TWI417659B - Photocurable colored composition and color filter using same - Google Patents

Description

Photocurable coloring composition and color filter using the same

The present invention relates to a photocurable coloring composition which is useful for forming a color filter for a liquid crystal display element (LCD) or a solid-state image pickup element (CCD, CMOS, etc.), and color filter produced using the same sheet.

In recent years, various types of displays such as televisions, personal computers, and portable telephones have been required to have high image quality and high chroma, and in particular, for displays for televisions, large screens are also required. At present, the mainstream of these displays is a liquid crystal display. Therefore, in order to achieve high image quality, high chroma, and large screen as described above, the technology of color filters used in liquid crystal displays has become very important. . Specifically, it relates to a step of producing a color filter, and a technique suitable for the photocurable coloring composition thereof.

Regarding the high definition of the color filter, in order to make the line width of the pattern formation of the color filter finer, the pattern exposure and subsequent development thereof have evolved to form a pattern with good precision. Further, in terms of high chroma, it has become a necessary condition for the hue adjustment and high concentration of the colorant. However, the curable composition suitable for the conventional pigment dispersion system has problems such as color unevenness due to the relatively coarse particles of the pigment, which makes it difficult to further improve the resolution, thereby causing use. A color filter of a pigment is not suitable for use in a fine pattern requiring a solid-state image sensor. Therefore, there has been proposed a technique in which a coloring agent is an organic solvent-soluble dye in place of a pigment (see, for example, Japanese Laid-Open Patent Publication No. 2-127602).

The coloring agent is preferably used in the case of using a dye or in the case of using a pigment, although it is necessary to increase the coloring agent content in the colored curable composition for color filter manufacturing, but it is relatively easy to cause The content of the photopolymerization initiator and the photopolymerizable monomer which are required for curing the colored curable composition is limited, or the exposure wavelength light required for curing is prevented from reaching the interface of the glass support, and the like It is necessary to take the high sensitivity of the hardenable coloring composition or the high adhesion to the support.

Moreover, in recent years, with the expansion of the substrate size, the manufacture of large-area color filters is indispensable, but in order to maintain the previous productivity without changing the energy cost in the process, it is necessary to shorten the coating. Cloth time, exposure time, etc., therefore, has evolved in order to improve the wettability of the photocurable coloring composition to the glass support, or the short exposure time (less exposure amount) to achieve a rapid coating speed. The high sensitivity of the photocurable coloring composition is required.

In addition, in the case of large screen, since the small defects after the color filter is manufactured will significantly affect the production yield, the heat resistance or light resistance of the curable composition for forming the colored pattern is obtained from the result. Sexuality also requires a higher level than before.

Heretofore, the curable composition for color filter production uses, for example, a polyfunctional acrylate which combines a carboxyl group-containing binder polymer, a neopentyl glycol hexaacrylate, and a photopolymerization initiator. a composition, and a highly sensitive photopolymerization initiator in such a radiation-sensitive linear composition already has 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Proposal of tetraphenyldiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, etc. (see, for example, Japanese invention patents) Japanese Laid-Open Patent Publication No. Hei. No. 6-75372 and Japanese Patent Application Laid-Open No. Hei No. 6-75373.

Further, a photopolymerization initiator which can be applied to a curable composition has a proposal that can be applied to a photopolymerization initiator which is used in a printing plate or a photosensitive radioactive composition, for example, a proposal as described below. : 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4' ,5,5'-tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkyloxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, etc. (see, for example, Japanese invention patent special public Zhao Japanese Patent Publication No. 48-38403 and Japanese Laid-Open Patent Publication No. 62-174204.

However, the curability of any of the curable compositions as described above has not yet reached a level that can be satisfied, so that when it is hardened, it is necessary to irradiate high-energy radiation. When such a curable composition is used to form a colored pattern of a color filter, if the amount of irradiation is insufficient, problems such as peeling or chipping of the pattern, reduction of residual film ratio, or pixel intensity are caused, and even The colored pattern of the color filter causes, for example, a problem that the resolution of the resolution and the support are lowered.

As described above, a curable coloring composition which can be cured with high sensitivity and has excellent pattern formability even in the case of containing a high concentration of a coloring agent is desired, and is obtained by using it. A color filter having a resolution, a color pattern having a superior adhesion to a support, but is not specifically provided at present.

The present invention has been made in view of the above problems as described above, and has the object of achieving the following objects.

That is, the object of the present invention is to provide a film which can be cured under high sensitivity even in the case of containing a high concentration of a coloring agent, has excellent developability, and has excellent pattern formability, and can be formed to have superior properties. The coloring pattern of both the developability and the adhesion to the glass support is a photocurable coloring composition which is useful for producing a color filter, and has a high resolution obtained by using it, and has superior and supportive properties. A color filter of a color pattern of the adhesion of the body.

As a result of intensive studies, the inventors of the present invention have found that the above-mentioned problems can be solved by a photocurable coloring composition containing a polymer compound having a specific photopolymerization initiator and a specific side chain structure. The present invention has been completed. That is, the method for solving the above problem is as follows.

(1) A photocurable coloring composition comprising a heterocyclic ring-containing photopolymerization initiator selected from the group consisting of the following formulas (I) to (V), which has a poly(A) group in a side chain a coloring pigment dispersed by an alkali-soluble graft polymer compound of an acrylate chain, and a compound having an ethylenically unsaturated group capable of addition polymerization: In the formula (I), W represents an aryl group, X represents a hydrogen atom, an alkyl group or an aryl group, Y represents a fluorine atom, a chlorine atom or a bromine atom, and n represents an integer of 1 to 3; In the formula (II), the Q system represents a bromine atom or a chlorine atom, and the P system represents -CQ ₃ , -NH ₂ , -NHR, -N(R) ₂ , or -OR, wherein the Q system is as described above. Synonymous, R represents a phenyl group or an alkyl group, and W represents an aromatic group, a heterocyclic type group, or a monovalent group represented by the formula (II-A) shown below, n Department represents 0, 1 or 2; In the general formula (II-A), Z-O- or -S-, R is synonymous with R in the description of P in the above formula (II); In the formula (III), X represents a bromine atom or a chlorine atom, m and n each independently represent an integer of 0 to 3, and R ¹ represents a group represented by the formula (III-A) shown below. ; In the formula (III-A), R ² represents a hydrogen atom or ORc, wherein Rc represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ³ represents a bromine atom, a chlorine atom, an alkyl group, Alkenyl, aryl, or alkoxy; In the formula (IV), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the formula (IV-A) or (IV-B) shown below, R ³ , R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and X and Y systems each independently represent a chlorine atom or a bromine atom, and m and n each independently represent 0, 1, or 2, In the general formulae (IV-A) and (IV-B), R ⁵ , R ⁶ and R ⁷ each independently represent an alkyl group or an aryl group;

(2) The photocurable coloring composition according to the above item (1), wherein the alkali-soluble graft polymer compound having a poly(meth)acrylate chain in a side chain has an aromatic side chain base.

(3) A photocurable coloring composition comprising a heterocyclic ring-containing photopolymerization initiator selected from the group consisting of the following formulas (I) to (V), having (A') at a side chain end a polymer compound of an alkylene oxide chain (-(R ¹ O) _n R ² ), (B) an alkali-soluble group (-Acid), and (C) an aromatic group (-Ar), a coloring agent, And a compound having an addition polymerizable ethylenically unsaturated group: In the formula (I), W represents an aryl group, X represents a hydrogen atom, an alkyl group or an aryl group, Y represents a fluorine atom, a chlorine atom or a bromine atom, and n represents an integer of 1 to 3; In the formula (II), the Q system represents a bromine atom or a chlorine atom, and the P system represents -CQ ₃ , -NH ₂ , -NHR, -N(R) ₂ , or -OR, wherein the Q system is as described above. Synonymous, R represents phenyl or alkyl, W represents an aromatic group, a heterocyclic group, or a monovalent group represented by the following formula (II-A), and n represents 0, 1 Or 2; In the general formula (II-A), Z-O- or -S-, R is synonymous with the above formula (II); In the formula (III), X represents a bromine atom or a chlorine atom, m and n each independently represent an integer of 0 to 3, and R ¹ represents a group represented by the formula (III-A) shown below. ; In the formula (III-A), R ² represents a hydrogen atom or ORc, wherein Rc represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ³ represents a bromine atom, a chlorine atom, an alkyl group, Alkenyl, aryl, or alkoxy; In the formula (IV), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the formula (IV-A) or (IV-B) shown below, R ³ , R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, X, Y each independently represents a chlorine atom or a bromine atom, and m and n each independently represent 0, 1 or 2; In the general formulae (IV-A) and (IV-B), R ⁵ , R ⁶ and R ⁷ each independently represent an alkyl group or an aryl group;

(4) A color filter comprising a light-curing composition comprising a photocurable coloring composition as described in the item (1), (2) or (3), which is attached to a glass support. The layered body of the colored layer is subjected to pattern exposure to harden the exposed field of the photocurable colored layer, and to develop a colored pattern obtained by the unexposed field.

The first photocurable coloring composition of the present invention (hereinafter, referred to as a "curable composition" as appropriate), which comprises a specific photopolymerization initiator having a hetero ring in a molecule, by being in a side chain A color pigment having an alkali-soluble graft polymer compound having a poly(meth)acrylate chain and a compound having an ethylenically unsaturated group which can be subjected to addition polymerization.

Although the mechanism of action of the present invention is not clear, it is possible that the photopolymerization initiator in the photocurable coloring composition will be caused by its heterocyclic structure, and also because it has poly (in the side chain) as a pigment dispersant. The side chain structure of the graft polymer compound of the methyl acrylate chain forms a good interaction with the stanol group or metal ion present on the glass surface of the substrate, thereby improving pattern formation after exposure-development And improve the adhesion durability of the colored pattern on the color filter. In addition, an alkali-soluble graft polymer compound having a poly(meth)acrylate chain in a side chain has a superior pigment dispersing energy, so that the pigment can be uniformly dispersed without being agglomerated, and a polymer compound at the periphery of the pigment The side chain structure is arranged in a radial shape, and the affinity of the poly(meth)acrylate chain to a specific initiator having a heterocyclic structure is good, and thus the pigment by using the pigment dispersant may be accompanied The photopolymerization initiator is uniformly dispersed in the system. A photopolymerization initiator which usually has a heterocyclic structure in a molecule is liable to self-agglomerate, but a specific initiator having high sensitivity due to interaction with a pigment using a specific dispersant can also be uniformly dispersed. It is highly sensitized by exposure to light, and the adhesion to the support is improved. On the other hand, in the unexposed portion, the developer permeability is uniformized, so that the coating film is quickly formed. Dissolved to reveal excellent developability. The photocurable coloring composition of the present invention can coexist with both the adhesion between the hardened film and the glass support and the excellent developability, and can also be confirmed in the examples described later.

The second photocurable coloring composition of the present invention (hereinafter, referred to as "curable composition" as appropriate) is a photopolymerization initiator having a specific heterocyclic ring in the molecule, and has a side chain terminal. (A') a polymer compound of an alkylene oxide chain (-(R ¹ O) _n R ² ), (B) an alkali-soluble group (-Acid), and (C) an aromatic group (-Ar) .

Although the mechanism of action of the present invention is not clear, it is possible that the photopolymerization initiator in the photocurable coloring composition will be caused by its heterocyclic structure, and the specific polymer compound will be caused by the ring existing at the end of the side chain. The oxyalkylene chain and the aromatic group are simultaneously present, and form a good interaction with the stanol group or the metal ion present on the glass surface of the substrate, thereby improving pattern formation after exposure-development and improving color filter The adhesion durability of the colored pattern of the light sheet. Further, there is a possibility that the polymer compound having an alkylene oxide chain in the side chain promotes high adhesion to the support by the interaction as described above in the exposed portion, and the ring is not exposed in the exposed portion. The characteristics of the oxyalkylene chain or the alkali-soluble group which is simultaneously present in the molecule enhance the developer permeability, so that the coating film is rapidly dissolved to exhibit excellent developability. The photocurable coloring composition of the present invention can coexist with both the adhesion between the hardened film and the glass support and the excellent developability, and can also be confirmed in the examples described later.

According to the present invention, it is possible to provide a film which can be cured under high sensitivity, has excellent developability, and has excellent pattern formability even in the case of containing a high concentration coloring agent, and can be formed with excellent development. The colored pattern in which both the properties and the adhesion to the glass support are coexisting can be favorably used for the production of the photocurable coloring composition of the color filter.

Further, by using the photocurable coloring composition of the present invention as described above, it is possible to provide a color filter having a high resolution and a coloring pattern having excellent adhesion to a support.

[Best Embodiment of the Invention]

Hereinafter, the photocurable coloring composition of the present invention and a color filter obtained using the same will be described in detail.

[First photocurable coloring composition]

The first photocurable coloring composition of the present invention is characterized by having a heterocyclic photopolymerization initiator containing (1) a compound selected from the group consisting of the compounds represented by the following formulas (I) to (V) (under The text is appropriately referred to as "specific initiator"); (2) a color pigment dispersed by an alkali-soluble graft polymer compound having a poly(meth)acrylate chain in a side chain; and (3) having an additive A compound which forms a polymerized ethylenically unsaturated group.

