JP7449765B2 - Photosensitive colored resin compositions, cured products, color filters, display devices - Google Patents

Description

The present invention relates to a photosensitive colored resin composition, a cured product, a color filter, and a display device.

In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays has increased. The penetration rate of mobile displays (mobile phones, smartphones, tablet PCs) is increasing, and the market for liquid crystal displays is expanding. Organic light emitting display devices such as organic EL displays, which have high visibility due to their self-emission, are also attracting attention as next-generation image display devices.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, when forming a color image on a liquid crystal display device, light that has passed through a color filter is colored as it is in the color of each pixel that makes up the color filter, and the lights of these colors are combined to form a color image. In addition to conventional cold cathode tubes, organic light emitting elements that emit white light or inorganic light emitting elements that emit white light may be used as light sources in this case. Organic light emitting display devices use color filters for color adjustment and the like.

Here, the color filter generally includes a substrate, a colored layer formed on the substrate and consisting of colored patterns of the three primary colors of red, green, and blue, and formed on the substrate so as to partition each colored pattern. It has a light shielding part.
As a method for forming a colored layer in a color filter, for example, a colored resin composition is prepared by adding a binder resin, a photopolymerizable compound, and a photoinitiator to a coloring material dispersion obtained by dispersing a coloring material with a dispersant or the like. After coating on a glass substrate and drying, a colored pattern is formed by exposing using a photomask and developing, and the pattern is fixed by heating to form a colored layer. These steps are repeated for each color to form a color filter.

In recent years, as the demand for higher brightness of color filters has increased, the concentration of coloring material in the colored layer of color filters has become higher than before, which has relatively reduced the amount of components required for photopolymerization, making it easier to pattern. is becoming difficult. Furthermore, in order to improve the productivity of color filters, it is required to reduce the cumulative exposure amount required for patterning, and how to ensure the curability necessary for patterning has become a major issue.

In order to ensure the curability necessary for patterning the colored layer, a photoinitiator with a relatively small molecular weight, such as Irgacure 907, is used as a highly sensitive photoinitiator in colored resin compositions for color filters. However, this caused contamination of photomasks and heating furnaces due to sublimate.
Therefore, Patent Document 1 discloses a specific oxime ester compound as a highly sensitive photopolymerization initiator that has excellent stability, low sublimation, and is activated by efficiently absorbing near-ultraviolet light such as 365 nm. are doing.
Further, as a highly sensitive photoinitiator, for example, Patent Document 2 discloses a specific o-acyloxime compound as a photoinitiator that is highly reactive, easy to synthesize, and easy to handle.
Further, Patent Document 3 discloses a specific oxime ester compound as a highly sensitive photoinitiator.

International Publication No. 2015/152153 Japanese Patent Application Publication No. 2000-80068 Japanese Patent Application Publication No. 2006-516246

Conventionally, color filters have been formed on glass substrates, but in recent years there has been a demand for forming color filters directly on element substrates.
Since elements such as organic light-emitting elements have low heat resistance, it is said that heat treatment in the manufacturing process of directly forming a color filter on the element substrate is preferably performed at 90° C. or lower. In a normal color filter manufacturing process, a colored layer is hardened by heat treatment at about 230° C. on a glass substrate, whereas hardening of the colored layer due to heat is difficult to proceed with heat treatment at 90° C. or lower. Therefore, in order to give the colored layer the solvent resistance required in the subsequent process, it is necessary to sufficiently cure the colored layer by exposure. In order to accelerate the curing of the colored layer by exposure to light, it is possible to use a highly sensitive initiator. However, a highly sensitive initiator tends to have a large amount of line width shift, and when producing a thin line pattern, there is a problem that the pattern size becomes larger than expected. Furthermore, even if the colored layer contains a highly sensitive initiator and is cured by exposure to light, the required solvent resistance cannot always be obtained by heat treatment at 90° C. or lower.

The present invention has been made in view of the above circumstances, and aims to provide a photosensitive colored resin composition that can form a colored layer with good solvent resistance even during low-temperature heat treatment while suppressing the amount of line width shift. purpose. Another object of the present invention is to provide a color filter and a display device formed using the photosensitive colored resin composition.

The photosensitive colored resin composition according to the present invention contains a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
The dispersant contains a (meth)acrylate copolymer-based dispersant,
The photoinitiator contains a compound represented by the following general formula (A).

(wherein R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN,
R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocyclic group of number 2 to 20,
The hydrogen atoms of the groups represented by R ¹¹ , R ¹² and R ¹³ are further represented by R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² - OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , ^{CSOR 21} , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocyclic group of number 2 to 20,
The hydrogen atoms of the groups represented by R ²¹ , R ²² and R ²³ may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group,
The alkylene moiety of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO- may contain 1 to 5 of them, provided that oxygen atoms are not adjacent to each other,
R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; ,
The alkyl portion of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ may have a branched side chain or may be a cyclic alkyl,
R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; , the alkyl portion of the group represented by R ³ may have a branched side chain or may be a cyclic alkyl, and R ³ and R ⁷ and R ³ and R ⁸ are each taken together. It may form a ring,
The hydrogen atom of the group represented by R ³ is further R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , which may be substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ represent a hydroxyl group, CN or a halogen atom, and R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ and R ⁷ may each be taken together to form a ring,
R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl portion of the group represented by R ¹⁴ , R ¹⁵ and R ¹⁶ has a branched side chain. Often, R ⁸ may be a cyclic alkyl, R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ represents a hydroxyl group, CN or a halogen atom,
k represents 0 or 1. )

The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is formed by curing the photosensitive colored resin composition according to the present invention. It is a thing.

A display device according to the present invention includes the color filter according to the present invention.

According to the present invention, it is possible to provide a photosensitive colored resin composition that can form a colored layer with good solvent resistance even during low-temperature heat treatment while suppressing the amount of line width shift. Moreover, according to the present invention, a color filter and a display device formed using the photosensitive colored resin composition can be provided.

FIG. 1 is a schematic diagram showing an example of a color filter of the present invention. FIG. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. FIG. 3 is a schematic diagram showing an example of an organic light emitting display device of the present invention. FIG. 4 is a diagram schematically showing a part of an example of the structure of the graft copolymer used in the present invention. FIG. 5 is a schematic diagram illustrating the taper angle (θ1) of the cross-sectional shape of the colored layer having a thin line pattern. FIG. 6 is a schematic diagram illustrating the taper angle (θ2) of the cross-sectional shape of micropores in the colored layer.

Hereinafter, the photosensitive colored resin composition, cured product, color filter, and display device according to the present invention will be explained in detail in order.
Note that in the present invention, light includes electromagnetic waves with wavelengths in visible and non-visible regions, as well as radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 μm or less and electron beams.
In the present invention, (meth)acryloyl represents each of acryloyl and methacryloyl, (meth)acrylic represents each of acrylic and methacryl, and (meth)acrylate represents each of acrylate and methacrylate.
Furthermore, in this specification, "~" indicating a numerical range is used to include the numerical values written before and after it as a lower limit value and an upper limit value.

I. Photosensitive colored resin composition
The photosensitive colored resin composition according to the present invention contains a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
The dispersant contains a (meth)acrylate copolymer-based dispersant,
The photoinitiator contains a compound represented by the following general formula (A).

(wherein R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN,
R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocyclic group of numbers 2 to 20,
The hydrogen atoms of the groups represented by R ¹¹ , R ¹² and R ¹³ are further represented by R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² - OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , ^{CSOR 21} , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocyclic group of numbers 2 to 20,
The hydrogen atoms of the groups represented by R ²¹ , R ²² and R ²³ may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group,
The alkylene moiety of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO- may contain 1 to 5 of them, provided that oxygen atoms are not adjacent to each other,
R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; ,
The alkyl portion of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ may have a branched side chain or may be a cyclic alkyl,
R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; , the alkyl portion of the group represented by R ³ may have a branched side chain or may be a cyclic alkyl, and R ³ and R ⁷ and R ³ and R ⁸ are each taken together. May form a ring,
The hydrogen atom of the group represented by R ³ is further R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , which may be substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ represent a hydroxyl group, CN or a halogen atom, and R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ and R ⁷ may each be taken together to form a ring,
R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl portion of the group represented by R ¹⁴ , R ¹⁵ and R ¹⁶ has a branched side chain. Often, R ⁸ may be a cyclic alkyl, R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ represents a hydroxyl group, CN or a halogen atom,
k represents 0 or 1. )

The photosensitive colored resin composition according to the present invention uses the above-mentioned (meth)acrylate copolymer-based dispersant as a dispersant, and contains the compound represented by the general formula (A) as a photoinitiator. , it is possible to form a colored layer with good solvent resistance even when low temperature heat treatment is performed after exposure while suppressing the amount of line width shift. Although the mechanism for producing such an effect is not yet clear, it is presumed to be as follows.

In order to form a colored layer with good solvent resistance even during low-temperature heat treatment, it is necessary to make the cured state of the colored layer uniform within the colored layer, but the compatibility between the initiator and other components depends on the cured state. It is thought that this will affect the A photosensitive resin coloring composition usually contains a dispersant in order to uniformly disperse the coloring material. Even if the initiator used in the present invention is used, depending on the dispersant used, line width shifts may become large or a colored layer having sufficient solvent resistance may not be obtained by low-temperature heat treatment. It is thought that when the compatibility between the initiator and other components is low, the initiator tends to be unevenly distributed on the surface of the colored layer, and curing progresses further on the surface of the colored layer, resulting in a large line width shift.
On the other hand, in the photosensitive resin composition of the present invention, the above-mentioned (meth)acrylate copolymer-based dispersant is used as a dispersant, and the compound represented by the above general formula (A) is contained as a photoinitiator. Therefore, the compatibility between the initiator and other components is improved, and the initiator is more likely to exist uniformly in the colored layer. Therefore, curing progresses only on the surface and the line width shift is suppressed from increasing, and the colored layer hardens uniformly, reducing unreacted components and reducing the internal stress of the colored layer, so when immersed in a solvent, It is estimated that the change in the colored layer will be smaller. The combination of the dispersant and photoinitiator provides sufficient solvent resistance even during low-temperature heat treatment. This is presumed to be due to high compatibility.
Furthermore, when the (meth)acrylate copolymer-based dispersant is a graft copolymer with branched solvent affinity moieties or a copolymer with an acid value, the compatibility with the initiator and other components is improved. It is presumed that the initiator can be kept uniformly and stably in the film, and the solvent resistance can also be improved.

The photosensitive colored resin composition according to the present invention contains at least a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, and has the effects of the present invention. It may further contain other components within a range that does not impair the properties.
Hereinafter, each component of the photosensitive colored resin composition according to the present invention will be explained in detail in order from the dispersant and photoinitiator, which are the characteristic combination of the present invention.

<Dispersant>
In the present invention, a (meth)acrylate copolymer-based dispersant is used as the dispersant.
The (meth)acrylate copolymer-based dispersant refers to a dispersant that is a copolymer and contains at least a structural unit derived from (meth)acrylate.
The (meth)acrylate copolymer-based dispersant is preferably a copolymer containing a structural unit that functions as a coloring material adsorption site and a constitutional unit that functions as a solvent affinity site, and functions as a solvent affinity site. It is preferable that the structural units include at least (meth)acrylate-derived structural units.

Examples of the structural unit functioning as a coloring material adsorption site include a structural unit derived from an ethylenically unsaturated monomer that is copolymerizable with a structural unit derived from (meth)acrylate. The colorant adsorption site may be a structural unit derived from an ethylenically unsaturated monomer containing an acidic group or a structural unit derived from an ethylenically unsaturated monomer containing a basic group.
As the structural unit derived from the basic group-containing ethylenically unsaturated monomer, a structural unit represented by the following general formula (I) is preferable from the viewpoint of excellent dispersibility.

（一般式（Ｉ）中、Ｒ^４１は水素原子又はメチル基、Ａ^１は２価の連結基、Ｒ^４２及びＲ^４３は、それぞれ独立して、水素原子、又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ^４２及びＲ^４３が互いに結合して環構造を形成してもよい。）

(In general formula (I), R ⁴¹ is a hydrogen atom or a methyl group, A ¹ is a divalent linking group, R ⁴² and R ⁴³ are each independently a hydrogen atom or a hydrocarbon that may contain a heteroatom) (Represents a group, and R ⁴² and R ⁴³ may be bonded to each other to form a ring structure.)

In general formula (I), A ¹ is a divalent linking group. Examples of the divalent linking group include a straight chain, branched or cyclic alkylene group, a straight chain, branched or cyclic alkylene group having a hydroxyl group, an arylene group, -CONH- group, -COO- group, -NHCOO- group, ether group (-O- group), thioether group (-S- group), and combinations thereof. In the present invention, the direction of bonding of the divalent linking group is arbitrary. That is, when the divalent linking group contains -CONH-, -CO may be on the carbon atom side of the main chain and -NH may be on the nitrogen atom side of the side chain, or conversely, -NH may be on the side chain nitrogen atom side. -CO may be on the side chain nitrogen atom side.
Among them, from the viewpoint of dispersibility, A ¹ in general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group is preferably a divalent linking group. , and an alkylene group having 1 to 10 carbon atoms.

Examples of the hydrocarbon group in R ⁴² and R ⁴³ which may include a heteroatom include an alkyl group, an aralkyl group, and an aryl group.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a tert-butyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclohexyl group, and the number of carbon atoms in the alkyl group is as follows: 1 to 18 are preferable, and among them, a methyl group or an ethyl group is more preferable.
Examples of the aralkyl group include benzyl group, phenethyl group, naphthylmethyl group, and biphenylmethyl group. The number of carbon atoms in the aralkyl group is preferably 7 to 20, more preferably 7 to 14.
Further, examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The number of carbon atoms in the aryl group is preferably 6 to 24, more preferably 6 to 12. Note that the above preferred number of carbon atoms does not include the number of carbon atoms of substituents.
A hydrocarbon group containing a hetero atom has a structure in which a carbon atom in the above hydrocarbon group is replaced with a hetero atom, or a structure in which a hydrogen atom in the above hydrocarbon group is replaced with a substituent containing a hetero atom. has. Examples of the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom.
Further, the hydrogen atom in the hydrocarbon group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.

The expression that R ⁴² and R ⁴³ are bonded to each other to form a ring structure means that R ⁴² and R ⁴³ form a ring structure via a nitrogen atom. The ring structure formed by R ⁴² and R ⁴³ may contain a heteroatom. Although the ring structure is not particularly limited, examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

In the present invention, among others, R ⁴² and R ⁴³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R ⁴² and R ⁴³ are combined to form a pyrrolidine ring, It is preferable that a piperidine ring or a morpholine ring is formed.

Monomers for inducing the structural unit represented by the above general formula (I) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, etc. Examples include alkyl group-substituted amino group-containing (meth)acrylates, and alkyl group-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide and dimethylaminopropyl (meth)acrylamide. Among them, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide are preferably used because they improve dispersibility and dispersion stability.
In the polymer, the structural unit represented by the general formula (I) may consist of one type, or may contain two or more types of structural units.

Furthermore, the structural unit functioning as a colorant adsorption site is selected from the group consisting of at least a part of the nitrogen site possessed by the structural unit represented by the general formula (I), an organic acid compound, and a halogenated hydrocarbon. At least one kind may form a salt (hereinafter, such a copolymer may be referred to as a salt-type copolymer).
As the organic acid compound, a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are particularly preferable, and as the halogenated hydrocarbon, among others, a compound represented by the following general formula (2) is preferable. ) are preferred. That is, as at least one selected from the group consisting of the organic acid compound and halogenated hydrocarbon, it is preferable to use one or more compounds selected from the group consisting of the following general formulas (1) to (3). can.

(In the general formula (1), R ^a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -O- R ^e represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms ^, a vinyl group, a phenyl group or benzyl group which may have a substituent, or a C 1 to 4 Represents a (meth)acryloyl group via an alkylene group. In general formula (2), R ^b , R ^b' , and R ^b'' each independently represent a hydrogen atom, an acidic group or an ester group thereof, or a substituent. a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group or benzyl group which may have a substituent, or -O- R ^f represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, a vinyl group which may have a substituent, and a vinyl group having a substituent ^. represents an optional phenyl group or benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom.In the general formula (3) , R ^c and R ^d each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or a benzyl group which may have a substituent, Alternatively, it represents -O-R ^e , where R ^e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or a carbon number Represents a (meth)acryloyl group via 1 to 4 alkylene groups.However, at least one of R ^c and R ^d contains a carbon atom.)

Each symbol in the general formulas (1) to (3) may be the same as described in International Publication No. 2016/104493.
It is preferable that the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid from the viewpoint of excellent dispersibility and dispersion stability of the coloring material. Preferred examples of organic acid compounds used in such dispersants include those described in JP-A-2012-236882 and the like.
Further, the halogenated hydrocarbon is preferably at least one of allyl halides such as allyl bromide and benzyl chloride, and aralkyl halides, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.

In the salt-type copolymer, the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is such that it forms a salt with the terminal nitrogen moiety of the structural unit represented by general formula (I). Therefore, the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is 0 with respect to the terminal nitrogen moiety of the structural unit represented by general formula (I). The amount is preferably 0.01 mol or more, more preferably 0.05 mol or more, even more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more. When it is at least the above lower limit, the effect of improving coloring material dispersibility due to salt formation is likely to be obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, even more preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When it is below the above upper limit, it can provide excellent development adhesion and solvent resolubility.
Note that at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used alone or in combination of two or more. When two or more types are combined, it is preferable that the total content is within the above range.

