituted with 1 hydrogen atom of an aliphatic group or an aromatic ring group, or 1 carbon atom of an aliphatic group is contained to form a cyclic hydrocarbon group as a side chain.
(R15、R16)
In the above general formula (III), R 15 and R 16 each independently represent a 2-valent aliphatic group optionally having a substituent.
Examples of the 2-valent aliphatic group include linear, branched, and cyclic groups. Of these, a linear group is preferable from the viewpoint of developing solubility, and a cyclic group is preferable from the viewpoint of reducing penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, more preferably 10 or less. When the lower limit value is not less than the upper limit value, a strong film is easily obtained, surface roughness is less likely to occur, adhesion to a substrate tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film is easily suppressed, and resolution tends to be improved.
Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of rigidity of the skeleton.
Specific examples of the 2-valent branched aliphatic group include: the above-mentioned 2-valent linear aliphatic group has a structure such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like as a side chain.
The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 12 or less, preferably 10 or less. When the lower limit value is not less than the upper limit value, a strong film tends to be easily obtained, and adhesion to a substrate tends to be good, and when the upper limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film tends to be easily suppressed, and resolution tends to be improved. Specific examples of the 2-valent cyclic aliphatic group include groups obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and dicyclopentadiene. Among these, from the viewpoint of rigidity of the skeleton, a group in which 2 hydrogen atoms are removed from the adamantane ring is preferable.
Examples of the substituent optionally contained in the 2-valent aliphatic group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, no substitution is preferable.
(m、n)
In the general formula (III), m and n each independently represent an integer of 0 to 2. When the ratio is equal to or higher than the lower limit, patterning suitability is improved, and surface roughness is less likely to occur, and when the ratio is equal to or lower than the upper limit, development is improved. From the viewpoint of developability, m and n are preferably 0, while from the viewpoints of patterning suitability and surface roughness, m and n are preferably 1 or more each independently.
In addition, from the viewpoint of adhesion to a substrate, the partial structure represented by the above general formula (III) is preferably a partial structure represented by the following general formula (III-1).
[ Chemical formula 29]
In the formula (III-1), R 13、R15、R16, m and n have the same meanings as those of the formula (III);
R α represents a 1-valent cyclic hydrocarbon group optionally having a substituent;
p is an integer of 1 or more;
the benzene ring in formula (III-1) is optionally further substituted with an optional substituent;
* Indicating the bonding location.
(Rα)
In the above general formula (III-1), R α represents a 1-valent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.
The number of rings of the aliphatic cyclic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and is usually 6 or less, preferably 4 or less, more preferably 3 or less. When the lower limit value is not less than the upper limit value, a strong film tends to be easily obtained, and surface roughness tends to be less likely to occur, and when the upper limit value is not more than the upper limit value, patterning characteristics tend to be good. The combination of the upper limit and the lower limit is preferably 1 to 6, more preferably 2 to 4, and further preferably 2 to 3.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the lower limit value is not less than the upper limit value, a strong film tends to be easily obtained, and surface roughness tends to be less likely to occur, and when the upper limit value is not more than the upper limit value, patterning characteristics tend to be good. The combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, particularly preferably 8 to 15.
Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring, and the like. Among these, an adamantane ring is preferable from the viewpoint of strong film characteristics.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the lower limit value is not less than the upper limit value, a strong film tends to be easily obtained, and surface roughness tends to be less likely to occur, and when the upper limit value is not more than the upper limit value, patterning characteristics tend to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 3 to 5.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and is preferably 30 or less, more preferably 20 or less, more preferably 15 or less. When the lower limit value is not less than the upper limit value, a strong film tends to be easily obtained, and surface roughness tends to be less likely to occur, and when the upper limit value is not more than the upper limit value, patterning characteristics tend to be good. The combination of the upper limit and the lower limit is preferably 4 to 30, more preferably 5 to 20, and still more preferably 6 to 15.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, and the like. Among these, a fluorene ring is preferable from the viewpoint of developing solubility.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: alkyl groups having 1 to 5 carbon atoms such as hydroxyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group and the like; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, no substitution is preferable.
P represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. When the lower limit value is not less than the upper limit value, the film curing degree and the film residue ratio tend to be good, and when the upper limit value is not more than the upper limit value, the development property tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 3, more preferably 2 to 3.
Among these, from the viewpoint of the strong film curing degree, R α is preferably a 1-valent aliphatic cyclic group, and more preferably an adamantyl group.
As described above, the benzene ring in formula (III-1) is optionally further substituted with an optional substituent. Examples of the substituent include: hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of substituents is not particularly limited, and may be 1 or 2 or more.
Among these, from the viewpoint of patterning characteristics, no substitution is preferable.
Specific examples of the partial structure represented by the above formula (III-1) are given below.
[ Chemical formula 30]
[ Chemical formula 31]
[ Chemical formula 32]
[ Chemical formula 33]
[ Chemical formula 34]
From the viewpoints of rigidity of the skeleton and membrane hydrophobization, the partial structure represented by the general formula (III) is preferably a partial structure represented by the following general formula (III-2).
[ Chemical formula 35]
In the formula (III-2), R 13、R15、R16, m and n have the same meanings as those of the formula (III);
r β represents an optionally substituted 2-valent cyclic hydrocarbon group;
the benzene ring in formula (III-2) is optionally further substituted with an optional substituent;
* Indicating the bonding location.
(Rβ)
In the above formula (III-2), R β represents a 2-valent cyclic hydrocarbon group.
Examples of the cyclic hydrocarbon group include an aliphatic cyclic group and an aromatic cyclic group.
The number of rings of the aliphatic cyclic group is not particularly limited, and is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the lower limit is not less than the above-mentioned lower limit, a strong film tends to be easily obtained, and surface roughness tends not to be easily generated, and when the upper limit is not more than the above-mentioned upper limit, deterioration of surface smoothness and sensitivity of the film tends to be easily suppressed, and resolution tends to be improved. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5.
The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less carbon atoms. When the lower limit value is not less than the upper limit value, the film roughness during development tends to be suppressed, and when the lower limit value is not more than the upper limit value, the film surface smoothness and sensitivity deterioration tend to be suppressed, and the resolution tends to be improved. The combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 35, and further preferably 8 to 30.
Specific examples of the aliphatic ring in the aliphatic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring, and the like. Among these, an adamantane ring is preferable from the viewpoint of storage stability.
On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is usually 10 or less, preferably 5 or less. When the lower limit is not less than the above-mentioned lower limit, a strong film tends to be easily obtained, and surface roughness tends not to be easily generated, and when the upper limit is not more than the above-mentioned upper limit, deterioration of surface smoothness and sensitivity of the film tends to be easily suppressed, and resolution tends to be improved. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5, and further preferably 3 to 5.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. When the lower limit is not less than the above-mentioned lower limit, a strong film tends to be easily obtained, and surface roughness tends not to be easily generated, and when the upper limit is not more than the above-mentioned upper limit, deterioration of surface smoothness and sensitivity of the film tends to be easily suppressed, and resolution tends to be improved. The combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, particularly preferably 10 to 15.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, and the like. Among these, a fluorene ring is preferable from the viewpoint of developability.
Examples of the substituent optionally contained in the cyclic hydrocarbon group include: alkyl groups having 1 to 5 carbon atoms such as hydroxyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group and the like; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, no substitution is preferable.
Among these, R β is preferably a 2-valent aliphatic cyclic group, more preferably a 2-valent adamantane cyclic group, from the viewpoints of storage stability and electrical characteristics.
On the other hand, from the viewpoint of low hygroscopicity and patterning characteristics of the coating film, R β is preferably a 2-valent aromatic ring group, more preferably a 2-valent fluorene ring group.
As described above, the benzene ring in the formula (III-2) may be further substituted with an optional substituent. Examples of the substituent include: hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of substituents is not particularly limited, and may be 1 or 2 or more. In addition, 2 benzene rings in the formula (III-2) may be bonded together via these substituents.
Among these, from the viewpoint of patterning characteristics, no substitution is preferable. In addition, from the viewpoint of less tendency to cause film reduction, etc., methyl substitution is preferable.
Specific examples of the partial structure represented by the above formula (III-2) are given below.
[ Chemical formula 36]
[ Chemical formula 37]
[ Chemical formula 38]
[ Chemical formula 39]
On the other hand, from the viewpoints of film residue and patterning characteristics, the partial structure represented by the above formula (III) is preferably a partial structure represented by the following formula (III-3).
[ Chemical formula 40]
In the formula (III-3), R 13、R14、R15、R16, m and n have the same meanings as those of the formula (III);
R Z represents a hydrogen atom or a polyacid residue.
The polyacid residue is a 1-valent group obtained by removing 1 OH group from a polyacid or an anhydride thereof. It should be noted that 1 OH group may be further removed to be shared with R Z in the other molecule represented by formula (III-3), that is, a plurality of molecules represented by formula (III-3) may be linked by R Z.
Examples of the polybasic acid include one or more selected from the group consisting of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endo-methyltetrahydrophthalic acid, hexachloro norbornene diacid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable from the viewpoint of patterning characteristics.
The partial structure represented by the above formula (III-3) contained in the 1-molecule (C1-2) epoxy (meth) acrylate resin may be one kind or 2 or more kinds, and for example, R Z may be a hydrogen atom and R Z may be a polyacid residue.
The number of the partial structures represented by the above formula (III) contained in the 1-molecule (C1-2) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and is preferably 20 or less, more preferably 15 or less, and further preferably 10 or less. When the lower limit value is not less than the upper limit value, a strong film is easily obtained, surface roughness is less likely to occur, and electric characteristics are likely to be improved, and when the lower limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film is likely to be suppressed, and resolution is likely to be improved.
The weight average molecular weight (Mw) of the (C1-2) epoxy (meth) acrylate resin in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, further preferably 3000 or more, particularly preferably 3500 or more, and is preferably 30000 or less, more preferably 20000 or less, further preferably 10000 or less, further preferably 7000 or less, particularly preferably 5000 or less. When the lower limit value is not less than the upper limit value, patterning characteristics tend to be good, and when the upper limit value is not more than the upper limit value, a strong film tends to be easily obtained, and surface roughness tends to be less likely to occur. The combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 2000 to 20000, further preferably 3000 to 10000, further preferably 3500 to 7000, particularly preferably 3500 to 5000.
The acid value of the (C1-2) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10mgKOH/g or more, more preferably 20mgKOH/g or more, still more preferably 40mgKOH/g or more, still more preferably 60mgKOH/g or more, particularly preferably 80mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, still more preferably 120gKOH/g or less. When the lower limit value is not less than the upper limit value, a strong film tends to be easily obtained, and when the lower limit value is not more than the upper limit value, development solubility tends to be improved and resolution tends to be good. The combination of the upper limit and the lower limit is preferably 10 to 200mgKOH/g, more preferably 20 to 150mgKOH/g, still more preferably 40 to 150mgKOH/g, still more preferably 60 to 120mgKOH/g, particularly preferably 80 to 120mgKOH/g.
The binder resin (C) contained in the colored photosensitive resin composition and pigment dispersion of the present invention may contain a binder resin other than the (C1) epoxy (meth) acrylate resin (hereinafter, simply referred to as "(C2) other binder resin").
As the other binder resin (C2), for example, there may be mentioned: acrylic resin, carboxyl group-containing epoxy resin, carboxyl group-containing urethane resin, novolak resin, polyvinyl phenol resin, etc., and these resins may be used alone or in combination of two or more.
In the colored photosensitive resin composition of the present invention, the (C) binder resin contains 75 mass% or more of (C1) epoxy (meth) acrylate resin. By incorporating 75 mass% or more of the (C1) epoxy (meth) acrylate resin in the (C) binder resin, it is considered that the heat resistance of the cured product is also improved, and the amount of outgas generated after formation of the cured product can be reduced.
(C1) The content of the epoxy (meth) acrylate resin relative to the binder resin (C) is not particularly limited, but is preferably 80% by weight or more, more preferably 85% by weight or more, still more preferably 90% by weight or more, particularly preferably 95% by weight or more, and is usually 100% by weight or less. When the lower limit value is not less than the above, the degassing tends to be suppressed. The combination of the upper limit and the lower limit is preferably 75 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.
[1-4] (D) photopolymerizable monomer
The colored photosensitive resin composition of the present invention comprises (D) a photopolymerizable monomer. By including (D) the photopolymerizable monomer, the sensitivity is improved.
The photopolymerizable monomer (D) used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specific examples include: and (meth) acrylic acid, alkyl (meth) acrylate, acrylonitrile, styrene, and esters of carboxylic acids having 1 ethylenically unsaturated bond with polyhydric alcohols or monohydric alcohols.
In the present invention, it is particularly desirable to use a polyfunctional olefinic monomer having 2 or more ethylenically unsaturated groups in 1 molecule. The number of the ethylenic unsaturated bonds of the polyfunctional olefinic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and is preferably 8 or less, more preferably 7 or less. When the lower limit value is not less than the upper limit value, the sensitivity tends to be high, and when the upper limit value is not more than the upper limit value, the solubility in a solvent tends to be improved. The combination of the upper limit and the lower limit is preferably 2 to 8, more preferably 4 to 8, and even more preferably 5 to 7.
As examples of the polyfunctional olefinic monomer, there may be mentioned, for example: esters of aliphatic polyhydroxy compounds with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of a polyhydroxy compound such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound with an unsaturated carboxylic acid and a polycarboxylic acid.