[Second light curable coloring composition]

The second photocurable coloring composition of the present invention is characterized by having (1) a heterocyclic photopolymerization initiator selected from the group consisting of the following formulas (I) to (V); (2'(A') alkylene oxide chain (-(R ¹ O) _n R ² ), (B) alkali-soluble group (-Acid), and (C) having an aromatic group (-Ar) at the side chain terminal A molecular compound (hereinafter referred to as "specific polymer compound" as appropriate); (2") a colorant; and (3) a compound having an addition-polymerizable ethylenically unsaturated group.

"Ingredients"

Hereinafter, each component contained in the photocurable coloring composition of the present invention will be described in order.

<(1) A heterocyclic photopolymerization initiator selected from the compounds represented by the general formulae (I) to (V) shown below> The curable colored layer of the present invention contains a heterocyclic structure in a molecule. A specific photopolymerization initiator.

In the formula (I), W represents an aryl group, X represents a hydrogen atom, an alkyl group or an aryl group, Y represents a fluorine atom, a chlorine atom or a bromine atom, and n represents an integer of 1 to 3.

The aryl group or the alkyl group as described above may further have a substituent, and the substituent which may be introduced includes an aryl group such as a phenyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group or a fluorenyl group. , nitro, dialkylamino, sulfonyl derivatives, and the like.

Specific examples of the compound represented by the formula (I) include: 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(pair -Cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, and the like.

In addition, a halogenated methyl-s-triazole of a specific initiator suitable for use in the present invention The compound is a vinyl-halomethyl-s-triazole represented by the formula (II) shown in the following Japanese Patent Publication No. 59-1281. The compound is disclosed in Japanese Laid-Open Patent Publication No. 53-133428, which is represented by the following formula (III): 2-(naphthoquinone-1-yl)-4,6-bis-halogen Methyl-s-trinitrogen a compound; and 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazole of the formula (IV) shown below Compound.

In the formula (II), the Q system represents a bromine atom or a chlorine atom, and the P system represents -CQ ₃ , -NH ₂ , -NHR, -N(R) ₂ , or -OR, wherein the Q system is as described above. Synonymous, R represents a phenyl group or an alkyl group, W represents an aromatic group, a heterocyclic group, or a monovalent group represented by the formula (II-A) shown below, and n represents 0. 1 or 2.

In the formula (II), the aromatic group or the heterocyclic group may further have a substituent, and the substituent which may be introduced includes an aryl group such as a phenyl group, a halogen atom, an alkoxy group or an alkoxycarbonyl group. An aryloxycarbonyl group, a decyl group, a nitro group, a dialkylamino group, a sulfonyl derivative, and the like.

In the general formula (II-A), Z-O- or -S-, R is synonymous with R in the description of P in the above formula (II).

Specific examples of the compound represented by the formula (II) include: 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazo 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazole 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazole Wait.

In the formula (III), X represents a bromine atom or a chlorine atom, m and n are each independently an integer of 0 to 3, and R ¹ represents a compound represented by the formula (III-A) shown below. base:

In the formula (III-A), R ² represents a hydrogen atom or ORc, wherein Rc represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ³ represents a bromine atom, a chlorine atom or an alkyl group. , alkenyl, aryl, or alkoxy.

The alkyl group, the alkenyl group, the aryl group or the alkoxy group as described above may further have a substituent, and the substituent which may be introduced includes an aryl group such as a phenyl group, a halogen atom, an alkoxy group or an alkoxycarbonyl group. An aryloxycarbonyl group, a decyl group, a nitro group, a dialkylamino group, a sulfonyl derivative, and the like.

Specific examples of the specific initiator represented by the formula (III) include: 2-(naphthoquinone-1-yl)-4,6-bis-trichloromethyl-s-triazo , 2-(4-methoxy-naphthoquinol-1-yl)-4,6-bis-trichloromethyl-s-triazole , 2-(4-ethoxy-naphthoquinol-1-yl)-4,6-bis-trichloromethyl-s-triazole ,2-(4-butoxy-naphthoquinol-1-yl)-4,6-bis-trichloromethyl-s-triazole ,2-[4-(2-methoxyethyl)-naphthoquinone-1-yl]-4,6-bis-trichloromethyl-s-triazo 2-[4-(2-ethoxyethyl)-naphthoquinone-1-yl]-4,6-bis-trichloromethyl-s-triazole 2-[4-(2-Butoxyethyl)-naphthoquinone-1-yl]-4,6-bis-trichloromethyl-s-triazole , 2-(2-methoxy-naphthoquinol-1-yl)-4,6-bis-trichloromethyl-s-triazole , 2-(6-methoxy-5-methyl-naphthoquinol-2-yl)-4,6-bis-trichloromethyl-s-triazole ,2-(6-methoxy-naphthoquinol-2-yl)-4,6-bis-trichloromethyl-s-triazole , 2-(5-methoxy-naphthoquinol-1-yl)-4,6-bis-trichloromethyl-s-triazole ,2-(4,7-dimethoxy-naphthoquinol-1-yl)-4,6-bis-trichloromethyl-s-triazo ,2-(6-ethoxy-naphthoquinol-2-yl)-4,6-bis-trichloromethyl-s-triazo ,2-(4,5-dimethoxy-naphthoquinol-1-yl)-4,6-bis-trichloromethyl-s-triazole Wait.

In the formula (IV), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the formula (IV-A) or (IV-B) shown below. R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and X and Y each independently represent a chlorine atom or a bromine atom, and m and n each independently represent 0, 1 or 2, respectively. .

The alkyl group, the aryl group, the alkoxy group as described above may further have a substituent, and the substituent which may be introduced includes an aryl group such as a phenyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, and an aryloxy group. A carbonyl group, a mercapto group, a nitro group, a dialkylamino group, a sulfonyl derivative or the like.

In the general formulae (IV-A) and (IV-B), R ⁵ , R ⁶ and R ⁷ each independently represent an alkyl group or an aryl group.

The alkyl group and the aryl group as described above may further have a substituent, and examples of the substituent which may be introduced include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, Mercapto, nitro, dialkylamino, sulfonyl derivatives, and the like.

In the formula (IV), R ¹ and R ² may form a heterocyclic ring composed of a non-metal atom together with a nitrogen atom to which they are bonded, and in this case, the hetero ring includes the following By.

Specific examples of the specific initiator represented by the formula (IV) include: 4-[p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloro) Methyl)-s-trinitrogen 4-[o-methyl-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[o-methyl-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole , 4-(p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole 4-[p-N,N-bis(phenyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole , 4-(p-N-chloroethylcarbonylaminophenyl)-2,6-di(trichloromethyl)-s-triazole 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]2,6-di(trichloromethyl)-s-triazole 4-[M-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[Inter-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[Inter-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[M-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl-2,6-di(trichloromethyl)-s-triazo 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[o-fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[Inter-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[M-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole 4-[Inter]fluoro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazole , 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(o-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(o-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(m-bromo-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(m-chloro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(m-fluoro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(o-chloro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole , 4-(o-fluoro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triazole Wait.

The lophine dimer which exhibits the basic structure represented by the above formula (V) means 2,4,5-triphenylimidazole composed of two oxophene residues. Base dimer.

Specific examples of the compound which exhibits the basic structure represented by the general formula (V) include: 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer, 2-(o-fluoro Phenyl)-4,5-diphenylimidazolyl dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazolyl dimer, 2-(p-methoxy) Phenyl)-4,5-diphenylimidazolyl dimer, 2-(p-dimethoxyphenyl)-4,5-diphenylimidazolyl dimer, 2-(2,4- Dimethoxyphenyl)-4,5-diphenylimidazolyl dimer, 2-(p-methylhydrothiophenyl)-4,5-diphenylimidazolyl dimer, and the like.

The specific initiators are characterized in that they have a radical generating site and a heterocyclic ring structure in the molecule, but the heterocyclic ring is formed from the viewpoint of interaction with a glass support as described later. It is preferred that the heterocyclic ring contains two or more nitrogen atoms, and from the same viewpoint, it is more preferable to have three nitrogen atoms and three nitrogen atoms. The triazine skeleton, specifically, more preferably a compound represented by the formula (II) to the formula (IV). The preferred mode is a compound represented by the formula (IV), and among the compounds represented by the formula (IV), at least one of R ³ and R ⁴ is a halogen atom.

The heterocyclic ring as described above may also be a substituent, and the substituent which may be introduced includes an alkyl group, a phenyl group, a halogenated alkyl group and the like, but among them, a halogenated alkyl group or a heterocyclic ring is preferred, and particularly preferably Trinitrogen The ring has a halogenated alkyl direct bond.

The specific initiators may be used singly or in combination of two or more.

The content of the specific initiator in the photocurable coloring composition is preferably in the range of 0.1 to 15.0% by mass, more preferably 0.5 to 10.0% by mass in terms of solid content, and polymerization is carried out in this range. The reaction can be carried out efficiently, and the resulting cured film also has superior strength.

(Other photopolymerization initiator) Further, the curable composition may contain, in addition to the specific initiator as described above, a photopolymerization initiator other than the above, in addition to the effect of the present invention.

The photopolymerization initiator usable herein is a compound which is decomposed by light and which can initiate and promote a compound having an addition polymerizable ethylenically unsaturated group as described later, and is preferably at a wavelength. The area of 300 to 500 nm has an absorber.

The "photopolymerization initiator" includes, for example, an organic halogenated compound, an oxadiazole, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxidation compound, an azo compound, a coumarin compound, and a stack. A nitrogen compound, a metallocene compound, a biimidazole compound, an organic boronic acid compound, a disulfonic acid compound, an oxime ester compound, a phosphonium salt compound, or a mercaptophosphine (oxide) compound.

Among them, from the viewpoint of high sensitivity, it is preferably selected from trihalomethyltrinitrogen It is at least one compound selected from the group consisting of a compound, a biimidazole-based compound, and an anthraquinone-based compound, and is preferably a biimidazole-based compound.

The content of the photopolymerization initiator which can be used in combination is preferably 0% by mass or more and 75% by mass or less, more preferably 0 to 50% by mass based on the specific initiator as described above.

Further, the total amount of the specific initiator and the other photopolymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.1 to 30% by mass, particularly preferably from 0.3 to 20% by mass, based on the total solid content of the composition. . Excellent sensitivity and pattern formation can be obtained in this range.

(Sensitizer) These specific initiators can be used in combination with a sensitizer.

The sensitizer which can be used in the present invention is preferably one which can increase the sensitivity of the radical initiator by an electron transport mechanism or an energy transfer mechanism.

Further, the sensitizer includes those belonging to the following compounds and having an absorption wavelength in a wavelength range of 300 nm (330 nm) to 450 nm.

Specific examples of "sensitizers" include, for example, polynuclear aromatics (for example, phenanthrene, anthracene, anthracene, anthracene, terphenyl, 9,10-dialkoxyfluorene); Classes (eg, fluorescent yellow, blush, red algae, rhodamine B, bengal rose); oxysulfide Isopropyl oxysulfide Diethyl oxysulfide Chlorooxysulfide ); cyanines (eg, thiaquinoline blue, oxaquinoline blue); merocyanoids (eg, procyanidins, carbonyl anthocyanins); anthracyclines; thiazide Classes (eg, thiazide, methylene blue, toluidine blue); acridines (eg, acridine orange, chloroflavin, acridine flavin); terpenoids (eg, guanidine); horned sharks (eg, , horn shark 鎓); coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarin, thiophene Class, brown , styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinophthalones, indigo, styryl, pyran Antimony compound, pyrrole compound, pyrazole triazole compound, benzothiazole compound, barbituric acid derivative, thiobarbituric acid derivative, acetophenone, benzophenone, oxygen sulfur An aromatic ketone compound such as Michler's ketone or a heterocyclic compound such as N-aryl oxazolidinone.

Further, such a sensitizer may be subjected to various chemical modifications to improve the properties of the curable composition.

For example, an exposure can be achieved by bonding a sensitizer to an addition polymerizable compound structure (for example, an acrylonitrile group or a methacrylic acid group) by a covalent bond, an ionic bond, a hydrogen bond or the like. The film is increased in strength or inhibits unnecessary precipitation of a specific sensitizer from the film after exposure.

Further, a partial structure having a radical generating energy by a sensitizer and a photopolymerization initiator as described above (for example, an alkyl halide, an onium, a peroxide, a diimidazole, a hydrazine, a hydrazine) The bond between the reductive decomposition site of imidazole or the like, or the oxidative cleavage site of a borate ester (or borate), an amine, a trimethyldecylmethyl group, a carboxymethyl group, a carbonyl group, an imide, etc.) The sensitivity is improved particularly in a state where the concentration of the initiating system is low.

The sensitizer may be used alone or in combination of two or more.

The content of the sensitizer is preferably from 0.1% by mass to 20% by mass, more preferably from 0.2% by mass to 20% by mass, based on the total solid content of the curable composition.