As a method for preparing a salt-type copolymer, at least one member selected from the group consisting of the organic acid compound and halogenated hydrocarbon is added to a solvent in which the copolymer before salt formation is dissolved or dispersed, and the mixture is stirred. , and a method of heating if necessary.
Note that the terminal nitrogen moiety of the structural unit represented by the general formula (I) of the copolymer and at least one member selected from the group consisting of the organic acid compound and halogenated hydrocarbon form a salt. The presence and proportion thereof can be confirmed by known methods such as NMR.

The copolymer having the structural unit represented by the general formula (I) has the structural unit represented by the general formula (I) from the viewpoint of dispersibility and dispersion stability, and has ( A graft copolymer having a structural unit derived from meth)acrylate, and a block having an A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit derived from (meth)acrylate. More preferably, it is at least one type of copolymer.
Hereinafter, the graft copolymer and the block copolymer will be explained in order.

A graft copolymer having a structural unit represented by the general formula (I) and having a (meth)acrylate-derived structural unit in the graft polymer chain includes a structural unit represented by the general formula (I) and a (meth)acrylate-derived structural unit in the graft polymer chain. A graft copolymer having a structural unit represented by the following general formula (II), and at least a part of the nitrogen moiety of the structural unit represented by the general formula (I) of the graft copolymer and an organic Examples include at least one salt-type graft copolymer in which a salt is formed with at least one selected from the group consisting of acid compounds and halogenated hydrocarbons.

（一般式（ＩＩ）中、Ｒ^４１’は水素原子又はメチル基、Ａ^２は直接結合又は２価の連結基、Ｐｏｌｙｍｅｒはポリマー鎖を表し、当該ポリマー鎖の構成単位には、（メタ）アクリレート由来の構成単位が含まれる。）

(In general formula (II), R ^41' is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, and Polymer represents a polymer chain, and the constituent units of the polymer chain include (meth)acrylate (Contains the derived constituent units)

In the general formula (II), A ² is a direct bond or a divalent linking group. The divalent linking group in ^A2 is not particularly limited as long as it is capable of linking a carbon atom derived from an ethylenically unsaturated double bond to a polymer chain. Examples of the divalent linking group in A ² include those similar to the divalent linking group in A ¹ above.
Among these, from the viewpoint of dispersibility, A ² in general formula (II) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group is preferably a divalent linking group. , and a divalent linking group containing an alkylene group having 1 to 10 carbon atoms.

In the general formula (II), Polymer represents a polymer chain, and the constitutional units of the polymer chain include (meth)acrylate-derived constitutional units. The graft copolymer has a structural unit represented by the general formula (II) having a specific polymer chain, so that it has good solvent affinity and good dispersibility and dispersion stability of the coloring material. In addition, the compatibility with the photoinitiator described below is also improved.
Examples of the structural unit of the polymer chain include a structural unit represented by the following general formula (IV).

（一般式（ＩＶ）中、Ｒ^４４”は水素原子又はメチル基、Ａ^４は２価の連結基、Ｒ^５０は、水素原子、又はヘテロ原子を含んでもよい炭化水素基である。）

(In general formula (IV), R ^44'' is a hydrogen atom or a methyl group, A ⁴ is a divalent linking group, and R ⁵⁰ is a hydrogen atom or a hydrocarbon group that may contain a hetero atom.)

Examples of the divalent linking group for A ⁴ include those similar to the divalent linking group for A ¹ above. In the present invention, as a structural unit derived from (meth)acrylate, a structural unit represented by general formula (IV) in which A ⁴ in general formula (IV) is a divalent linking group containing a -COO- group is used. , at least included. From the viewpoint of solubility in organic solvents used in color filter applications, A ⁴ in general formula (IV) may contain a divalent linking group containing a -CONH- group.

Examples of the hydrocarbon group in the hydrocarbon group that may contain a heteroatom in R ⁵⁰ include an alkyl group, an alkenyl group, an aryl group, and combinations thereof such as an aralkyl group and an alkyl-substituted aryl group. Examples of the hydrocarbon group in the hydrocarbon group that may contain a heteroatom in R ⁵⁰ include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, and an alkyl-substituted group. Combinations of these include aryl groups and the like.
The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n- Examples include nonyl group, n-lauryl group, n-stearyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, and lower alkyl group-substituted adamantyl group. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched, or cyclic. Examples of such alkenyl groups include vinyl, allyl, and propenyl groups. Although there is no limitation on the position of the double bond in the alkenyl group, from the viewpoint of the reactivity of the obtained polymer, it is preferable that the double bond is located at the terminal of the alkenyl group. The alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.
Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The number of carbon atoms in the aryl group is preferably 6 to 24, more preferably 6 to 12.
Further, examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, and may further have a substituent. The number of carbon atoms in the aralkyl group is preferably 7 to 20, more preferably 7 to 14.
Furthermore, a linear or branched alkyl group having 1 to 30 carbon atoms may be bonded to the aromatic ring such as the aryl group or aralkyl group as a substituent.

Among the hydrocarbon groups in R ⁵⁰ , from the viewpoint of dispersion stability, alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 12 carbon atoms which may be substituted with an alkyl group, and alkyl groups. It is preferably one or more selected from the group consisting of an optionally substituted aralkyl group having 7 to 14 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an n-butyl group. -nonyl group, n-lauryl group, n-stearyl group, a phenyl group which may be substituted with an alkyl group, and a benzyl group.

Examples of the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. Examples of hydrocarbon groups that may contain heteroatoms include -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, - S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O- , -O-NH-, and other connecting groups.
Further, the hydrocarbon group may have a substituent within a range that does not interfere with the dispersion performance of the graft copolymer, and examples of the substituent include a halogen atom, a hydroxyl group, a carboxy group, an alkoxy group, Examples include nitro group, cyano group, epoxy group, isocyanate group, and thiol group.

Further, the hydrocarbon group which may contain a hetero atom in R ⁵⁰ may have a structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a linking group containing a hetero atom. For example, the structural unit represented by general formula (IV) may have a structure in which a structural unit derived from (meth)acrylic acid is reacted with glycidyl (meth)acrylate. That is, the structure of -A ⁴ -R ⁵⁰ in general formula (IV) is represented by -COO-CH ₂ CH(OH)CH ₂ -OCO-CR=CH ₂ (wherein, R is a hydrogen atom or a methyl group). It is also possible to have a structure in which Further, the structural unit represented by the general formula (IV) may have a structure in which a structural unit derived from hydroxyalkyl (meth)acrylate is reacted with 2-isocyanatoalkyl (meth)acrylate. That is, R ⁵⁰ in general formula (IV) is -R'-OCONH-R''-OCO-CR=CH ₂ (where R' and R'' are each independently an alkylene group, and R is a hydrogen atom or a methyl group. ) may be the structure shown.

Examples of monomers inducing the structural unit represented by general formula (IV) include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. Acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate , dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, (meth)acrylic acid, 2-methacryloyloxyethyl succinate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2- Hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, methoxypolyethylene glycol with an ethylene oxide chain repeating unit number of less than 19 ( Those having structural units derived from meth)acrylate, polyethylene glycol (meth)acrylate, phenoxyethylene glycol (meth)acrylate, etc. are preferred. However, it is not limited to these.

In the present invention, as the ^R50 , it is preferable to use one having excellent solubility in the organic solvent described below, and may be appropriately selected according to the organic solvent used in the coloring material dispersion. Specifically, when the organic solvent is an ether-alcohol acetate-based, ether-based, ester-based, or alcohol-based organic solvent that is commonly used as an organic solvent for colorant dispersions, methyl group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, benzyl group, cyclohexyl group, dicyclopentanyl group, hydroxyethyl group, phenoxyethyl group, adamantyl group, methoxypolyethylene glycol group, methoxypolypropylene glycol group , polyethylene glycol group, etc. are preferred.

The graft copolymer has a structural unit represented by the following general formula (III) and a structural unit represented by the following general formula (III') in the structural unit of the polymer chain in the structural unit represented by the general formula (II). Containing at least one kind of structural unit selected from the group consisting of the following structural units reduces the development time of the photosensitive resin composition and improves the solvent resistance of the cured product of the photosensitive colored resin composition. This is preferable because it provides even better results.
The structural units represented by the following general formula (III) and the structural units represented by the following general formula (III') are structural units included in the structural units represented by the general formula (IV).

(In general formula (III), R ⁴⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁴⁵ is an ethylene group or a propylene group, R ⁴⁶ is a hydrogen atom or a hydrocarbon group, m represents a number from 3 to 80.
In general formula (III'), R ^44' is a hydrogen atom or a methyl group, A ^3' is a divalent linking group, R ⁴⁷ is an alkylene group having 1 to 10 carbon atoms, and R ⁴⁸ is an alkylene group having 3 to 7 carbon atoms. The alkylene group R ⁴⁹ is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 or more and 40 or less. )

Examples of the divalent linking group for A ³ include those similar to the divalent linking group for A ¹ above. Among them, from the viewpoint of solubility in organic solvents used for color filter applications, A ³ in general formula (III) is preferably a divalent linking group containing a -CONH- group or a -COO- group. , -CONH- group or -COO- group, and even more preferably -COO- group.

The m represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and represents a number of 3 or more, but from the viewpoint of suppressing the occurrence of water stains, it is preferably 19 or more, and more preferably 21 or more. . Note that water staining refers to this phenomenon in which water stains appear after rinsing with pure water after alkaline development. Such water stains disappear after post-baking, so there is no problem with the product, but when the patterned surface is inspected after development, it is detected as an irregularity abnormality, making it difficult to distinguish between normal and abnormal products. arise. Therefore, if the inspection sensitivity of the inspection device is lowered in the appearance inspection, the yield of the final color filter product will be lowered, which poses a problem. Water absorption into the cured film can be cited as a cause of water stains on the cured film of the photosensitive resin composition. Since the alkali-soluble resin in the cured film has acidic groups such as carboxy groups, it easily absorbs water. It is also believed that the acidic group forms a metal salt with an alkali metal typically contained in an alkaline developer during development, thereby further increasing water absorption. The oxygen atoms contained in the polyethylene oxide chain or polypropylene oxide chain can be captured by forming a complex with a metal such as an alkali metal. As the number of repeating units of polyethylene oxide chains or polypropylene oxide chains increases, the complex formation constant increases and the ability to capture metal molecules increases, which suppresses the formation of alkali metal salts in alkali-soluble resins and increases the amount of infiltration into the cured film. It is assumed that water absorption can be suppressed. In addition, the oxygen atoms contained in the polyethylene oxide chain or polypropylene oxide chain interact with the acidic groups such as the carboxyl groups of the alkali-soluble resin contained in the photosensitive resin composition through hydrogen bonds, thereby forming an alkali of the acidic group. It is presumed that metal salt formation can be suppressed and water absorption into the cured film can be suppressed.
When m is 19 or more, as shown in FIG. 4, the graft copolymer 11 comprises a structural unit 21 represented by general formula (I) and a structural unit represented by general formula (II). 22, at least a portion of the nitrogen moieties of the structural unit 21 represented by the general formula (I), and at least one selected from the group consisting of an organic acid compound and a halogenated hydrocarbon. The structural unit 22 represented by the general formula (II) may have a general formula containing a polyethylene oxide chain or a polypropylene oxide chain 26 having a specific number of repeats in the polymer chain 24. A structural unit 25 represented by (III) is included. In the specific graft copolymer used in the present invention, the structural units of the polymer chain 24 grafted in this way include a structural unit 25 having a polyethylene oxide chain or a polypropylene oxide chain having a specific repeating number. , the grafted polymer chains 24 themselves have a branched structure. As a result, the specific surface area of the metal-trapping part of the dispersant becomes larger, and the metal-trapping effect by the oxygen atoms contained in the polyethylene oxide chain or polypropylene oxide chain becomes more pronounced, improving the water absorption suppressing effect. It is estimated that the occurrence of water stains due to water absorption can be suppressed. It is presumed that these effects of suppressing water absorption into the cured film can suppress the occurrence of water stains due to water absorption.
On the other hand, the upper limit of m is 80 or less, but is preferably 50 or less from the viewpoint of solubility in organic solvents used in color filter applications.

The hydrocarbon group for R ⁴⁶ may be the same as the hydrocarbon group for R ⁵⁰ above.
Examples of the hydrocarbon group for R ⁴⁶ include, from the viewpoint of dispersion stability and compatibility, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group, and The alkyl group is preferably one or more selected from the group consisting of optionally substituted aralkyl groups having 7 to 14 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group. The alkyl group is preferably one or more selected from the group consisting of an n-nonyl group, an n-lauryl group, an n-stearyl group, an optionally substituted phenyl group, and a benzyl group.

Further, in the general formula (III'), examples of the divalent linking group of A ^3' include the same divalent linking group as the divalent linking group of A ¹ above. Among them, from the viewpoint of solubility in organic solvents used for color filter applications, A ^3' in general formula (III') should be a divalent linking group containing a -CONH- group or a -COO- group. is preferable, -CONH- group or -COO- group is more preferable, and -COO- group is even more preferable.
In the general formula (III'), R ⁴⁷ is an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 2 to 8 carbon atoms is particularly preferable from the viewpoint of resolubility in a solvent.
R ⁴⁸ is an alkylene group having 3 to 7 carbon atoms, and among them, an alkylene group having 3 to 5 carbon atoms, and more preferably an alkylene group having 5 carbon atoms, from the viewpoint of adhesion to the substrate.
R ⁴⁹ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group for R ⁴⁹ may be the same as the hydrocarbon group for R ⁴⁶ .

The n in the general formula (III') represents the number of repeating units of the ester chain, and is a number of 1 or more, but from the viewpoint of shortening the development time and satisfying excellent solvent resistance at the same time, n is 2 or more. It is preferable that there be one, and more preferably three or more.
On the other hand, the upper limit of n is 40 or less, but is preferably 20 or less from the viewpoint of solubility in organic solvents used in color filter applications.

In the polymer chain, at least one type of structural unit selected from the group consisting of the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III') is one type alone. However, two or more types may be mixed.
In the polymer chain, the inclusion of the structural unit represented by the general formula (III) makes the effect of the solvent affinity part by the oxygen atom more pronounced, shortening the development time of the photosensitive resin composition, It is preferable from the viewpoint of improving solvent resistance.

Among them, m is added to the structural unit of the polymer chain in the structural unit represented by the general formula (II) from the viewpoint of improving the water stain suppressing effect, improving solvent resistance, and improving the development residue suppressing effect. At least one type selected from the group consisting of structural units represented by the general formula (III) where m is 19 or more and 80 or less, and a structural unit represented by the general formula (III) where m is 3 or more and 10 or less It is more preferable to contain at least one kind selected from the group consisting of a structural unit represented by the general formula (III) in which m is 19 or more and 50 or less. , and at least one selected from the group consisting of structural units represented by the general formula (III) in which m is 3 or more and 8 or less.

The structural unit of the polymer chain in the structural unit represented by the general formula (II) is at least one selected from the group consisting of structural units represented by the general formula (III) in which m is 19 or more and 80 or less. When containing, the total proportion of the structural units represented by the general formula (III) where m is 19 or more and 80 or less, when the total structural units of the polymer chain is 100% by mass, the water stain suppressing effect is determined. The content is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more.On the other hand, in terms of solvent resolubility and water stain suppression effect Therefore, it is preferably 75% by mass or less, more preferably 65% by mass or less, and even more preferably 50% by mass or less.

The structural unit of the polymer chain in the structural unit represented by the general formula (II) is at least one selected from the group consisting of structural units represented by the general formula (III) in which m is 19 or more and 80 or less. and at least one kind selected from the group consisting of structural units represented by the general formula (III) where m is 3 or more and 10 or less; The total proportion of the structural units represented by III) is preferably 20% by mass or more, when all the structural units of the polymer chain are 100% by mass. On the other hand, from the viewpoint of solvent resolubility, in the polymer chain, the total proportion of the structural units represented by the general formula (III) where m is 3 or more and 10 or less is 100% by mass of all the structural units of the polymer chain. When expressed as %, it is preferably 80% by mass or less, more preferably 60% by mass or less.
Further, in the polymer chain, a mixture of a structural unit represented by the general formula (III) where m is 19 or more and 80 or less and a structural unit represented by the general formula (III) where m is 3 or more and 10 or less From the viewpoint of improving the development residue suppressing effect, the ratio is determined by the structural unit represented by the general formula (III) where m is 19 or more and 80 or less, and the structural unit represented by the general formula (III) where m is 3 or more and 10 or less. When the total with the structural units is 100 parts by mass, the total of the structural units represented by the general formula (III) where m is 19 or more and 80 or less is preferably 3 parts by mass or more, and 6 parts by mass or more. It is more preferable that the amount is 80 parts by mass or less, and more preferably 60 parts by mass or less.