Examples of the esters of the aliphatic polyhydroxy compounds and unsaturated carboxylic acids include esters of aliphatic polyhydroxy compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylates obtained by replacing the acrylates of these exemplified compounds with methacrylates, itaconic esters obtained by similarly replacing the acrylates with itaconic esters, crotonates obtained by replacing the crotonates, and maleic acid esters obtained by replacing the maleates.
Examples of the ester of the aromatic polyhydroxy compound with the unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and 1,2, 3-trimellitic acid triacrylate.
The ester obtained by the esterification reaction of the polycarboxylic acid and the unsaturated carboxylic acid with the polyhydroxy compound is not necessarily a single substance, and a typical specific example thereof is a condensate of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensation products of methacrylic acid, terephthalic acid and pentaerythritol; condensation products of acrylic acid, adipic acid, butanediol, and glycerol, and the like.
Further, as examples of the polyfunctional olefinic monomer used in the present invention, urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reaction products of a polyvalent epoxy compound and a hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate are useful.
Examples of the urethane (meth) acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Japanese chemical Co., ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by New Zhongcun chemical Co., ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Co Rong She chemical Co., ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV B (manufactured by Japanese synthetic chemical Co., ltd.), and the like.
Among these, from the viewpoint of curability, as the (D) photopolymerizable monomer, an alkyl (meth) acrylate is preferably used, and dipentaerythritol hexaacrylate is more preferably used.
They may be used alone or in combination of 2 or more.
[1-5] (E) photopolymerization initiator
The colored photosensitive resin composition of the present invention contains (E) a photopolymerization initiator. (E) The photopolymerization initiator is a component that directly absorbs light to cause a decomposition reaction or a hydrogen abstraction reaction, and thus has a function of generating a polymerization active radical. If necessary, additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be added.
Examples of the photopolymerization initiator include metallocene compounds containing a titanium compound described in Japanese patent application laid-open No. 59-152396 and Japanese patent application laid-open No. 61-151197; hexaarylbisimidazole derivatives described in Japanese patent application laid-open No. 2000-56118; halomethylation described in Japanese patent application laid-open No. 10-39503Diazole derivatives, halomethyl s-triazine derivatives, N-aryl-alpha-amino acids such as N-phenylaminoacetic acid, N-aryl-alpha-amino acid salts, radical activators such as N-aryl-alpha-amino acid esters, and alpha-aminoalkylbenzophenone derivatives; and oxime ester derivatives described in JP 2000-80068A, JP 2006-367550A, etc.
Specifically, examples of the titanium-containing derivatives include: dicyclopentadiene titanium dichloride, dicyclopentadiene diphenyl titanium, dicyclopentadiene bis (2, 3,4,5, 6-pentafluorobenz-1-yl) titanium, dicyclopentadiene bis (2, 3,5, 6-tetrafluoro-ben-1-yl) titanium, dicyclopentadiene bis (2, 4, 6-trifluoroben-1-yl) titanium, dicyclopentadiene bis (2, 6-difluoroben-1-yl) titanium, dicyclopentadiene bis (2, 4-difluoroben-1-yl) titanium, bis (methylcyclopentadienyl) bis (2, 3,4,5, 6-pentafluorobenz-1-yl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluoroben-1-yl) titanium, dicyclopentadiene [2, 6-difluoro-3- (prop-1-yl) -ben-1-yl ] titanium, and the like.
Further, examples of the diimidazole derivatives include: 2- (2 '-chlorophenyl) -4, 5-diphenylimidazole 2-mer, 2- (2' -chlorophenyl) -4, 5-bis (3 '-methoxyphenyl) imidazole 2-mer, 2- (2' -fluorophenyl) -4, 5-diphenylimidazole 2-mer, 2- (2 '-methoxyphenyl) -4, 5-diphenylimidazole 2-mer, (4' -methoxyphenyl) -4, 5-diphenylimidazole 2-mer, and the like.
In addition, as halomethylationThe diazole derivatives include: 2-trichloromethyl-5- (2' -benzofuranyl) -1,3,4-Diazole, 2-trichloromethyl-5- [ beta- (2' -benzofuranyl) vinyl ] -1,3,4-Diazole, 2-trichloromethyl-5- [ beta- (2' - (6 "-benzofuranyl) vinyl) ] -1,3,4-Diazole, 2-trichloromethyl-5-furyl-1, 3,4-Diazoles, and the like.
Examples of the halomethyl s-triazine derivatives include: 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxynaphthyl) -4, 6-bis (trichloromethyl) s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4, 6-bis (trichloromethyl) s-triazine, and the like.
Further, examples of the α -aminoalkylbenzophenone derivatives include: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisopentyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, and the like.
As the photopolymerization initiator, oxime ester derivatives (oxime ester compounds and ketoxime ester compounds) are effective in terms of sensitivity and plateability, and the use of an alkali-soluble resin containing a phenolic hydroxyl group is disadvantageous in terms of sensitivity, so that oxime ester derivatives (oxime ester compounds and ketoxime ester compounds) having excellent sensitivity are particularly useful.
Examples of the oxime ester compound include compounds having a partial structure represented by the following general formula (IX), and oxime ester compounds represented by the following general formula (IX-A) are preferable.
[ Chemical formula 41]
In the formula (IX), R 22 represents an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkylacyl group having 3 to 8 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminoalkylcarbonyl group having 2 to 10 carbon atoms, an aroyl group having 7 to 20 carbon atoms, a heteroarylaroyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms or an aryloxycarbonyl group having 7 to 20 carbon atoms, respectively.
[ Chemical formula 42]
In the formula (IX-A), R 21a represents a hydrogen atom, or an optionally substituted alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 25 carbon atoms, heteroarylalkyl group having 1 to 20 carbon atoms, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl group or heteroarylsulfanyl group having 1 to 20 carbon atoms, aminoalkyl group having 1 to 20 carbon atoms, alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkylacyl group having 3 to 8 carbon atoms, aroyl group having 7 to 20 carbon atoms, heteroaroyl group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, or cycloalkylalkyl group having 1 to 10 carbon atoms, respectively;
R 21b represents an optional substituent comprising an aromatic hydrocarbon ring or an aromatic heterocyclic ring (heteroaromatic ring).
R 21a may be bonded to R 21b to form a ring, and examples of the bonding group include an alkylene group having 1 to 10 carbon atoms, a polyethylene group (- (CH=CH) r -), a polyethylenic group (- (C≡C) r -), or a combination thereof, each of which may have a substituent (where R is an integer of 0 to 3).
In the formula (IX-A), R 22a represents an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroaryloxyalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkylacyl group having 3 to 8 carbon atoms, an alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminocarbonyl group having 2 to 10 carbon atoms, an aroyl group having 7 to 20 carbon atoms, a heteroarylacyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms or an aryloxycarbonyl group having 7 to 20 carbon atoms.
R 22 in the above general formula (IX) and R 22a in the above general formula (IX-A) are preferably alkanoyl groups having 2 to 12 carbon atoms, heteroaryloxyalkanoyl groups having 1 to 20 carbon atoms or cycloalkanoyl groups having 3 to 8 carbon atoms.
As R 21a in the above general formula (IX-A), unsubstituted methyl, ethyl, propyl, and propyl substituted with N-acetyl-N-acetoxyamino are preferable.
Further, R 21b in the above general formula (IX-A) is preferably an optionally substituted carbazolyl group, an optionally substituted fluorenyl group, an optionally substituted thioxanthonyl group or an optionally substituted phenylsulfide group.
Examples of the substituent of any of the above general formulae (IX) and (IX-A) include: alkyl, aromatic hydrocarbon ring (aryl), aliphatic ring, aromatic heterocyclic, halogen, hydroxyl, carboxyl, amino, amide, etc.
The oxime ester compounds preferred in the present invention are specifically exemplified by the following compounds, but are not limited thereto.
[ Chemical formula 43]
[ Chemical formula 44]
The ketoxime ester compound may be a compound having a partial structure represented by the following general formula (X), and the ketoxime ester compound represented by the following general formula (X-A) is preferable.
[ Chemical formula 45]
In the above general formula (X), R 24 has the same meaning as R 22 in the above general formula (IX).
[ Chemical formula 46]
In the above general formula (X-A), R 23a represents an optionally substituted phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthio alkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an aroyl group having 7 to 20 carbon atoms, a heteroarylacyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms;
r 23b represents an optional substituent comprising an aromatic hydrocarbon ring or an aromatic heterocyclic ring (heteroaromatic ring).
R 23a may be bonded to R 23b to form a ring, and examples of the bonding group include an alkylene group having 1 to 10 carbon atoms, a polyethylene group (- (CH=CH) r -), a polyethylenic group (- (C≡C) r -), or a combination thereof, each of which may have a substituent (where R is an integer of 0 to 3).
In the general formula (X-A), R 24a represents an optionally substituted alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkyloyl group having 4 to 8 carbon atoms, benzoyl group having 7 to 20 carbon atoms, heteroaroyl having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, or alkylaminocarbonyl group having 2 to 20 carbon atoms, respectively.
R 24 in the above general formula (X) and R 24a in the above general formula (X-A) are preferably alkanoyl groups having 2 to 12 carbon atoms, heteroaryloxyalkanoyl groups having 1 to 20 carbon atoms, cycloalkanoyl groups having 3 to 8 carbon atoms or aroyl groups having 7 to 20 carbon atoms.
R 23a in the above general formula (X-A) is preferably an unsubstituted ethyl group, propyl group, butyl group, or ethyl or propyl group substituted with methoxycarbonyl group.
Further, R 23b in the above general formula (X-A) is preferably an optionally substituted carbazolyl group, an optionally substituted fluorenyl group or an optionally substituted phenylsulfide group.
Examples of the optional substituent in the general formulae (X) and (X-A) include: alkyl, aromatic hydrocarbon ring (aryl), aliphatic ring, aromatic heterocyclic, halogen, hydroxyl, carboxyl, amino, amide, etc.
The ketoxime ester compounds preferred in the present invention are specifically exemplified by the following compounds, but are not limited thereto.
[ Chemical formula 47]
[ Chemical formula 48]
These oxime ester compounds and ketoxime ester compounds are known per se, and are one of a series of compounds described in, for example, japanese patent application laid-open No. 2000-80068 and Japanese patent application laid-open No. 2006-3679. In the present invention, the photopolymerization initiator (E) is preferably an oxime ester compound and/or a ketoxime ester compound from the viewpoint of sensitivity.
The photopolymerization initiator may be used alone or in combination of 2 or more.
The photopolymerization initiator (E) may be exemplified by, in addition to the above-mentioned substances: benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; benzophenone derivatives such as benzophenone, michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone; acetophenone derivatives such as 2, 2-dimethoxy-2-phenylacetophenone, 2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α -hydroxy-2-methylphenyl acetone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- (4' -methylthiophenyl) -2-morpholinopropane-1-one, and 1, 1-trichloromethyl (p-butylphenyl) ketone; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, and 2, 4-diisopropylthioxanthone; benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; phenazine derivatives such as 9, 10-dimethylbenzophenazine (9, 10-dimethylbenzphenazine); and anthrone derivatives such as benzanthrone.
Among these photopolymerization initiators, the following compounds are more preferable as the compounds containing the partial structure represented by the above general formula (IX) among oxime ester derivatives from the viewpoints of sensitivity, solubility in solvents and pattern adhesion upon development,
[ Chemical formula 49]
[ Chemical formula 50]
Or the following compounds as the compounds containing the partial structure represented by the above general formula (X).
[ Chemical formula 51]
[ Chemical formula 52]
[ Chemical formula 53]
(E) The photopolymerization initiator may be used alone or in combination of 2 or more.
In order to improve the sensitivity, a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source may be blended into the photopolymerization initiator (E) as needed. Examples of the sensitizing dye include: the xanthene dye described in Japanese patent application laid-open No. 4-221958, japanese patent application laid-open No. 4-219756, japanese patent application laid-open No. 3-239703, japanese patent application laid-open No. 5-289335, coumarin dye having a heterocyclic ring, 3-oxocoumarin compound described in Japanese patent application laid-open No. 3-239703, japanese patent application laid-open No. 5-289335, methylenepyrrole dye described in Japanese patent application laid-open No. 6-19240, and amino groups such as those described in Japanese patent application laid-open No. 47-2528, japanese patent application laid-open No. 54-155292, japanese patent application laid-open No. 45-37377, japanese patent application laid-open No. 48-84183, japanese patent application laid-open No. 52-112681, japanese patent application laid-open No. 58-15503, japanese patent application laid-60-88005, japanese patent application laid-open No. 59-56403, japanese patent application laid-2-69, japanese patent application laid-open No. 57-168088, japanese patent application laid-open No. 5-107761, japanese patent application laid-open No. 5-open No. 45-37377, japanese patent application laid-open No. 5-32240, and Japanese patent application laid-open No. 5-288818 have an amino group such as a skeleton. Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are benzophenone compounds such as 4,4 '-dimethylaminobenzophenone, 4' -diethylaminobenzophenone, 2-aminobenzophenone, 4 '-diaminobenzophenone, 3' -diaminobenzophenone and 3, 4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoAzole, 2- (p-diethylaminophenyl) benzoAzole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoAzole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoAzole, 2, 5-bis (p-diethylaminophenyl) -1,3,4-And compounds containing p-dialkylaminophenyl groups such as oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2, 5-bis (p-diethylaminophenyl) -1,3, 4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, and (p-diethylaminophenyl) pyrimidine. Of these, 4' -dialkylaminobenzophenone is most preferred. The sensitizing dye may be used alone or in combination of 2 or more kinds.
Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as N-butylamine and N-methyldiethanolamine, and mercapto compounds described later. The polymerization accelerator may be used alone or in combination of 2 or more.
[1-6] Other compounding ingredients of colored photosensitive resin composition
In addition to the above components, the colored photosensitive resin composition of the present invention may be suitably blended with an adhesion improving agent such as a silane coupling agent, a coating property improving agent, a development improving agent, an ultraviolet absorber, an antioxidant, a surfactant, a pigment derivative, and the like.
[1-6-1] Adhesion improving agent
In order to improve the adhesion to the substrate, the colored photosensitive resin composition of the present invention may contain an adhesion-improving agent. As the adhesion improving agent, a silane coupling agent, a phosphate group-containing compound, and the like are preferable.
As the kind of the silane coupling agent, 1 kind of various silane coupling agents such as epoxy, acrylic, amino and the like may be used alone, or 2 kinds or more may be mixed and used.
As a preferable silane coupling agent, for example, there may be mentioned: (meth) acryloyloxy silanes such as 3-methacryloxypropyl methyl dimethoxy silane and 3-methacryloxypropyl trimethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane, epoxysilanes such as 3-epoxypropoxypropyl methyl diethoxy silane and 3-epoxypropoxypropyl triethoxy silane, ureido silanes such as 3-ureido propyl triethoxy silane, and isocyanate silanes such as 3-isocyanatopropyl triethoxy silane are particularly preferable as the silane coupling agent of the epoxysilanes.
As the phosphate group-containing compound, phosphate esters containing a (meth) acryloyl group are preferable, and compounds represented by the following general formulae (XI-A), (XI-B) or (XI-C) are more preferable.
[ Chemical formula 54]
In the above general formulae (XI-A), (XI-B) and (XI-C), R 51 represents a hydrogen atom or a methyl group;
l and l' represent integers of 1 to 10;
m represents 1,2 or 3.
These phosphate group-containing compounds may be used singly or in combination of 2 or more.
[1-6-2] Pigment derivative
In order to improve dispersibility and preservability, the colored photosensitive resin composition of the present invention may contain a pigment derivative as a dispersing aid.
Examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone and diOxazines, anthraquinones, indanthrenes, perylenes, pyrenones, diketopyrrolopyrroles, and di-enesAmong these, phthalocyanines and quinophthalones are preferable.
Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc., which may be bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, etc., and among the substituents of the pigment derivative, a sulfonic acid group is preferable. In addition, a plurality of these substituents may be substituted on one pigment skeleton.
Specific examples of the pigment derivative include a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinophthalone, a sulfonic acid derivative of anthraquinone, a sulfonic acid derivative of quinacridone, a sulfonic acid derivative of diketopyrrolopyrrole, and diSulfonic acid derivatives of oxazine, and the like. These pigment derivatives may be used singly or in combination of 2 or more.
[1-6-3] Photoacid generator
The photoacid generator is a compound capable of generating an acid by ultraviolet rays, and the crosslinking reaction is performed in the presence of a crosslinking agent such as a melamine compound by the action of the acid generated when exposure is performed. Among such photoacid generators, those having high solubility in solvents, particularly solvents used for photosensitive coloring compositions, are preferable, and examples thereof include: diphenyliodoXylyl iodidePhenyl (p-methoxybenzyl) iodideBis (m-nitrophenyl) iodo ]Bis (p-tert-butylphenyl) iodo ]Bis (p-chlorophenyl) iodineBis (n-dodecyl) iodineP-isobutylphenyl (p-tolyl) iodideP-isopropylphenyl (p-tolyl) iodideIsodiaryl iodidesOr a sulfonium organoboron complex such as a chloride, bromide or borofluoride of triarylsulfonium such as triphenylsulfonium, hexafluorophosphate, hexafluoroarsenite, aromatic sulfonate, tetrakis (pentafluorophenyl) borate, etc., diphenylphenylmethylsulfonylmethyl sulfonium (n-butyl) triphenylborate, etc., or a triazine compound such as 2-methyl-4, 6-bis (trichloromethyl) triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) triazine, etc., but the present invention is not limited thereto.
[1-6-4] Crosslinking agent
The colored photosensitive resin composition of the present invention may further contain a crosslinking agent, and for example, melamine or guanamine compounds may be used. Examples of the crosslinking agent include melamine or guanamine compounds represented by the following general formula (XII).
[ Chemical formula 55]
In the formula (XII), R 61 represents a-NR 66R67 group or an aryl group having 6 to 12 carbon atoms;
When R 61 is-NR 66R67 group, one of R 62、R63、R64、R65、R66 and R 67 represents-CH 2OR68 group, and when R 61 is an aryl group having 6 to 12 carbon atoms, one of R 62、R63、R64 and R 65 represents-CH 2OR68 group;
the remaining groups in R 62、R63、R64、R65、R66 and R 67 each independently represent a hydrogen atom or a-CH 2OR68 group;
r 68 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Wherein the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and the phenyl group or the naphthyl group may be bonded with a substituent such as an alkyl group, an alkoxy group or a halogen atom. The number of carbon atoms of the alkyl group and the alkoxy group is about 1 to 6, respectively. In the above, the alkyl group represented by R 68 is a methyl group or an ethyl group, and more preferably a methyl group.
The melamine-based compound corresponding to the general formula (XII), namely, the compound of the following general formula (XII-A) includes: hexamethylol melamine, pentamethylene melamine, tetramethylol melamine, hexamethoxymethyl melamine, pentamethoxymethyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, and the like.
[ Chemical formula 56]
In the formula (XII-A), in the case that one of R 62、R63、R64、R65、R66 and R 67 is aryl, one of R 62、R63、R64 and R 65 represents a-CH 2OR68 group;
the remaining groups in R 62、R63、R64、R65、R66 and R 67 each independently represent a hydrogen atom or a-CH 2OR68 group;
R 68 represents a hydrogen atom or an alkyl group.
The guanamine compound corresponding to the general formula (XII), that is, the compound in which R 61 in the general formula (XII) is an aryl group, includes: tetramethylol benzoguanamine, trimethoxy methyl benzoguanamine, tetraethoxy methyl benzoguanamine, and the like.
In addition, a crosslinking agent having a hydroxymethyl group or a hydroxymethyl alkyl ether group may also be used, examples of which are listed below:
2, 6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2, 6-bis (hydroxymethyl) phenol, 5-ethyl-1, 3-bis (hydroxymethyl) perhydro-1, 3, 5-triazin-2-one (known as N-ethyldimethylol triazinone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3, 5-bis (hydroxymethyl) perhydro-1, 3,5- Diazin-4-one (known as dimethylol aldol) or its dimethyl ether form, and tetramethylol glyoxal diurea (tetramethyrol glyoxal diureine) or its tetramethyl ether form.
It should be noted that one kind of these crosslinking agents may be used alone, or two or more kinds may be used in combination. When the crosslinking agent is used, the amount thereof is preferably 0.1 to 15% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.
[1-6-5] Mercapto compound
In order to improve the adhesion to the substrate, a mercapto compound may be added as a polymerization accelerator.
Examples of the type of the mercapto compound include 2-mercaptobenzothiazole and 2-mercaptobenzothiazoleAnd aliphatic heterocyclic compounds such as oxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1, 4-dimethylmercaptobenzene, butandiol dimercaptopropionate, butandiol dimercaptoacetate, ethylene glycol dimercaptoacetate, trimethylol propane trimercapto acetate, butandiol dimercaptopropionate, trimethylol propane trimercapto propionate, trimethylol propane trimercapto acetate, pentaerythritol tetramercapto propionate, pentaerythritol tetramercapto acetate, trihydroxyethyl trimercapto propionate, ethylene glycol bis (3-mercapto butyrate), butanediol bis (3-mercapto butyrate), 1, 4-bis (3-mercapto butyryloxy) butane, trimethylol propane tris (3-mercapto butyrate), pentaerythritol tetrakis (3-mercapto isobutyrate), pentaerythritol tris (3-mercapto isobutyrate), butanediol bis (3-mercapto isobutyrate), trimethylolpropane tris (3-mercapto isobutyrate), 1,3, 5-tris (3-mercapto butoxy ethyl) -1,3, 5-triazine (3, 6-triazine (3H) -and the like. These mercapto compounds may be used alone or in combination of 2 or more.
[1-6-6] Surfactant
In order to improve the coatability, a surfactant may be contained in the colored photosensitive resin composition of the present invention.
As the surfactant, various surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants can be used. Among them, nonionic surfactants are preferably used because of low possibility of adversely affecting various properties, and among them, fluorine-based and silicone-based surfactants are effective in terms of coatability.
Examples of the commercial products of these surfactants include: BM-1000, BM-1100, FC430, and DFX-18, respectively, manufactured by BM Chemie, "Megafac F-142D"、"Megafac F-172"、"Megafac F-173"、"Megafac F-183"、"Megafac F-470"、"Megafac F-475"、"Megafac F-478"、"Megafac F-554"、"Megafac F-559"、3M Japan, and NEOS, respectively.
Examples of the silicone-based surfactant include commercially available products such as "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", "SH8400", BYK300"," BYK323"," BYK325"," BYK330", and" KP340", made by the company of ceri corning.
The surfactant may contain a surfactant other than a fluorine-based surfactant and a silicone-based surfactant, and examples of the other surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.
The surfactant may be used alone, or may be used in combination of 2 or more kinds in any combination and ratio. Among them, a combination of a silicone surfactant and a fluorine surfactant is preferable. The combination of the silicone surfactant and the fluorine surfactant includes, for example: BYK-300 or BYK-330/DIC F-475, F-478, F-554 or F-559.
[1-6-7] Liquid repellent
The colored photosensitive resin composition of the present invention may contain a liquid repellent agent. In particular, when the colored photosensitive resin composition of the present invention is used to prepare a partition wall and an organic electroluminescent element is produced by an inkjet method, it is preferable to contain a liquid repellent. Since the liquid repellency is imparted to the surface of the partition wall by the inclusion of the liquid repellency, it is considered that the obtained partition wall can prevent color mixing of pixels of the organic layer.
Examples of the liquid repellent include silicone-containing compounds and fluorine-containing compounds, and liquid repellents having a crosslinking group (hereinafter also referred to as "crosslinking group-containing liquid repellents") are preferable. Examples of the crosslinking group include an epoxy group and an ethylenically unsaturated group, and from the viewpoint of suppressing the outflow of the liquid repellent component of the developer, the ethylenically unsaturated group is preferable.
It is considered that when a cross-linking group-containing liquid repellent is used, a cross-linking reaction on the surface of the formed coating film can be accelerated when the coating film is exposed, and the liquid repellent is less likely to flow out during the development treatment, and as a result, the resulting partition wall can exhibit high liquid repellency.
When a fluorine compound is used as the liquid repellent, the fluorine compound tends to be oriented on the surface of the partition wall and to exert an effect of preventing bleeding and color mixing of the ink. More specifically, there is a tendency that: the group having fluorine atoms can play a role of repelling ink and preventing ink from bleeding and color mixing due to the ink entering the adjacent region beyond the partition wall.
Specific examples of the crosslinking group-containing liquid repellent, particularly the ethylenically unsaturated group-containing fluorine-based compound include, for example: and fluorinated organic compounds such as perfluoroalkyl sulfonic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl alkylene oxide adduct, perfluoroalkyl trialkylammonium salt, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, oligomer containing perfluoroalkyl group, hydrophilic group and new oil group, carbamate containing perfluoroalkyl group and hydrophilic group, perfluoroalkyl ester, and perfluoroalkyl phosphate.
As the commercial products of these fluorine-containing compounds, fluorine-containing organic compounds commercially available under the trade names such as "DEFENSAMCF-300", "DEFENSAMCF-310", "DEFENSAMCF-312", "DEFENSAMCF-323", "MEGAFAC RS-72-K" by DIC, and "fluoro FC-431", "fluoro FC-4430", "fluoro FC-4432" by 3M Japan, and "Optool DAC-HP" by Asahi Kabushiki Kaisha, "Asahi Guard AG710"、"Surfron S-382"、"Surfron SC-101"、"Surfron SC-102"、"Surfron SC-103"、"Surfron SC-104"、"Surfron SC-105"、"Surfron SC-106"、, inc. can be used.
In this way, in the case of using a fluorine-based compound as the liquid repellent, the fluorine atom content in the liquid repellent is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 50% by mass or less, more preferably 25% by mass or less. When the lower limit value is equal to or higher than the upper limit value, the contact angle tends to be high, and when the upper limit value is equal to or lower than the upper limit value, the outflow to the pixel portion tends to be suppressed.
The molecular weight of the liquid repellent is not particularly limited, and may be a low molecular weight compound or a high molecular weight compound. Since the high molecular weight body is resistant to the flow of the liquid repellent by firing, the liquid repellent tends to be resistant to the flow out of the partition wall, and from such a point of view, the number average molecular weight of the liquid repellent is preferably 100 or more, more preferably 500 or more, and preferably 100,000 or less, more preferably 10,000 or less.