When the concentration of the colorant in the curable composition is extremely high, and the light transmittance of the formed color pattern (photosensitive layer) is extremely low, specifically, the additive is not added. When the light transmittance of the photosensitive layer formed by the sensitizer of 365 nm is 10% or less, the effect can be remarkably exhibited.

<(2) A coloring pigment dispersed by an alkali-soluble graft polymer compound having a poly(meth)acrylate chain in a side chain> The coloring agent usable in the first photocurable coloring composition of the present invention is A colored pigment dispersed by an alkali-soluble graft polymer compound (hereinafter, referred to as "specific dispersant" as appropriate) having a poly(meth)acrylate chain in a side chain.

(Specific Dispersant) First, a specific dispersant will be described. The specific dispersant is an alkali-soluble graft polymer compound characterized by having a poly(meth)acrylate chain in a side chain, and therefore, it is required to have a molecule in the molecule together with the (A) poly(meth)acrylate chain ( B) An alkali-soluble group (-Acid), which is preferably present at the terminal side of the side chain from the viewpoint of developability. Further, a preferred mode is one in which the side chain structure has (C) an aromatic group (-Ar).

The main chain structure of the specific dispersing agent (polymer type dispersing agent) is not particularly limited, but preferred examples include polymethacrylate, polyacrylate, polymethacrylamide, and polydecylamine. Further, polystyrene or the like, and two or more kinds of copolymers containing a structural unit selected from the above polymers are also preferable.

Among the above, particularly preferred examples include polymethacrylate, polystyrene, and a copolymer containing methacrylic acid and styrene as structural units.

The specific dispersant in the present invention will have a structure of (A) a poly(meth)acrylate chain, (B) an alkali-soluble group, and preferably a further (C) aromatic group as a graft chain, respectively. The unit can be prepared by copolymerization. Next, the structural unit of the specific dispersing agent constituting the present invention is suitably described in order.

<(A) Structural unit having a poly(meth)acrylate chain> Poly(meth)acrylate chain as a graft chain contained in the specific polymer type dispersant of the present invention, including polymethacrylate a polyacrylate, and a copolymer having a main component as a main component, wherein the chain structure is a side chain of a structural unit, and a structural unit connected via an appropriate linking group is copolymerized to constitute a specific dispersion. Agent.

Specific examples of the graft chain which can be introduced include: polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl methacrylate, polymethyl acrylate, poly Ethyl acrylate, in addition, a chain structure composed of copolymerization of methyl methacrylate and styrene is also a preferred example.

Further, the structure for connecting the linking group of the graft chain and the main chain is not particularly limited, but from the viewpoint of easiness of production, it is preferred to contain one or more sulfur atoms in the linking structure (S )By.

The "linking group" includes alkyl, phenyl, -O-, -S-, and -OC(=O)-, etc., which are bonded singly or in combination of plural. The number of atoms between the main chain structure and the poly(meth) acrylate chain (used only for the total number of atoms linking the main chain to the poly(meth) acrylate chain) is preferably from 3 to 15. Further, the linking group may have a hydroxyl group, an ester group or the like as a substituent.

Regarding the chain length of the poly(meth)acrylate chain, it is preferred that the (meth) acrylate structural unit is bonded to 30 to 1,000, more preferably 50 to 500.

Hereinafter, specific examples ((A-1) to (A-7)) of structural units having a (A) poly(meth)acrylate chain in a side chain suitable for constituting the specific dispersant of the present invention, and structures thereof The weight average molecular weight (Mw) of the unit is explained together, but the present invention is not limited to these.

The structural units are preferably contained in an amount of from 5 to 70 mol%, more preferably from 5 to 40 mol%, based on the (2) specific dispersant.

<(B) Structural unit having an alkali-soluble group (-Acid) The (B) alkali-soluble group (-Acid) contained in the specific dispersing agent of the present invention is preferably an acid group of pKa 1 to 11.

The "acid group" preferably includes a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a carboxylic acid group, a phenol group (phenolic hydroxyl group), more preferably a phosphate group, a phosphonic acid group or a carboxylic acid group.

The phenol group as described above may be one having a substituent, and the substituent which may be introduced is preferably a halogen atom, a carboxylic acid group, a hydroxyl group, a decylamino group, an alkoxy group having 1 to 10 carbon atoms, and 1 to 10 alkoxycarbonyl.

Hereinafter, specific examples ((B-1) to (B-20)) of structural units having a (B) alkali-soluble group at the side of a side chain which are suitable for constituting the specific dispersing agent of the present invention will be listed, but the present invention does not Restricted to those who are.

The structural unit as described above preferably contains 5 to 80 mol%, more preferably 5 to 60 mol%, based on the amount of the specific dispersant.

<(C) Structural unit having an aromatic group (-Ar) In the specific dispersing agent of the present invention, in addition to the essential components as described above, it is preferred to further have (C) an aromatic group (-Ar). The "(C) aromatic group" means a functional group selected from a heteroaromatic ring group having 4 or more carbon atoms and an aromatic ring group having 6 or more carbon atoms.

Preferred specific examples of the "aromatic group" include a furanyl group, a thiophene ring group, a pyrrole ring group, an indolenine ring group, a pyridine ring group, a quinoline ring group, a phenyl group, and a naphthyl group. Base, anthracene ring base. The aromatic group may also be a substituent, and the substituent which may be introduced includes a halogen atom, a carboxylic acid group, a hydroxyl group, a decylamino group, an alkyl group having 1 to 12 carbon atoms, and a carbon atom. The number is 6 to 20, the aryl group, the alkoxy group having 1 to 10 carbon atoms, the alkoxycarbonyl group having 1 to 10 carbon atoms, and the like. More preferred is phenyl or naphthyl.

Hereinafter, specific examples ((C-1) to (C-16)) of structural units having a (C) aromatic group at the side of a side chain which are suitable for constituting the specific dispersing agent of the present invention will be listed, but the present invention does not Subject to these.

The structural unit as described above is preferably contained in an amount of from 5 to 70 mol%, more preferably from 5 to 50 mol%, based on the (2) specific polymer compound.

(A), (B), and, if necessary, a specific dispersing agent (specific polymer compound) obtained by copolymerizing each structural unit as described above having a functional group represented by (C) at the side of a side chain The preferred weight average molecular weight is from 3,000 to 200,000, more preferably from 3,000 to 50,000, most preferably from 3,000 to 10,000.

Hereinafter, specific examples ((P-1) to (P-11)) of the specific dispersant used in the present invention are used for constituting the structural unit of the polymer type dispersant and the polymerization molar ratio, and the weight thereof The average molecular weight (Mw) is expressed. The structural units (A-○), (B-○), and (C-○) shown below are shown in the description of the structural unit having the functional groups (A) to (C) as described above. The specific example code.

Further, the invention is not limited to the exemplified compounds.

The specific polymeric dispersant which can be used in the present invention can be synthesized by a conventional method to date.

Specifically, a monomer of each unit can be obtained by thermally polymerizing an azo initiator in a solvent.

(Coloring pigment) The coloring pigment which can be dispersed by the specific dispersing agent is not particularly limited, and various conventional pigments suitable for the use of a color filter can be used in combination of two or more kinds depending on the purpose.

As the pigment which can be used in the photocurable coloring composition of the present invention, various conventional inorganic pigments or organic pigments can be used. In addition, when it is considered that the photocurable colored layer to be formed is preferably a high light transmittance regardless of either an inorganic pigment or an organic pigment, it is preferred to use a pigment having a fine particle size as much as possible, and if it is also considered In the case of rationality, the average particle diameter of the pigment as described above is preferably from 0.01 μm to 0.1 μm, more preferably from 0.01 μm to 0.05 μm. Further, the inorganic pigments include metal oxides, metal compounds represented by metal-missing salts, and the like, and specifically include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, lanthanum. Metal oxides, etc., and composite oxides of such metals.

"Organic pigment" includes, for example, CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199; CI Pigment Orange 36, 38, 43, 71; CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270; CI Pigment Violet 19, 23, 32, 39; CI Pigment Blue 1, 2, 15, 15:1, 15:3, 15:6, 16, 22, 60, 66; CI Pigment Green 7, 36 37; CI pigment brown 25, 28; CI pigment black 1, 7; carbon black and the like.

In the present invention, those having a basic N atom in the structural formula of the pigment are particularly suitably used. These pigments having a basic N atom exhibit excellent dispersibility in the composition of the present invention. Although the reason is very clear, it is presumed that it is due to the good affinity of the photosensitive polymerization component and the pigment.

Pigments suitable for use in the present invention include those enumerated below. However, the invention is not limited to these.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; CI Pigment Orange 36, 71; CI Pigment Red 122, 150, 171, 175, 177, 209 224, 242, 254, 255, 264; CI Pigment Violet 19, 23, 32; CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; CI Pigment Black 1.

These organic pigments can be used singly or in combination for improving color purity. Specific examples of the combination are as follows. For example, a red pigment may be used: at least one of an anthraquinone pigment, an anthraquinone pigment, a diketopyrrolopyrrole pigment alone or the like, a diazo yellow pigment, an isoporphyrin yellow pigment, and a quinoline yellow. It is a mixture of yellow pigment or lanthanide red pigment. For example, the lanthanide pigments include CI Pigment Red 177, the lanthanide pigments include CI Pigment Red 155, CI Pigment Red 224, and the diketopyrrolopyrrole pigments include CI Pigment Red 254, which is preferably in color reproducibility. At least one of the compounds is mixed with CI Pigment Yellow 139. Further, the mass ratio of the red pigment to the yellow pigment is preferably from 100:5 to 100:50. When it is 100:4 or less, there is a possibility that it is difficult to suppress the light transmittance of 400 nm to 500 nm and the color purity cannot be improved. In addition, if it is 100:51 or more, the dominant wavelength will be shifted to a short wavelength, and the deviation from the target hue of the NTSC (National Television System Committee) will be widened. In particular, the mass ratio is most suitable in the range of 100:10 to 100:30. In addition, when the red pigments are combined with each other, they can be adjusted in accordance with the chromaticity.

Further, the green pigment may be a halogenated anthraquinone pigment alone or a diazo yellow pigment, a quinoline yellow pigment, a methine azo yellow pigment or an isoporphyrin yellow pigment. mixing. For example, such examples are preferably a mixture of C.I. Pigment Green 7, 36, 37 and C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180 or C.I. Pigment Yellow 185. The quality of the green pigment and the yellow pigment is preferably from 100:5 to 100:150. If the mass ratio is less than 100:5, there is a possibility that it is difficult to suppress the light transmittance of 400 nm to 450 nm so that the color purity cannot be improved. On the other hand, if it exceeds 100:150, it may cause the dominant wavelength to be longer than the long wavelength, so that the deviation from the target hue of the NTSC (National Television System Committee) will be widened. The weight bit is preferably in the range of 100:30 to 100:120.

Blue pigments can be used alone as anthraquinone pigments, or use them with dioxins It is a blend of purple pigments. Preferably, for example, a mixture of CI Pigment Blue 15:6 and CI Pigment Violet 23 is used. The quality of the blue pigment and the purple pigment is preferably from 100:0 to 100:30, more preferably from 100:0 to 100:10.

Further, the pigment for the black matrix is a mixture of carbon, titanium carbon, iron oxide, titanium oxide or the like, preferably a combination of carbon and titanium carbon. In addition, the quality of carbon and titanium carbon is preferably in the range of 100:0 to 100:60. If it is 100:61 or more, there is a possibility that the dispersion stability may be lowered.

In the pigment of the present invention, the average particle diameter r (unit: nm) is preferably in the range of 20 ≦ r ≦ 300, more preferably 125 ≦ r ≦ 250, and particularly preferably 30 ≦ r ≦ 200. By using such pigments having an average particle diameter r, high contrast ratio and high light transmittance red and green pixels can be obtained. The "average particle diameter" means the average particle diameter of the secondary particles aggregated by the primary particles (single microcrystals) of the pigment.

In addition, the particle size distribution of the secondary particles of the pigment which can be used in the present invention (hereinafter, simply referred to as "particle size distribution") is preferably two (average particle diameter ± 100) nm. The secondary particle system should account for 70% by mass or more, preferably 80% by mass or more.

(Preparation of a pigment dispersed as a dispersant) a pigment having an average particle diameter and a particle size distribution as described above, by using a commercially available pigment and other pigments as needed (the average particle size usually exceeds 300) The nanoparticles are mixed together to form a pigment mixture mixed with a specific dispersant and a solvent, and mixed by using a pulverizer such as a ball mill, a roller mill or the like. Stir it and prepare it. By the pigment obtained as described above, it is usually in the form of a pigment dispersion.

The particular dispersant will adsorb to the surface of the pigment and act to prevent re-agglomeration of the pigment. The specific dispersant is a graft type polymer having an anchoring site to the surface of the pigment. It is preferred to use a pigment derivative for the purpose of promoting the adsorption of the polymer-type dispersant. The method of modifying the surface includes the above-described pigment derivative (the functional group which is introduced into the amine, the sulfonyl group, the sulfonic acid group, the carboxylic acid group, the hydroxyl group, the ester group, etc. of the pigment-forming nucleus of the pigment. A method of mixing with a specific dispersant when forming a pigment. The mixing ratio of the pigment derivative is in the range of 3 to 20% by mass, preferably 5 to 10% by mass based on the total of the pigment and the pigment derivative. In the present invention, it is preferred to use a combination of a surface-modified pigment derivative and a specific dispersant.