From the viewpoint of satisfying dispersion stability, high contrast, shortening of development time, and excellent solvent resistance at the same time, when the total constituent units of the polymer chain are 100% by mass, it is expressed by the general formula (III). The total proportion of at least one kind of structural unit selected from the group consisting of the structural unit represented by the general formula (III') and the structural unit represented by the general formula (III') is preferably 1% by mass or more, and preferably 2% by mass or more. It is more preferable that the amount is at least 4% by mass, and even more preferably 4% by mass or more. The total proportion of at least one kind of structural unit selected from the group consisting of the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III') is determined in terms of solvent resolubility. Therefore, when the total constituent units of the polymer chain are 100% by mass, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

In the polymer chain, the number of structural units represented by the general formula (IV) including the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III') is one type. It may be used alone, or two or more types may be mixed.
From the viewpoint of dispersibility and dispersion stability of the coloring material, the total proportion of the structural units represented by the general formula (IV) is 70% by mass or more when all the structural units of the polymer chain are 100% by mass. The content is preferably 90% by mass or more, and more preferably 90% by mass or more. On the other hand, from the viewpoint of satisfying dispersion stability and excellent solvent resistance at the same time, the total proportion of the structural units represented by the general formula (IV) in the polymer chain is set to 100% of all the structural units of the polymer chain. When expressed as mass %, it may be 100 mass %.
Among them, the total proportion of structural units derived from (meth)acrylate is 60% by mass when all the structural units of the polymer chain are 100% by mass from the viewpoint of dispersion stability, solvent resistance, and compatibility with the initiator. It is preferably at least 80% by mass, more preferably at least 80% by mass. On the other hand, in order to simultaneously satisfy dispersion stability and excellent solvent resistance, the total proportion of (meth)acrylate-derived structural units in the polymer chain was set to 100% by mass of all structural units of the polymer chain. Sometimes it may be 100% by mass.

The structural units of the polymer chain in the structural units represented by the general formula (II) of the graft copolymer include the structural units represented by the general formula (III) and the structural units represented by the general formula (III'). In addition to the structural units represented by the general formula (IV) including the structural units shown in FIG.
Other structural units include structural units derived from monomers having an unsaturated double bond that can be copolymerized with the monomer that induces the structural unit represented by the general formula (IV).
Examples of monomers for inducing other structural units include styrenes such as styrene and α-methylstyrene, and vinyl ethers such as phenyl vinyl ether.

In the polymer chain in the structural units represented by the general formula (II) of the graft copolymer, the total proportion of other structural units is 100 In terms of mass %, it is preferably 30 mass % or less, more preferably 10 mass % or less.

The weight average molecular weight Mw of the polymer chains in the Polymer is preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, from the viewpoint of dispersibility and dispersion stability of the coloring material. , more preferably 15,000 or less, even more preferably 12,000 or less.
By being within the above range, it is possible to maintain a sufficient steric repulsion effect as a dispersant, and the specific surface area of the solvent-affinity part of the dispersant is increased, which allows the solvent to penetrate into the coating film and reach the coloring material. In addition, when polyethylene oxide chains or polypropylene oxide chains are included, the interaction with oxygen atoms becomes significant, shortening development time, improving solvent resistance, and even reducing water stains. It is possible to improve the effect of suppressing the generation of development residues and development residues.

Further, as a guideline, it is preferable that the polymer chain in the Polymer has a solubility at 23° C. of 20 (g/100 g solvent) or more in the organic solvent used in combination.
The solubility of the polymer chain can be determined based on the fact that the raw material into which the polymer chain is introduced when preparing the graft copolymer has the above-mentioned solubility. For example, when a polymerizable oligomer (macromonomer) containing a polymer chain and a group having an ethylenically unsaturated double bond at its terminal is used to introduce a polymer chain into a graft copolymer, the polymerizable oligomer is It is sufficient if it has solubility. Furthermore, after a copolymer is formed with a monomer containing a group having an ethylenically unsaturated double bond, a polymer chain containing a reactive group capable of reacting with a reactive group contained in the copolymer is used to form a copolymer. When introducing a polymer chain, it is sufficient that the polymer chain containing the reactive group has the above-mentioned solubility.

In the graft copolymer, the structural unit represented by the general formula (I) is preferably contained in a proportion of 3 to 60% by mass, more preferably 6 to 45% by mass, and 9 to 30% by mass. % is more preferable. If the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the proportion of the affinity portion with the coloring material in the graft copolymer will be appropriate, and it will be soluble in organic solvents. Since deterioration in properties can be suppressed, adsorption to the coloring material becomes good, and excellent dispersibility and dispersion stability can be obtained.
On the other hand, in the graft copolymer, the structural unit represented by the general formula (II) is preferably contained in a proportion of 40 to 97% by mass, more preferably 55 to 94% by mass, and more preferably 70 to 94% by mass. 91% by mass is more preferred. If the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the proportion of the solvent affinity moiety in the graft copolymer will be appropriate, and it will have sufficient steric properties as a dispersant. In addition to retaining the repulsion effect, the specific surface area of the solvent-affinity part of the dispersant increases, making it possible to suppress the penetration of solvents into the coating film and reach of the coloring material, and to prevent the solvent from entering the coating film or reaching the coloring material. When chains are included, the interaction with oxygen atoms becomes significant, which shortens development time, improves solvent resistance, and further improves the effects of suppressing water stains and development residues. Can be done.

The graft copolymer used in the present invention includes a structural unit other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), as long as the effects of the present invention are not impaired. In addition, it may contain other structural units. As other structural units, appropriately select ethylenically unsaturated double bond-containing monomers that can be copolymerized with the ethylenically unsaturated double bond-containing monomer that induces the structural unit represented by the general formula (I). It is possible to copolymerize and introduce other structural units.
Examples of other structural units copolymerized with the structural unit represented by the general formula (I) include the structural units represented by the general formula (IV).
In addition, the content ratio of the above-mentioned structural units is the structural unit represented by the above-mentioned general formula (I), the structural unit represented by the above-mentioned general formula (II), and It is calculated from the amount of the monomer that induces the structural unit represented by the general formula (IV).

Further, from the viewpoint of dispersibility and dispersion stability, the weight average molecular weight Mw of the graft copolymer is preferably 4000 or more, more preferably 6000 or more, and even more preferably 8000 or more. . On the other hand, from the viewpoint of solvent resolubility, it is preferably 50,000 or less, more preferably 30,000 or less.
In the present invention, the mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). The measurement was carried out using Tosoh's HLC-8120GPC, the elution solvent was N-methylpyrrolidone added with 0.01 mol/liter of lithium bromide, and the polystyrene standards for the calibration curve were Mw 377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh), and the measurement columns were TSK-GEL ALPHA-M x 2 (manufactured by Tosoh). It is.

(Method for producing graft copolymer)
In the present invention, the method for producing the graft copolymer includes producing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II). Any method that can be used may be used, and is not particularly limited. When producing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), for example, a monomer represented by the following general formula (Ia) and a polymerizable oligomer (macromonomer) consisting of the aforementioned polymer chain and a group having an ethylenically unsaturated double bond at its terminal as a copolymerization component to produce a graft copolymer. Can be mentioned.
If necessary, other monomers may be used to produce the graft copolymer using known polymerization methods.

（一般式（Ｉａ）中、Ｒ^４１、Ａ^１、Ｒ^４２及びＲ^４３は、一般式（Ｉ）と同様である。）

(In general formula (Ia), R ⁴¹ , A ¹ , R ⁴² and R ⁴³ are the same as in general formula (I).)

Furthermore, when producing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), the monomer represented by the general formula (Ia) and other monomers containing ethylenically unsaturated double bonds to form a copolymer, which contains a reactive group that can react with a reactive group contained in the copolymer. Polymer chains may be used to introduce polymer chains. Specifically, for example, after synthesizing a copolymer having a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond forming group, a functional group that reacts with the substituent is synthesized. The polymer chain may be introduced by reacting the polymer chain containing the polymer chain.
For example, a copolymer having a glycidyl group in the side chain is reacted with a polymer chain having a carboxyl group at the end, or a copolymer having an isocyanate group in the side chain is reacted with a polymer chain having a hydroxyl group at the end. Polymer chains can be introduced by
In addition, in the polymerization, additives commonly used in polymerization, such as a polymerization initiator, a dispersion stabilizer, a chain transfer agent, etc., may be used.

Next, a block copolymer having an A block containing a structural unit represented by the general formula (I) and a B block containing a (meth)acrylate-derived structural unit will be described.
In the present invention, the arrangement of each block of the block copolymer is not particularly limited, and may be, for example, an AB block copolymer, an ABA block copolymer, a BAB block copolymer, or the like. Among these, AB block copolymers and ABA block copolymers are preferred in terms of their excellent dispersibility.

The A block is a block that functions as a coloring material adsorption site, and includes at least the structural unit represented by the general formula (I). At least a portion of the nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer and at least one member selected from the group consisting of organic acid compounds and halogenated hydrocarbons have formed a salt. A salt type block copolymer may also be used.
The A block may have a structural unit other than the structural unit represented by the general formula (I) within the scope of achieving the object of the present invention, and the A block may have a structural unit other than the structural unit represented by the general formula (I). Any structural unit that can be copolymerized can be contained. Specifically, for example, the structural unit represented by the general formula (IV) may be mentioned.
The content of the structural unit represented by general formula (I) in the A block of the block copolymer before salt formation is 50 to 100% by mass based on the total mass of all the structural units of the A block. It is preferably 80 to 100% by weight, more preferably 100% by weight. This is because the higher the proportion of the structural unit represented by the general formula (I), the better the adsorption power to the coloring material, and the better the dispersibility and dispersion stability of the block copolymer. In addition, the content ratio of the said structural unit is calculated from the charged mass at the time of synthesizing the A block which has a structural unit represented by general formula (I).

In addition, the content ratio of the structural unit represented by general formula (I) in the block copolymer before salt formation is determined from the viewpoint of good dispersibility and dispersion stability. It is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total mass of. The content ratio of each structural unit in the block copolymer is calculated from the charged mass when synthesizing the block copolymer before salt formation.
In addition, the structural unit represented by general formula (I) only needs to have affinity with the coloring material, and may be composed of one type or may contain two or more types of structural units. good.

The B block is a block that functions as a solvent affinity site and includes at least a (meth)acrylate-derived structural unit.
The structural unit derived from (meth)acrylate may be the same as described above.
The B block is selected from among monomers having an unsaturated double bond that can be copolymerized with the monomer inducing the structural unit represented by the general formula (I), depending on the solvent so as to have solvent affinity. It is preferable to select and use them. As a guideline, it is preferable to introduce the B block so that the solubility of the copolymer at 23° C. is 20 (g/100 g solvent) or more in the solvent used in combination. The B block portion may consist of one type of structural unit, or may include two or more types of structural units.
Examples of the structural unit included in the B block include the structural unit represented by the general formula (IV).

In the block copolymer used as the dispersant of the present invention, the number m of the structural unit represented by the general formula (I) and the number n of other structural units constituting the solvent-compatible block part are The ratio m/n is preferably within the range of 0.01 or more and 1 or less, and is preferably within the range of 0.05 or more and 0.7 or less from the viewpoint of dispersibility and dispersion stability of the coloring material. More preferred.

Among the block copolymers used as the dispersant of the present invention, the A block containing the structural unit represented by the general formula (I), the structural unit derived from the carboxy group-containing monomer, and the structural unit derived from (meth)acrylate are used. A block copolymer containing B block, and at least a part of the nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer, an organic acid compound, and a halogenated hydrocarbon. The block copolymer and at least one of the salt type block copolymers have an acid value of 1 to 1. 18 mgKOH/g and a glass transition temperature of 30°C or higher are preferable from the viewpoints of improving solvent resistance and suppressing the generation of development residues in combination with the specific initiator used in the present invention. .
The B block in this case includes a (meth)acrylate-derived structural unit as an essential component, but may be the same as the B block of International Publication No. 2016/104493.

As the carboxyl group-containing monomer, a monomer that can be copolymerized with a monomer having a structural unit represented by general formula (I) and that contains an unsaturated double bond and a carboxyl group can be used. Examples of such monomers include (meth)acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. In addition, addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono(meth)acrylates can also be used. Furthermore, monomers containing an acid anhydride group such as maleic anhydride, itaconic anhydride, and citraconic anhydride may be used as a precursor of the carboxy group. Among these, (meth)acrylic acid is particularly preferred in terms of copolymerizability, cost, solubility, glass transition temperature, and the like.

The content ratio of the structural unit derived from the carboxy group-containing monomer in the block copolymer before salt formation may be appropriately set so that the acid value of the block copolymer falls within the above-mentioned specific acid value range. Although not limited, it is preferably 0.05% by mass or more and 4.5% by mass or less, and 0.07% by mass or more and 3.7% by mass or less, based on the total mass of all constituent units of the block copolymer. It is more preferable that there be.
When the content ratio of the structural unit derived from the carboxyl group-containing monomer is equal to or higher than the lower limit value, the effect of suppressing development residue is exhibited, and when the content ratio is lower than the upper limit value, it is suppressed by deterioration of development adhesion and solvent resolubility. Deterioration can be prevented.
The structural unit derived from the carboxyl group-containing monomer may have the above-mentioned specific acid value, and may consist of one type or may contain two or more types of structural units.

Further, it is preferable that a structural unit derived from a hydroxyl group-containing monomer be included in the B block of the block copolymer from the viewpoint of improving development adhesion. When the B block contains a structural unit derived from a hydroxyl group-containing monomer, the development speed is further improved. Note that the hydroxyl group here refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.

As the structural unit derived from the hydroxyl group-containing monomer, a monomer containing an unsaturated double bond and a hydroxyl group that can be copolymerized with the monomer inducing the structural unit represented by general formula (I) can be used. Examples of such monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerin mono(meth)acrylate. Acrylate, polyethylene glycol mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate with 1 mole of ε-caprolactone adduct, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and the like.
From the viewpoint of improving development adhesion, one or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate is particularly preferred.

In the block copolymer before salt formation, the content of the structural unit derived from the hydroxyl group-containing monomer is preferably 1% by mass or more, and 2% by mass, based on the total mass of all the structural units of the block copolymer. It is more preferably at least 3% by mass, even more preferably at least 3% by mass, and particularly preferably at least 4% by mass. The development adhesion can be made preferable as it is more than the above lower limit. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is below the above upper limit, it can be preferred from the point of view that the introduction ratio of other useful monomers can be increased. In addition, the content ratio of the above-mentioned structural units is calculated from the charged mass when synthesizing the block copolymer before salt formation.

The lower limit of the acid value of at least one of the block copolymer and the salt-type block copolymer is preferably 1 mgKOH/g or more, and 2 mgKOH/g or more from the viewpoint of suppressing development residue. It is more preferable. In addition, the acid value of at least one of the block copolymers and salt-type block copolymers should be set at an upper limit of 18 mgKOH/g or less in order to prevent deterioration of development adhesion and solvent resolubility. It is preferably at most 16 mgKOH/g, more preferably at most 14 mgKOH/g, even more preferably at most 14 mgKOH/g.
The acid value of at least one kind of the block copolymer and salt type block copolymer can be determined by the method described in International Publication No. 2016/104493.

The glass transition temperature of at least one of the block copolymer and salt-type block copolymer is preferably 30°C or higher from the viewpoint of development adhesion, particularly preferably 32°C or higher, and more preferably 35°C or higher. . On the other hand, from the viewpoint of operability during use, such as ease of accurate weighing, the temperature is preferably 200° C. or lower.
The glass transition temperature of at least one of the block copolymer and salt-type block copolymer is determined by differential scanning calorimetry (DSC) in accordance with JIS K7121. When two or more peaks indicating the glass transition temperature are observed, the peak with the largest peak area, that is, the area of the portion protruding from the baseline of the obtained chart, is taken as the representative value of the glass transition temperature.

The mass average molecular weight Mw of the block copolymer is not particularly limited, but from the viewpoint of improving colorant dispersibility and dispersion stability, it is preferably 1000 or more and 20000 or less, and 2000 or more and 15000 or less. is more preferable, and more preferably 3,000 or more and 12,000 or less.
Here, the mass average molecular weight (Mw) can be measured in the same manner as described above.

In addition, from the viewpoints of dispersion stability, solvent resistance, and compatibility with the initiator, the total proportion of the structural units derived from (meth)acrylate is set to 100% by mass of all the structural units in the B block of the block copolymer. When this happens, it is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. On the other hand, in order to satisfy dispersion stability and excellent solvent resistance at the same time, the total proportion of (meth)acrylate-derived structural units is 100% by mass when all the structural units in the B block are 100% by mass. It may be %. When the B block contains structural units derived from the carboxy group-containing monomer, the total proportion of the (meth)acrylate-derived structural units is different from the total proportion of the structural units derived from the carboxy group-containing monomer in the B block. When the unit is 100% by mass, it may be 100% by mass.

In addition, the content ratio of the structural unit represented by the above general formula (IV) in the block copolymer before salt formation is determined by the total mass of all the structural units of the block copolymer from the viewpoint of improving colorant dispersibility. It is preferably 40 to 95% by mass, more preferably 50 to 90% by mass. In addition, the content ratio of the above-mentioned structural units is calculated from the charged mass when synthesizing the block copolymer before salt formation.

Among the (meth)acrylate copolymers containing the structural unit represented by the general formula (I), copolymers with an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less have good dispersibility and form a coating film. This is preferable because it does not sometimes precipitate foreign matter and improves brightness and contrast.
When the amine value is within the above range, it has excellent viscosity stability over time and heat resistance, as well as alkali developability and solvent resolubility. In the present invention, the amine value of the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more. It is more preferable that On the other hand, from the viewpoint of solvent resolubility, the amine value of the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) is preferably 110 mgKOH/g or less, and 105 mgKOH/g. It is more preferable that it is below.
The amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if the amino group forms a salt with the organic acid compound in the dispersant, the organic acid compound is usually dissociated, so the block copolymer itself used as the dispersant is The amine value of can be measured.