The content of the liquid repellent in the colored photosensitive resin composition of the present invention is usually 0.01 mass% or more, preferably 0.05 mass% or more, more preferably 0.1 mass% or more, and usually 1 mass% or less, preferably 0.5 mass% or less, more preferably 0.3 mass% or less, relative to the total solid content. When the liquid repellent amount is equal to or larger than the lower limit, the liquid repellency tends to be high, and when the liquid repellent amount is equal to or smaller than the upper limit, the outflow of the liquid repellent to the pixel portion tends to be suppressed.
[1-6-8] Ultraviolet absorber
The colored photosensitive resin composition of the present invention may further contain an ultraviolet absorber. The ultraviolet absorber is added for the following purposes: the light curing distribution is controlled by absorbing a specific wavelength of a light source for exposure with an ultraviolet absorber. By adding the ultraviolet absorber, there is a tendency that effects such as improvement of taper angle and shape after development, elimination of residues remaining in non-exposed portions after development, and the like can be obtained. As the ultraviolet absorber, a compound having a maximum absorption at a wavelength of 250nm to 400nm, for example, can be used from the viewpoint of blocking the light absorption of the initiator.
As the ultraviolet absorber, benzotriazole-based compounds and/or triazine-based compounds are preferable. By containing the benzotriazole-based compound and/or the triazine-based compound, it is considered that the light absorption rate of the initiator at the film bottom can be reduced, and the difference in the curing area of the film surface layer and the film bottom can be reduced, thereby obtaining an effect of increasing the taper angle.
Examples of the benzotriazole compounds include: 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate in combination with 2-ethylhexyl-3- [ 3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl ] propionate, 2- [ 2-hydroxy-3, 5-bis (. Alpha.,. Alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -2H-benzotriazol-2-phenyl) -2H-benzotriazole, 2- (3-tert-butyl-5-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-2-phenyl) benzotriazol-2-hydroxy-2-phenyl) propionate 3- (2H-benzotriazol-2-yl) -5- (1, 1-dimethylethyl) -4-hydroxy, C7-9 side chain and straight chain alkyl ester.
Examples of commercially available benzotriazole compounds include: SUMISORB 200, SUMISORB, 250, SUMISORB 300, SUMISORB, 340, SUMISORB 350 (manufactured by Sumitomo Chemical Co., ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by Mitsui Chemical Co., ltd. )、TINUVIN PS、TINUVIN99-2、TINUVIN109、TINUVIN384-2、TINUVIN326、TINUVIN900、TINUVIN928、TINUVIN928、TINUVIN1130(BASF Co., ltd., )、EVERSORB70、EVERSORB71、EVERSORB72、EVERSORB73、EVERSORB74、EVERSORB75、EVERSORB76、EVERSORB234、EVERSORB77、EVERSORB78、EVERSORB80、EVERSORB81(, taiwan Yongchu Chemical Co., ltd.), tomisorb 100, tomisorb 600 (manufactured by API Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB, SEESORB706, SEESORB707, SEESORB709 (manufactured by SHIPRO KASEI), RUVA-93 (manufactured by Otsuka Chemical Co., ltd.), and the like.
As the triazine compound, there can be mentioned: 2- [4, 6-bis (2, 4-xylyl) -1,3, 5-triazin-2-yl ] -5-octyloxyphenol, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- [3- (dodecyloxy) -2-hydroxypropoxy ] phenol, the reaction product of 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine with glycidic acid (2-ethylhexyl) ester, 2, 4-bis [ 2-hydroxy-4-butoxyphenyl ] -6- (2, 4-dibutoxyphenyl) -1, 3-5-triazine, and the like. Among these, the hydroxyphenyl triazine compound is preferable from the viewpoints of taper angle and exposure sensitivity.
Examples of the commercially available triazine compound include: TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (manufactured by BASF), and the like.
[1-6-9] Polymerization inhibitor
The colored photosensitive resin composition of the present invention may contain a polymerization inhibitor. It is considered that the inclusion of the polymerization inhibitor prevents radical polymerization, and thus the taper angle of the resulting cured product can be increased.
Examples of the polymerization inhibitor include: hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, 2, 6-di-tert-butyl-4-methylphenol (BHT), and the like. Among these polymerization inhibitors, 2, 6-di-t-butyl-4-methylphenol, hydroquinone or methoxyphenol is preferred from the viewpoint of polymerization inhibition ability.
The polymerization inhibitor preferably contains one or more than 2 kinds. In general, in the production of the binder resin (C), a polymerization inhibitor may be contained in the resin, or in addition to the polymerization inhibitor contained in the resin, the same or different polymerization inhibitor may be added in the production of the photosensitive resin composition.
The content of the polymerization inhibitor in the colored photosensitive resin composition is usually 0.0005 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and usually 0.1 mass% or less, preferably 0.08 mass% or less, more preferably 0.05 mass% or less, relative to the total solid content of the colored photosensitive resin composition. When the lower limit value is equal to or higher than the upper limit value, the taper angle tends to be increased, and when the upper limit value is equal to or lower than the lower limit value, the sensitivity tends to be maintained.
[1-6-10] Inorganic filler
In order to improve the strength as a cured product and to improve the excellent flatness and taper angle of a coating film formed by appropriate interaction with (C) a binder resin (formation of a matrix structure), an inorganic filler may be further contained in the colored photosensitive resin composition of the present invention. Examples of such inorganic fillers include: talc, silica, alumina, barium sulfate, magnesium oxide, or a substance obtained by subjecting them to surface treatment with various silane coupling agents.
The average particle diameter of these inorganic fillers is usually 0.005 to 20. Mu.m, preferably 0.01 to 10. Mu.m. The average particle diameter in this embodiment is a value measured by a laser diffraction/scattering particle size distribution measuring apparatus manufactured by Beckman Coulter, or the like. Among these inorganic fillers, silica sol and silica sol modified products in particular tend to have excellent dispersion stability and excellent cone angle improving effect, and therefore, blending is preferable. When the colored photosensitive resin composition of the present invention contains these inorganic fillers, the specific gravity thereof is usually 5 mass% or more, preferably 10 mass% or more, and usually 80 mass% or less, preferably 70 mass% or less, with respect to the total solid content, from the viewpoint of sensitivity.
[1-7] Solvent
The colored photosensitive resin composition and the pigment dispersion liquid of the present invention generally contain a solvent. By containing the solvent, a colorant such as a pigment can be dispersed in the solvent, and coating becomes easy.
The colored photosensitive resin composition of the present invention is usually used in a state in which (a) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, (E) a photopolymerization initiator, and other various materials used as needed are dissolved or dispersed in a solvent. Similarly, the pigment dispersion liquid of the present invention is usually used in a state in which (a) a colorant, (B) a dispersant, (C) a binder resin, and other various materials used as needed are dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferred from the viewpoints of dispersibility and coatability.
Among the organic solvents, from the viewpoint of coatability, a solvent having a boiling point in the range of 100 to 300 ℃ (under the conditions of a pressure of 1013.25hPa, hereinafter, the boiling points are the same), and more preferably, a solvent having a boiling point in the range of 120 to 280 ℃ is selected.
Examples of such organic solvents include the following solvents.
Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether;
Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
glycol diacetates such as ethylene glycol diacetate, 1, 3-butanediol diacetate and 1, 6-hexanediol diacetate;
alkyl acetates such as cyclohexyl acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethylisobutyl ether, and dihexyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl amyl ketone;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bisdicyclohexane;
aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
Chain or cyclic esters such as amyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl decanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and gamma-butyrolactone;
alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
halogenated hydrocarbons such as chlorobutane and chloropentane;
Ether ketones such as methoxy methyl pentanone;
nitriles such as acetonitrile and benzonitrile.
Examples of the commercially available organic solvents corresponding to the above are: mineral spirits (MINERAL SPIRIT), varsol #2, apco #18solvent, apco thinner, socal solvent nos. 1 and 2, solvesso #150, shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve ("cellosolve (cellosolve)" is a registered trademark, the same applies hereinafter), ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (diglyme) (all trade names), and the like.
These organic solvents may be used alone or in combination of 2 or more.
When the partition walls and the colored spacers are formed by photolithography, an organic solvent having a boiling point in the range of 100 to 200 ℃ is preferably selected as the organic solvent. More preferably an organic solvent having a boiling point of 120 to 170 ℃.
Among the above organic solvents, glycol alkyl ether acetates are preferred in view of good balance of coatability, surface tension, and the like, and high solubility of constituent components in the composition.
In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Among them, propylene glycol monomethyl ether is preferred, particularly from the viewpoint of solubility of constituent components in the composition. If the amount of the addition of the glycol monoalkyl ether is too large, the pigment tends to be aggregated, and the storage stability such as the viscosity of the colored photosensitive resin composition to be obtained thereafter tends to be lowered, and therefore the proportion of the glycol monoalkyl ether in the solvent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.
In addition, it is also preferable to use an organic solvent having a boiling point of 150℃or higher (hereinafter, sometimes referred to as "high boiling point solvent"). When used in combination with such a high boiling point solvent, the colored photosensitive resin composition is difficult to dry, but has an effect of preventing the uniform dispersion state of the pigment in the composition from being damaged in the case of rapid drying. That is, for example, the effect of preventing occurrence of a foreign matter defect at the tip of the slit nozzle due to precipitation and solidification of a coloring agent or the like is obtained. Among the above solvents, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable from the viewpoint of high effect.
The content of the high boiling point solvent in the organic solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass. When the lower limit value is not less than the above-mentioned lower limit value, it is possible to suppress occurrence of a foreign matter defect due to precipitation and solidification of a coloring material or the like at the tip of the slit nozzle, and when the lower limit value is not more than the above-mentioned upper limit value, it is possible to suppress a lowering of the drying temperature of the composition, and thus it is possible to suppress problems such as a tact defect and pin marks of pre-baking (pre-bak) in the reduced pressure drying process.
The high boiling point solvent having a boiling point of 150 ℃ or higher may be glycol alkyl ether acetate, or may be glycol alkyl ether, and in this case, the high boiling point solvent having a boiling point of 150 ℃ or higher may not be additionally contained.
Examples of the preferable high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1, 3-butanediol diacetate, 1, 6-hexanediol diacetate, and triacetin among the above-mentioned various solvents.
< Amount of component to be blended in colored photosensitive resin composition >
In the colored photosensitive resin composition of the present invention, the content of the colorant (a) is usually 20 mass% or more, preferably 25 mass% or more, more preferably 30 mass% or more, and preferably 60 mass% or less, more preferably 50 mass% or less, still more preferably 45 mass% or less, still more preferably 40 mass% or less, relative to the total solid content in the colored photosensitive resin composition. When the Optical Density (OD) is equal to or higher than the lower limit, sufficient Optical Density (OD) tends to be easily obtained, and when the Optical Density (OD) is equal to or lower than the upper limit, sufficient image formability tends to be easily ensured. The combination of the upper limit and the lower limit is preferably 20 to 60% by mass, more preferably 25 to 50% by mass, still more preferably 30 to 45% by mass, particularly preferably 30 to 40% by mass.
In the colored photosensitive resin composition and the pigment dispersion liquid of the present invention, the content of the (A1) organic black pigment relative to the (a) colorant is usually 10 mass% or more, preferably 30 mass% or more, more preferably 50 mass% or more, still more preferably 70 mass% or more, still more preferably 80 mass% or more, particularly preferably 90 mass% or more, and usually 100 mass% or less. When the content of the organic black pigment (A1) in the colorant (a) is equal to or higher than the lower limit, a coating film having a desired black color tone tends to be obtained and a coating film having high strength tends to be obtained. The combination of the upper limit and the lower limit is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, still more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, particularly preferably 80 to 100% by mass, and most preferably 90 to 100% by mass.
In the colored photosensitive resin composition and the pigment dispersion liquid of the present invention, the (A1) organic black pigment and the (A2) organic colored pigment may be contained in the (a) colorant. In this case, the content ratio of the (A1) organic black pigment to the (a) colorant is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and is usually 90% by mass or less, preferably 80% by mass or less, more preferably 60% by mass or less. The content of the organic coloring pigment (A2) is usually 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and is usually 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less. When the lower limit value is equal to or higher than the upper limit value, the taper angle tends to be reduced, and when the upper limit value is equal to or lower than the upper limit value, a black-colored coating film tends to be obtained.
The content of the organic black pigment (A1) is usually 15 parts by mass or more, preferably 20 parts by mass or more, and usually 900 parts by mass or less, preferably 800 parts by mass or less, more preferably 500 parts by mass or less, and still more preferably 200 parts by mass or less, based on 100 parts by mass of the organic coloring pigment (A2).
In the colored photosensitive resin composition and pigment dispersion of the present invention, (A1) an organic black pigment and (A3) carbon black may be contained in the (a) colorant. In this case, the content ratio of the (A1) organic black pigment to the (a) colorant is usually 50% by mass or more, preferably 60% by mass or more, and usually 95% by mass or less, preferably 90% by mass or less. The content of the carbon black (A3) is usually 5 mass% or more, preferably 10 mass% or more, and usually 50 mass% or less, preferably 40 mass% or less. When the lower limit value is set to be equal to or higher than the lower limit value, sufficient Optical Density (OD) tends to be obtained, and when the upper limit value is set to be equal to or lower than the upper limit value, a high volume resistance value and a low relative permittivity tend to be obtained, and wrinkles and the like are less likely to occur at the time of curing. The content of the (A1) organic black pigment is usually 100 parts by mass or more, preferably 150 parts by mass or more, and usually 2000 parts by mass or less, preferably 1000 parts by mass or less, based on 100 parts by mass of the (A3) carbon black.