The specific dispersing agent of the present invention may be used singly or in combination of two or more. In addition, it is also possible to use other conventional dispersing agents as long as it does not impair the efficacy of the present invention.

The content of the specific dispersant in the first curable composition of the present invention is preferably from 1 to 80% by mass, more preferably from 5 to 70% by mass, still more preferably from 10 to 60% by mass, based on the pigment. Further, in the case of using a pigment derivative which improves the sorption property of the dispersant, the amount of the specific dispersant used is preferably in the range of from 1 to 30% by mass, more preferably in the range of from 3 to 30% by mass based on the pigment derivative. It is particularly preferably in the range of 5 to 15% by mass in the range of 20% by mass.

<Other Pigment Dispersants Which Can Be Used Together> The dispersant (other pigment dispersant) which can be used in combination with the specific dispersant as described above in the present invention includes: a polymer type dispersant [for example, polyamidoamine and Salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic copolymers And naphthalenesulfonic acid formaldehyde condensate], and polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like.

The polymer type dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer by its structure.

The polymeric dispersant will adsorb to the surface of the pigment and act to prevent re-agglomeration of the pigment. Therefore, the polymer type dispersant preferably includes a terminal-modified polymer having a anchoring site to the surface of the pigment, a graft polymer, and a block polymer.

Specific examples of the pigment dispersant which can be used in the present invention include: "Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylate), 110 (acid group-containing copolymer) manufactured by BYK Chemie Co., Ltd. ), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymeric copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)"; EFKA Manufactured "EFKA 4047, 4050, 4010, 4165 (polyurethane), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester amide) ), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (anthraquinone derivative), 6750 (azo pigment derivative)"; Ajinomoto Fine-Techno Co., Ltd. (Ajinomoto Fine- "Ajisper PB821, PB822" manufactured by Techno Co., Inc.; "FLOWLEN TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., Ltd., " POLYFLOW No. 50E, No. 300 (acrylic copolymer); "DISPARLON KS-860, 873SN, 874, #2150 (fat) manufactured by Kusumoto Chemicals, Ltd. Polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725"; "DEMOL RN, N (naphthalenesulfonic acid formaldehyde polycondensate) manufactured by Kao Corp. ), MS, C, SN-B (aromatic sulfonic acid formaldehyde polycondensate), "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene fluorenyl) Phenyl ether)", "ACETAMIN 86 (stearylamine acetate)"; "SOLSPARCE 5000 (anthraquinone derivative), 22000 (azo pigment derivative), 13240 (polyesteramine) manufactured by Lubrizol Corp. ), 3000, 17000, 27000 (polymer having a functional portion at the end portion), 24000, 28000, 32000, 38500 (graft-type polymer)"; "Nikkol T106 (polyoxidation) manufactured by Nikko Chemicals Co., Ltd. Ethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), and the like.

When these dispersing agents are used in combination, they may be used singly or in combination of two or more. The amount of the other polymer-type dispersant to be added to the specific dispersant is preferably 0% by mass or more and 75% by mass or less, more preferably 0 to 50% by mass based on the specific dispersing agent.

In the present invention, in the photocurable coloring composition of the present invention, the coloring pigment and the coloring pigment dispersed by the specific dispersing agent are from the viewpoint of hardening sensitivity and color density. The total content of the specific dispersant is preferably 30% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 85% by mass or less, more preferably more preferably the total solid content of the curable composition. 50% by mass or more and 80% by mass or less.

When the color filter is too small, when a color filter is produced by the curable composition of the present invention, an appropriate chromaticity tends not to be obtained. In the case of too much, although photohardening is not sufficiently performed, the strength of the film should be lowered, and the development latitude at the time of alkali development tends to be narrow, but the specific sensitization of the present invention Since the agent has a high light absorption efficiency, even when a high concentration of a coloring agent is contained in the curable composition, the effect of improving the sensitivity can be remarkably exhibited.

<(2') has (A') alkylene oxide chain (-(R ¹ O) _n R ² ), (B) alkali-soluble group (-Acid), and (C) aromatic group at the end of the side chain (- Polymer compound of Ar) The specific polymer compound used in the present invention has three functional groups as described below in the side chain: (A,) alkylene oxide chain (-(R ¹ O) _n R ² ) (B) Alkali-soluble (-Acid) (C) aromatic group (-Ar)

The main chain structure of the specific polymer compound is not particularly limited, but preferred examples include polymethacrylate, polyacrylate, polymethacrylamide, polyacrylamide, polystyrene, and the like. Further, it is also preferred to contain two or more kinds of copolymers selected from the structural units constituting the polymers.

Among these, more preferred examples include polymethacrylate, polystyrene, and a copolymer containing methacrylic acid and styrene as structural units.

Next, the three functional groups which the specific polymer compound of the present invention has at the end of the side chain will be described in order.

<Side chain end structure: (A') alkylene oxide chain (-(R ¹ O) _n R ² )>(A') alkylene oxide chain of a side chain terminal functional group contained in the polymer compound of the present invention, The system can be represented by the following formula (A'): -(R ¹ O) _n R ² (A')

In the formula (A'), R ¹ represents a saturated hydrocarbon linking group.

The R ^{1 group} includes an alkylene group having 2 to 10 carbon atoms, or the like, and may have a branched chain or ring structure in its structure. R ¹ preferably represents an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, more preferably an ethyl group or a propyl group.

The R ² group represents a hydrogen atom, a hydrocarbon group, or a mercapto group (RCO). Among them, the hydrocarbon group includes an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and the like. Further, R in the mercapto group (RCO) is preferably the same as the hydrocarbon group as described above.

R ² specifically preferably includes a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, a benzyl group, a phenyl group, a naphthyl group, a cyclohexyl group, an ethyl fluorenyl group. And a propyl fluorenyl group and a benzhydryl group are more preferably a hydrogen atom, a methyl group or a phenyl group.

The n system is preferably from 2 to 100, more preferably from 4 to 50, most preferably from 4 to 20.

When an (A') alkylene oxide chain functional group is to be introduced into a side chain of a specific polymer compound, a structural unit having a functional group represented by the formula (A') as described above in the side chain is used as a copolymerization. The ingredients are all right.

Specific examples of the structural unit having an alkylene oxide chain at the end of the side chain [(A'-1) to (A'-16)] are listed below, but the present invention is not limited thereto.

The structural unit is preferably contained in an amount of 5 to 70 mol%, more preferably 10 to 50 mol%, based on the (2') specific polymer compound.

<Side chain end structure: (B) alkali-soluble group (-Acid)> The (B) alkali-soluble group (-Acid) of the side chain terminal functional group contained in the polymer compound of the present invention represents a pKa of 1 to 11. Acid base. The description of the alkali-soluble group of the component (2) is also applicable to the alkali-soluble group.

The structural unit is preferably contained in an amount of from 5 to 70 mol%, more preferably from 10 to 50 mol%, based on the (2) specific polymer compound.

<Side chain end structure: (C') aromatic group (-Ar)> (C') aromatic group (-Ar) in the present invention, which represents a heteroaromatic ring group selected from a carbon number of 4 or more And a functional group having an aromatic ring group having 6 or more carbon atoms.

The description of the (C) aromatic group of the component (2) is also applicable to the aromatic group.

The structural unit as described above is preferably contained in an amount of from 5 to 70 mol%, more preferably from 10 to 50 mol%, based on the (2') specific polymer compound.

The specific polymer compound having a functional group represented by (A'), (B), or (C) at the side of the side chain as described above preferably has a weight average molecular weight of from 3,000 to 200,000, more preferably from 3,000 to 50,000. The best is in the range of 3,000 to 10,000.

Hereinafter, a specific example of the (2') specific polymer compound of the present invention [(P'-1) to (P'-11)] will be used for constituting the structural unit of the polymer compound and the polymerized molar The ratio and its weight average molecular weight (Mw) are expressed. The structural units (A'-○), (B-○), and (C-○) shown below are the descriptions of the functional groups (A'), (B), and (C) as described above. The specific example code of the structural unit marked in . Further, the invention is not limited to the exemplified compounds.

The (2') specific polymer compound which can be used in the present invention can be synthesized by a conventional method to date.

Specifically, a monomer of each unit can be obtained by thermally polymerizing an azo initiator in a solvent.

The content of the (2') specific polymer compound in the photocurable coloring composition of the present invention is preferably converted into solid content from the viewpoint of coexisting both contrast and film curability. The range is from 5 to 50% by mass, more preferably from 5 to 30% by mass.

<(2") Coloring Agent> The second photocurable coloring composition of the present invention contains a coloring agent.

The coloring agent to be used in the present invention is not particularly limited, and various dyes or pigments conventionally used for color filter applications may be used alone or in combination of two or more. The colorant is preferably a pigment from the viewpoint of light resistance.

The description of the colored pigments as described above is also applicable to the pigments.

In the present invention, when the colorant is a dye, the composition can be uniformly dissolved to produce a curable composition.

A dye which can be used as a coloring agent contained in the curable composition of the present invention is not particularly limited, and a conventional dye for a conventional color filter can be used. For example, Japanese Laid-Open Patent Publication No. 64-90403, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 6-35183, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Publication No. 4-249549, Japanese Patent Application Laid-Open No. Hei No. 10-123316, Japanese Patent Application Laid-Open No. Hei No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. 2001-48823, Japanese Patent Laid-Open No. Hei 8-15522, and Japanese Invention Patent Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 2002-14220, Japanese Patent Laid-Open Publication No. 2002-14221, Japanese Patent Laid-Open Publication No. 2002-14222, Japanese Patent Laid-Open Publication No. 2002-14223, Japanese Patent Application Laid-Open No. Hei No. A coloring matter such as Japanese Patent Publication No. 8-72558, Japanese Patent Application Laid-Open No. Hei 8- No. No. Hei.

As the chemical structure, a pyrazole azo type, an anilino azo type, a triphenylmethane type, an anthraquinone type, an anthrapyridone type, a benzylidene type, an oxoline type (OXONOL) type, and a pyrazole triazole couple can be used. Nitrogen, pyridone azo, cyanine, thiophene Department, pyrrolopyrazole, methine azo, A dye such as a cord, an anthracycline, a benzopyran, or an indigo.

Further, in the case of a photoresist system which is developed with water or alkali, it is also suitable to use an acid dye and/or from the viewpoint of completely removing the binder and/or the dye of the light non-irradiated portion by development. The case of derivatives.

Others are also suitable for use with direct dyes, basic dyes, mordant dyes, acid mord dyes, ice dyes, disperse dyes, oil-soluble dyes, food dyes, and/or such derivatives.

The acid dye is not particularly limited as long as it has an acidic group such as a sulfonic acid or a carboxylic acid, but should be considered in its entirety and solubility in an organic solvent or developer, salt formation with a basic compound, and absorbance. It is selected in accordance with the necessary properties of interaction with other components in the composition, light resistance, heat resistance and the like.

Specific examples of the acid dye are listed below, but are not limited thereto. Examples include: acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chrome violet K; acid fuchsin; acid green 1, 3, 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; Acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; food Use Yellow (Food Yellow) 3; and derivatives of these dyes.

Wherein, the acid dye is preferably acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324:1; acid orange 8, 51, 56, 63 , 74; acid red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217; acid purple 7; acid yellow 17, 25, 29, 34 , 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; acid green 25 and the like dyes and derivatives of such dyes.

In addition, the azo system other than the above, Is also an acid dye of the cordierin system, CI Solvent Blue 44, 38; CI Solvent Orange 45; Rhodamine B, Rhodamine 110, etc. Derivatives of such dyes are also suitable for use.

Wherein the (2") colorant is preferably selected from the group consisting of triallyl methane, lanthanide, methine azo, benzylidene, oxaphthalocyanine, cyanine, and thiophene Department, pyrrolopyrazole, methine azo, A coloring agent based on a system, an anthracycline system, a benzopyrazole system, an indigo system, a pyrazole azo system, an anilino azo system, a pyrazole triazole azo system, a pyridone azo system, or an anthrapyridone.

The content of the (2") coloring agent contained in the second photocurable coloring composition of the present invention is preferably from 25 to 95% by mass, more preferably from 30 to 90% by mass based on the total solid content of the composition. %, further preferably 40 to 80% by mass.

When the color filter is too small, when a color filter is produced by the curable composition of the present invention, an appropriate chromaticity tends not to be obtained. On the other hand, if there is too much, the photohardening cannot be sufficiently performed, so that the strength of the film should be lowered, and the development latitude at the time of alkali development tends to be narrow, but it is specific to the present invention. Since the sensitizer has high light absorption efficiency, even when the curable composition contains a high concentration of the coloring agent, the effect of improving the sensitivity can be remarkably exhibited.