The content ratio (mol %) of each structural unit in the copolymer in the dispersant can be determined from the amount of raw materials charged during production, or can be measured using an analytical device such as NMR. Further, the structure of the dispersant can be measured using NMR, various types of mass spectrometry, and the like. In addition, the dispersant is decomposed by thermal decomposition as necessary, and the resulting decomposition products are analyzed using high performance liquid chromatography, gas chromatograph mass spectrometry, NMR, elemental analysis, XPS/ESCA, TOF-SIMS, etc. You can ask for it.

In the present invention, at least one of the above-mentioned (meth)acrylate copolymer-based dispersants is used as the dispersant, and its content is determined by the type of coloring material used and the solid content in the photosensitive colored resin composition described below. It is selected as appropriate depending on the concentration, etc.
The content of the dispersant is preferably blended in a proportion of 2% by mass to 30% by mass, particularly preferably 3% by mass to 25% by mass, based on the total solid content of the photosensitive colored resin composition. . If it is more than the above lower limit, the dispersibility and dispersion stability of the coloring material will be excellent, and the storage stability of the photosensitive colored resin composition will be more excellent. Moreover, if it is below the said upper limit, developability will become good. In particular, when forming a colored layer with a high concentration of coloring material, the content of the dispersant is 2% by mass to 25% by mass, more preferably 3% by mass, based on the total solid content of the photosensitive colored resin composition. It is preferable to blend it in a proportion of ~20% by mass.
In the present invention, the solid content includes everything other than the solvent described below, and also includes monomers etc. dissolved in the solvent.

<Photoinitiator>
The photoinitiator in the photosensitive colored resin composition of the present invention contains a compound represented by the following general formula (A). Since it contains a photoinitiator, which is a compound represented by the following general formula (A), in combination with the specific dispersant, the initiator can be easily present uniformly in the colored layer, and only the surface is cured. The progress of line width shift is suppressed and the colored layer is uniformly cured, which improves the curability of the coating film and improves the solvent resistance of the cured product of the photosensitive colored resin composition. Conceivable.

(Compound represented by the following general formula (A))
The oxime ester compound represented by the following general formula (A) used in the present invention has geometric isomers due to oxime double bonds, but these are not distinguished. That is, in this specification, the compound represented by the following general formula (A), the compound represented by the following general formula (B) which is a preferred form of the compound described below, and its exemplary compounds are a mixture of both or either one of them. It represents one of the isomers, and is not limited to the structure showing the isomer.

(wherein R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN,
R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocyclic group of number 2 to 20,
The hydrogen atoms of the groups represented by R ¹¹ , R ¹² and R ¹³ are further represented by R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² - OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , ^{CSOR 21} , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocyclic group of number 2 to 20,
The hydrogen atoms of the groups represented by R ²¹ , R ²² and R ²³ may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group,
The alkylene moiety of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO- may contain 1 to 5 of them, provided that oxygen atoms are not adjacent to each other,
R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; ,
The alkyl portion of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ may have a branched side chain or may be a cyclic alkyl,
R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; , the alkyl portion of the group represented by R ³ may have a branched side chain or may be a cyclic alkyl, and R ³ and R ⁷ and R ³ and R ⁸ are each taken together. It may form a ring,
The hydrogen atom of the group represented by R ³ is further R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , which may be substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ represent a hydroxyl group, CN or a halogen atom, and R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ and R ⁷ may each be taken together to form a ring,
R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl portion of the group represented by R ¹⁴ , R ¹⁵ and R ¹⁶ has a branched side chain. Often, R ⁸ may be a cyclic alkyl, R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ represents a hydroxyl group, CN or a halogen atom,
k represents 0 or 1. )

The number of carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (A) is from 1 to Examples of the alkyl group of 20 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t -octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.

The aryl group having 6 to 30 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (A) is, for example, Examples include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl, and the like.

In the above general formula (A), the arylalkyl group having 7 to 30 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ includes, for example , benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and the like.

The heterocyclic group having 2 to 20 carbon atoms represented by R ³ , R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (A) is: For example, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl, etc. Examples include 5- to 7-membered heterocycles.
In the above general formula (A), the ring that can be formed by combining R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ³ and R ⁷ , and R ³ and R ⁸ is: For example, 5- to 7-membered rings such as a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring are preferably mentioned.

Further, halogen atoms represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the above general formula (A), and R ³ , R ¹¹ , R ¹² in the above general formula (A) , R ¹³ , R ²¹ , R ²² and R ²³ include fluorine, chlorine, bromine, and iodine.

In the above general formula (A), the alkylene moiety of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -O-, -S-, -COO-, -OCO -, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO- from 1 to 1 under the condition that oxygen atoms are not adjacent to each other. It may contain 5 divalent groups, and in this case, the divalent groups contained may be one type or two or more types of groups, and in the case of groups that can be contained consecutively, two or more groups may be contained consecutively. .

In addition, the alkyl (alkylene) moiety of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in the above general formula (A) has a branched side chain. It may also be a cyclic alkyl.
Among the compounds represented by the above general formula (A), those in which R ³ is an optionally fused aromatic ring or the compounds represented by the following general formula (B) have high sensitivity and are easy to manufacture. This is preferred because it is easy.

（式中、Ｒ^１、Ｒ^２、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８及びｋは、上記一般式（Ｉ）と同じであり、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４及びＲ^３５は、それぞれ独立に、Ｒ^１１、ＯＲ^１１、ＳＲ^１１、ＣＯＲ^１１、ＣＯＮＲ^１５Ｒ^１６、ＮＲ^１２ＣＯＲ^１１、ＯＣＯＲ^１１、ＣＯＯＲ^１４、ＳＣＯＲ^１１、ＯＣＳＲ^１１、ＣＯＳＲ^１４、ＣＳＯＲ^１１、水酸基、ニトロ基、ＣＮ又はハロゲン原子を表し、Ｒ^３１とＲ^３２、Ｒ^３２とＲ^３３、Ｒ^３３とＲ^３４及びＲ^３４とＲ^３５はそれぞれ一緒になって環を形成していてもよい。）

(In the formula, R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and k are the same as in the above general formula (I), and R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ , hydroxy acid base , represents a nitro group, CN, or a halogen atom, and R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , and R ³⁴ and R ³⁵ may each be taken together to form a ring.)

Examples of rings formed by combining R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ and R ³⁴ and R ³⁵ include R ⁴ and R ⁵ , R ⁵ and R ⁶ and R ⁶ Examples of the ring that can be formed by combining and R ⁷ , R ³ and R ⁷ , and R ³ and R ⁸ include the same rings as those listed above.

In the above general formulas (A) and (B), R ¹ is an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms; R ¹¹ is an aryl group having 6 to 12 carbon atoms; An alkyl group having 1 to 8 atoms is preferable because it has high solvent solubility, a methyl group, ethyl group, or phenyl group as R ² is preferable because it has high reactivity, and R ⁴ to R ⁷ are hydrogen An atom or a cyano group, especially a hydrogen atom, is preferred because it is easy to synthesize, a hydrogen atom as R ⁸ is preferred because it is easy to synthesize, and k is preferably 1 because it has high sensitivity. In (B), at least one of R ³¹ to R ³⁵ is a nitro group, CN, a halogen atom, or COR ¹¹ , and R ¹¹ is an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms. It is preferable to have high sensitivity, and it is more preferable that at least one of R ³¹ to R ³⁵ is a nitro group, CN, or a halogen atom, and it is especially preferable that R ³³ is a nitro group, CN, or a halogen atom. .

Preferred specific examples of the compound represented by the above general formula (A) include the following compounds. In addition, compound No. 1, which is described in International Publication No. 2015/152153, 1~No. 212 is mentioned.

The compound represented by the above general formula (A) can be obtained by, for example, referring to International Publication No. 2015/152153, and selecting the solvent, reaction temperature, reaction time, purification method, etc. as appropriate depending on the materials used. Can be synthesized. Alternatively, commercially available products may be appropriately obtained and used.

(Other photoinitiators)
The photoinitiator in the photosensitive colored resin composition of the present invention contains an oxime ester photoinitiator represented by the general formula (A), but in order to better adjust the sensitivity, It may contain a photoinitiator different from the compound represented by (A). In addition, other photoinitiators used in the photosensitive colored resin composition of the present invention include a chain transfer agent in addition to the photopolymerization initiator.
Among these, in addition to the compound represented by the general formula (A), the photoinitiator in the photosensitive colored resin composition of the present invention further includes an oxime ester different from the compound represented by the general formula (A). At least one selected from the group consisting of an α-aminoketone photoinitiator, a biimidazole photoinitiator, a thioxanthone photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent. It is preferable to contain a seed because when patterning the colored layer and forming desired micropores in the colored layer at the same time, development residues in the micropores are suppressed and the cross-sectional shape of the micropores becomes good. In other words, when using a more sensitive photoinitiator to form a colored layer, after radicals are generated, the radicals move to the unexposed area, while maintaining the shape of the unexposed area inside the exposed area. Moreover, it is difficult to form the peripheral portion of the unexposed portion without deteriorating the dimensional accuracy. Oxime ester photoinitiator, α-aminoketone photoinitiator, biimidazole photoinitiator, thioxanthone photoinitiator, acylphosphine oxide photoinitiator different from the compound represented by the general formula (A) At least one selected from the group consisting of , and mercapto chain transfer agents has the property of curing the intermediate to deep portions of the coating film, and tends to suppress curing of only the surface of the coating film.
Therefore, in addition to the compound represented by the general formula (A), an oxime ester photoinitiator different from the compound represented by the general formula (A), an α-aminoketone photoinitiator, a biimidazole By containing a combination of at least one selected from the group consisting of photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents, while maintaining good sensitivity, It is now possible to cure the coating film from the surface to the deep part in a well-balanced manner, making it possible to control the cross-sectional shape of the micropores, so that the taper angle (θ2) (see Figure 6) of the cross-sectional shape of the micropores is less than 90°. It becomes good.
In addition to the compound represented by the general formula (A), an oxime ester photoinitiator different from the compound represented by the general formula (A), an α-aminoketone photoinitiator, a biimidazole Containing a combination of at least one selected from the group consisting of photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, and mercapto chain transfer agents improves the sensitivity of unexposed areas. control, and the effect of suppressing development residue inside the micropores becomes high.

When an oxime ester photoinitiator different from the compound represented by the general formula (A) is used as the other photoinitiator, the cross-sectional shape of the micropores described above is improved, and development residue is suppressed. In addition to this effect, it is also preferable because it tends to have a good cross-sectional shape when forming a thin line pattern.
Examples of the oxime ester photoinitiator different from the compound represented by the general formula (A) include 1,2-octadione-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime) ), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime), JP 2000-80068, JP 2001 It can be appropriately selected from the oxime ester photoinitiators described in Japanese Patent Publication No. 233842, Japanese Translated Patent Publication No. 2010-527339, Japanese Patent Application Publication No. 2010-527338, Japanese Unexamined Patent Publication No. 2013-041153, etc.
The oxime ester photoinitiator different from the compound represented by the general formula (A) is preferably one having a carbazole skeleton, diphenyl sulfide skeleton, or fluorene skeleton from the viewpoint of improving sensitivity. An oxime ester photoinitiator having a carbazole skeleton or a diphenyl sulfide skeleton is preferable from the viewpoint of improving the sensitivity easily when combined with the compound represented by the general formula (A), and also from the viewpoint of the cross-sectional shape of the colored layer.

Examples of oxime ester photoinitiators having a carbazole skeleton include ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime ) (for example, Irgacure OXE02, manufactured by BASF), methanone, [8-[[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2 -ethylhexyl)-11H-benzo[a]carbazol-5-yl]-, (2,4,6-trimethylphenyl) (for example, Irgacure OXE-03, manufactured by BASF), ethanone, 1-[9-ethyl-6 -(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-,1-(o-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazole) -3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-,o-acetyloxime, 1-propanone,3-cyclopentyl-1-[9-ethyl-6-(2- methylbenzoyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (for example, TR-PBG-304, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), 1-propanone, 3-cyclopentyl-1- [2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-,1-(o-acetyloxime), ethanone, 2-cyclohexyl-1-[2-(2-pyrimidinyloxy)-9H-carbazole -3-yl]-,1-(o-acetyloxime), ethanone, 2-cyclohexyl-1-[2-(2-pyrimidinylthio)-9H-carbazol-3-yl]-,1-(o-acetyl oxime), 1-octanone, 1-[4-[3-[1-[(acetyloxy)imino]ethyl]-6-[4-[(4,6-dimethyl-2-pyrimidinyl)thio]-2- Methylbenzoyl]-9H-carbazol-9-yl]phenyl]-,1-(o-acetyloxime) (for example, EXTA-9, manufactured by Union Chemical), commercially available products include ADEKA OPT-N-1919 (manufactured by ADEKA) ), Adeka Arcles NCI-831 (manufactured by ADEKA), and the like.
The oxime ester photoinitiator having a carbazole skeleton may be used alone or in combination of two or more, and among them, 1-propanone, 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl) )-9H-carbazol-3-yl]-,1-(o-acetyloxime) (for example, TR-PBG-304, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), ethanone, 1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (for example, Irgacure OXE02, manufactured by BASF), or methanone, (9-ethyl-6-nitro-9H-) It is preferable to use carbazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-,o-acetyloxime from the viewpoint of high sensitivity.

Examples of the oxime ester photoinitiator having a diphenyl sulfide skeleton include an oxime ester compound represented by the following chemical formula (C-1), 1,2-octadione, 1-[4-(phenylthio)phenyl]-,2 -(o-benzoyloxime] (for example, Irgacure OXE01, manufactured by BASF), 1,2-propanedione, 3-cyclopentyl-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime) For example, TR-PBG-305 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), 1,2-propanedione, 3-cyclopentyl-1-[4-[(2-hydroxyethoxy)phenylthio]phenyl]-,2-(o -acetyloxime], 1-pentanone, 1-[4-[4-(2-benzofuranylcarbonyl)phenylthio]phenyl]-4-methyl, 1-(o-acetyloxime), commercially available as TR-PBG -3057 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), Adeka Arcles NCI-930 (manufactured by ADEKA Corporation), and Irgacure OXE04 (manufactured by BASF Corporation).

As the oxime ester photoinitiator having a fluorene skeleton, an oxime ester compound represented by the general formula (1) described in International Publication No. 2018/062105 (oxime ester compound represented by the following general formula (D)) can be mentioned. The oxime ester compound represented by the following general formula (D) may be the same as the oxime ester compound represented by the general formula (1) described in International Publication No. 2018/062105.

(In general formula (D), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group, and R ^c represents a thioether bond (-S-), an ether bond (-O-), and a carbonyl bond (- is a hydrocarbon group which may contain at least one divalent linking group selected from CO-), Z is a hydrogen atom or -(C=O)R ^d , and R ^d is an oxygen atom and a sulfur atom, or a heterocyclic group that does not contain a nitrogen atom and contains at least one selected from an oxygen atom and a sulfur atom, and R ^e is a hydrocarbon group having 1 to 10 carbon atoms.)

As the oxime ester photoinitiator having a fluorene skeleton, a compound represented by the following compound (D-1) is more preferable. Further, as a commercially available product, for example, TR-PBG-365 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.) can be mentioned.

Examples of the α-aminoketone photoinitiator include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2-benzyl-2- (dimethylamino)-1-(4-morpholinophenyl)-1-butanone (e.g. Irgacure 369, manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[ Examples include 4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF).
The α-aminoketone photoinitiator may be used alone or in combination of two or more, and among them, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one and 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone is more preferred from the viewpoint of suppressing development residue within the micropores and improving the cross-sectional shape of the micropores.

Examples of the biimidazole photoinitiator include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl) )-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl- 1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and the like.
The biimidazole photoinitiator may be used alone or in combination of two or more, among which 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1 , 2'-biimidazole is preferable from the viewpoint of suppressing development residue within the micropores and improving the cross-sectional shape of the micropores.

Examples of the thioxanthone photoinitiator include 2,4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2,4-dichlorothioxanthone.
The thioxanthone-based photoinitiator may be used alone or in combination of two or more types, and among them, 2,4-isopropylthioxanthone and 2,4-diethylthioxanthone are used because development residues in micropores are suppressed. , is preferable from the viewpoint of improving the cross-sectional shape of the micropores.

Acylphosphine oxide photoinitiators have the property of being less likely to yellow due to heat, and are therefore suitable for improving brightness; however, they generally have low sensitivity and may not provide sufficient curability. However, it is preferable to combine it with the compound represented by the general formula (A) because it improves the overall coating film curability, suppresses development residue within the micropores, and improves the cross-sectional shape of the micropores.
Examples of the acylphosphine oxide photoinitiator include benzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide, 3, 4-dimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylethoxyphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2 , 4,4-trimethyl-pentylphosphine oxide, bis(2,6-dimethylbenzoyl)-ethylphosphine oxide and the like.
The acylphosphine oxide photoinitiator may be used alone or in combination of two or more, and among them, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide improves coating film curability. Preferable from this point of view.

Mercapto-based chain transfer agents have the property of accepting radicals from slow-reacting radicals and accelerating the reaction, improving overall coating film curing properties, suppressing development residue within micropores, and improving the cross-section of micropores. This is preferable from the viewpoint of improving the shape.
Examples of mercapto chain transfer agents include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, and 3-mercapto-5-methoxybenzoimidazole. Mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3- mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyl pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and tetraethylene glycol bis(3-mercaptopropionate).
The mercapto chain transfer agent may be used alone or in combination of two or more, and 2-mercaptobenzothiazole is particularly preferred from the standpoint of improving the reaction rate.