In addition, in the colored photosensitive resin composition and the pigment dispersion liquid of the present invention, (A1) an organic black pigment, (A2) an organic coloring pigment, and (A3) carbon black may be contained in the colorant (a) at the same time. In this case, the content ratio of the (A1) organic black pigment to the (a) colorant is usually 10 mass% or more, preferably 20 mass% or more, and is usually 80 mass% or less, preferably 70 mass% or less. The content of the organic coloring pigment (A2) is usually 10 mass% or more, preferably 20 mass% or more, and usually 60 mass% or less, preferably 50 mass% or less. The content of the carbon black (A3) is usually 5 mass% or more, preferably 10 mass% or more, and usually 50 mass% or less, preferably 40 mass% or less. In this case, the content ratio of the (A1) organic black pigment is usually 15 parts by mass or more, preferably 20 parts by mass or more, and usually 800 parts by mass or less, preferably 700 parts by mass or less, based on 100 parts by mass of the (A2) organic coloring pigment. The content of the (A1) organic black pigment is usually 40 parts by mass or more, preferably 50 parts by mass or more, and usually 1000 parts by mass or less, preferably 900 parts by mass or less, based on 100 parts by mass of the (A3) carbon black.
The content of the dispersant (B) in the solid content of the colored photosensitive resin composition is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less. When the content is equal to or higher than the lower limit, dispersibility tends to be excellent, and when the content is equal to or lower than the upper limit, surplus dispersant tends to be reduced and development tends to be excellent. The combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, still more preferably 5 to 15% by mass, and particularly preferably 5 to 10% by mass.
The content of the dispersant (B) is usually 5 parts by mass or more, preferably 10 parts by mass or more, and usually 50 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the colorant (a). When the content is equal to or higher than the lower limit, dispersibility tends to be excellent, and when the content is equal to or lower than the upper limit, surplus dispersant tends to be reduced and development tends to be excellent. The combination of the upper limit and the lower limit is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass.
In the colored photosensitive resin composition according to the first aspect of the present invention, the content of the acrylic dispersant is not particularly limited, but is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less, of the solid content of the colored photosensitive resin composition. When the content is equal to or higher than the lower limit, dispersibility tends to be excellent, and when the content is equal to or lower than the upper limit, surplus dispersant tends to be reduced and development tends to be excellent. The combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, still more preferably 5 to 15% by mass, and particularly preferably 5 to 10% by mass.
In the colored photosensitive resin composition according to the first aspect of the present invention and the pigment dispersion liquid according to the third aspect of the present invention, the content of the acrylic dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, and usually 50 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the colorant (a). When the content is equal to or higher than the lower limit, dispersibility tends to be excellent, and when the content is equal to or lower than the upper limit, surplus dispersant tends to be reduced and development tends to be excellent. The combination of the upper limit and the lower limit is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass.
(C) The content ratio of the binder resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and is usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, based on the total solid content of the colored photosensitive resin composition of the present invention. When the lower limit value is set to be equal to or higher than the lower limit value, a strong film tends to be easily obtained, and when the upper limit value is set to be equal to or lower than the upper limit value, penetration of the developer into the exposed portion tends to be easily suppressed to be low, and deterioration of surface smoothness and sensitivity of the film tends to be easily suppressed. The combination of the upper limit and the lower limit is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, still more preferably 30 to 50% by mass, and particularly preferably 40 to 50% by mass.
The content of the (C1) epoxy (meth) acrylate resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, particularly preferably 40% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, relative to the total solid content of the colored photosensitive resin composition of the present invention. When the lower limit value is not less than the upper limit value, a strong film tends to be easily obtained, and when the lower limit value is not more than the upper limit value, deterioration of surface smoothness and sensitivity of the film tends to be easily suppressed. The combination of the upper limit and the lower limit is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, still more preferably 30 to 60% by mass, particularly preferably 35 to 60% by mass, and most preferably 40 to 50% by mass.
In the present invention, the content ratio of the epoxy (meth) acrylate resin having the repeating unit structure represented by the above general formula (II) and/or the epoxy (meth) acrylate resin having the partial structure represented by the above general formula (III) (when both are included, the total content ratio thereof) in the binder resin (C) is not particularly limited, but is preferably 75 mass% or more, more preferably 80 mass% or more, still more preferably 85 mass% or more, still more preferably 90 mass% or more, particularly preferably 95 mass% or more, and further, usually 100 mass% or less. When the lower limit value is not less than the above, the degassing adaptability tends to be excellent. The combination of the upper limit and the lower limit is preferably 75 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.
The content ratio of the photopolymerizable monomer (D) is usually 1% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, and is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, with respect to the total solid content of the colored photosensitive resin composition. When the lower limit value is equal to or higher than the upper limit value, the sensitivity tends to be high, and when the lower limit value is equal to or lower than the upper limit value, the development tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, and still more preferably 8 to 15% by mass.
The content ratio of the photopolymerization initiator (E) is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, particularly preferably 3% by mass or more, and is usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less, relative to the total solid content of the colored photosensitive resin composition of the present invention. When the lower limit value is not less than the upper limit value, good sensitivity tends to be obtained, and when the lower limit value is not more than the upper limit value, the amount of the binder resin and the photopolymerizable monomer which are suitable for development tends to be ensured. The combination of the upper limit and the lower limit is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, still more preferably 1 to 8% by mass, still more preferably 2 to 5% by mass, and particularly preferably 3 to 5% by mass.
When the photopolymerization initiator (E) is used together with the polymerization accelerator, the content of the polymerization accelerator is preferably 0.05 mass% or more, and usually 10 mass% or less, preferably 5 mass% or less, based on the total solid content of the colored photosensitive resin composition of the present invention. The polymerization accelerator is usually 0.1 part by mass or more, preferably 0.2 part by mass or more, and usually 100 parts by mass or less, preferably 50 parts by weight or less, based on 100 parts by mass of the photopolymerization initiator (D).
When the content ratio of the polymerization accelerator is equal to or higher than the lower limit, good sensitivity tends to be obtained, and when the content ratio is equal to or lower than the upper limit, solubility of the unexposed portion in the developer tends to be good.
In addition, the proportion of the sensitizing dye in the colored photosensitive resin composition of the present invention is usually 0.5 mass% or more, preferably 1 mass% or less, and usually 20 mass% or less, preferably 15 mass% or less, more preferably 10 mass% or less, of the total solid content in the colored photosensitive resin composition from the viewpoint of sensitivity.
When the adhesion improving agent is used, the content thereof is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.4 to 2% by mass, based on the total solid content in the colored photosensitive resin composition. When the content ratio of the adhesion-improving agent is equal to or higher than the lower limit, adhesion tends to be improved, and when the content ratio is equal to or lower than the upper limit, good sensitivity tends to be obtained, and residues are less likely to be generated after development.
In the case of using the surfactant, the content thereof is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, and most preferably 0.03 to 0.3% by mass, based on the total solid content in the colored photosensitive resin composition. When the content ratio of the surfactant is not less than the above lower limit, smoothness and uniformity of the coating film tend to be obtained, and when the content ratio is not more than the upper limit, occurrence of streaks and the like tends to be suppressed.
The colored photosensitive resin composition of the present invention is prepared by using the organic solvent described above and adjusting the organic solvent so that the solid content concentration thereof is usually 5 to 50% by mass, preferably 10 to 30% by mass.
Physical Properties of colored photosensitive resin composition
The colored photosensitive resin composition of the present invention can be preferably used for black matrix formation applications in addition to the partition walls and the colored spacers, and is preferably black in view of the fact that the Optical Density (OD) of the film thickness 1 μm corresponding to the film is 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more, and particularly preferably 1.3 or more.
In addition, when the organic electroluminescent element is applied to a member having a high area ratio in the image display region of the image display device, such as a partition wall, the color tone is preferably closer to black, and from the viewpoint of the color tone x after curing is preferably 0.20 or more, more preferably 0.25 or more, further preferably 0.30 or more, and preferably 0.50 or less, more preferably 0.45 or less, further preferably 0.40 or less. The chromaticity y is preferably 0.20 or more, more preferably 0.25 or more, still more preferably 0.30 or more, and is preferably 0.50 or less, more preferably 0.45 or less, still more preferably 0.40 or less.
[2] Pigment dispersion composition and composition
The components and the compositions constituting the pigment dispersion liquid of the present invention will be described.
The pigment dispersion liquid of the present invention (hereinafter, may be simply referred to as "pigment dispersion liquid") contains (a) a colorant, (B) a dispersant, and (C) a binder resin. Typically further comprises a solvent. As described later, the pigment dispersion liquid of the present invention can be preferably used as one of the raw materials used for producing the colored photosensitive resin composition.
As the (a) colorant, (B) dispersant, (C) binder resin and solvent used in the pigment dispersion, those exemplified as the (a) colorant, (B) dispersant, (C) binder resin and solvent used in the colored photosensitive resin composition can be preferably used.
In the pigment dispersion liquid of the present invention, (a) the colorant contains the aforementioned (A1) organic black pigment. A coating film obtained by coating a colored photosensitive resin composition produced using a pigment dispersion containing the organic black pigment (A1) tends to form a cured product having a color tone closer to black, which can realize high resistance, low dielectric constant and high light shielding rate.
In addition, the (B) dispersant includes an acrylic dispersant. When a colored photosensitive resin composition is produced by using a pigment dispersion liquid containing an acrylic dispersant, the adhesiveness of the pattern upon development tends to be good.
In addition, (C) the binder resin contains (C1) an epoxy (meth) acrylate resin. The use of a pigment dispersion containing a (C1) epoxy (meth) acrylate resin tends to reduce the amount of outgas generated after the formation of a cured product in the production of a colored photosensitive resin composition.
< Amount of component to be blended in pigment Dispersion >
In the pigment dispersion liquid of the present invention, the content of the colorant (a) is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, particularly preferably 55% by mass or more, and is usually 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, with respect to the total solid content in the pigment dispersion liquid. When the concentration is equal to or higher than the above-mentioned lower limit, a colored photosensitive resin composition can be produced at a proper solid content concentration, and when the concentration is equal to or lower than the above-mentioned upper limit, dispersibility tends to be good. The combination of the upper limit and the lower limit is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, still more preferably 40 to 70% by mass, particularly preferably 50 to 60% by mass, and most preferably 55 to 60% by mass.
In the pigment dispersion of the present invention, the content of the dispersant (B) is usually 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and is usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, relative to the total solid content in the pigment dispersion. When the content is not less than the above-mentioned lower limit, dispersibility tends to be good, and when the content is not more than the above-mentioned upper limit, surplus dispersant can be reduced, and development of the obtained colored photosensitive resin composition tends to be good. The combination of the upper limit and the lower limit is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 5 to 30% by mass, still more preferably 5 to 20% by mass, and particularly preferably 10 to 15% by mass.
In the pigment dispersion liquid of the present invention, the content of the acrylic dispersant is usually 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and is usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less, with respect to the total solid content in the pigment dispersion liquid. When the lower limit value is not less than the above-mentioned lower limit value, dispersibility tends to be good and pattern adhesion tends to be good at the time of development of the cured product, and when the upper limit value is not more than the above-mentioned upper limit value, development of the obtained colored photosensitive resin composition tends to be good. The combination of the upper limit and the lower limit is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 5 to 30% by mass, still more preferably 5 to 20% by mass, and particularly preferably 10 to 15% by mass.
In the pigment dispersion of the present invention, the content of the binder resin (C) is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 25% by mass or more, and is usually 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, relative to the total solid content in the pigment dispersion. When the amount of the colorant in the obtained colored photosensitive resin composition is set to the above-described lower limit value or more, dispersibility tends to be good, and when the amount of the colorant in the obtained colored photosensitive resin composition is set to the above-described upper limit value or less, sufficient light shielding property tends to be ensured. The combination of the upper limit and the lower limit is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass, still more preferably 20 to 35% by mass, and particularly preferably 25 to 30% by mass.
In the pigment dispersion of the present invention, the content of the (C1) epoxy (meth) acrylate resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 25% by mass or more, and is usually 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, based on the total solid content in the pigment dispersion. When the lower limit value is not less than the upper limit value, the deaeration adaptability of the cured product tends to be good, and when the upper limit value is not more than the upper limit value, the amount of the colorant in the obtained colored photosensitive resin composition can be optimized, and sufficient light-shielding property tends to be ensured. The combination of the upper limit and the lower limit is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass, still more preferably 20 to 35% by mass, and particularly preferably 25 to 30% by mass.
The pigment dispersion of the present invention is prepared by using the aforementioned organic solvent and adjusting the organic solvent so that the solid content concentration thereof is usually 5 to 50% by mass, preferably 10 to 30% by mass.
[3] Method for producing colored photosensitive resin composition
The colored photosensitive resin composition of the present invention (hereinafter, sometimes referred to as "resist") can be prepared by a usual method.
In general, (a) the colorant is preferably dispersed in advance using a paint shaker, a sand mill, a ball mill, a roller mill, a stone mill, an air mill, a homogenizer, or the like. By the dispersion treatment, (a) the colorant is micronized, and thus, the coating characteristics of the resist are improved.
The dispersion treatment is generally preferably performed in a system in which a part or all of (a) the colorant, the organic solvent, (B) the dispersant, and (C) the binder resin are used in combination (hereinafter, the mixture to be supplied to the dispersion treatment, and the composition obtained in the treatment are sometimes referred to as "ink" or "pigment dispersion"). In particular, if a polymeric dispersant is used as the dispersant (B), thickening (excellent dispersion stability) of the obtained ink and resist with time can be suppressed, which is preferable.