<(3) Compound having an ethylenically unsaturated group which can be subjected to addition polymerization> A compound having an addition-polymerizable ethylenically unsaturated group which can be used in the present invention (hereinafter, appropriately referred to as "polymerizable compound" ") is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial jaw region of the present invention, and it can be utilized in the present invention without particular limitation. These have chemical forms such as monomers, prepolymers, i.e., dimers, trimers, and oligomers, or mixtures thereof, and the like, and the like. Examples of the monomer and its copolymer include: an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), or an ester thereof, hydrazine. The amine is preferably an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound. Further, an unsaturated carboxylic acid ester having a core-requiring substituent such as a hydroxyl group, an amine group or a sulfhydryl group, or an addition reaction product of a monofunctional or polyfunctional isocyanate or epoxy group, and a monofunctional group, Further, a polyfunctional carboxylic acid, a carboxylic acid ester having a core-requiring substituent such as a hydroxyl group, an amine group or a thiol group, or a dehydration condensation reaction product of a guanamine may be suitably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or a guanamine having an isocyanate group or an electrophilic substituent such as an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and A substituted carboxylic acid ester or a guanamine having a detachable substituent such as a halogen group or a tosyloxy group, and a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol are also suitable for use. . Further, in other examples, a compound group of a saturated phosphonic acid, styrene, vinyl ether or the like may be substituted instead of the unsaturated carboxylic acid as described above.

Specific examples of the monomer of the aliphatic polyol compound and the ester of the unsaturated carboxylic acid include: "acrylate" includes ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butyl diacrylate. Alcohol ester, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) ether , trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl tetraacrylate Alcohol ester, neopentyl glycol tetraacrylate, di neopentyl glycol diacrylate, di pentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentoxide, sorbitol hexaacrylate Alcohol ester, tris(propylene methoxyethyl) cyanide, polyester acrylate oligomer, isomeric cyanuric acid EO modified triacrylate, and the like.

"Methacrylate" includes: tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate , trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, neopentyl dimethacrylate Tetraol ester, neopentyl glycol trimethacrylate, neopentyl glycol tetramethacrylate, dineopentyl glycol dimethacrylate, dineopentaerythritol hexamethacrylate, trimethacrylic acid Sorbitol ester, sorbitan tetramethacrylate, bis[p-(3-methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(meth)醯oxyethoxy)phenyl]dimethylmethane and the like.

"Iconic acid esters" include: diethylene glycol iconate, propylene glycol diconiate, 1,3-butylene glycol diconiate, 1,4-butanediol diaconate , Icylene tetramethylene glycol ester, diconcanic acid pentaerythritol ester, tetraconcanic acid sorbitol ester, and the like. The "crotonate" includes ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, neopentyl glycol dicrotonate, and sorbitol tetracrotonate. The "isocrotonate" includes ethylene glycol diisocrotonate, neopentyl glycol diisocrotonate, and sorbitol tetraisocrotonate. "maleate" includes: ethylene dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, tetrabutylene Sorbitol ester and the like.

Examples of the other esters are, for example, those disclosed in Japanese Laid-Open Patent Publication No. Sho 51-47334, Japanese Laid-Open Patent Publication No. 57-196231, or Japanese Patent Publication No. 57-196231 Japanese Patent Publication No. 59-5240, Japanese Patent Application Laid-Open No. 59-5241, Japanese Patent Application Laid-Open No. 2-226149-A. Those containing an amine group and the like are also suitable for use. Further, the ester monomer as described above can also be used as a mixture.

Further, specific examples of the monomer of the aliphatic polyamine compound and the carboxylic acid of the unsaturated carboxylic acid are: methylene bis-acrylamide, methylene bis-methyl acrylamide, 1,6-hexa Methyl bis-acrylamide, 1,6-hexamethylene bis-methyl acrylamide, di-ethyltriamine propylene amide, xylene bis acrylamide, xylene bis methacrylamide Wait. Other preferred examples of the amide-based monomer include those having a cyclohexylene structure disclosed in Japanese Laid-Open Patent Publication No. 54-21726.

Further, a urethane-based addition polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also suitably used, and specific examples thereof include, for example, Japanese Laid-Open Patent Publication No. 48-41708. In the polyisocyanate compound having two or more isocyanate groups in one molecule, two or more molecules are added to a vinyl monomer having a hydroxyl group represented by the formula (Aa) shown below. A polymerizable vinyl vinyl urethane compound or the like.

CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH (Aa) (however, in the formula (Aa), R ⁴ and R ⁵ represent H or CH ₃ ).

In addition, for example, the urethane acrylates disclosed in Japanese Laid-Open Patent Publication No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, and Japanese Invention Patent No. 2-16765; Ethylene oxide having an inventive patent No. 58-49860, Japanese Patent No. 56-17654, Japanese Patent No. 62-39417, and Japanese Patent No. 62-39418 The urethane compound of the skeleton is also suitable for use. In addition, an amine-based structure is contained in the molecule by using the invention disclosed in Japanese Laid-Open Patent Publication No. SHO-63-277653, Japanese Patent Application Laid-Open No. Hei No. 63-260909, and Japanese Patent Application Laid-Open No. Hei No. 1-105238. An addition-polymerizable compound of a sulfide structure can produce a photocurable coloring composition having a very excellent photosensitive rate.

Other examples include, for example, polyester acrylates disclosed in Japanese Laid-Open Patent Publication No. 48-64183, Japanese Patent Publication No. Sho 49-43191, and Japanese Patent Publication No. Sho 52-490490. A polyfunctional acrylate or methacrylate such as an epoxy acrylate which reacts an epoxy resin with (meth)acrylic acid. In addition, it also includes a specific unsaturated compound disclosed in Japanese Patent Publication No. Sho 46-43946, Japanese Patent Application Laid-Open No. Hei No. 1-40337, Japanese Patent Application No. Hei No. 1-40336; A vinyl phosphonic acid-based compound such as JP-A No. 2-25493. Further, a structure containing a perfluoroalkyl group disclosed in Japanese Laid-Open Patent Publication No. 61-22048 is also suitable for use. In addition, it can also be referred to as a photocurable monomer and oligomer in Japanese Association of Associations, Vol. 20, No. 7, pp. 300 to 308 (1984).

The details of the use of the addition polymerizable compound, such as the structure, the use alone or in combination, and the amount of addition, can be arbitrarily set in accordance with the final performance design of the curable composition. These lines can be selected, for example, from the viewpoints described below.

The sensitivity is preferably a structure in which the content of the unsaturated group per molecule is large, and in most cases, it is preferably a difunctional or higher. Further, when it is desired to increase the strength of the cured film, it is preferably a trifunctional or higher functional group, and a different functional number is used in combination. It is also effective to adjust the sensitivity and strength by using different polymerizable groups (for example, acrylate, methacrylate, styrene compound, or vinyl ether compound).

In addition, for the compatibility and dispersibility of other components (for example, photopolymerization initiator, colorant (pigment, dye), etc., binder polymer, etc.) contained in the curable composition, the addition of the polymerization compound. The use method is an important factor. For example, it is also possible to improve the compatibility by using a low-purity compound or a combination of two or more addition polymerizable compounds. In addition, it is also possible to select a specific structure for the purpose of improving the adhesion between the curable composition layer and the substrate.

The first photocurable coloring composition of the present invention may be (1) a specific initiator as described above, (2) a color pigment dispersed by a specific dispersing agent, and (3) having an addition polymerization. The ethylenically unsaturated group-containing compound and, if necessary, the sensitizer, optionally contain any of the components as detailed below.

The second photocurable coloring composition of the present invention may have (1) a specific initiator, (2') a specific polymer compound, (2") a coloring agent, and (3) an addition polymerizable polymer as described above. The ethylenically unsaturated group-containing compound and, if necessary, the sensitizer, optionally contain any of the components detailed below. Hereinafter, any of the components used in the present invention will be described.

<Dispersant> When the (2") coloring agent of the second photocurable coloring composition of the present invention contains a pigment, the photocurable coloring composition is preferably from the viewpoint of improving the dispersibility of the pigment. Contains a dispersing agent.

As the dispersing agent (pigment dispersing agent) which can be used in the present invention, the above-mentioned pigment dispersing agent can be used.

These dispersing agents may be used singly or in combination of two or more. In the present invention, it is particularly preferred to use a combination of a pigment derivative and a polymer type dispersant.

The content of the dispersant in the second curable composition of the present invention is preferably from 1 to 80% by mass, more preferably from 5 to 70% by mass, still more preferably from 10 to 60% by mass based on the pigment.

In the case of using a polymer type dispersant, the amount thereof is preferably in the range of 5 to 100% by mass, more preferably 10 to 80% by mass based on the pigment. Further, when a pigment derivative is used, it is preferably used in an amount of from 1 to 30% by mass, more preferably from 3 to 20% by mass, particularly preferably from 5 to 15% by mass based on the pigment. The range of %.

When a pigment and a dispersant of a colorant are used, the sum of the content of the colorant and the dispersant is preferably from the viewpoint of the hardening sensitivity and the color concentration, with respect to the total solid content of the curable composition constituting the second. It is 30% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 85% by mass or less, and still more preferably 50% by mass or more and 80% by mass or less.

<Binder Polymer> The photocurable coloring composition of the present invention contains a binder polymer as needed for the purpose of improving the properties of the formed film and the like.

The binder is preferably a linear organic polymer. These "linear organic polymers" can be used arbitrarily. In order to carry out water development or weak alkaline water development, it is preferred to select a linear organic polymer which is soluble or swellable to water or weakly alkaline water. The linear organic polymer is selected not only as a film forming agent but also as a water, weak alkaline water or organic solvent developer. For example, water development can be carried out when a water-soluble organic polymer is used. The linear organic polymer is a radical polymer having a carboxylic acid group in a side chain, and is disclosed, for example, in Japanese Laid-Open Patent Publication No. 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japan. Japanese Patent No. 58-12577, Japanese Patent No. 54-25957, Japanese Patent Laid-Open No. 54-92723, Japanese Patent Laid-Open No. 59-53836, Japanese Patent Application No. 59-71048, that is, a resin having a carboxyl group alone or a copolymerized resin, a monomer having an acid anhydride alone or copolymerized to hydrolyze or semi-esterify or semi-esterify an acid anhydride unit An epoxy acrylate in which an epoxy resin is modified with an unsaturated monocarboxylic acid and an acid anhydride. A single system having a carboxyl group includes: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, etc., and a single system having an acid anhydride includes: Adipic anhydride and the like.

Further, an acidic cellulose derivative having the same carboxylic acid group in the side chain can be used. In addition to this, it is useful to add a cyclic acid anhydride to a polymer having a hydroxyl group or the like.

When an alkali-soluble resin is used as the copolymer, the compound used for the copolymerization may also be used in addition to the monomer as mentioned before. Examples of other monomers include the compounds of (1) to (12) as follows: (1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate An ester, an aliphatic hydroxy group such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate or 4-hydroxybutyl methacrylate, and Acrylates.

(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid -2-chloroethyl ester, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, acrylic acid 2 An alkyl acrylate such as allyloxyethyl acrylate or propargyl acrylate.

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, methacrylic acid 2 -ethylhexyl ester, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate Ester, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate An alkyl methacrylate such as an ester.

(4) acrylamide, methacrylamide, N-methylol acrylamide, N-ethylpropane decylamine, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyl Ethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide , N,N-diallyl acrylamide, N,N-diallyl methacrylamide, allyl acrylamide, allyl methacrylamide, etc. Acrylamide.

(5) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. Vinyl ethers.

(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate.

(7) Styrene such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene or p-ethoxylated styrene.

(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, and the like.

(11) maleimide, N-propylene decyl acrylamide, N-ethyl methacryl decylamine, N-propenyl methacrylamide, N-(p-chlorophenyl An unsaturated quinone imine such as methacrylamide.

(12) A methacrylic monomer in which a hetero atom is bonded to the α-position. For example, it includes compounds disclosed in Japanese Patent Application Laid-Open No. 2001-115595, and the specification of Japanese Patent Application No. 2001-115598.

Among these, a (meth)acrylic resin having an allyl group or a vinyl ester group and a carboxyl group in a side chain; and Japanese Patent Laid-Open Publication No. 2000-187322, Japanese Patent Application Laid-Open No. 2002- An alkali-soluble resin having a double bond in a side chain of the Japanese Patent Publication No. 62698 or an alkali-soluble resin having a guanamine group in a side chain disclosed in Japanese Laid-Open Patent Publication No. 2001-242612, which has superior film strength and sensitivity. The balance between degree and developability is therefore preferred.

In addition, it is disclosed in Japanese Invention Patent No. 7-12004, Japanese Invention Patent Special Fair No. 7-120041, Japanese Invention Patent Special Fair No. 7-120042, Japanese Invention Patent Special Fair No. 8-12424, Japanese Invention An acid-based urethane containing an acid group, such as Japanese Patent Laid-Open No. 63-287944, Japanese Patent Application Laid-Open No. Hei 63-287947, Japanese Patent Application Laid-Open No. Hei No. 1-271741, and Japanese Patent No. Hei 10-116232 An ester-based adhesive polymer or a urethane-based adhesive polymer having an acid group and a double bond in a side chain disclosed in Japanese Laid-Open Patent Publication No. 2002-107918, which has excellent strength. Conducive to brush resistance. Low exposure suitability.