The total content of photoinitiators used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but with respect to the total solid content of the photosensitive colored resin composition, It is preferably in the range of 0.1% by mass or more and 12.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less. If this content is above the above lower limit, photocuring will proceed sufficiently, suppressing the elution of the exposed area during development, and improving solvent resistance.On the other hand, if this content is below the above upper limit, line width will shift. can be suppressed, and a reduction in brightness due to yellowing of the colored layer obtained can be suppressed.
Note that the solid content refers to everything other than the solvent, and includes liquid polyfunctional monomers and the like.
Further, the total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is preferably 1% by mass or more and 20% by mass or less, based on the total of the alkali-soluble resin, polyfunctional monomer, and initiator. More preferably, it is within the range of 2% by mass or more and 15% by mass or less. If this content is above the above lower limit, photocuring will proceed sufficiently, suppressing the elution of the exposed area during development, and improving solvent resistance.On the other hand, if this content is below the above upper limit, line width will shift. can be suppressed, and a reduction in brightness due to yellowing of the colored layer obtained can be suppressed.

When the photoinitiator contains a compound represented by the general formula (A) and the other photoinitiator, the compound represented by the general formula (A) is added to the total amount of the photoinitiator. The content of the compound is preferably 10% by mass or more and 98% by mass or less, from the viewpoint of suppressing line width shift, improving solvent resistance, suppressing development residue in micropores, and improving the cross-sectional shape of micropores. It is more preferably 30% by mass or more and 95% by mass or less, and it is even more preferably 30% by mass or more and 95% by mass or less. From the viewpoint of the cross-sectional shape of the pores, the content is even more preferably 50% by mass or more and 90% by mass or less, and particularly preferably 60% by mass or more and 90% by mass or less.

<Color material>
In the present invention, the coloring material is not particularly limited as long as it can produce the desired color when forming the colored layer of the color filter, and various organic pigments, inorganic pigments, dispersible dyes, and dyes may be used. Salt-forming compounds and the like can be used alone or in combination of two or more. Among them, organic pigments are preferably used because they have high color development and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colorists); specifically, compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colorists); .) Can list things that are numbered.

C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, and C. I. Pigment Yellow 150 derivative pigment;
C. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73;
C. I. Pigment violet 1, 19, 23, 29, 32, 36, 38;
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57: 1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 269, 272, 291;
C. I. Pigment Blue 15, 15:3, 15:4, 15:6, 60;
C. I. pigment green 7, 36, 58, 59, 62, 63;
C. I. Pigment Brown 23, 25;
C. I. Pigment black 1, 7.

Further, specific examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine blue, navy blue, oxidized Examples include chrome green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

For example, when forming a pattern of a light-shielding layer on a substrate of a color filter using a coloring material dispersion according to the present invention as a photosensitive colored resin composition described below, a black pigment with high light-shielding properties is blended into the ink. . As the black pigment with high light-shielding properties, for example, inorganic pigments such as carbon black and triiron tetroxide, or organic pigments such as cyanine black can be used.

Examples of the above-mentioned dispersible dye include dyes that have become dispersible by adding various substituents to the dye or by using the dye in combination with a solvent with low solubility.
The salt-forming compound of the dye refers to a compound in which the dye forms a salt with a counter ion, such as a salt-forming compound of a basic dye and an acid, a salt-forming compound of an acidic dye and a base, and soluble in a solvent. It also includes lake pigments in which the dye is insolubilized in a solvent using a known lake formation (salt formation) method.
In the present invention, the dispersibility and dispersion stability of the coloring material can be improved by using a coloring material containing at least one selected from dyes and salt-forming compounds of dyes in combination with the dispersant of the present invention. Can be done.

The dye can be appropriately selected from conventionally known dyes. Examples of such dyes include azo dyes, metal complex azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
As a guideline, if the amount of dye dissolved in 10 g of solvent (or mixed solvent) is 10 mg or less, it can be determined that the dye can be dispersed in the solvent (or mixed solvent).

Among these, the coloring material is at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, quinophthalone dyes, coumarin dyes, cyanine dyes, and salt-forming compounds of these dyes. When it is contained, it is preferable because it has a high effect of suppressing sublimation or precipitation of the coloring material due to the use of the dispersant, and it is possible to form a colored layer with high brightness. In addition, the coloring material preferably contains at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, and quinophthalone dyes.

Examples of diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, 255, 264, 272, 291, and diketopyrrolopyrrole pigments represented by the following general formula (i), among which C. I. Pigment Red 254, 272, 291, and at least one diketopyrrolopyrrole pigment in which R ²¹ and R ²² in the following general formula (i) are each a 4-bromophenyl group is preferred.

（一般式（ｉ）中、Ｒ^５１及びＲ^５２は、それぞれ独立に、４－クロロフェニル基、又は４－ブロモフェニル基である。）

(In general formula (i), R ⁵¹ and R ⁵² are each independently a 4-chlorophenyl group or a 4-bromophenyl group.)

Examples of quinophthalone pigments include C.I. I. Pigment Yellow 138 and the like.
Examples of copper phthalocyanine pigments include C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, C. I. Pigment Green 7, 36, etc., among which C. I. Pigment Blue 15:6 is preferred.
Examples of zinc phthalocyanine pigments include C.I. I. Pigment Green 58, 59, and the like.
Examples of quinophthalone dyes include C.I. I. Disperse Yellow 54, 64, 67, 134, 149, 160, C. I. Examples include Solvent Yellow 114 and 157, among which C. I. Disperse Yellow 54 is preferred.

The average primary particle size of the coloring material used in the present invention is not particularly limited as long as it can produce the desired color when used as a colored layer of a color filter, and it varies depending on the type of coloring material used. is preferably within the range of 10 to 100 nm, more preferably 15 to 60 nm. By having the average primary particle size of the coloring material within the above range, a display device equipped with a color filter manufactured using the photosensitive colored resin composition according to the present invention has high contrast and high quality. be able to.

Further, the average dispersed particle size of the coloring material in the photosensitive colored resin composition varies depending on the type of coloring material used, but it is preferably within the range of 10 to 100 nm, and preferably within the range of 15 to 60 nm. is more preferable.
The average dispersed particle size of the coloring material in the photosensitive colored resin composition is the dispersed particle size of the coloring material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is something that To measure the particle size using a laser light scattering particle size distribution meter, the photosensitive colored resin composition is appropriately diluted with a solvent used in the photosensitive colored resin composition to a concentration that can be measured using a laser light scattering particle size distribution meter ( For example, 1000 times, etc.), and can be measured at 23° C. by a dynamic light scattering method using a laser light scattering particle size distribution analyzer (for example, Nanotrac particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle size here is the volume average particle size.

The coloring material used in the present invention can be produced by a known method such as a recrystallization method or a solvent salt milling method. Alternatively, a commercially available coloring material may be used after being subjected to a fine treatment.

In the photosensitive colored resin composition according to the present invention, the content of the coloring material is not particularly limited. From the viewpoint of dispersibility and dispersion stability, the content of the coloring material is 3% by mass to 65% by mass, more preferably 4% to 60% by mass, based on the total solid content of the photosensitive colored resin composition. It is preferable to mix them in proportions. If it is above the above lower limit, the colored layer will have sufficient color density when the photosensitive colored resin composition is applied to a predetermined thickness (usually 1.0 μm to 5.0 μm). Moreover, if it is below the said upper limit, a colored layer which is excellent in storage stability, and has sufficient hardness and adhesiveness with the substrate can be obtained. In particular, when forming a colored layer with a high coloring material concentration, the total content of the coloring material is 15% by mass to 65% by mass, more preferably 25% by mass based on the total solid content of the photosensitive colored resin composition. % to 60% by mass.

<Alkali-soluble resin>
The alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder resin and are soluble in the alkaline developer used in pattern formation.
In the present invention, the alkali-soluble resin can be defined as having an acid value of 40 mgKOH/g or more.

As the alkali-soluble resin, a conventionally known alkali-soluble resin can be appropriately selected and used, for example, the alkali-soluble resin described in International Publication No. 2016/104493 can be appropriately selected and used.
Preferred alkali-soluble resins in the present invention are resins having acidic groups, usually carboxyl groups, and specifically, acrylic copolymers having carboxyl groups and styrene-acrylic copolymers having carboxyl groups. Examples thereof include epoxy (meth)acrylate resins having a carboxyl group, and acrylic resins such as an acrylic copolymer having a carboxyl group and a styrene-acrylic copolymer having a carboxyl group are preferably used. Among these, those having a carboxy group in the side chain and further having a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain are particularly preferable. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Furthermore, two or more of these acrylic copolymers, acrylic resins such as styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination.

The alkali-soluble resin used in the photosensitive colored resin composition may be used alone or in combination of two or more types, and there is no particular restriction on the content, but the photosensitive colored resin The amount of the alkali-soluble resin is preferably 5% to 60% by weight, more preferably 10% to 40% by weight based on the total solid content of the composition. When the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability can be obtained, and when the content of the alkali-soluble resin is at or below the above upper limit, film roughness and pattern chipping may occur during development. It can be suppressed.

<Photopolymerizable compound>
The photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited as long as it can be polymerized by the photoinitiator, and usually a compound having two or more ethylenically unsaturated double bonds is used. It is preferably a polyfunctional (meth)acrylate that is suitably used and has two or more acryloyl groups or methacryloyl groups.
Such polyfunctional (meth)acrylates may be appropriately selected from conventionally known ones. Specific examples include those described in JP-A No. 2013-029832.

One type of these polyfunctional (meth)acrylates may be used alone, or two or more types may be used in combination. In addition, when the photosensitive colored resin composition of the present invention is required to have excellent photocurability (high sensitivity), the polyfunctional (meth)acrylate has three polymerizable double bonds (trifunctional). Poly(meth)acrylates of trivalent or higher polyhydric alcohols and dicarboxylic acid modified products thereof are preferable, and specifically, trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, etc. are preferable. (meth)acrylate, succinic acid modified product of pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate ) Preferred are succinic acid-modified acrylates, dipentaerythritol hexa(meth)acrylate, and the like.

The content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but the content of the photopolymerizable compound is preferably 5% by mass to 60% by mass based on the total solid content of the photosensitive colored resin composition. % by weight, more preferably within the range of 10% by weight to 40% by weight. When the content of the photopolymerizable compound is at least the above lower limit, photocuring will proceed sufficiently, the exposed portion will be able to suppress elution during development, line width shift will be suppressed, and solvent resistance will be good, and Alkaline developability is sufficient when the content of the photopolymerizable compound is below the above upper limit.
The content ratio of the photopolymerizable compound and the photoinitiator used in the photosensitive colored resin composition is such that line width shift is suppressed, solvent resistance is improved, and development residues are reduced. From the viewpoint of improving the suppressing effect and the cross-sectional shape of micropores, the total content of the photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the photopolymerizable compound. The amount is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

<Solvent>
The solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with the components in the photosensitive colored resin composition and can dissolve or disperse them. Solvents can be used alone or in combination of two or more.
Specific examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol, and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; Ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, Ester solvents such as ethyl lactate and cyclohexanol acetate; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1 - Glycol ether acetate solvents such as butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); Propylene glycol diacetate , 1,3-butylene glycol diacetate and other diacetates; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol Glycol ether solvents such as dimethyl ether; aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; cyclic ether solvents such as tetrahydrofuran ; Unsaturated hydrocarbon solvents such as benzene, toluene, xylene, and naphthalene; Saturated hydrocarbon solvents such as N-heptane, N-hexane, and N-octane; Organic solvents such as aromatic hydrocarbons such as toluene and xylene can be mentioned. Among these solvents, glycol ether acetate solvents, carbitol acetate solvents, glycol ether solvents, and ester solvents are preferably used from the viewpoint of solubility of other components. Among them, the solvents used in the present invention include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and 3-methoxybutyl acetate, from the viewpoint of solubility of other components and suitability for coating.

In the photosensitive colored resin composition according to the present invention, the content of the solvent may be appropriately set within a range that allows the colored layer to be formed with high precision. It is usually preferably within the range of 55% by mass to 95% by mass, particularly preferably within the range of 65% by mass to 88% by mass, based on the total amount of the photosensitive colored resin composition containing the solvent. More preferred. When the content of the above-mentioned solvent is within the above-mentioned range, excellent coating properties can be obtained.

<Other ingredients>
The photosensitive colored resin composition of the present invention may contain various additives as necessary. Examples of additives include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, etc. .
Specific examples of surfactants and plasticizers include those described in JP-A No. 2013-029832.

The photosensitive colored resin composition of the present invention preferably further contains an antioxidant from the viewpoint of suppressing the amount of line width shift. By containing an antioxidant in combination with the compound represented by the general formula (A), the photosensitive colored resin composition of the present invention prevents excessive radical chains from impairing curability when forming a cured film. Since the reaction can be controlled, linearity is further improved when forming a thin line pattern, and the ability to form a thin line pattern according to the designed mask line width is improved. In addition, heat resistance can be improved, and reduction in brightness after exposure and post-baking can be suppressed, so brightness can be improved.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from conventionally known antioxidants. Specific examples of antioxidants include hindered phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants , hydrazine antioxidants, etc. It is preferable to use a hindered phenol antioxidant from the viewpoint of improving the ability to form a thin line pattern according to the width design and from the viewpoint of heat resistance. It may also be a latent antioxidant as described in International Publication No. 2014/021023.

Examples of the hindered phenolic antioxidant include pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name : IRGANOX1010, manufactured by BASF), 1,3 , 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris (4-hydroxy-3,5- Di-tert-butylbenzyl) mesitylene (product name: Irganox 1330, manufactured by BASF), 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (product name: Sumilizer MDP-S, manufactured by Sumitomo Chemical) ), 6,6'-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate ( Trade name: Irgamod 195 (manufactured by BASF), etc. Among them, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name : IRGANOX1010, manufactured by BASF) is preferred from the viewpoint of heat resistance and light resistance.

The amount of the antioxidant to be blended is preferably 0.1 parts by mass to 10.0 parts by mass, and 0.5 parts by mass based on 100 parts by mass of the total solid content in the colored resin composition. Parts to 5.0 parts by mass are more preferable. If it is more than the above lower limit, the ability to form a fine line pattern according to the designed mask line width is improved and the heat resistance is excellent. On the other hand, if it is below the above upper limit, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.

In addition, the amount of the antioxidant to be blended is 1 part by mass to 250 parts by mass per 100 parts by mass of the oxime ester photoinitiator containing the compound represented by the general formula (A). It is preferably 3 parts by weight to 80 parts by weight, and even more preferably 5 parts to 45 parts by weight. Within the above range, the effect of the above combination is excellent.

Examples of the silane coupling agent include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403. , KBM-303, KBM-802, KBM-803, KBE-9007, and X-12-967C (manufactured by Shin-Etsu Silicone Co., Ltd.). Among them, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103, which have methacrylic groups and acrylic groups, are preferred from the viewpoint of adhesion to the SiN substrate.

The content of the silane coupling agent is preferably 0.05 parts by mass or more and 10.0 parts by mass or less based on 100 parts by mass of the total solid content in the photosensitive colored resin composition. , more preferably 0.1 parts by mass or more and 5.0 parts by mass or less. If it is greater than or equal to the lower limit value and less than or equal to the upper limit value, the adhesion to the substrate is excellent.

<Method for producing photosensitive colored resin composition>
The method for producing a photosensitive colored resin composition of the present invention includes a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various additive components used as desired. A method in which the coloring material can be uniformly dispersed in the solvent using a dispersant is preferable from the viewpoint of improving contrast, and can be prepared by mixing using a known mixing means.
As a method for preparing the resin composition, for example, (1) first, a coloring material and a dispersant are added to a solvent to prepare a coloring material dispersion, and to the dispersion, an alkali-soluble resin and light are added. A method of mixing a polymerizable compound, a photoinitiator, and various additive components used as desired; (2) A method of mixing a polymerizable compound, a photoinitiator, and various additive components used as desired; A method of simultaneously adding and mixing the agent and various additive components used as desired; (3) In a solvent, a dispersing agent, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and optionally used. A method in which various additive components are added and mixed, and then a coloring material is added and dispersed; (4) A coloring material dispersion is prepared by adding a coloring material, a dispersant, and an alkali-soluble resin into a solvent. A method of further adding and mixing an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and various additive components used as desired to the dispersion; and the like.
Among these methods, methods (1) and (4) above are preferred because they can effectively prevent agglomeration of the coloring material and uniformly disperse it.

The method for preparing the coloring material dispersion can be appropriately selected from conventionally known dispersion methods. For example, (1) a dispersant is mixed in advance with a solvent and stirred to prepare a dispersant solution, and then, if necessary, an organic acid compound is mixed to form a salt between the amino group of the dispersant and the organic acid compound. let A method of mixing this with the coloring material and other components as necessary and dispersing using a known stirrer or dispersion machine; (2) Mixing the dispersant with a solvent and stirring to prepare a dispersant solution; , a method of mixing the coloring material and, if necessary, an organic acid compound, and further, if necessary, other components, and dispersing the mixture using a known stirrer or disperser; (3) mixing a dispersant into a solvent and stirring; , prepare a dispersant solution, then mix the coloring material and other components as necessary, make a dispersion liquid using a known stirrer or dispersion machine, and then add an organic acid compound as necessary. Examples include methods to do so.