Therefore, in the step of producing a resist, it is preferable to produce a pigment dispersion liquid containing at least (a) a colorant, an organic solvent, and (B) a dispersant.
When a dispersion treatment is performed on a liquid containing all the components blended in the colored photosensitive resin composition, there is a possibility that highly reactive components are modified due to heat release generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
When the colorant (A) is dispersed by a sand mill, glass beads or zirconia beads having a particle diameter of about 0.1 to 8mm are preferably used. The dispersion conditions are usually such that the temperature is in the range of 0℃to 100℃and preferably room temperature to 80℃and the suitable time for the dispersion is not the same depending on the composition of the liquid and the size of the dispersion apparatus, and therefore, the dispersion may be appropriately adjusted. The general criteria for dispersion are: the gloss of the ink was controlled so that the 20-degree specular gloss (JIS Z8741) of the resist was in the range of 50 to 300. When the glossiness of the resist is equal to or higher than the lower limit, coarse pigment (colorant) particles remaining due to insufficient dispersion treatment can be suppressed, and development property, adhesion, resolution, and the like tend to be more sufficient. Further, when the gloss value is not more than the above-mentioned upper limit, the pigment is prevented from being broken to generate a large amount of ultrafine particles, and the dispersion stability tends to be easily maintained.
The dispersion particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3. Mu.m, and can be measured by a dynamic light scattering method or the like. Next, the ink obtained by the dispersion treatment is mixed with the other components contained in the resist to prepare a uniform mixed solution. In the resist manufacturing process, fine dust is often mixed into the liquid, and thus the obtained resist is desirably subjected to a filtration treatment by a filter or the like.
[4] Cured product and method for forming same
[4-1] Cured product
The colored photosensitive resin composition of the present invention can be cured to obtain a cured product. The cured product of the colored photosensitive resin composition can be preferably used as a partition wall or a colored spacer.
[4-1-1] Partition wall
The colored photosensitive resin composition of the present invention can be used for forming a partition wall, particularly a partition wall for dividing an organic layer of an organic electroluminescent element. Examples of the organic layer used for the organic electroluminescent element include an organic layer used for a hole injection layer, a hole transport layer, or a hole transport layer over a positive hole injection layer as described in japanese patent application laid-open No. 2016-165396.
[4-1-2] Colored spacers
The colored photosensitive resin composition of the present invention can be preferably used as a resist for a colored spacer in addition to a spacer. When a spacer is used for a TFT-type LCD, a TFT serving as a switching element may malfunction due to light incident on the TFT, and a colored spacer may be used to prevent this (for example, refer to japanese patent application laid-open No. 8-234212).
[4-2] Method of Forming
Next, a method for producing a partition wall or a colored spacer using the colored photosensitive resin composition of the present invention will be described. The black matrix and other cured products may be formed by the same method.
[4-2-1] Support
The material of the support for forming the partition wall and the colored spacer is not particularly limited as long as the support has a proper strength. As a material of the transparent substrate, for example, a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene and polyethylene, a thermoplastic resin sheet such as polycarbonate, polymethyl methacrylate and polysulfone, a thermosetting resin sheet such as an epoxy resin, an unsaturated polyester resin and a poly (meth) acrylic resin, and various glasses are mentioned. Among them, glass and heat-resistant resins are preferable from the viewpoint of heat resistance. In addition, transparent electrodes such as ITO and IZO may be formed on the substrate surface. In addition to the transparent substrate, it may be formed on the TFT array.
In order to improve the surface properties such as adhesion, the support may be subjected to a corona discharge treatment, an ozone treatment, a film formation treatment of various resins such as a silane coupling agent and a urethane resin, if necessary.
The thickness of the transparent substrate is usually in the range of 0.05 to 10mm, preferably 0.1 to 7 mm. In the case of performing the film formation treatment of various resins, the film thickness is usually in the range of 0.01 to 10. Mu.m, preferably 0.05 to 5. Mu.m.
[4-2-2] Coating of colored photosensitive resin composition
The application of the colored photosensitive resin composition to the substrate may be performed by spin coating, wire bar (Wire bar) method, flow coating, die coating, roll coating, spray coating, or the like. Among them, the die coating method is preferable from the viewpoint of greatly reducing the amount of the coating liquid to be used, completely eliminating the influence of fog or the like adhering to the coating liquid in the spin coating method, and suppressing the generation of foreign matters or the like.
If the thickness of the coating film is too large, development of the pattern may be difficult, and if it is too small, it may be difficult to increase the pigment concentration, and the desired color may not be exhibited. The thickness of the coating film is usually in the range of 0.2 to 10. Mu.m, more preferably in the range of 0.5 to 6. Mu.m, still more preferably in the range of 1 to 4. Mu.m, in terms of the film thickness after drying.
Drying of [4-2-3] coating film
The drying of the coating film after the substrate is coated with the colored photosensitive resin composition is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions may be appropriately selected depending on the type of the solvent component, the performance of the dryer to be used, and the like. The drying time is selected according to the kind of the solvent component, the performance of the dryer used, etc., and is usually selected in the range of 40 to 200℃for 15 seconds to 5 minutes, preferably 50 to 130℃for 30 seconds to 3 minutes.
The higher the drying temperature is, the more the adhesion of the coating film to the transparent substrate is improved, but if the drying temperature is too high, (C) the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. The drying step of the coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
[4-2-4] Exposure
The image exposure is performed by superimposing a negative mask pattern on a coating film of the colored photosensitive resin composition and irradiating the mask pattern with a light source of ultraviolet or visible light. In this case, in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable coating film and then exposed to light as necessary. The light source used for the image exposure is not particularly limited. Examples of the light source include: light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; and laser sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium-cadmium laser, and semiconductor laser. When light of a specific wavelength is used for irradiation, an optical filter may be used.
[4-2-5] Development
The partition wall and the colored spacer of the present invention can be produced as follows: after image exposure of a coating film formed from a colored photosensitive resin composition using the above-described light source, an image is formed on a substrate by development using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye, or a pigment.
As the basic compound, there may be mentioned: inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic basic compounds such as monoethanolamine, diethanolamine or triethanolamine, monomethyl amine, dimethyl amine or trimethyl amine, monoethyl amine, diethyl amine or triethyl amine, monoisopropyl amine or diisopropyl amine, n-butyl amine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethyl ammonium hydroxide (TMAH), and choline. These basic compounds may be a mixture of 2 or more kinds.
Examples of the surfactant include: nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters; anionic surfactants such as alkylbenzenesulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinates, and the like; amphoteric surfactants such as alkyl betaines and amino acids.
Examples of the organic solvent include: isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, and the like. The organic solvent may be used alone or in combination with an aqueous solution.
The conditions of the development treatment are not particularly limited, and the development treatment may be carried out by any of development methods such as a dipping development method, a spray development method, a brush development method, and an ultrasonic development method, usually at a development temperature in the range of 10 to 50 ℃, preferably 15 to 45 ℃, and particularly preferably 20 to 40 ℃.
[4-2-6] Heat curing treatment
The substrate after development is subjected to a heat curing treatment or a photo curing treatment, preferably a heat curing treatment. As the heat curing conditions in this case, the temperature is selected in the range of 100 to 280℃and preferably 150 to 250℃for a period of 5 to 60 minutes.
[5] Organic electroluminescent element, image display device, and illumination
[5-1] Organic electroluminescent element
The organic electroluminescent element of the present invention comprises the cured product of the colored photosensitive resin composition, for example, a partition wall.
For example, various organic electroluminescent elements can be manufactured using a substrate provided with a partition wall pattern manufactured by the method described above. The method for forming the organic electroluminescent element is not particularly limited, and it is preferable that the organic layer such as a pixel is formed by a wet process such as a vapor deposition method, a casting method, a spin coating method, or an ink jet printing method after the pattern of the partition wall is formed on the substrate by the above-described method, and the deposition method is a method of forming a film by sublimating a functional material in a vacuum state and adhering the sublimated functional material to the region surrounded by the partition wall on the substrate.
In the case of using an organic electroluminescent element as a pixel of an image display device, it is necessary to prevent light of a light-emitting layer of some pixels from leaking to other pixels, and in the case of using a metal electrode or the like, it is necessary to prevent degradation of image quality due to reflection of external light, and therefore, it is preferable to impart light-shielding properties to a partition wall constituting the organic electroluminescent element.
In addition, in the organic electroluminescent element, since electrodes need to be provided on the upper and lower surfaces of the partition wall, the partition wall is preferably high in impedance and low in dielectric constant from the viewpoint of insulation. Therefore, when a colorant is used for imparting light-shielding property to the partition wall, the organic black pigment (A1) described above having high resistance and low dielectric constant is preferably used.
[5-2] Image display device
The image display device of the present invention is not particularly limited as long as it displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display device. Examples thereof include a liquid crystal display device including the colored spacers described above, and an organic EL display device including the organic electroluminescent elements described above.
[5-2-1] Liquid crystal display device
The liquid crystal display device is not particularly limited in its type and structure as long as it includes the colored spacers described above. For example, the black matrix of the present invention is provided on a TFT element substrate, red, green, and blue pixels are formed, a surface coating is formed as needed, and then a transparent electrode such as ITO or IZO is further formed on the image thereon, and the transparent electrode is used as a part of a member of a color display, a liquid crystal display device, or the like. In addition, in some applications such as the partially in-plane-aligned drive system (IPS mode), a transparent electrode may not be formed.
In general, an alignment film is formed on a color filter, a photo spacer is formed on the alignment film, and then the alignment film is bonded to a counter substrate to form a liquid crystal cell, and liquid crystal is injected into the formed liquid crystal cell and connected to a counter electrode. As the alignment film, a resin film of polyimide or the like is suitable. In the formation of the alignment film, gravure printing and/or flexography is generally used, and the thickness of the alignment film is set to 10nm. After the alignment film is cured by heat firing, the alignment film is subjected to a surface treatment by ultraviolet irradiation or rubbing, and then the alignment film is processed into a surface state in which the tilt of the liquid crystal can be adjusted.
[5-2-2] Organic EL display device
The organic EL display device is not particularly limited as long as it includes the aforementioned organic electroluminescent element, and the type and structure of the image display device are not particularly limited, and for example, the organic electroluminescent element of an active driving type may be used for assembly according to a conventional method. For example, the image display device of the present invention can be formed by a method described in "organic EL display" (OHM corporation, release of the display at 8 months and 20 days of the year of the flat formation, time Ren Jingshi, the ampere kilowave vector, and the village Tian Yingxing). For example, an organic electroluminescent element that emits white light may be combined with a color filter to display an image, or an organic electroluminescent element that emits light of different colors such as RGB may be combined to display an image.
[5-3] Lighting
The illumination of the present invention includes the aforementioned organic electroluminescent element. The type and structure thereof are not particularly limited, and the organic electroluminescent element of the present invention may be used for assembly according to a conventional method. The organic electroluminescent element may be driven by a simple matrix or an active matrix.
In order to cause the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. The organic electroluminescent elements having different emission colors may be combined to mix the colors into white, or the color mixing ratio may be adjusted to provide a color mixing function.
Examples
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples unless the gist of the present invention is exceeded.
The following components of the colored photosensitive resin compositions used in the examples and comparative examples are as follows.
< Binder resin-I >)
"ZCR-1642H" (weight average molecular weight (Mw) 6500, acid value 98mgKOH/g, carboxyl group-containing epoxy (meth) acrylate resin) manufactured by Kagaku Kogyo Co., ltd.). The resin corresponds to (C1-1) and has a repeating unit structure represented by the formula (II-1), wherein R 11 is a methyl group, R 12 is a group represented by the formula (II-A), and R X is a tetrahydrophthalic acid residue.
< Binder resin-II >
[ Chemical formula 57]
50 Parts by mass of the epoxy compound (epoxy equivalent 264) having the above-described structure, 13.65 parts by mass of acrylic acid, 60.5 parts by mass of methoxybutyl acetate, 0.936 part by mass of triphenylphosphine, and 0.032 part by mass of p-methoxyphenol were charged into a flask equipped with a thermometer, a stirrer, and a cooling tube, and reacted at 90℃with stirring until the acid value became 5mgKOH/g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 Parts by mass of the above-mentioned epoxy acrylate solution, 0.74 part by mass of Trimethylolpropane (TMP), 3.95 parts by mass of biphenyl tetracarboxylic dianhydride (BPDA) and 2.7 parts by mass of tetrahydrophthalic anhydride (THPA) were charged into a flask equipped with a thermometer, a stirrer and a cooling tube, and the temperature was slowly raised to 105℃while stirring, so that the above-mentioned materials were reacted.
When the resin solution was made transparent, it was diluted with methoxybutyl acetate to prepare a solid content of 50% by mass, and a carboxyl group-containing epoxy (meth) acrylate resin having an acid value of 112mgKOH/g and a weight average molecular weight (Mw) of 4100 was obtained, which corresponds to (C1-2).