In addition, the acetal-modified polyvinyl alcohol-based binder having an acid group, such as the European Patent No. 993966, the European Patent No. 1204000, and the Japanese Patent Laid-Open No. 2001-318463, is high. Molecules, which have a superior balance of film strength and developability, are suitable for use.

Further, in addition to the above, the water-soluble linear organic polymer may be polyvinylpyrrolidone or polyethylene oxide. Further, in order to increase the strength of the hardened film, an alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin may be used.

The weight average molecular weight of the binder polymer which can be used in the present invention is preferably 5,000 or more, more preferably from 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, more preferably from 2,000 to 250,000. range. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably in the range of 1.1 to 10.

The binder polymer may be any of a random polymer, a block polymer, a graft polymer, and the like.

The binder polymer which can be used in the present invention can be synthesized by a conventionally known method. The solvent used in the synthesis includes, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide , N,N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl hydrazine, water, and the like. These solvents may be used singly or in combination of two or more.

In the synthesis of the binder polymer used in the present invention, the radical polymerization initiator to be used includes a conventional compound such as an azo initiator or a peroxide initiator.

If other binder polymers as described above are used, the content thereof is preferably from 0 to 50% by weight, more preferably from 0 to 50% by weight based on the component (2) or the (2') specific polymer compound as described above. It is in the range of 0 to 30% by weight.

<Co-sensitizer> The photocurable coloring composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has an effect of further increasing the sensitivity of the sensitizing dye or the initiator to the active radiation, or suppressing polymerization inhibition of the polymerizable compound due to oxygen.

Examples of such co-sensitizers include amines, for example, as disclosed in MRSander et al., "Journal of Polymer Society", Vol. 10, p. 3, 173 (1972), Japanese Invention Patent No. 44-20189, Japanese Patent Laid-Open No. 51-82102, Japanese Patent Laid-Open No. Hei 52-134692, Japanese Patent Laid-Open No. 59-138205, and Japanese Patent Laid-Open No. 60-84305 Japanese Laid-Open Patent Publication No. 62-18537, Japanese Patent Application Laid-Open No. Hei 64-33104, and Research Disclosure No. 33825, and the like, specifically, include: triethanolamine, p-dimethyl Ethylaminobenzoic acid ethyl ester, p-methylmercaptodimethylaniline, p-methylthiodimethylaniline, and the like.

Other examples of the "common sensitizer" include: mercaptans and sulfides, as disclosed in Japanese Laid-Open Patent Publication No. 53-702, Japanese Patent Publication No. Sho 55-500806, and Japanese Invention. The thiol compound of Japanese Laid-Open Patent Publication No. 5-142772, the disulfide compound of Japanese Laid-Open Patent Publication No. 56-75643, and the like, specifically, for example, 2-hydrothiobenzothiazole, 2-hydrogen Thiobenzoxazole, 2-hydrothiobenzimidazole, 2-hydrothio-4(3H)-quinazoline, β-hydrothionaphthalene, and the like.

Further, other examples of the co-sensitizer include: an amino acid compound (for example, N-phenylglycine), and an organometallic compound (for example, tributyltin acetate) disclosed in Japanese Patent Publication No. Sho 48-42965. A hydrogen donor which is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

The content of the co-sensitizer is preferably from 0.1 to 30% by weight based on the total solid content weight of the curable composition from the viewpoint of increasing the curing speed by the balance between the polymerization growth rate and the chain transfer rate. The range is more preferably in the range of 0.1 to 25% by mass, still more preferably in the range of 0.5 to 20% by mass.

<Polymerization inhibitor> The photocurable coloring composition of the present invention is an unnecessary thermal polymerization for preventing a compound having a polymerizable ethylenically unsaturated double bond during production or storage of a curable composition, and preferably contains A small amount of thermal polymerization inhibitor.

Thermal polymerization inhibitors which can be used in the present invention include: hydroquinone, p-methoxyphenol, di-tertiary-butyl-p-cresol, gallic phenol, tert-butyl catechol, benzoquinone , 4,4'-thiobis(3-methyl-6-tertiary-butylphenol), 2,2'-methylenebis(4-methyl-6-tertiary-butylphenol), N-nitrosophenylhydroxylamine first sulfonium salt and the like.

The amount of the thermal polymerization inhibitor added is preferably from about 0.01% by mass to about 5% by mass based on the total weight of the composition. Further, the photocurable coloring composition of the present invention may contain a higher fatty acid derivative such as rosin or decanoic acid amide, if necessary, in order to prevent polymerization inhibition by oxygen, in the drying process after coating. These compounds are unevenly biased on the surface of the photosensitive layer. The amount of the higher fatty acid derivative added is preferably from about 0.5% by mass to about 10% by mass based on the total of the composition.

<Adhesion Enhancer> In the present invention, in order to improve the adhesion to the hard surface (substrate) of the substrate, the photocurable coloring composition preferably contains an adhesion improving agent. The adhesion improving agent includes a decane coupling agent, a titanium coupling agent, and the like.

The "decane coupling agent" includes, for example, γ-(2-aminoethyl)aminopropyltrimethoxydecane, γ-(2-aminoethyl)aminopropyldimethoxydecane, --(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-methylpropene oxime Propyltrimethoxydecane, γ-methylpropenyloxypropyltriethoxydecane, γ-propyleneoxypropyltrimethoxydecane, γ-propyleneoxypropyltriethoxydecane , γ-isocyanate propyl trimethoxy decane, γ-isocyanate propyl triethoxy decane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxydecane . Hydrochloride, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, aminodecane, γ-hydrothiopropyltrimethoxydecane, γ -Hexylthiopropyltriethoxydecane, methyltrimethoxydecane, methyltriethoxydecane,vinyltriethoxydecane,gamma-chloropropyltrimethoxydecane,hexamethyldi Indole, γ-anilinopropyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, vinyl ginseng (β-methoxyethoxy)decane, octadecyl Methyl [3-(trimethoxydecyl)propyl]ammonium chloride, γ-chloropropylmethyldimethoxydecane, γ-hydrothiopropylmethyldimethoxydecane, methyl three Chlorodecane, dimethyldichlorodecane, trimethylchlorodecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, bisallyltrimethoxydecane, tetraethoxydecane , bis(trimethoxydecyl)hexane, phenyltrimethoxydecane, N-(3-propoxyoxy-2-hydroxypropyl)-3-aminopropyltriethoxydecane, N-( 3-methyl propylene oxime Oxy-2-hydroxypropyl)-3-aminopropyltriethoxydecane, (methacryloxymethyl)methyldiethoxydecane, (propyleneoxymethyl)methyldi Methoxydecane, etc.

Among them, preferred are γ-methacryloxypropyltrimethoxydecane, γ-methylpropenyloxypropyltriethoxydecane, γ-acryloxypropyltrimethoxydecane, γ- Propylene oxypropyl triethoxy decane, γ-hydrothiopropyltrimethoxy decane, γ-aminopropyl triethoxy decane, phenyl trimethoxy decane, preferably γ-methyl propylene Alkoxypropyltrimethoxydecane.

The amount of the adhesion enhancer added is preferably from 0.5 to 30% by mass, more preferably from 0.7 to 20% by mass, based on the total solid content of the curable composition.

<Other Additives> In addition, the photocurable coloring composition of the present invention may contain an inorganic filler or a plasticizer for improving the physical properties of the cured film, and a lipid-sensing agent capable of improving the adhesion of the ink on the surface of the photosensitive layer. And other conventional additives.

"Plasticizer" includes, for example, dioctyl phthalate, dodecyl phthalate, triethylene glycol dioctanoate, dimethyl glycol phthalate, tricresol phosphate Ester, dioctyl adipate, dibutyl sebacate, triethylene glyceryl, etc., in the case of using a bonding agent, relative to a compound having a ethylenically unsaturated double bond and a bonding agent The total weight is preferably 0% by mass or more and 10% by mass or less.

<Diluent> When the color filter is produced by using the photocurable coloring composition of the present invention, it can be used by being dissolved in various organic solvents when applied to a support.

The "organic solvent" which can be used at this time includes: acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol-ethyl Ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetamidine acetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether ester, ethylene glycol glycol Ethyl ether ester, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether ester, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N- Dimethylformamide, dimethyl hydrazine, γ-butyrolactone, methyl lactate, ethyl lactate, and the like.

These solvents may be used singly or in combination. The solid content concentration in the solution is preferably from 2 to 60% by mass.

[Color Filter] Next, the color filter of the present invention will be described.

The color filter of the present invention is formed by forming a photocurable colored layer composed of a photocurable coloring composition on the surface of a glass support, and then pattern-exposed by a mask or the like, and after exposure. The photohardenable colored layer is developed to form a colored pattern on the surface of the glass support.

The photocurable colored layer can be formed by applying a photocurable coloring composition onto a glass support and drying it, or by using a photocurable coloring composition in advance. The laminate method is used to adhere to the glass support.

<Glass Support> The support system to be used in the present invention includes, for example, soda lime glass for use in a liquid crystal display element, Pyrex glass, quartz glass, and adhesion of a transparent conductive film. In these cases, it is used for a photoelectric conversion element substrate such as a photographic element, for example, a germanium substrate or the like, or a complementary metal oxide semiconductor (CMOS) or the like. There is also a case where a light shielding layer such as a black strip for isolating each pixel is formed on the substrates.

Further, on the support, a base coat layer may be provided as needed to improve adhesion to the upper layer, to prevent diffusion of the substance, or to planarize the surface.

The method of applying the curable composition of the present invention to a support can be suitably used, for example, a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, or a screen printing method. Various coating methods such as printing methods.

The curable composition coated on the support is usually dried at 70 to 110 ° C for about 2 to 4 minutes to form a layer composed of the photocurable coloring composition.

The coating film thickness after drying of the curable composition is preferably from 0.1 to 10 μm, more preferably from 0.2 to 5 μm, still more preferably from 0.2 to 3 μm.

The photocurable coloring composition of the present invention can be cured under high sensitivity by exposure, has excellent developability in an unexposed portion, and exhibits a surface of a glass support for a photocurable coloring composition. High density.

The color filter of the present invention is characterized in that it has a colored pattern formed on the glass support by the above.

Specifically, the photocurable colored layer composed of the photocurable coloring composition of the present invention is subjected to pattern exposure by a specific mask pattern or by a scanning exposure method as described above, and only the coating by light irradiation is applied. The film portion is hardened, and then the unhardened region is developed with a developing solution to form a patterned film composed of pixels of three colors or four colors, whereby the color filter of the present invention can be obtained.

<Exposure Step> In the exposure step, pattern exposure is performed by exposing the photocurable colored layer as described above to a photomask, or by scanning exposure, to apply only the coating film portion to be irradiated with light. Hardening.

The exposure is preferably carried out by irradiation with radiation, and the radiation can be used for exposure, particularly preferably using ultraviolet rays such as g-line or i-line, and the light source is preferably a high-pressure mercury lamp. The exposure amount is preferably from 5 mJ/cm ² to 1500 mJ/cm ² , more preferably from 10 mJ/cm ² to 1,000 mJ/cm ² , most preferably from 10 mJ/cm ² to 800 mJ/cm ² .

<Developing Step> After the exposure step, an alkali development treatment is subsequently performed to elute the unexposed portion of the light in the exposure step to the aqueous alkali solution. Thereby, only the portion where the light is hardened remains.

The developer is preferably an organic alkali developer which does not cause damage to the circuit or the like of the substrate. The development temperature is usually from 20 ° C to 30 ° C, and the development time is usually from 20 to 90 seconds.

The "developing solution" is, for example, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-dioxin. An organic basic compound such as bicyclo[5,4,0]-7-undecene is diluted with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, of an aqueous alkaline solution. Further, when such a developing solution composed of an alkaline aqueous solution is used, the substrate is usually rinsed with pure water after development.

Further, the manufacturing method of the present invention may be carried out after the hardening composition layer forming step, the exposing step, and the developing step as described above, and may optionally include subjecting the formed coloring pattern to heat and/or exposure. Hardening hardening step.

Thereafter, a photocurable colored layer of another hue is formed, and the exposure step and the development step (and the optional hardening step) are repeated by repeating only the required number of hue, thereby obtaining what is desired. A color filter composed of a hue.

The color filter formed by the first photo-curable coloring composition of the present invention is used as a layer on a glass support, and a layer having a photocurable coloring composition capable of forming an interaction with glass is used. It is manufactured by a laminate and has excellent pattern formation. The formed color pattern will exhibit high adhesion to the support substrate, and the film structure composed of the curable composition will be superior in the unexposed portion. The uniformity does not cause a pigment which suppresses the permeability of the developer or agglomerates which generate a photopolymerization initiator, and the penetration of the developer can be uniformly and rapidly performed to exhibit high developability, so that excellent exposure can be formed. The sensitivity and the adhesion to the substrate of the exposed portion are excellent, and there is no high resolution image of the residual film. Therefore, it is suitably used as a solid-state imaging element such as a liquid crystal display element or a CCD, and is particularly suitable for use in, for example, a CCD element or CMOS having a high resolution of more than 1,000,000 pixels. The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving portion for constituting each pixel of the CCD and a micro mirror for collecting light.