Examples of the dispersion machine for performing the dispersion treatment include roll mills such as two-roll and three-roll mills, ball mills such as ball mills and vibrating ball mills, paint conditioners, bead mills such as continuous disk-type bead mills, and continuous annular bead mills. As preferred dispersion conditions for the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

<Application>
The photosensitive colored resin composition according to the present invention suppresses the amount of line width shift and has good solvent resistance even during low-temperature heat treatment, so it can be suitably used for color filter applications, and among others, organic EL elements, etc. It can be suitably used in applications such as forming a color filter directly on a substrate on which an element with low heat resistance is formed.

III. Color Filter The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, and at least one of the colored layers is composed of the photosensitive colored resin composition according to the present invention. It is a cured product.

The color filter according to the present invention will be explained with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of a color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention includes a substrate 1, a light shielding part 2, and a colored layer 3.

<Colored layer>
At least one of the colored layers used in the color filter of the present invention is a cured product of the photosensitive colored resin composition according to the present invention.
The colored layer is usually formed in an opening of a light-shielding portion on a substrate, which will be described later, and is usually composed of a colored pattern of three or more colors.
Further, the arrangement of the colored layers is not particularly limited, and may be a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type. Furthermore, the width, area, etc. of the colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, solid content concentration, viscosity, etc. of the photosensitive colored resin composition, but it is usually preferably in the range of 1 to 5 μm.

The colored layer can be formed, for example, by the method described below.
First, the above-mentioned photosensitive colored resin composition of the present invention is applied onto a substrate described below using a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. to form a wet coating film. Among these, spin coating and die coating are preferably used.
Next, the wet coating film is dried using a hot plate, an oven, etc., and then exposed to light through a mask with a predetermined pattern to photopolymerize the alkali-soluble resin, polyfunctional monomer, etc. and harden it. Use as a coating film. Examples of light sources used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, and metal halide lamps, and electron beams. The exposure amount is adjusted as appropriate depending on the light source used, the thickness of the coating film, etc.
Further, heat treatment may be performed after exposure to accelerate the polymerization reaction. The heating conditions are appropriately selected depending on the blending ratio of each component in the photosensitive colored resin composition used, the thickness of the coating film, etc.

Next, a coating film is formed in a desired pattern by developing with a developer and dissolving and removing unexposed areas. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. A suitable amount of a surfactant or the like may be added to this alkaline solution. Moreover, a general method can be adopted as a developing method.
After the development process, the developer is usually washed and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer. Note that, after the development treatment, heat treatment may be performed in order to sufficiently harden the coating film. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

<Light shielding part>
The light shielding part in the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be similar to that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include stripe shapes, matrix shapes, and the like. The light shielding portion may be a thin film of metal such as chromium formed by sputtering, vacuum evaporation, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, and organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, there are methods such as patterning by development using a photosensitive resist, patterning using an inkjet ink containing light-shielding particles, and thermal transfer of a photosensitive resist. be.

The film thickness of the light shielding part is set at about 0.2 to 0.4 μm in the case of a metal thin film, and set at about 0.5 to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin. be done.

<Substrate>
As the substrate, a transparent substrate, a silicon substrate, and a substrate in which a thin film of aluminum, silver, silver/copper/palladium alloy, etc. is formed on a transparent substrate or silicon substrate, which will be described later, are used. Other color filter layers, resin layers, transistors such as TFTs, circuits, etc. may be formed on these substrates.
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material that is transparent to visible light, and transparent substrates used in general color filters can be used. Specifically, non-flexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials that have flexibility such as transparent resin films, optical resin plates, and flexible glass. Examples include wood.
The thickness of the transparent substrate is not particularly limited, but may be, for example, about 100 μm to 1 mm depending on the use of the color filter of the present invention.
Note that the color filter of the present invention may include, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, etc., in addition to the above-described substrate, light shielding portion, and colored layer.

IV. Display Device A display device according to the present invention is characterized by having the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as a liquid crystal display device, an organic light emitting display device, and the like.

[Liquid crystal display device]
Examples of the liquid crystal display device of the present invention include a liquid crystal display device having the above-described color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. .
Such a liquid crystal display device of the present invention will be explained with reference to the drawings. FIG. 2 is a schematic diagram showing an example of a liquid crystal display device of the present invention. As illustrated in FIG. 2, a liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate, etc., and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may have a generally known configuration as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and any driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be suitably used.
Further, the counter substrate can be appropriately selected and used depending on the driving method of the liquid crystal display device of the present invention.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used depending on the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, methods generally used for manufacturing liquid crystal cells can be used, such as a vacuum injection method, a liquid crystal dropping method, and the like. After forming the liquid crystal layer by the method described above, the liquid crystal cell is gradually cooled to room temperature, thereby making it possible to orient the encapsulated liquid crystal.

[Organic light emitting display device]
Examples of the organic light emitting display device of the present invention include an organic light emitting display device having the above-described color filter according to the present invention and an organic light emitter.
The organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram showing an example of an organic light emitting display device of the present invention. As illustrated in FIG. 3, an organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80. An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method of stacking the organic light emitter 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter. Examples include a method in which an organic light emitting body 80 formed on a separate substrate is bonded onto an inorganic oxide film 60, and the like. For the transparent anode 71, hole injection layer 72, hole transport layer 73, light emitting layer 74, electron injection layer 75, cathode 76, and other structures in the organic light emitter 80, publicly known ones can be used as appropriate. The organic light emitting display device 100 manufactured in this manner is applicable to, for example, both a passive drive type organic EL display and an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may have a generally known configuration as an organic light emitting display device using a color filter.

Hereinafter, the present invention will be specifically explained by showing examples. The present invention is not limited to these descriptions.
The mass average molecular weight (Mw) of the copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention described above.

(Synthesis example 1: Synthesis of block copolymer 1)
Add 250 parts by mass of THF and 0.75 parts by mass of lithium chloride to a 500 mL round-bottomed 4-neck separable flask equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and thoroughly purge with nitrogen. Ta. After cooling the reaction flask to −60° C., 6.1 parts by mass of butyllithium (15% by mass hexane solution), 1.4 parts by mass of diisopropylamine, and 1.2 parts by mass of methyl isobutyrate were injected using a syringe. Monomers for B block: 9 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.4 parts by mass of n-butyl methacrylate (BMA), 7.5 parts by mass of benzyl methacrylate (BzMA), 47 parts by mass of methyl methacrylate (MMA) .5 parts by mass was added dropwise over 60 minutes using an addition funnel. After 30 minutes, 22.6 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. It was reprecipitated in hexane, purified by filtration and vacuum drying to obtain a block copolymer containing the structural unit represented by the general formula (I). (Amine value: 95 mgKOH/g, acid value: 0 mgKOH/g) Weight average molecular weight Mw was 7,600.

(Synthesis example 2: Synthesis of block copolymer 2)
Add 250 parts by mass of THF and 0.6 parts by mass of lithium chloride to a 500 mL round-bottomed 4-neck separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and thoroughly purge with nitrogen. Ta. After cooling the reaction flask to −60° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. B block monomers 1-ethoxyethyl methacrylate (EEMA) 2.2 parts by mass, 2-(trimethylsilyloxy)ethyl methacrylate (TMSMA) 29.1 parts by mass, 2-ethylhexyl methacrylate (EHMA) 12.8 parts by mass 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA) were added over 60 minutes using an addition funnel. dripped. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, purified by filtration and vacuum drying, and diluted with PGMEA to obtain a solution with a solid content of 30% by mass. Add 32.5 parts by mass of water, raise the temperature to 100°C and react for 7 hours, deprotect the EEMA-derived structural unit to obtain a methacrylic acid (MAA)-derived structural unit, and deprotect the TMSMA-derived structural unit. The structural unit was derived from 2-hydroxyethyl methacrylate (HEMA). The obtained block copolymer PGMEA solution was reprecipitated in hexane, purified by filtration, and vacuum drying to obtain block copolymer 2 (amine value 95 mgKOH/ g, acid value 8 mgKOH/g, Tg 38°C). The weight average molecular weight Mw was 7,730.

(Synthesis Example 3: Synthesis of salt-type block copolymer 3)
Block copolymer 1 was synthesized in the same manner as in Synthesis Example 1.
50 parts by mass of the obtained block copolymer 1 was dissolved in 102 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto, and the mixture was reacted at 90°C for 12 hours to obtain a PGMEA solution (solid content: 35%) of salt type block copolymer 3.

(Synthesis Example 4: Synthesis of salt-type block copolymer 4)
Block copolymer 2 was synthesized in the same manner as in Synthesis Example 2.
50 parts by mass of the obtained block copolymer 2 was dissolved in 102 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto, and the mixture was reacted at 90° C. for 12 hours to obtain a PGMEA solution (solid content: 35%) of salt type block copolymer 4.

(Synthesis Example 5: Synthesis of graft copolymer 5)
(1) Production of macromonomer A 70.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) was charged into a reactor equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and nitrogen The mixture was heated to a temperature of 90° C. while stirring under a stream of air. A monomer having a PEG chain (manufactured by Evonik, product name: VISIOMER MPEG 1005 MA W, R ^{4 4} in the general formula (III) is CH ₃ , A ³ is COO, R ^{4 5} is an ethylene group, R ^{4 6} is CH ₃ , m = 22) 2.0 parts by mass, methyl methacrylate (MMA) 98.0 parts by mass, mercaptoethanol 4.0 parts by mass, PGMEA 30 parts by mass, A mixed solution of 1.0 parts by mass of α,α'-azobisisobutyronitrile (AIBN) was added dropwise over 1.5 hours, and the mixture was reacted for an additional 3 hours. Next, the nitrogen flow was stopped, the reaction solution was cooled to 80°C, and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko KK), 0.125 g of dioctyl tin dilaurate, and 0.0 parts of p-methoxyphenol were added. A 50% solution of macromonomer A was obtained by adding 125 parts by mass and 30 parts by mass of PGMEA and stirring for 3 hours. The obtained macromonomer A was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol/L lithium bromide addition/polystyrene standard, and the weight average molecular weight (Mw) was confirmed. 4000, and the molecular weight distribution (Mw/Mn) was 1.6.

(2) Synthesis of graft copolymer 5 63.1 parts by mass of PGMEA was charged into a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and while stirring under a nitrogen stream, It was heated to a temperature of 85°C. 141 parts by mass of the macromonomer A solution (effective solid content 70.5 parts by mass), 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), 1.24 parts by mass of n-dodecylmercaptan, 49.4 parts by mass of PGMEA. A mixed solution of 1.0 parts by mass of AIBN and 1.0 parts by mass of AIBN was added dropwise over 1.5 hours, and after heating and stirring for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 10 minutes. By further aging at the same temperature for 1 hour, a 35.0% by mass solution of graft copolymer A was obtained. The obtained graft copolymer 5 had a weight average molecular weight (Mw) of 10,500 as a result of GPC measurement. The amine value was 105 mgKOH/g.

(Synthesis Example 6: Synthesis of graft copolymer 6)
(1) Production of macromonomer B 70.0 parts by mass of propylene glycol methyl ether acetate (PGMEA) was charged into a reactor equipped with a cooling tube, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer, and nitrogen The mixture was heated to a temperature of 90° C. while stirring under a stream of air. A monomer having a PEG chain (manufactured by Evonik, trade name: VISIOMER MPEG 1005 MA W, R ^{4 4} in the general formula (III) is CH ₃ , A ³ is COO, R ^{4 5} is an ethylene group, R ^{4 6} is CH ₃ , m = 22) 6.0 parts by mass, triethylene glycol monoethyl ether methacrylate (manufactured by Tokyo Kasei Kogyo, m = 3) 69.0 parts by mass, methacryl A mixed solution of 25.0 parts by mass of methyl acid (MMA), 4.0 parts by mass of mercaptoethanol, 30 parts by mass of PGMEA, and 1.0 parts by mass of α,α'-azobisisobutyronitrile (AIBN) was heated for 1.5 hours. The solution was added dropwise over the course of 3 hours, and the reaction was continued for an additional 3 hours. Next, the nitrogen flow was stopped, the reaction solution was cooled to 80°C, and 8.74 parts by mass of Karenz MOI (manufactured by Showa Denko KK), 0.125 g of dioctyl tin dilaurate, and 0.0 parts of p-methoxyphenol were added. A 50% solution of macromonomer B was obtained by adding 125 parts by mass and 30 parts by mass of PGMEA and stirring for 3 hours. The obtained macromonomer B was confirmed by GPC (gel permeation chromatography) under the conditions of N-methylpyrrolidone, 0.01 mol/L lithium bromide addition/polystyrene standard, and the weight average molecular weight (Mw) was confirmed. 5800, and the molecular weight distribution (Mw/Mn) was 1.6.

(2) Synthesis of graft copolymer 6 63.1 parts by mass of PGMEA was charged into a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and while stirring under a nitrogen stream, It was heated to a temperature of 85°C. 141 parts by mass of the macromonomer B solution (effective solid content 70.5 parts by mass), 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), 1.24 parts by mass of n-dodecylmercaptan, 49.4 parts by mass of PGMEA. A mixed solution of 1.0 parts by mass of AIBN and 1.0 parts by mass of AIBN was added dropwise over 1.5 hours, and after heating and stirring for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 10 minutes. By further aging at the same temperature for 1 hour, a 35.0% by mass solution of graft copolymer 6 was obtained. The obtained graft copolymer 6 had a weight average molecular weight (Mw) of 10,000 as a result of GPC measurement. The amine value was 105 mgKOH/g.

(Synthesis Example 7: Synthesis of graft copolymer 7)
(1) Production of macromonomer C 30.0 parts by mass of PGMEA was charged into a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was heated to a temperature of 90% while stirring under a nitrogen stream. Warmed to ℃. MMA 25.0 parts by mass, caprolactone-modified hydroxyethyl methacrylate (trade name: Plaxel FM5, manufactured by Daicel Corporation, caprolactone chain repeating number n = 5) (PCL-FM5) 75.0 parts by mass, mercaptopropionic acid 7.0 parts by mass A mixed solution of 1.0 parts by mass of AIBN was added dropwise over 1.5 hours, and the reaction was further continued for 3 hours. After cooling, this reaction solution was diluted with 200 parts by mass of tetrahydrofuran (THF) and reprecipitated with 3,000 parts by mass of hexane to obtain 106.0 parts by mass of white powder. Next, to 50.0 parts by mass of this white powder, 50.0 parts by mass of PGMEA, 3.7 parts by mass of glycidyl methacrylate (GMA), 0.15 parts by mass of N,N-dimethyldodecylamine, and 0.1 part by mass of p-methoxyphenol. Parts by mass were added, and the mixture was stirred at 110° C. for 24 hours while bubbling air. After cooling, this reaction solution was reprecipitated with 3000 parts by mass of hexane to obtain 52.0 parts by mass of macromonomer C.
The weight average molecular weight (Mw) of the obtained macromonomer C was 6,300, and the molecular weight distribution (Mw/Mn) was 1.6.

(2) Synthesis of graft copolymer 7 63.1 parts by mass of PGMEA was charged into a reactor equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and while stirring under a nitrogen stream, It was heated to a temperature of 85°C. 141 parts by mass of a solution of the macromonomer C dissolved in PGMEA (effective solid content 70.5 parts by mass), 29.5 parts by mass of 2-(dimethylamino)ethyl methacrylate (DMMA), 1.24 parts by mass of n-dodecylmercaptan. A mixed solution of 49.4 parts by mass of PGMEA and 1.0 parts by mass of AIBN was added dropwise over 1.5 hours, and after heating and stirring for 3 hours, a mixed solution of 0.10 parts by mass of AIBN and 6.0 parts by mass of PGMEA was added dropwise over 1.5 hours. The mixture was added dropwise over several minutes and further aged at the same temperature for 1 hour to obtain a 35.0% by mass solution of graft copolymer 7. The obtained graft copolymer 7 had a weight average molecular weight (Mw) of 13,000 as a result of GPC measurement. The amine value was 105 mgKOH/g.

(Synthesis Example 8: Synthesis of salt-type graft copolymer 8)
Graft copolymer 5 was synthesized in the same manner as Synthesis Example 5.
50 parts by mass of the obtained graft copolymer 5 was dissolved in 102 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto, and the mixture was reacted at 90° C. for 12 hours to obtain a PGMEA solution (solid content: 35%) of salt type block copolymer 8.

(Synthesis Example 9: Synthesis of salt-type graft copolymer 9)
Graft copolymer 6 was synthesized in the same manner as Synthesis Example 6.
50 parts by mass of the obtained graft copolymer 6 was dissolved in 102 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto, and the mixture was reacted at 90° C. for 12 hours to obtain a PGMEA solution (solid content: 35%) of salt type block copolymer 9.

(Synthesis Example 10: Synthesis of salt-type graft copolymer 10)
Graft copolymer 7 was synthesized in the same manner as Synthesis Example 7.
50 parts by mass of the obtained graft copolymer 7 was dissolved in 102 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto, and the mixture was reacted at 90° C. for 12 hours to obtain a PGMEA solution (solid content: 35%) of salt type block copolymer 10.