< Binder resin-III >
[ Chemical formula 58]
155 Parts by mass of an epoxy compound (EPICLON HP HH, polyglycidyl ether of dicyclopentadiene/phenol polymer, weight average molecular weight 1000, epoxy equivalent 270) represented by the above structural formula, 41 parts by mass of acrylic acid, 0.1 part by mass of p-methoxyphenol, 2.5 parts by mass of triphenylphosphine, and 130 parts by mass of propylene glycol monomethyl ether acetate were added to a reaction vessel, and the mixture was heated and stirred at 100℃until the acid value became 3.0mgKOH/g or less. It took 9 hours (acid value 2.9 mgKOH/g) for the acid value to reach the target value. Then, 74 parts by mass of tetrahydrophthalic acid was further added thereto and reacted at 120℃for 4 hours to obtain a binder resin-III solution having an acid value of 98mgKOH/g and a weight average molecular weight (Mw) of 3500, which corresponds to (C1-1).
< Adhesive resin-IV >
[ Chemical formula 59]
98.0 Parts by mass of an epoxy compound (epoxy equivalent 245) represented by the above structural formula, 28.8 parts by mass of acrylic acid, 113.0 parts by mass of 3-methoxybutyl acetate, 1.1 parts by mass of triphenylphosphine, and 0.02 parts by mass of p-methoxyphenol were charged into a flask equipped with a thermometer, a stirrer, and a cooling tube, and reacted at 90℃with stirring until the acid value became 5mgKOH/g or less. The reaction took 15 hours to obtain an epoxy acrylate solution.
To 189.1 parts by mass of the epoxy acrylate solution, 11.8 parts by mass of biphenyl tetracarboxylic dianhydride (BPDA) and 30.4 parts by mass of tetrahydrophthalic anhydride (THPA) were added and the mixture was gradually heated to 105 ℃ with stirring to react.
When the resin solution was made transparent, it was diluted with 3-methoxybutyl acetate to prepare a solid content of 55 mass%, and a binder resin-IV having an acid value of 110mgKOH/g and a weight average molecular weight (Mw) of 2800 was obtained, which corresponds to (C1-2).
< Binder resin-V >)
While stirring 145 parts by mass of propylene glycol monomethyl ether acetate with nitrogen substitution, the temperature was raised to 120℃and 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 66 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi chemical Co., ltd.) were added dropwise thereto, and it took 3 hours to add 8.47 parts by mass of 2,2' -azobis (2-methylbutyronitrile) dropwise, and stirring was continued at 90℃for 2 hours. Then, the reaction vessel was replaced with air, and 0.7 parts by mass of tris (dimethylaminomethyl) phenol and 0.12 parts by mass of hydroquinone were charged into 43.2 parts by mass of acrylic acid, and the reaction was continued at 100℃for 12 hours. Then, 56.2 parts by mass of tetrahydrophthalic acid (THPA) and 0.7 part by mass of triethylamine were added, and the mixture was reacted at 100℃for 3.5 hours. The weight average molecular weight (Mw) of the binder resin V thus obtained was about 8400, the acid value was 80mgKOH/g, and the double bond equivalent was 480g/mol.
< Colorant-I >
Irgaphor (registered trademark) Black S0100 CF (having a chemical structure represented by the following formula (I-1)) manufactured by BASF corporation
[ Chemical formula 60]
< Dispersant-I >)
BYK-LPN21116 (acrylic A-B block copolymer comprising an A block having a quaternary ammonium salt group and a tertiary amino group in the side chain and a B block having no quaternary ammonium salt group and no tertiary amino group) manufactured by BYK-Chemie Co., ltd., having an amine value of 70mgKOH/g and an acid value of 1mgKOH/g or less
The A block of the dispersant I contains repeating units of the following formulas (1 a) and (2 a), the B block contains repeating units of the following formula (3 a), and the content of the repeating units of the following formulas (1 a), (2 a) and (3 a) in the total repeating units of the dispersant I is 11.1 mol%, 22.2 mol% and 6.7 mol%, respectively.
[ Chemical formula 61]
< Dispersant-II >
DISPERBYK-167 (Carbamate Polymer dispersant) manufactured by BYK-Chemie Co
< Solvent-I >, a process for preparing the same
PGMEA: propylene glycol monomethyl ether acetate
< Solvent-II >
MB: 3-methoxy-1-butanol
< Solvent-III >
MBA: 3-Methoxybutyl acetate
< Photopolymerization initiator-I >)
< Diketone body >)
Ethylcarbazole (5 g, 25.61 mmol) and o-naphthaloyl chloride (5.13 g, 26.89 mmol) were dissolved in 30mL of dichloromethane, cooled to 2℃in an ice-water bath and stirred, alCl 3 (3.41 g, 25.61 mmol) was added. After stirring at room temperature for 3 hours, a solution of crotonyl chloride (2.81 g, 26.89 mmol) in 15mL of methylene chloride was added, alCl 3 (4.1 g, 30.73 mmol) was added, and the mixture was stirred for 1 hour and 30 minutes. The reaction solution was poured into 200mL of ice water, 200mL of methylene chloride was added thereto, and the organic layer was separated. The recovered organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a white solid of diketone (10 g).
< Oxime body >)
Diketone (3.00 g, 7.19 mmol), NH 2 OH HCl (1.09 g, 15.81 mmol) and sodium acetate (1.23 g, 15.08 mmol) were mixed with 30mL of isopropanol and refluxed for 3 hours.
After completion of the reaction, the reaction mixture was concentrated, and 30mL of ethyl acetate was added to the obtained residue, followed by washing with 30mL of a saturated aqueous sodium hydrogencarbonate solution and 30mL of a saturated brine, and drying with anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 3.01g of a solid. This was purified by column chromatography to obtain 2.22g of an oxime as a pale yellow solid.
< Oxime ester body >)
Oxime (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to dichloromethane 20mL and ice-cooled, triethylamine (1.77 g, 17.5 mmol) was added dropwise and the reaction was maintained for 1 hour. After confirming the disappearance of the starting material by thin layer chromatography, water was added to stop the reaction. The reaction mixture was washed 2 times with 5mL of saturated aqueous sodium bicarbonate solution, 2 times with 5mL of saturated brine, and dried over anhydrous sodium sulfate. After filtration, the organic layer was concentrated under reduced pressure, and the obtained residue was purified by column chromatography (ethyl acetate/hexane=volume ratio 2/1) to obtain 0.79g of photopolymerization initiator-I (compound of the following chemical structure) as a pale yellow solid. The chemical shift of photopolymerization initiator-I is shown below.
1H NMR(CDCl3)：δ1.17(d,3H),1.48(t,3H),1.81(s,3H),2.16(s,3H),2.30(s,3H),3.17-3.32(m,2H),4.42(q,2H),4.78-4.94(br,1H),7.45-7.59(m,5H),7.65(dd,1H),7.95(m,2H),8.04(m,2H),8.14(dd,1H),8.42(d,1H),8.64(d,1H)
[ Chemical formula 62]
< Photopolymerizable monomer >)
DPHA: dipentaerythritol hexaacrylate manufactured by Japanese Kaisha Co., ltd
< Surfactant >)
Megafac F-559 manufactured by DIC Co., ltd
< Additive >)
KAYAMER PM-21 (phosphoric acid ester containing methacryloyl group) manufactured by Japanese chemical Co., ltd
Preparation of pigment Dispersion 1-6
The colorant (pigment), dispersant, binder resin were added in the proportions shown in table 1 as the solid content, and the solvent was further mixed so as to have the mass ratios shown in table 1. The solution was subjected to a dispersion treatment at 25 to 45℃for 3 hours using a paint shaker. As the beads, zirconia beads of 0.5mm phi were used, to which 2.5 times the mass of the dispersion was added. After the completion of the dispersion, the beads were separated from the dispersion by a filter, and pigment dispersions 1 to 6 were prepared.
TABLE 1
Examples 1 to 6, reference example 1 and comparative example 1
Using the pigment dispersions 1 to 6 prepared above, the respective components were added so that the ratio of the solid components was set to the blending ratio in table 2, PGMEA was further added so that the content of the entire solid components was 22 mass%, and the resultant was stirred and dissolved to prepare a colored photosensitive resin composition. Using the obtained colored photosensitive resin composition, a pattern was produced and evaluated by a method described later.
TABLE 2
The numerical value of the blending ratio (parts by mass) in the table represents parts by mass converted to solid content
Method for manufacturing spacer substrate
On an ITO substrate (deposited with film thickness) using a spin coaterThe glass substrate of ITO of (c) is coated with each colored photosensitive resin composition. Subsequently, the resultant was dried by heating on a hot plate at 100℃for 80 seconds to form a coating film.
The obtained coating film was subjected to exposure treatment using an exposure mask having linear openings of various widths having an opening width of 5 to 50 μm (5 to 20 μm:1 μm interval, 25 to 50 μm:5 μm interval). The exposure gap (distance between the exposure mask and the coated surface) was 5. Mu.m. As the irradiation light, ultraviolet rays having an intensity of 32mW/cm 2 at a wavelength of 365nm were used, and the exposure amount was set to 60mJ/cm 2. The ultraviolet irradiation was performed in air.
Then, the development was stopped with pure water after spray development at 25℃under a water pressure of 0.05MPa using a developer made of 2.38% by mass aqueous TMAH (tetramethylammonium hydroxide) solution, and the resulting solution was washed with water and spray. The spray development time was adjusted to be 1.2 times the time for dissolving and removing the unexposed coating film, in the range of 10 to 120 seconds.
By the above operation, a pattern in which unnecessary portions are removed is obtained. The substrate on which the pattern was formed was heated in an oven at 230℃for 45 minutes to cure the pattern, thereby obtaining a linear pattern (pattern 1) having a film thickness of 2.5. Mu.m. In addition, an entire bread-coating pattern (pattern 2) having a film thickness of 2.5 μm was produced in the same manner except that the exposure mask was not used.
< Evaluation of substrate adhesion >
Table 2 shows the value of the mask opening width (μm) which is the smallest in width among the openings which remain on the substrate with good pattern resolution in the pattern corresponding to the linear openings of 5 to 50 μm as the minimum adhesion. The smaller the value, the more excellent the substrate adhesion, and if the minimum adhesion is 20 μm or less, the development adhesion to development is practically sufficient, and in particular, if it is 10 μm or less, the development adhesion to development is excellent.
< Evaluation method of degassing >)
About 3mg of the coating film was cut out from the substrate of pattern 2, and a sample for degassing measurement was obtained.
The sample was warmed from room temperature to 500℃at 10℃per minute under an air atmosphere (Flow 200 ml/min) using TG-DTA6300 (HITACHI HIGH-TECH SCIENCE Corporation), and the weight loss at this time was measured. Table 2 shows the weight reduction (mass%) of the total binder resin amount contained in each colored photosensitive resin composition when the temperature was raised from room temperature to 400 ℃. The weight reduction (mass%) of each colored photosensitive resin composition with respect to the total solid content thereof at a temperature elevated from room temperature to 400 ℃ was as follows in example 1:26.8, example 2:30.2, example 3:29.7, example 4:27.9, example 5:30.8, example 6:31.9, reference example 1:25.6, comparative example 1:33.7.
< Chroma >
Using the substrate of pattern 2 of example 1, a chromaticity (D65 light source) in an XYZ color system was calculated by measuring a specular reflectance of 5 degrees at a wavelength of 380 to 780nm from the coating film side using a spectrophotometer UV-3100 (manufactured by shimadzu corporation) with an aluminum vapor deposition plate as a reference plate.
Sx=0.323 and sy=0.329 for the substrate of example 1.
It was confirmed that the coated substrates using the colored photosensitive resin compositions of examples 1 to 6 and reference example 1 were excellent in degassing property.
In contrast, it was confirmed that the coated substrate using the colored photosensitive resin composition of comparative example 1 had poor degassing properties.
The binder resins of the colored photosensitive resin compositions of examples 1 to 6 and reference example 1 contained a higher proportion of epoxy (meth) acrylate resin than the colored photosensitive resin composition of comparative example 1. Since the epoxy (meth) acrylate resin has a rigid skeleton, thermal decomposition is less likely to occur, and since the skeleton is rigid and adopts an aligned structure at the time of curing, a film having high crosslinkability is formed, and it is considered that the degassing property is improved by increasing the content of the epoxy (meth) acrylate resin in the binder resin.
On the other hand, it was confirmed that the coated substrates using the colored photosensitive resin compositions of examples 1to 6 were excellent in development adhesion of thin line patterns, as compared with the coated substrate using the colored photosensitive resin composition of reference example 1. Even the colored photosensitive resin composition of reference example 1 was sufficiently applicable as a spacer for an organic electroluminescent element of normal resolution, suggesting that the colored photosensitive resin compositions of examples 1to 6 were applicable as a spacer for an organic electroluminescent element of high resolution.
It is considered that the dispersant contained in the colored photosensitive resin composition of reference example 1 is not an acrylic dispersant, and therefore the developer is likely to penetrate into the film during development, and the fine line pattern is unlikely to remain on the substrate.
In contrast, since the dispersing agent contained in the colored photosensitive resin compositions of examples 1to 6 is an acrylic dispersing agent and has a main skeleton with a soft linear molecular structure, most of the adsorbing groups are adsorbed to the colorant, and therefore it is considered that the colorant is uniformly dispersed in the colored photosensitive resin composition, and the colorant as a developer-insoluble component in the obtained coating film is uniformly arranged to form a dense film, and penetration of the developer into the film during development is suppressed, and the film can be formed on the substrate even in a fine line pattern.
In addition, in the colored photosensitive resin compositions of examples 1 to 6, the content of the epoxy (meth) acrylate resin contained in the obtained colored photosensitive resin composition can be increased by preparing the colored photosensitive resin composition using the pigment dispersion liquid 1 to 5 containing the epoxy (meth) acrylate resin as the binder resin.