The color filter formed by the second photocurable coloring composition of the present invention is used as a layer on a glass support, and a layer having a photocurable coloring composition capable of forming an interaction with glass is used. It is manufactured by a laminate, and has excellent pattern formation properties, and the formed color pattern can exhibit high adhesion to the support substrate, and in the unexposed portion, a specific polymer due to inclusion in the curable composition is exhibited. Since the side chain structure of the compound has high developability, it is possible to form a high-resolution image having excellent exposure sensitivity and excellent adhesion to a substrate of an exposed portion without a residual film. Therefore, it is suitably used as a solid-state imaging element such as a liquid crystal display element or a CCD, and is particularly suitable for use in, for example, a CCD element or CMOS having a high resolution of more than 1,000,000 pixels. The color filter of the present invention can be used, for example, as a color filter disposed between a light receiving portion for constituting each pixel of the CCD and a micro mirror for collecting light.

"Embodiment"

Hereinafter, the present invention will be further specifically described by way of examples, but it is not limited to the examples described below. In addition, unless otherwise noted, "%" and "parts" are based on quality.

[Example 1]

Here, a photo-curable coloring composition α-1 containing a coloring agent (pigment) is prepared, and a color filter for use in a liquid crystal display element is produced by using the curable composition α-1 as an example.

[1. Preparation of photocurable coloring composition α-1] 1-1. Preparation of pigment dispersion liquid (Q1): Green color will be 40 parts by mass of CI Pigment Green 36 and CI Pigment Yellow 219 used as a pigment. /70 (mass ratio) mixture, 7 parts by mass as a dispersing agent (about 4.51 parts by mass of solid content) BYK2001 (Disperbyk: BYK Chemie (BYK), solid content concentration: 45.1% by mass), 3 parts by mass The specific dispersing agent of the present invention [exemplified compound (P-1)] and a mixture of 150 parts by mass of ethyl 3-ethoxypropionate as a solvent are mixed in a bead mill. The mixture was stirred for 20 hours to prepare a pigment dispersion (Q1).

The average particle diameter of the pigment of the obtained pigment dispersion liquid (Q1) was 170 nm as measured by a dynamic light scattering method.

1-2. Preparation of Photocurable Coloring Composition α-1 (Coating Liquid) The components constituting α-1 were mixed as shown below, and the solid component was dissolved in a solvent to prepare a curable composition A-1.

[2. Production of Color Filter] 2-1. Formation of Curable Composition Layer The photocurable coloring composition α-1 containing the pigment prepared as described above was used as a photoresist solution at 550. After performing slit coating on a glass substrate of mm × 650 mm under the conditions described below, it was left in standby for 10 minutes, and then vacuum drying and prebake (100 ° C, 80 seconds) Clock) to form a photocurable colored layer.

(Gap coating condition) Clearance of the opening of the front end of the coating head: 50 μm Coating speed: 100 mm/sec Distance between substrate and coating head: 150 μm Coating thickness (dry thickness): 2 μm coating Temperature: 23 ° C

2-2. After exposure and development, the surface of the photocurable colored layer is exposed to a pattern using a 2.5 kW ultra-high pressure mercury lamp, and after exposure, the coating film is entirely organic. A 10% aqueous solution of a developer (trade name: CD, manufactured by FUJIFILM Arch Co., Ltd.) was coated and allowed to stand for 60 seconds.

2-3. Heat treatment After standing, spray pure water on the photo-curable coloring composition layer to spray off the developer, and then apply the photo-curing treatment and development treatment to the coating film at 220 Heat in an oven at °C for 1 hour (post baking). Thereby, a colored pattern is formed on the glass substrate to obtain a color filter.

[3. Performance Evaluation] The color filter laminate formed on the glass substrate by using the photocurable coloring composition α-1 (coating liquid) prepared as described above was evaluated in the following manner. The exposure pattern formation property of the photocurable colored layer and the substrate adhesion of the coloring pattern of the color filter. The results are shown in Table 1.

3-1. Pattern Formability of Coating Film (Colored Layer) The photocurable coloring composition α-1 (coating liquid) was applied onto a glass substrate and dried to form a layer having a film thickness of 1.0 μm. The conditions of the spin coating were subjected to spin coating at 300 rpm for 5 seconds, then spin coating at 800 rpm for 20 seconds, and drying conditions were set at 100 ° C for 80 seconds. Next, a test reticle having a line width of 10 μm was used and exposed at an exposure amount of 50 mJ/cm ² . Next, development was carried out at 25 ° C using a developing solution of 60% CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) until the residual film of the unexposed portion completely disappeared. (The disappearance of the residual film confirms the residual state of the pigment component by the dark field of the optical microscope). Thereafter, the substrate was washed with running water for 20 seconds, and then spray-dried to terminate pattern formation. The film thickness after development in the region irradiated with light in the exposure step was measured, and the ratio of the film thickness after development to the film thickness before exposure was measured according to the following criteria. The higher the ratio, in other words, the less the film reduction, the higher the exposure sensitivity, and the shorter the development time required for the state in which the residual film is not present (having superior developability), because the two coexist, indicating that Excellent pattern formation.

○: 95% or more; △: less than 95 to 85% or more; X: less than 85%.

3-2. Substrate adhesion The coloring pattern on the color filter after post-baking was confirmed by a usual method using an optical microscope and an SEM (scanning electron microscope) photograph to evaluate the substrate adhesion. The details of the evaluation method are as follows.

<Substrate Adhesion> The evaluation of the adhesion of the substrate was to observe whether or not a pattern defect or a gap with the substrate occurred. For these assessment items, the assessment is carried out on the basis of the benchmarks described below. When the evaluation is ○ and Δ, the substrate adhesion is a practically problem-free level.

○: The pattern defect and the gap with the substrate were not observed at all; △: no pattern defect was observed, and although there was a portion where the gap was observed between the substrate and the substrate, it was a practically problem-free level. ;X: A pattern defect is clearly observed, which is a level that cannot be used practically.

[Examples 2 to 12]

The specific initiator (compound 1), the pigment dispersion liquid (Q1), and the specific dispersant used in preparing the pigment dispersion liquid in the composition α-1 used in the preparation of photocurable coloring composition α-1 The photocurable coloring compositions α-2 to α-12 were prepared in the same manner as in Example 1 except that at least one of them was changed as shown in the following Table 1. These were used, and color filters having a colored pattern were each produced in the same manner as in Example 1. Further, the evaluation was carried out in the same manner as in Example 1 except that the coloring layer using the pigment dispersion liquid Q4 was exposed at an exposure amount of 200 mJ/cm ² . The results are shown in Table 1.

Further, the structures of the specific initiators (Compound 2 to Compound 5) used herein are as follows. Further, a specific dispersant is selected from the exemplary compounds [(P-2) to (P-11)].

Preparation of Pigment Dispersion (Q2): Red is a mixture of 40 parts by weight of CI Pigment Red 254 and CI Pigment Red 177 (80/20 by weight) used as a pigment, and 10 parts by weight as a dispersant (solid content) About 4.51 parts by weight of BYK2001 (Disperbyk: manufactured by BYK Chemie (BYK), solid content concentration: 45.1% by weight), 3 parts by weight of the specific dispersing agent (P-1) of the present invention, 150 weight as a solvent a mixture of 3-ethyl ethoxypropionate mixed with a bead mill. The mixture was stirred for 20 hours to prepare a pigment dispersion (Q2).

The average particle diameter of the pigment of the obtained pigment dispersion liquid (Q2) was 150 nm as measured by a dynamic light scattering method.

Preparation of pigment dispersion (Q3): Blue is a mixture of 35 parts by mass of CI Pigment Blue 15:6 used as a pigment and 90/10 (mass ratio) of CI Pigment Violet 23, and 10 parts by mass as a dispersing agent. (Kylon 2001 (Disperbyk: manufactured by BYK Chemie (BYK) Co., Ltd., solid content concentration: 45.1% by mass), 3 parts by mass of the specific dispersant (P-1) of the present invention, and used as a solid component (about 4.51 parts by mass) A mixture of 150 parts by mass of a solvent of ethyl 3-ethoxypropionate, mixed in a bead mill. Stir for 20 hours to prepare a pigment dispersion (Q3).

The average particle diameter of the pigment of the obtained pigment dispersion liquid (Q3) was 170 nm as measured by a dynamic light scattering method.

Preparation of Pigment Dispersion (Q4): Black is made up of 27 parts by mass of REGAL (Cabot Corp.) carbon black, particle size 31 nm, pH 9, DBP oil supply of 42 ml. /100 parts, blackness My value is 235), 6 parts by mass of benzyl methacrylate/methacrylic acid copolymer (copolymerization ratio of 70/30 molar ratio, weight average molecular weight of 30,000), 2 a mixture of a specific dispersant (P-1) of the present invention and 65 parts by mass of propylene glycol monomethyl ether acetate, mixed in a bead mill. The mixture was stirred for 20 hours to prepare a pigment dispersion (Q4).

The average particle diameter of the pigment of the obtained pigment dispersion liquid (Q4) was 100 nm as measured by a dynamic light scattering method.

[Comparative Examples 1 to 16]

In the formation of the photocurable colored layer, in addition to the specific photopolymerizable initiator of the photocurable coloring composition α-1, the pigment dispersion liquid (Q1), and the specific dispersing agent used in the adjustment of the pigment dispersion liquid The photocurable coloring compositions β-1 to β-16 for comparison were prepared in the same manner as in Example 1 except that at least one of the other compounds shown in Table 1 or the compound for comparison was used, and the same was used. A color filter of the colored pattern is formed and then evaluated. The results are shown in Table 1.

The structure of the comparative photopolymerization initiator [Comparative Compound 1 to Comparative Compound 4] and the comparative polymer compound [(Y-1) to (Y-6)] used in the comparative example is as follows. Further, the structure of the comparative polymer compound is represented by a structural unit for constituting the polymer compound, a polymerization molar ratio, and a weight average molecular weight (Mw) thereof. The structural units (A-○), (B-○), and (C-○) shown below represent the structural units listed in the description of the functional groups (A) to (C) as described above. Specific example symbols.

As is apparent from the results of Table 1, the color filters of Examples 1 to 12 produced by using the first photocurable coloring composition containing a specific initiator and a specific polymer compound have superior pattern formation properties. The substrate of the colored pattern formed is excellent in adhesion, and the first photocurable coloring composition of the present invention can be used to obtain high exposure sensitivity, superior developability, and pattern formation. A color filter having excellent adhesion to a substrate of a colored pattern.

On the other hand, the photopolymerization initiators used Comparative Examples 5 to 8 of the comparative compounds outside the scope of the present invention, or Comparative Examples 1 to 4 in which the pigment dispersion liquid was prepared using only the comparative dispersant outside the scope of the present invention. In any of 9 to 16, the pattern formation property and the adhesion to the substrate are inferior to those of the examples, and therefore it is known that by using a coloring pigment which is a specific initiator and dispersed by a specific dispersant, The photohardenable coloring composition of the present invention can attain the superior effects of the present invention.

[Example 13]

In this paragraph, an example of a color filter for producing a liquid crystal display element using the photocurable coloring composition α '-1 containing a coloring agent (pigment) and using the curable composition α '-1 is used. To explain.

[1. Preparation of photocurable coloring composition α '-1] 1-1. Preparation of pigment dispersion liquid (Q1'): Green type will be 40 parts by mass of CI Pigment Green 36 and CI Pigment Yellow 219 used as a pigment. a 30/70 (mass ratio) mixture, 10 parts by mass as a dispersing agent (about 4.51 parts by mass in terms of solid content), BYK2001 (Disperbyk: BYK Chemie (BYK), a solid concentration of 45.1% by mass), and A mixture of 150 parts by mass of ethyl 3-ethoxypropionate as a solvent is mixed in a bead mill. The mixture was stirred for 15 hours to prepare a pigment dispersion (Q1').

The average particle diameter of the pigment of the obtained pigment dispersion liquid (Q1') was 200 nm as measured by a dynamic light scattering method.

1-2. Preparation of photocurable coloring composition α '-1 (coating liquid) The composition of α '-1 is composed as shown below, and the solid component is dissolved in a solvent to prepare a hardening composition A'- 1.

[2. Production of color filter] A color filter was produced in the same manner as in Example 1 except that the photocurable coloring composition α-1 was used instead of the photocurable coloring composition α-1. Light film.

[3. Performance Evaluation] A photocurable colored layer in which a color filter laminate is formed on a glass substrate by using the photocurable coloring composition α'-1 (coating liquid) prepared as described above. The exposure pattern formation property and the substrate adhesion of the coloring pattern of the color filter, except that the photocurable coloring composition α'-1 is used instead of the photocurable coloring composition α-1, and the substituted pigment dispersion liquid Q1 is used. The evaluation was carried out in the same manner as in Example 1 except that the pigment dispersion liquid Q1' was used.