(Preparation example 1: Preparation of alkali-soluble resin A)
A polymerization tank was charged with 300 parts by mass of PGMEA, and the temperature was raised to 100°C under a nitrogen atmosphere, followed by 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA), and perbutyl. 6 parts by mass of O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecylmercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining the temperature at 100°C, and 2 hours after the completion of dropping the main chain forming mixture, 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to stop the polymerization.
Next, while blowing air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, the temperature was raised to 110°C, and then 0.8 parts by mass of triethylamine was added and the temperature was kept at 110°C for 15 hours. An addition reaction was carried out to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40% by mass).
The weight average molecular weight was measured using polystyrene as a standard substance and THF as an eluent using Shodex GPC System-21H. The acid value was measured based on JIS K 0070.

(Production Example 1: Production of coloring material dispersion R(1))
In a 225 mL mayonnaise bottle, 64.9 parts by mass of PGMEA, 13.5 parts by mass of alkali-soluble resin A solution of Preparation Example 1 (solid content 40 mass%), PGMEA solution of block copolymer 1 of Synthesis Example 1 (solid content 35%). 9.2 parts by mass (% by mass) were added and stirred. 0.39 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Co., Ltd.) was added thereto, and the mixture was stirred at room temperature for 30 minutes.
There, C. I. Pigment Red 177 (PR177), 9.6 parts by mass, C.I. I. 2.4 parts by mass of Pigment Red 254 (PR254) and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added, shaken for 1 hour in a paint shaker (manufactured by Asada Tekko Co., Ltd.) as preliminary crushing, and then 2.4 parts by mass of Pigment Red 254 (PR254) and 100 parts by mass of zirconia beads with a particle size of 0. The dispersion was changed to 200 parts of 1 mm zirconia beads, and dispersion was carried out for 4 hours in a paint shaker as main disintegration to obtain coloring material dispersion R (1). In addition, the block copolymer 1 is salt-formed with phenylphosphonic acid, and becomes the salt-type block copolymer 1.

(Production Example 2: Production of coloring material dispersion R(2))
In the production of colorant dispersion R(1) of Production Example 1, the colorant dispersion of Production Example 1 was used, except that block copolymer 1 of Synthesis Example 1 was changed to block copolymer 2 of Synthesis Example 2. Coloring material dispersion R(2) was obtained in the same manner as R(1). In addition, in the coloring material dispersion R(2), the block copolymer 2 is salt-formed with phenylphosphonic acid, and becomes the salt-type block copolymer 2.

(Production Example 3: Production of coloring material dispersion R(3))
In the production of colorant dispersion R(1) of Production Example 1, the colorant dispersion of Production Example 1 was used, except that block copolymer 1 of Synthesis Example 1 was changed to graft copolymer 5 of Synthesis Example 5. Coloring material dispersion R(3) was obtained in the same manner as R(1). In addition, in the coloring material dispersion R(3), the graft copolymer 5 is salt-formed with phenylphosphonic acid to become a salt-type graft copolymer 5.

(Production Example 4: Production of coloring material dispersion R(4))
In the production of colorant dispersion R(1) of Production Example 1, the colorant dispersion of Production Example 1 was used, except that block copolymer 1 of Synthesis Example 1 was changed to graft copolymer 6 of Synthesis Example 6. Coloring material dispersion R(4) was obtained in the same manner as R(1). In the coloring material dispersion R(4), the graft copolymer 6 is salt-formed with phenylphosphonic acid to become a salt-type graft copolymer 6.

(Production Example 5: Production of coloring material dispersion R(5))
In the production of colorant dispersion R(1) of Production Example 1, the colorant dispersion of Production Example 1 was used, except that block copolymer 1 of Synthesis Example 1 was changed to graft copolymer 7 of Synthesis Example 7. Coloring material dispersion R(5) was obtained in the same manner as R(1). In addition, in the coloring material dispersion R(5), the graft copolymer 7 is salt-formed with phenylphosphonic acid to become a salt-type graft copolymer 7.

(Example 1: Production of photosensitive colored resin composition R-1)
35.7 parts by mass of the coloring material dispersion R (1) obtained in Production Example 1, 3.52 parts by mass of the alkali-soluble resin A solution (solid content 40% by mass) obtained in Preparation Example 1, polyfunctional 5.64 parts by mass of monomer (trade name Aronix M-305, manufactured by Toagosei Co., Ltd.), 0.45 parts by mass of the oxime ester compound represented by the chemical formula (A-1) (alkali-soluble resin and 6% by mass based on the total of the functional monomer and initiator), 0.03 parts by mass of a fluorine-based surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 54.66 parts by mass of PGMEA were added. A photosensitive colored resin composition R-1 was obtained.

(Examples 2 to 8: Production of photosensitive colored resin compositions R-2 to R-8)
In Example 1, photosensitive colored resin compositions R-2 to R- were prepared in the same manner as photosensitive colored resin composition R-1, except that the type and amount of the initiator were changed as shown in Table 1. I got 8.

(Examples 9 to 12: Production of photosensitive colored resin compositions R-9 to R-12)
In Example 1, as shown in Table 1, colorant dispersion R(1) was changed to colorant dispersion R(2), R(3), R(4), or R(5). Except for this, photosensitive colored resin compositions R-9 to R-12 were obtained in the same manner as photosensitive colored resin composition R-1.

(Example 13: Production of photosensitive colored resin composition R-13)
35.7 parts by mass of coloring material dispersion R(1) obtained in Production Example 1, 3.49 parts by mass of alkali-soluble resin A solution obtained in Production Example 1, polyfunctional monomer (trade name Aronix M- 305, manufactured by Toagosei Co., Ltd.), 5.58 parts by mass of the oxime ester compound represented by the chemical formula (A-1), 0.45 parts by mass of the oxime ester compound represented by the chemical formula (A-1), and a fluorine-based surfactant (trade name Megafac R-08MH). , manufactured by DIC Corporation), 0.07 parts by mass of the antioxidant Irganox 1010 (1.0% by mass based on the total of the alkali-soluble resin, polyfunctional monomer, and initiator), and 54 parts by mass of PGMEA. .68 parts by mass was added to obtain photosensitive colored resin composition R-13.

(Production Example 6: Production of coloring material dispersion G(1))
In the production of coloring material dispersion R(1) of Production Example 1, C. I. Pigment Red 177 (PR177) 9.6 parts by mass, C.I. I. Pigment Red 254 (PR254) 2.4 parts by mass was replaced with C.I. I. Pigment Green 58 (PG58) 8.4 parts by mass, C.I. I. Colorant dispersion G(1) was obtained in the same manner as Colorant dispersion R(1) of Production Example 1, except that 3.6 parts by mass of Pigment Yellow 138 (PY138) was used. In addition, in the coloring material dispersion G(1), the block copolymer 1 is salt-formed with phenylphosphonic acid, and becomes the salt-type block copolymer 1.

(Production Examples 7 to 10: Production of coloring material dispersions G(2) to G(5))
In the production of coloring material dispersion G(1) of Production Example 6, block copolymer 1 of Synthesis Example 1 was added to block copolymer 2 of Synthesis Example 2, graft copolymer 5 of Synthesis Example 5, and synthesis example Colorant dispersion G(2) was prepared in the same manner as Colorant dispersion G(1) of Production Example 6, except that the graft copolymer 6 of Synthesis Example 6 was changed to Graft Copolymer 6 of Synthesis Example 7. , G(3), G(4) or G(5) were obtained.
In addition, in coloring material dispersions G(2) to G(5), block copolymer 2, graft copolymers 5, 6, and 7 are each formed into a salt with phenylphosphonic acid, and salt-type block copolymer 2 , salt-type graft copolymers 5, 6, and 7.

(Example 14: Production of photosensitive colored resin composition G-1)
In Example 1, the photosensitive colored resin composition R was changed from the coloring material dispersion R(1) obtained in Production Example 1 to the coloring material dispersion G(1) obtained in Production Example 6. Photosensitive colored resin composition G-1 was obtained in the same manner as in Example 1-1.

(Examples 15 to 21: Production of photosensitive colored resin compositions G-2 to G-8)
In Example 14, photosensitive colored resin compositions G-2 to G- were prepared in the same manner as photosensitive colored resin composition G-1, except that the type and amount of the initiator were changed as shown in Table 2. I got 8.

(Examples 22 to 25: Production of photosensitive colored resin compositions G-9 to G-12)
In Example 14, as shown in Table 2, colorant dispersion G(1) was changed to colorant dispersion G(2), G(3), G(4), or G(5). Other than that, photosensitive colored resin compositions G-9 to G-12 were obtained in the same manner as photosensitive colored resin composition G-1.

(Example 26: Production of photosensitive colored resin composition G-13)
In Example 13, the photosensitive colored resin composition R was replaced with the colorant dispersion G(1) obtained in Production Example 6, except that the colorant dispersion R(1) obtained in Production Example 1 was changed to the colorant dispersion G(1) obtained in Production Example 6. Photosensitive colored resin composition G-13 was obtained in the same manner as in Example 1-13.

(Production Example 11: Production of coloring material dispersion B(1))
In a 225 mL mayonnaise bottle, 64.9 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin A solution of Preparation Example 1 (solid content 40 mass%), the PGMEA solution of salt type block copolymer 3 of Synthesis Example 3 (solid content). 9.2 parts by mass (35% by mass) were added and stirred.
There, C. I. Pigment Blue 15:6 (PB15:6), 9.6 parts by mass, C.I. I. Add 2.4 parts by mass of Pigment Violet 23 (PV23) and 100 parts by mass of zirconia beads with a particle size of 2.0 mm, shake for 1 hour in a paint shaker (manufactured by Asada Tekko Co., Ltd.) as preliminary crushing, and then add 2.4 parts by mass of Pigment Violet 23 (PV23) and 100 parts by mass of zirconia beads with a particle size of 2.0 mm. The dispersion was changed to 200 parts of 1 mm zirconia beads, and dispersion was carried out for 4 hours in a paint shaker as main disintegration to obtain coloring material dispersion B (1).

(Production Examples 12 to 15: Production of coloring material dispersions B(2) to B(5))
In the production of colorant dispersion B(1) of Production Example 11, the PGMEA solution of salt-type block copolymer 3 of Synthesis Example 3 was added to the PGMEA solution of salt-type block copolymer 4 of Synthesis Example 4, and the PGMEA solution of salt-type block copolymer 4 of Synthesis Example 4 was added to Except for changing to the PGMEA solution of salt-type graft copolymer 8 in Synthesis Example 8, the PGMEA solution of salt-type graft copolymer 9 in Synthesis Example 9, or the PGMEA solution of salt-type graft copolymer 10 in Synthesis Example 10. Coloring material dispersion B(2), B(3), B(4), or B(5) was obtained in the same manner as coloring material dispersion B(1) of Production Example 11.

(Example 27: Production of photosensitive colored resin composition B-1)
In Example 1, the photosensitive colored resin composition R was prepared except that the coloring material dispersion R (1) obtained in Production Example 1 was changed to the coloring material dispersion B (1) obtained in Production Example 11. Photosensitive colored resin composition B-1 was obtained in the same manner as in Example 1-1.

(Examples 28 to 34: Production of photosensitive colored resin compositions B-2 to B-8)
In Example 27, photosensitive colored resin compositions B-2 to B- were prepared in the same manner as photosensitive colored resin composition B-1, except that the type and amount of the initiator were changed as shown in Table 3. I got 8.

(Examples 35 to 38: Production of photosensitive colored resin compositions B-9 to B-12)
In Example 27, as shown in Table 3, colorant dispersion B(1) was changed to colorant dispersion B(2), B(3), B(4), or B(5). Except for this, photosensitive colored resin compositions B-9 to B-12 were obtained in the same manner as photosensitive colored resin composition B-1.

(Example 39: Production of photosensitive colored resin composition B-13)
In Example 1, the photosensitive colored resin composition R was prepared except that the coloring material dispersion R (1) obtained in Production Example 1 was changed to the coloring material dispersion B (1) obtained in Production Example 11. Photosensitive colored resin composition B-13 was obtained in the same manner as in Example 1-13.

(Examples 40 to 52: Production of photosensitive colored resin compositions R-14 to R-26)
In each of Examples 1 to 13, as shown in Table 4, the oxime ester compound represented by the chemical formula (A-1) was changed to the oxime ester compound represented by the chemical formula (A-2). Photosensitive colored resin compositions R-14 to R-26 were obtained in the same manner as photosensitive colored resin compositions R-1 to R-13.

(Examples 53 to 65: Production of photosensitive colored resin compositions G-14 to G-26)
In each of Examples 14 to 26, as shown in Table 5, the oxime ester compound represented by the chemical formula (A-1) was changed to the oxime ester compound represented by the chemical formula (A-2). Photosensitive colored resin compositions G-14 to G-26 were obtained in the same manner as photosensitive colored resin compositions G-1 to G-13.

(Examples 66 to 78: Production of photosensitive colored resin compositions B-14 to B-26)
In each of Examples 27 to 39, as shown in Table 6, the oxime ester compound represented by the chemical formula (A-1) was changed to the oxime ester compound represented by the chemical formula (A-2). Photosensitive colored resin compositions B-14 to B-26 were obtained in the same manner as photosensitive colored resin compositions B-1 to B-13.

(Examples 79 to 84: Production of photosensitive colored resin compositions R-27 to R-32)
In Examples 1 and 9 to 13, as shown in Table 7, the oxime ester compound represented by the chemical formula (A-1) was changed to the oxime ester compound represented by the chemical formula (A-3). Except for the above, photosensitive colored resin compositions R-27 to R-32 were obtained in the same manner as photosensitive colored resin compositions R-1 and R-9 to R-13.

(Examples 85 to 90: Production of photosensitive colored resin compositions R-33 to R-38)
In Examples 1 and 9 to 13, as shown in Table 7, the oxime ester compound represented by the chemical formula (A-1) was changed to the oxime ester compound represented by the chemical formula (A-4). Except for the above, photosensitive colored resin compositions R-33 to R-38 were obtained in the same manner as photosensitive colored resin compositions R-1 and R-9 to R-13.

(Comparative Examples 1 to 3: Production of photosensitive colored resin compositions CR-1, CG-1 and CB-1)
In Example 1, Example 14, or Example 27, as shown in Table 7, the oxime ester compound represented by the chemical formula (A-1) was combined with an oxime ester photoinitiator having a carbazole skeleton, ethanone. ,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (trade name Irgacure OXE02, manufactured by BASF). In the same manner as in Example 1, Example 14, or Example 27, photosensitive colored resin compositions CR-1, CG-1, and CB-1 were produced.

(Comparative Production Examples 1 and 2: Production of Coloring Material Dispersions CR(1) and CR(2))
In the production of coloring material dispersion R(1) of Production Example 1, block copolymer 1 of Synthesis Example 1 was mixed with Ajisper PB821 (PB821, manufactured by Ajinomoto Fine-Techno Co., Inc., polyester-based) as shown in Table 7. dispersant, solid content 30% by mass) or Disperbyk-161 (BYK-161, manufactured by BYK Chemie, urethane dispersant, solid content 30% by mass), and the solid content is the same mass part as block copolymer 1. Colorant dispersion R (1) of Production Example 1 was used, except that phenylphosphonic acid was not added and the amount of PGMEA was adjusted so that the solid content of the dispersion was the same as Production Example 1. In the same manner as above, colorant dispersions CR(1) and CR(2) were obtained.

(Comparative Production Examples 3 and 4: Production of Coloring Material Dispersions CG (1) and CG (2))
In the production of coloring material dispersion G (1) of Production Example 6, block copolymer 1 of Synthesis Example 1 was mixed with Ajisper PB821 (PB821, manufactured by Ajinomoto Fine-Techno, Inc., polyester-based) as shown in Table 7. dispersant, solid content 30% by mass) or Disperbyk-161 (BYK-161, manufactured by BYK Chemie, urethane dispersant, solid content 30% by mass), and the solid content is the same mass part as block copolymer 1. Colorant dispersion G (1) of Production Example 6 was used, except that phenylphosphonic acid was not added and the amount of PGMEA was adjusted so that the solid content of the dispersion was the same as Production Example 6. In the same manner as above, colorant dispersions CG (1) and CG (2) were obtained.

(Comparative Production Examples 5 and 6: Production of Coloring Material Dispersions CB(1) and CB(2))
In the production of coloring material dispersion B(1) of Production Example 11, the PGMEA solution (solid content 35% by mass) of the salt-type block copolymer 3 of Synthesis Example 3 was added to Ajisper PB821 (35% by mass) as shown in Table 7. PB821, produced by Ajinomoto Fine Techno Co., Ltd., polyester dispersant, solid content 30% by mass), or Disperbyk-161 (BYK-161, manufactured by BYK Chemie, urethane dispersant, solid content 30% by mass), The coloring material dispersion of Production Example 11 was used so that the solid content was the same as that of Block Copolymer 1, and the amount of PGMEA was adjusted so that the solid content of the dispersion was the same as Production Example 11. Coloring material dispersions CB(1) and CB(2) were obtained in the same manner as B(1).

(Comparative Examples 4 to 5: Production of photosensitive colored resin compositions CR-2 and CR-3)
Example 1 was carried out in the same manner as in Example 1, except that colorant dispersion R(1) was changed to colorant dispersion CR(1) or CR(2), as shown in Table 7. A photosensitive colored resin composition CR-2 or CR-3 was produced.

(Comparative Examples 6-7: Production of photosensitive colored resin compositions CG-2 and CG-3)
Example 14 was carried out in the same manner as in Example 14, except that colorant dispersion G(1) was changed to colorant dispersion CG(1) or CG(2), as shown in Table 7. A photosensitive colored resin composition CG-2 or CG-3 was produced.