Claims (23)

1. A colored photosensitive resin composition comprising: (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator, wherein,
The (A) colorant comprises (A1) an organic black pigment, the (A1) organic black pigment contains at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound,
The (B) dispersant comprises an acrylic dispersant,
The binder resin (C) contains 75 mass% or more of (C1) an epoxy (meth) acrylate resin,
In the formula (I), R a1 and R a6 each independently represent a hydrogen atom, CH 3、CF3, a fluorine atom or a chlorine atom;
R a2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9 and R a10 each independently represent a hydrogen atom, a halogen atom 、Ra11、COOH、COORa11、COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、OOCNRa11Ra12、NO2、NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12、N＝CH2、N＝CHRa11、N＝CRa11Ra12、SH、SRa11、SORa11、SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11 or SO 2NRa11Ra12;
And, at least one combination selected from the group consisting of R a2 and R a3、Ra3 and R a4、Ra4 and R a5、Ra7 and R a8、Ra8 and R a9, and R a9 and R a10 are optionally bonded directly to each other, or bonded to each other by bridging with an oxygen atom, a sulfur atom, NH, or NR a11;
R a11 and R a12 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
2. The colored photosensitive resin composition according to claim 1, wherein the content of the (C1) epoxy (meth) acrylate resin in the (C) binder resin is 85 mass% or more.
3. The colored photosensitive resin composition according to claim 1 or 2, wherein the (C1) epoxy (meth) acrylate resin comprises one or both of an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (III),
In the formula (II), R 11 represents a hydrogen atom or a methyl group;
R 12 represents an optionally substituted 2-valent hydrocarbon group;
the benzene ring in formula (II) is optionally further substituted with any substituent;
* The bonding position is indicated by the number of the bonding sites,
In the formula (III), R 13 each independently represents a hydrogen atom or a methyl group;
r 14 represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R 15 and R 16 each independently represent an optionally substituted 2-valent aliphatic group;
m and n each independently represent an integer of 0 to 2;
* Indicating the bonding location.
4. The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the acrylic dispersant is an acrylic dispersant containing a nitrogen atom.
5. The colored photosensitive resin composition according to any one of claims 1 to 4, wherein the content of the (a) colorant is 60 mass% or less with respect to the total solid content of the colored photosensitive resin composition.
6. The colored photosensitive resin composition according to any one of claims 1 to 5, wherein the (a) colorant further comprises one or both of (A2) an organic coloring pigment and (A3) carbon black.
7. The colored photosensitive resin composition according to any one of claims 1 to 6, wherein the content of the (A1) organic black pigment in the (a) colorant is 10 mass% or more.
8. The colored photosensitive resin composition according to any one of claims 1 to 7, which is used for forming a partition wall of an organic electroluminescent element.
9. A colored photosensitive resin composition for forming a partition wall of an organic electroluminescent element, the colored photosensitive resin composition comprising: (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator, wherein,
The (A) colorant comprises (A1) an organic black pigment, the (A1) organic black pigment contains at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound,
The binder resin (C) contains 75 mass% or more of (C1) an epoxy (meth) acrylate resin,
In the formula (I), R a1 and R a6 each independently represent a hydrogen atom, CH 3、CF3, a fluorine atom or a chlorine atom;
R a2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9 and R a10 each independently represent a hydrogen atom, a halogen atom 、Ra11、COOH、COORa11、COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、OOCNRa11Ra12、NO2、NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12、N＝CH2、N＝CHRa11、N＝CRa11Ra12、SH、SRa11、SORa11、SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11 or SO 2NRa11Ra12;
And, at least one combination selected from the group consisting of R a2 and R a3、Ra3 and R a4、Ra4 and R a5、Ra7 and R a8、Ra8 and R a9, and R a9 and R a10 are optionally bonded directly to each other, or bonded to each other by bridging with an oxygen atom, a sulfur atom, NH, or NR a11;
R a11 and R a12 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
10. The colored photosensitive resin composition according to claim 9, wherein the content of the (C1) epoxy (meth) acrylate resin in the (C) binder resin is 85 mass% or more.
11. The colored photosensitive resin composition according to claim 9 or 10, wherein the (C1) epoxy (meth) acrylate resin comprises one or both of an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (III),
In the formula (II), R 11 represents a hydrogen atom or a methyl group;
R 12 represents an optionally substituted 2-valent hydrocarbon group;
the benzene ring in formula (II) is optionally further substituted with any substituent;
* The bonding position is indicated by the number of the bonding sites,
In the formula (III), R 13 each independently represents a hydrogen atom or a methyl group;
r 14 represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R 15 and R 16 each independently represent an optionally substituted 2-valent aliphatic group;
m and n each independently represent an integer of 0 to 2;
* Indicating the bonding location.
12. The colored photosensitive resin composition according to any one of claims 9 to 11, wherein the content of the (a) colorant is 60 mass% or less with respect to the total solid content of the colored photosensitive resin composition.
13. The colored photosensitive resin composition according to any one of claims 9 to 12, wherein the (a) colorant further comprises one or both of (A2) an organic coloring pigment and (A3) carbon black.
14. The colored photosensitive resin composition according to any one of claims 9 to 13, wherein the content of the (A1) organic black pigment in the (a) colorant is 10 mass% or more.
15. A partition wall composed of the colored photosensitive resin composition according to any one of claims 1 to 14.
16. An organic electroluminescent element comprising the partition wall according to claim 15.
17. An image display device comprising the organic electroluminescent element according to claim 16.
18. An illumination comprising the organic electroluminescent element of claim 16.
19. A pigment dispersion comprising: a colorant, a dispersant and a binder resin, wherein,
The (A) colorant comprises (A1) an organic black pigment, the (A1) organic black pigment contains at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound,
The (B) dispersant comprises an acrylic dispersant,
The (C) binder resin comprises (C1) an epoxy (meth) acrylate resin,
In the formula (I), R a1 and R a6 each independently represent a hydrogen atom, CH 3、CF3, a fluorine atom or a chlorine atom;
R a2、Ra3、Ra4、Ra5、Ra7、Ra8、Ra9 and R a10 each independently represent a hydrogen atom, a halogen atom 、Ra11、COOH、COORa11、COO-、CONH2、CONHRa11、CONRa11Ra12、CN、OH、ORa11、COCRa11、OOCNH2、OOCNHRa11、OOCNRa11Ra12、NO2、NH2、NHRa11、NRa11Ra12、NHCORa12、NRa11CORa12、N＝CH2、N＝CHRa11、N＝CRa11Ra12、SH、SRa11、SORa11、SO2Ra11、SO3Ra11、SO3H、SO3 -、SO2NH2、SO2NHRa11 or SO 2NRa11Ra12;
And, at least one combination selected from the group consisting of R a2 and R a3、Ra3 and R a4、Ra4 and R a5、Ra7 and R a8、Ra8 and R a9, and R a9 and R a10 are optionally bonded directly to each other, or bonded to each other by bridging with an oxygen atom, a sulfur atom, NH, or NR a11;
R a11 and R a12 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
20. The pigment dispersion according to claim 19, wherein the content of the dispersant (B) is 10 parts by mass or more based on 100 parts by mass of the colorant (a).
21. The pigment dispersion according to claim 19 or 20, wherein the (C1) epoxy (meth) acrylate resin comprises one or both of an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (III),
In the formula (II), R 11 represents a hydrogen atom or a methyl group;
R 12 represents an optionally substituted 2-valent hydrocarbon group;
the benzene ring in formula (II) is optionally further substituted with any substituent;
* The bonding position is indicated by the number of the bonding sites,
In the formula (III), R 13 each independently represents a hydrogen atom or a methyl group;
r 14 represents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R 15 and R 16 each independently represent an optionally substituted 2-valent aliphatic group;
m and n each independently represent an integer of 0 to 2;
* Indicating the bonding location.
22. The pigment dispersion according to any one of claims 19 to 21, wherein the acrylic dispersant is an acrylic dispersant containing a nitrogen atom.
23. The pigment dispersion liquid according to any one of claims 19 to 22, which is used for producing a colored photosensitive resin composition.
CN202410172111.4A 2016-12-02 2017-11-29 Colored photosensitive resin composition, pigment dispersion liquid, partition wall, organic electroluminescent element, image display device, and illumination Pending CN118151488A (en)

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Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118151488A (en) * 2016-12-02 2024-06-07 三菱化学株式会社 Colored photosensitive resin composition, pigment dispersion liquid, partition wall, organic electroluminescent element, image display device, and illumination
JP6950478B2 (en) * 2017-11-14 2021-10-13 東洋インキＳｃホールディングス株式会社 Photosensitive coloring compositions and color filters for color filters
JP2019160473A (en) * 2018-03-09 2019-09-19 三菱ケミカル株式会社 Coloring photosensitive composition for forming organic electroluminescent element partition, partition, organic electroluminescent element, image display device, and lighting
CN112313579A (en) * 2018-07-20 2021-02-02 三菱化学株式会社 Photosensitive colored resin composition, cured product, image display device, and illumination
JP7299036B2 (en) * 2019-02-21 2023-06-27 サカタインクス株式会社 Coloring composition and coloring resist composition
CN113597580B (en) * 2019-05-31 2024-08-02 株式会社力森诺科 Photosensitive resin composition, photosensitive resin film, multilayer printed wiring board, semiconductor package, and method for producing multilayer printed wiring board
WO2021045193A1 (en) * 2019-09-06 2021-03-11 三菱ケミカル株式会社 Photosensitive coloring composition, cured product, image display device and pigment dispersion liquid for image display devices
KR102696631B1 (en) * 2020-03-16 2024-08-21 동우 화인켐 주식회사 A photosensitive resin composition for forming partition wall, a partition wall structure prepared using the composition, and a display device comprising the partition wall structure
KR20230076816A (en) 2020-09-28 2023-05-31 미쯔비시 케미컬 주식회사 Photosensitive coloring composition, cured product, organic electroluminescent device and image display device
JP2022065931A (en) 2020-10-16 2022-04-28 山陽色素株式会社 Black pigment dispersion
KR20230076845A (en) * 2020-11-13 2023-05-31 가부시끼가이샤 레조낙 Pigment Dispersion Composition and Photosensitive Coloring Composition
KR20220095288A (en) 2020-12-29 2022-07-07 삼성디스플레이 주식회사 Display device and tiled display device including the same
TW202244161A (en) 2021-02-18 2022-11-16 日商三菱化學股份有限公司 Photosensitive colored composition, cured object, banks, organic electroluminescent element, and image display device
KR20230157944A (en) * 2021-03-17 2023-11-17 도레이 카부시키가이샤 Organic EL display device
JPWO2022230792A1 (en) 2021-04-28 2022-11-03
JP2023004245A (en) 2021-06-25 2023-01-17 山陽色素株式会社 Black pigment dispersion and chromatic color pigment dispersion
KR20240063852A (en) 2021-09-29 2024-05-10 도레이 카부시키가이샤 Photosensitive compositions, cured products, and organic EL display devices
EP4371672A1 (en) 2022-07-29 2024-05-22 LG Energy Solution, Ltd. Slot die coater
WO2024122565A1 (en) * 2022-12-06 2024-06-13 三菱ケミカル株式会社 Photosensitive colored resin composition, cured product, partition wall, organic electroluminescent element, color filter, and image display device

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011146375A (en) * 2009-12-17 2011-07-28 Mitsubishi Chemicals Corp Photosensitive composition for partition, and display device of organic electroluminescent element
JP5923960B2 (en) * 2011-08-05 2016-05-25 住友化学株式会社 Colored curable resin composition
CN105556390B (en) 2013-09-25 2020-02-28 三菱化学株式会社 Photosensitive coloring composition, black matrix, coloring spacer, image display device and pigment dispersion liquid
KR101474803B1 (en) * 2014-03-27 2014-12-19 제일모직주식회사 Method of manufacturing black column spacer, black column spacer, and color filter
JP6344967B2 (en) * 2014-05-08 2018-06-20 東洋インキＳｃホールディングス株式会社 Photosensitive coloring composition, brightness adjusting layer, color filter, and color display device
CN104238269A (en) * 2014-09-19 2014-12-24 江苏博砚电子科技有限公司 Photosensitive resin composition and application thereof
JP2016109763A (en) * 2014-12-03 2016-06-20 東レ株式会社 Photosensitive composition, solid state image sensor prepared therewith and method for producing the same
JP6464764B2 (en) * 2015-01-16 2019-02-06 Jsr株式会社 Radiation-sensitive coloring composition, spacer, method for forming the same, and liquid crystal display device
JP6543968B2 (en) * 2015-03-06 2019-07-17 三菱ケミカル株式会社 Photosensitive coloring composition, cured product, coloring spacer, and image display device
JP6528475B2 (en) * 2015-03-10 2019-06-12 三菱ケミカル株式会社 Photosensitive coloring composition, cured product, coloring spacer, and image display device
US10896942B2 (en) * 2015-03-11 2021-01-19 Toray Industries, Inc. Organic EL display device and method for manufacturing same
TWI723994B (en) * 2015-05-22 2021-04-11 日商富士軟片股份有限公司 Colored composition, film, color filter, pattern forming method, method of manufacturing color filter, solid-state imaging element, and infrared sensor
CN118151488A (en) * 2016-12-02 2024-06-07 三菱化学株式会社 Colored photosensitive resin composition, pigment dispersion liquid, partition wall, organic electroluminescent element, image display device, and illumination

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