[Examples 14 to 24]

In the embodiment 13, the specific initiator (compound 1) and/or the pigment dispersion (Q1') in the composition α'-1 substituted for the photocurable coloring composition α'-1 is replaced by the following table. The photocurable coloring compositions α'-2 to α'-12 were prepared in the same manner as in Example 13 except for the above. Then, a color filter having a colored pattern was obtained in the same manner as in Example 13 using these, respectively. Further, the evaluation was carried out in the same manner as in Example 13 except that the coloring layer using the pigment dispersion liquid Q4' was exposed by an exposure amount of 200 mJ/cm ² . The results are shown in Table 2.

The specific initiators (Compound 2 to Compound 5) used herein are as described above. Further, the details of the pigment dispersions Q2' to Q4' are as follows.

Preparation of pigment dispersion (Q2'): Red is a mixture of 40 parts by mass of CI Pigment Red 254 and CI Pigment Red 177 used as a pigment in an 80/20 (mass ratio) mixture, and 10 parts by mass as a dispersing agent (solid) BYK2001 (Disperbyk: manufactured by BYK Chemie (BYK) Co., Ltd., solid content concentration: 45.1% by mass), and 150 parts by mass of ethyl 3-ethoxypropionate as a solvent, a mixture of about 4.51 parts by mass) Liquid, mixed with a ball mill. The mixture was stirred for 20 hours to prepare a pigment dispersion (Q2').

The average particle diameter of the pigment of the obtained pigment dispersion liquid (Q2') was 170 nm as measured by a dynamic light scattering method.

Preparation of pigment dispersion (Q3'): blue is a mixture of 35 parts by mass of CI Pigment Blue 15:6 used as a pigment and 90/10 (mass ratio) of CI Pigment Violet 23, and 10 mass used as a dispersing agent. Part (about 4.51 parts by mass of solid content) BYK2001 (Disperbyk: manufactured by BYK Chemie (BYK), solid content concentration: 45.1% by mass), and 150 parts by mass of ethyl 3-ethoxypropionate used as a solvent The mixture is composed of a ball mill. The mixture was stirred for 20 hours to prepare a pigment dispersion (Q3').

The average particle diameter of the pigment of the obtained pigment dispersion (Q3') was 200 nm as measured by a dynamic light scattering method.

Preparation of pigment dispersion (Q4'): Black is made up of 27 parts by mass of REGAL used as a pigment (carbon black manufactured by Cabot Corporation, particle size of 31 nm, pH 9, DBP oil supply of 42 ml/100 parts, Blackness My value is 235), 6 parts by mass of benzyl methacrylate/methacrylic acid copolymer (copolymerization ratio: 70/30 molar ratio, weight average molecular weight: 30,000), and 65 parts by mass of acetic acid 2. A mixture of propylene glycol monomethyl ether ester mixed with a bead mill. The mixture was stirred for 20 hours to prepare a pigment dispersion (Q4').

The average particle diameter of the pigment of the obtained pigment dispersion (Q4') was 150 nm as measured by a dynamic light scattering method.

[Comparative Examples 17 to 32]

When the photocurable colored layer is formed, the specific photopolymerization initiator of the photocurable coloring composition α'-1 and the specific polymer compound are other compounds shown in Table 2 or a compound for comparison, In the same manner as in Example 13, the comparative photocurable coloring compositions β'-1 to β'-16 were prepared, and a color filter using the colored pattern formed therefrom was prepared, and then evaluated. The results are shown in Table 2.

The structure of the comparative photopolymerization initiator [Comparative Compound 1 to Comparative Compound 4] used in the comparative example was as described above. Further, the structure of the comparative polymer compound [(Y'-1) to (Y'-6)] is as follows. Further, the structure of the comparative polymer compound is represented by a structural unit for constituting the polymer compound, a polymerization molar ratio, and a weight average molecular weight (Mw) thereof. The structural units (A'-○), (B-○), and (C-○) shown below are shown in the description of the functional groups (A'), (B), and (C) as described above. The symbol of the concrete instance of the structural unit represented.

As is apparent from the results of Table 2, the color filter systems of Examples 13 to 24 which were obtained by using the second photocurable coloring composition containing a specific initiator and a specific polymer compound had excellent pattern formation properties. The substrate of the colored pattern formed is excellent in adhesion, and by using the photocurable coloring composition of the present invention, a substrate having a high exposure sensitivity and excellent pattern formation property and a colored pattern formed can be obtained. A color filter with excellent adhesion.

On the other hand, the photopolymerization initiators used Comparative Examples 21 to 24 of the comparative compounds outside the scope of the present invention, or Comparative Examples 17 to 20, 25 to 32 using the comparative polymer compounds, and Examples In contrast, both the pattern formability and the adhesion to the substrate are poor. Therefore, it is known that the present invention can be obtained by using the photocurable coloring composition of the present invention containing a specific initiator and a specific polymer compound. Superior efficacy.

Claims (12)

A photocurable coloring composition comprising: a heterocyclic photopolymerization initiator selected from the group consisting of compounds represented by the following general formulae (I) to (V), having poly(meth)acrylic acid in a side chain a color pigment dispersed by an alkali-soluble graft polymer compound of an ester chain, and a compound having an ethylenically unsaturated group capable of addition polymerization, In the formula (I), W represents an aryl group, X represents a hydrogen atom, an alkyl group or an aryl group, Y represents a fluorine atom, a chlorine atom or a bromine atom, and n represents an integer of 1 to 3; In the formula (II), the Q system represents a bromine atom or a chlorine atom, and the P system represents -CQ ₃ , -NH ₂ , -NHR, -N(R) ₂ , or -OR, wherein the Q system is as described above. Synonymous, R represents phenyl or alkyl, W represents an aromatic group, a heterocyclic group, or a monovalent group represented by the following formula (II-A), and n represents 0, 1 or 2; In the general formula (II-A), Z-O- or -S-, R is synonymous with the above formula (II); In the formula (III), X represents a bromine atom or a chlorine atom, m and n are each independently an integer of 0 to 3, and R ¹ represents a group represented by the following formula (III-A); In the formula (III-A), R ² represents a hydrogen atom or ORc, wherein Rc represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ³ represents a bromine atom, a chlorine atom, an alkyl group, Alkenyl, aryl, or alkoxy; In the formula (IV), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the following formula (IV-A) or (IV-B), R ³ , R ⁴ , each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, X, Y systems independently represent a chlorine atom or a bromine atom, respectively, m, n are independently represented by 0, 1 or 2; In the general formulae (IV-A) and (IV-B), R ⁵ , R ⁶ and R ⁷ each independently represent an alkyl group or an aryl group; The photocurable coloring composition of the first aspect of the invention, wherein the alkali-soluble graft polymer compound having a poly(meth)acrylate chain in a side chain further has an aromatic group in a side chain. The photocurable coloring composition according to claim 1 or 2, wherein the heterocyclic photopolymerization initiator is selected from the compounds represented by the formulae (I) to (IV); the alkali-soluble grafting The polymer compound contains (A) a structural unit having a poly(meth)acrylate chain and (B) having a group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and a phenolic hydroxyl group. The structural unit of the alkali-soluble group serves as a copolymerization component. A color filter comprising a layered body having a photocurable colored layer composed of a photocurable coloring composition of the first aspect of the patent application, which is attached to a glass support, to expose the pattern The exposed region of the subsequent photocurable colored layer is hardened, and the colored pattern obtained by the unexposed regions is developed. a color filter that is attached to a glass support and has The layered body of the photocurable colored layer composed of the photocurable coloring composition of the second aspect of the invention is subjected to pattern exposure, and the exposed region of the photocurable colored layer after the pattern exposure is cured, and the unexposed area is developed. The colored pattern produced. The color filter of claim 4 or 5, wherein in the photocurable coloring composition, the heterocyclic photopolymerization initiator is selected from the group consisting of the formulae (I) to (IV) The alkali-soluble graft polymer compound contains (A) a structural unit having a poly(meth)acrylate chain and (B) having a selected from the group consisting of a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and a phenolic hydroxyl group. The structural unit of the alkali-soluble group in the group formed as a copolymerization component. A photocurable coloring composition comprising a heterocyclic photopolymerization initiator selected from the group consisting of compounds represented by the following general formulae (I) to (V), having an (A') alkylene oxide chain at a side chain terminal (-(R ¹ O) _n R ² (wherein R ¹ is an alkylene group having 2 to 10 carbon atoms or having a branched chain or ring structure in its structure; R ² represents a hydrogen atom, a hydrocarbon group, Or a fluorenyl group; n is an integer of 2 to 100)), (B) an alkali-soluble group (-Acid), and (C) an aromatic group (-Ar) polymer compound, a coloring agent, and an addition polymerization a compound of an ethylenically unsaturated group, In the formula (I), W represents an aryl group, X represents a hydrogen atom, an alkyl group or an aryl group, Y represents a fluorine atom, a chlorine atom or a bromine atom, and n represents an integer of 1 to 3; In the formula (II), the Q system represents a bromine atom or a chlorine atom, and the P system represents -CQ ₃ , -NH ₂ , -NHR, -N(R) ₂ , or -OR, wherein the Q system is as described above. Synonymous, R represents phenyl or alkyl, W represents an aromatic group, a heterocyclic group, or a monovalent group represented by the following formula (II-A), and n represents 0, 1 or 2; In the general formula (II-A), Z-O- or -S-, R is synonymous with the above formula (II); In the formula (III), X represents a bromine atom or a chlorine atom, m and n are each independently an integer of 0 to 3, and R ¹ represents a group represented by the following formula (III-A); In the formula (III-A), R ² represents a hydrogen atom or ORc, wherein Rc represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ³ represents a bromine atom, a chlorine atom, an alkyl group, Alkenyl, aryl, or alkoxy; In the formula (IV), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by the following formula (IV-A) or (IV-B), R ³ , R ⁴ , each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, X, Y systems independently represent a chlorine atom or a bromine atom, respectively, m, n are independently represented by 0, 1 or 2; In the general formulae (IV-A) and (IV-B), R ⁵ , R ⁶ and R ⁷ each independently represent an alkyl group or an aryl group; . The photocurable coloring composition of claim 7, wherein the heterocyclic photopolymerization initiator is selected from the group consisting of compounds represented by the formulae (I) to (IV); -(COO)-(C ₂ H ₄ O) _n R ² or -(CONH)-(C ₂ H ₄ O) _n R ² (wherein R ² represents a hydrogen atom, a hydrocarbon group, or a fluorenyl group, and n represents 2~ 100) a structural unit (A), a structural unit (B) having an alkali-soluble group (-Acid) at a terminal, and a structural unit (C) having an aromatic group (-Ar) at a terminal as a copolymerization component; The content of the unit (A), the structural unit ( B ) and the structural unit (C) is a polymer compound of 5 to 70 mol%, respectively. The photocurable coloring composition of claim 7, wherein the heterocyclic photopolymerization initiator is selected from the group consisting of compounds represented by the formulae (I) to (IV); -(C ₂ H ₄ O) _n R ² (wherein R ² represents a hydrogen atom, a hydrocarbon group, or a fluorenyl group, n represents 2 to 100) of the structural unit (A), and has an alkali-soluble group (-Acid) at the terminal The structural unit (B) and the structural unit (C) having an aromatic group (-Ar) at the terminal are used as a copolymerization component; the content of the structural unit (A), the structural unit ( B ) and the structural unit (C) are respectively A polymer compound at 5 to 70 mol%. A color filter comprising a layered body having a photocurable colored layer composed of a photocurable coloring composition of the seventh aspect of the patent application, which is attached to a glass support, and which exposes the pattern The exposed region of the subsequent photocurable colored layer is hardened, and the colored pattern obtained by the unexposed regions is developed. The color filter of claim 10, wherein in the photocurable coloring composition, the heterocyclic photopolymerization initiator is selected from the group consisting of the compounds represented by the general formulae (I) to (IV); The polymer compound contains only -(COO)-(C ₂ H ₄ O) _n R ² or -(CONH)-(C ₂ H ₄ O) _n R ² (wherein R ² represents a hydrogen atom, a hydrocarbon group, Or a fluorenyl group, n represents a structural unit of 2 to 100) (A), a structural unit having an alkali-soluble group (-Acid) at the terminal (B), and a structural unit having an aromatic group (-Ar) at the terminal (C) As a copolymerization component; the content of the structural unit (A), the structural unit ( B ), and the structural unit (C) is a polymer compound of 5 to 70 mol%, respectively. The color filter of claim 10, wherein in the photocurable coloring composition, the heterocyclic photopolymerization initiator is selected from the group consisting of the compounds represented by the general formulae (I) to (IV); The polymer compound contains a structural unit (A) having only -(C ₂ H ₄ O) _n R ² (wherein R ² represents a hydrogen atom, a hydrocarbon group, or a fluorenyl group, and n represents 2 to 100), and has a terminal unit at the terminal a structural unit (B) of an alkali-soluble group (-Acid), and a structural unit (C) having an aromatic group (-Ar) at a terminal as a copolymerization component; the structural unit (A), a structural unit ( B ), and a structure The content of the unit (C) is a polymer compound of 5 to 70 mol%, respectively.