(Comparative Examples 8 to 9: Production of photosensitive colored resin compositions CB-2 and CB-3)
Example 27 was carried out in the same manner as in Example 27, except that colorant dispersion B(1) was changed to colorant dispersion CB(1) or CB(2), as shown in Table 7. A photosensitive colored resin composition CB-2 or CB-3 was produced.

[Evaluation method]
The photosensitive colored resin composition obtained in each Example and each Comparative Example was coated onto a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater to form a cured coating film with a thickness of 3. After coating the film to a thickness of .0 μm, it was dried at 80° C. for 3 minutes using a hot plate to form a coating film on the glass substrate. This coating film was exposed to ultraviolet light of 40 mJ/cm ² using an ultra-high pressure mercury lamp through a patterned photomask (chrome mask) in which a 20 μm x 20 μm chrome mask was placed at the center of an independent thin line with an opening size of 90 μm x 300 μm. By exposing to light, a post-exposure coating film was formed on the glass substrate. Next, spin development was performed using a 0.05 wt % potassium hydroxide aqueous solution as a developer, and the development treatment was performed by allowing the developer to soak in the developer for 60 seconds and then washing with pure water to form a coating film in the form of an independent fine line pattern having micropores. I got it. Thereafter, by post-baking in a clean oven at 90° C. for 25 minutes, a colored layer in the form of an independent fine line pattern having micropores was formed. The following evaluation was performed on the obtained colored layer.

<Line width shift amount evaluation>
The width of the fine line pattern of the colored layer in the area corresponding to the opening width of 90 μm of the chrome mask used during exposure was measured at five locations using an optical microscope, and the amount of line width shift was evaluated based on the difference between the average line width and the target line width. did.
(Line width shift amount evaluation criteria)
A: Difference from the target line width is within 1.5 μm B: Difference from the target line width is more than 1.5 μm and within 3.0 μm C: Difference from the target line width is 3.0 μm or less. Exceeding 0 μm and within 4.0 μm D: Difference from the target line width exceeds 4.0 μm If the evaluation result is B, the line width shift amount is good, and if the evaluation result is A, the line width shift amount is Are better.

<Solvent resistance (PGME resistance) evaluation>
After measuring the thickness of the colored layer obtained, it was immersed in propylene glycol monomethyl ether (PGME) for 10 minutes, air-dried, and the thickness was measured again. Note that a stylus-type step film thickness meter "P-15Tencor" (manufactured by Instruments) was used to measure the film thickness. Film thickness after solvent immersion/film thickness before solvent immersion x 100 was calculated as the remaining film rate.
(Solvent resistance evaluation criteria)
A: Remaining film rate after solvent immersion is 98% or more B: Remaining film rate after solvent immersion is 96% or more and less than 98% C: Remaining film rate after solvent immersion is 94% or more and less than 96% D: After solvent immersion The remaining film rate is less than 94%. If the evaluation result is B, the solvent resistance is good, and if the evaluation result is A, the solvent resistance is excellent.

<Evaluation of cross-sectional shape of colored layer in thin line pattern>
The cross-sectional shape in the thickness direction of the colored layer in the form of an independent fine line pattern was observed using a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification: 10,000 times), and the colored layer was evaluated according to the following evaluation criteria. The taper angle (θ1) of the cross-sectional shape (see FIG. 5) was evaluated.
(Evaluation criteria for cross-sectional shape of patterned colored layer)
A: Taper angle (θ1) is 15 degrees or more and less than 70 degrees B: Taper angle (θ1) is 70 degrees or more and less than 90 degrees C: Taper angle (θ1) is 90 degrees or more and less than 100 degrees D: Taper angle (θ1) is 100 degrees or more If the evaluation result is B, the cross-sectional shape of the colored layer is good, and if the evaluation result is A, the cross-sectional shape of the colored layer is excellent.

<Cross-sectional shape of micropore>
The cross-sectional shape of the colored layer in the thickness direction of the micropores was observed using a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification: 10,000 times), and the taper of the cross-sectional shape of the micropores was determined according to the following evaluation criteria. The angle (θ2) (see FIG. 6) was evaluated.
(Evaluation criteria for cross-sectional shape of micropores)
A: Taper angle (θ2) is 15 degrees or more and less than 70 degrees B: Taper angle (θ2) is 70 degrees or more and less than 90 degrees C: Taper angle (θ2) is 90 degrees or more and less than 100 degrees D: Taper angle (θ2) is 100 degrees or more If the evaluation result is B, the cross-sectional shape of the micropore is good, and if the evaluation result is A, the cross-sectional shape of the micropore is excellent.

<Residues inside micropores>
The micropores were observed using a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification: 5000 times), and the residue inside the micropores was evaluated according to the following evaluation criteria.
(Evaluation criteria for residue inside micropores)
A: No residue was observed at all.
B: A slight residue is observed only at the end of the hole.
C: A small amount of residue is observed throughout the hole D: A large amount of residue is observed throughout the hole If the evaluation result is B, the residue inside the micropore is good, and the evaluation result is A. If there is, it is excellent for removing residue inside micropores.

<Development residue suppression evaluation>
The photosensitive colored resin compositions obtained in Examples and Comparative Examples were post-baked onto glass substrates (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater, and then coated to a thickness of 2.0 μm. After applying the coating to a thickness that would form a colored layer, it was dried using a hot plate at 80° C. for 3 minutes to form a colored layer on the glass substrate. The glass plate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass aqueous potassium hydroxide solution as an alkaline developer, and then washed with pure water. After visually observing the area where the colored layer is formed after development, wipe it thoroughly with a lens cleaner containing ethanol (trade name: Toraysee MK Clean Cloth, manufactured by Toray Industries, Inc.), and visually check the degree of coloration of the lens cleaner. Observed.
(Development residue suppression evaluation criteria)
A: No development residue was visually confirmed, and the lens cleaner was not colored at all. B: No development residue was visually observed, and the lens cleaner was slightly colored. C: Slight development residue was confirmed visually. D: Development residue was visually confirmed and coloration of the lens cleaner was confirmed. If the evaluation result is B, the development residue suppression effect is good, and if the evaluation result is A. It has an excellent effect of suppressing development residue.

<Water stain suppression evaluation>
The photosensitive colored resin compositions obtained in Examples and Comparative Examples were each coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35", 100 mm x 100 mm with a thickness of 0.7 mm) using a spin coater. After post-baking, the film was coated to a thickness that would form a 2.0 μm thick colored layer, then dried using a hot plate at 60°C for 3 minutes, and then heated to 30 mJ/cm using an ultra-high pressure mercury lamp without using a photomask. A colored layer was formed on the glass substrate by irradiating the entire surface with ultraviolet rays of step ² . Next, the development process was performed by performing shower development using 0.05 wt% potassium (KOH) as a developer for 60 seconds and then washing with pure water. Immediately after the washed substrate was rotated for 10 seconds and the water was removed by centrifugation, the following Water stains were evaluated by measuring the contact angle of pure water.
To measure the contact angle of pure water, a droplet of 1.0 μL of pure water is dropped on the surface of the colored layer immediately after centrifugal removal of the water, and the static contact angle after 10 seconds of droplet landing is measured according to the θ/2 method. I measured it. The measurement was carried out using a contact angle meter DM 500 manufactured by Kyowa Interface Science.
(Water stain suppression evaluation criteria)
A: Contact angle of 70 degrees or more B: Contact angle of 50 degrees or more and less than 70 degrees C: Contact angle of 30 degrees or more and less than 50 degrees D: Contact angle of less than 30 degrees If the water stain suppression evaluation standard is A or B, it can be used for practical purposes. However, if the evaluation result is A, the effect is better.

In Tables 1 to 7, the compound represented by the general formula (A) and other initiators that are different from the compound represented by the general formula (A) are as follows.
<Compound represented by the above general formula (A)>
・A-1: A compound represented by the chemical formula (A-1) ・A-2: A compound represented by the chemical formula (A-2) ・A-3: A compound represented by the chemical formula (A-3) Compound A-4: Compound represented by the above chemical formula (A-4) <Other initiators>
・Initiator 1: Oxime ester photoinitiator having a carbazole skeleton, trade name ADEKA ARCLES NCI-831, manufactured by ADEKA ・Initiator 2: α-aminoketone photoinitiator, 2-benzyl-2-(dimethylamino) )-1-(4-morpholinophenyl)-1-butanone (trade name Irgacure 369, manufactured by BASF)
・Initiator 3: α-aminoketone photoinitiator, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by BASF)
・Initiator 4: Mercapto chain transfer agent, 2-mercaptobenzothiazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
・Initiator 5: Biimidazole photoinitiator, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Kurogane Kasei Co., Ltd. )
・Initiator 6: Thioxanthone photoinitiator, 2,4-diethylthioxanthone (trade name DOUBLECURE DETX, manufactured by Double Bond Chemical)
・Initiator 7: Acylphosphine photoinitiator, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name Irgacure 819, manufactured by BASF)

[Summary of results]
The comparative photosensitive colored resin compositions of Comparative Examples 1 to 3, which did not use the compound represented by the general formula (A) specified in the present invention as a photoinitiator, had a large line width shift amount and did not require low-temperature heat treatment. The solvent resistance was poor.
Even if the compound represented by the general formula (A) specified in the present invention is used as a photoinitiator, the comparative photosensitivity of Comparative Examples 4 to 9 using a polyester dispersant or a urethane dispersant as a dispersant The colored resin composition had a large amount of line width shift and poor solvent resistance due to low temperature heat treatment.
In contrast, the photosensitive colored resin compositions of Examples 1 to 90 in which at least a compound represented by general formula (A) was used as a photoinitiator and a (meth)acrylate copolymer-based dispersant was used as a dispersant. It was shown that it is possible to form a colored layer with good solvent resistance even by low-temperature heat treatment while suppressing the amount of line width shift.
In the examples, the photoinitiator further includes an oxime ester photoinitiator, an α-aminoketone photoinitiator, a biimidazole photoinitiator, and a thioxanthone photoinitiator different from the compound represented by the general formula (A). When at least one selected from the group consisting of a photoinitiator, an acylphosphine oxide photoinitiator, and a mercapto chain transfer agent is contained, the cross-sectional shape of the micropores becomes good and the residue inside the micropores is reduced. was shown to be suppressed.
Furthermore, when a (meth)acrylate copolymer dispersant having an acid value of 1 to 18 mgKOH/g and a glass transition temperature of 30°C or higher is used as a dispersant, the compound represented by the general formula (A) can be It has been shown that the combination of the above improves solvent resistance and suppresses the generation of development residues.
In addition, as a dispersant, a group consisting of a graft copolymer and a structural unit represented by the general formula (III) and a structural unit represented by the following general formula (III') as the structural unit of the graft polymer chain. It has been shown that the use of a (meth)acrylate copolymer-based dispersant containing at least one constituent unit selected from the above improves solvent resistance in combination with the compound represented by the general formula (A). It was done. In particular, when the structural unit of the graft polymer chain contains a structural unit represented by the general formula (III) (where m represents a number of 19 or more and 80 or less), the effect of suppressing the occurrence of water stains may be improved. Shown.
Furthermore, it has been shown that addition of an antioxidant improves the amount of line width shift.

1 Substrate 2 Light shielding part 3 Colored layer 5 Microhole 10 Color filter 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device 50 Organic protective layer 60 Inorganic oxide film 71 Transparent anode 72 Hole injection layer 73 Hole transport layer 74 Light emitting layer 75 Electrons Injection layer 76 Cathode 80 Organic light emitter 100 Organic light emitting display device

Claims (12)

Contains a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
The dispersant contains a (meth)acrylate copolymer-based dispersant,
A photosensitive colored resin composition, wherein the photoinitiator contains a compound represented by the following general formula (A).

(wherein R ¹ and R ² each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN,
R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocyclic group of number 2 to 20,
The hydrogen atoms of the groups represented by R ¹¹ , R ¹² and R ¹³ are further represented by R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² - OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , ^{CSOR 21} , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom Represents a heterocyclic group of number 2 to 20,
The hydrogen atoms of the groups represented by R ²¹ , R ²² and R ²³ may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group,
The alkylene moiety of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO- may contain 1 to 5 of them, provided that oxygen atoms are not adjacent to each other,
R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; ,
The alkyl portion of the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ may have a branched side chain or may be a cyclic alkyl,
R ³ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; , the alkyl portion of the group represented by R ³ may have a branched side chain or may be a cyclic alkyl, and R ³ and R ⁷ and R ³ and R ⁸ are each taken together. It may form a ring,
The hydrogen atom of the group represented by R ³ is further R ²¹ , OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , NR ²² COR ²¹ , OCOR ²¹ , COOR ²¹ , SCOR ²¹ , OCSR ²¹ , COSR ²¹ , CSOR ²¹ , which may be substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹⁴ , CONR ¹⁵ R ¹⁶ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹⁴ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹⁴ , CSOR ¹¹ represent a hydroxyl group, CN or a halogen atom, and R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ and R ⁷ may each be taken together to form a ring,
R ¹⁴ , R ¹⁵ and R ¹⁶ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl portion of the group represented by R ¹⁴ , R ¹⁵ and R ¹⁶ has a branched side chain. Often, R ⁸ may be a cyclic alkyl, R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ represents a hydroxyl group, CN or a halogen atom,
k represents 0 or 1. ) The photoinitiator further includes an oxime ester photoinitiator, an α-aminoketone photoinitiator, a biimidazole photoinitiator, a thioxanthone photoinitiator different from the compound represented by the general formula (A), The photosensitive colored resin composition according to claim 1, containing at least one selected from the group consisting of an acylphosphine oxide photoinitiator and a mercapto chain transfer agent. The (meth)acrylate copolymer-based dispersant comprises a graft copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II), and the graft copolymer having a structural unit represented by the following general formula (II). A salt-type graft in which at least a part of the nitrogen moieties of the structural unit represented by the general formula (I) of the polymer and at least one member selected from the group consisting of organic acid compounds and halogenated hydrocarbons form a salt. Containing at least one copolymer,
A group consisting of a structural unit represented by the following general formula (III) and a structural unit represented by the following general formula (III') in the structural unit of the polymer chain in the structural unit represented by the following general formula (II). The photosensitive colored resin composition according to claim 1 or 2, comprising at least one structural unit selected from the following.

(In general formula (I), R ⁴¹ is a hydrogen atom or a methyl group, A ¹ is a divalent linking group, R ⁴² and R ⁴³ are each independently a hydrogen atom or a hydrocarbon that may contain a heteroatom) represents a group, and R ⁴² and R ⁴³ may be bonded to each other to form a ring structure.
In general formula (II), R ^41' is a hydrogen atom or a methyl group, A ² is a direct bond or a divalent linking group, and Polymer represents a polymer chain, and the constituent units of the polymer chain include (meth)acrylate-derived units. Contains the following building blocks. )

(In general formula (III), R ⁴⁴ is a hydrogen atom or a methyl group, A ³ is a divalent linking group, R ⁴⁵ is an ethylene group or a propylene group, R ⁴⁶ is a hydrogen atom or a hydrocarbon group, m represents a number from 3 to 80.
In the general formula (III'), R ^44' is a hydrogen atom or a methyl group, A ^3' is a divalent linking group, R ⁴⁷ is an alkylene group having 1 to 10 carbon atoms, and R ⁴⁸ is an alkylene group having 3 to 7 carbon atoms. The alkylene group R ⁴⁹ is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 or more and 40 or less. ) The (meth)acrylate copolymer-based dispersant has an A block containing a structural unit represented by the following general formula (I), a B block containing a structural unit derived from a carboxy group-containing monomer, and a structural unit derived from (meth)acrylate. and a group consisting of at least a part of the nitrogen moiety of the structural unit represented by the following general formula (I) of the block copolymer, an organic acid compound, and a halogenated hydrocarbon. The block copolymer and at least one of the salt block copolymers have an acid value of 1 to 18 mgKOH/g. The photosensitive colored resin composition according to any one of claims 1 to 3, which has a glass transition temperature of 30° C. or higher.

(In general formula (I), R ⁴¹ is a hydrogen atom or a methyl group, A ¹ is a divalent linking group, R ⁴² and R ⁴³ are each independently a hydrogen atom or a hydrocarbon that may contain a heteroatom) (Represents a group, and R ⁴² and R ⁴³ may be bonded to each other to form a ring structure.) In the (meth)acrylate copolymer-based dispersant, a configuration represented by the general formula (III) is added to the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer. The photosensitive colored resin composition according to claim 3, which contains a unit. In the (meth)acrylate copolymer-based dispersant, a configuration represented by the general formula (III) is added to the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer. The photosensitive colored resin composition according to claim 3, which contains a unit (where m represents a number of 19 or more and 80 or less). The photosensitive colored resin composition according to any one of claims 1 to 6, further comprising an antioxidant. The photoinitiator further includes an oxime ester photoinitiator, an α-aminoketone photoinitiator, a biimidazole photoinitiator, a thioxanthone photoinitiator different from the compound represented by the general formula (A), Containing at least one member selected from the group consisting of an acylphosphine oxide photoinitiator and a mercapto chain transfer agent,
The photosensitizer according to any one of claims 1 to 7, wherein the content of the compound represented by the general formula (A) is 50% by mass or more and 90% by mass or less with respect to the total amount of the photoinitiator. Colored resin composition. The photosensitive colored resin composition according to any one of claims 1 to 8, which is used for forming a color filter directly on an element substrate. A cured product of the photosensitive colored resin composition according to any one of claims 1 to 9 . A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive colored resin composition according to claims 1 to 8 . filter. A display device comprising the color filter according to claim 11 .

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