JP4846484B2 - Photocurable coloring composition and color filter using the same - Google Patents

Description

  The present invention relates to a photocurable coloring composition useful for forming a color filter used for a liquid crystal display element (LCD), a solid-state imaging element (CCD, CMOS, etc.), and a color filter obtained using the same.

  In recent years, various displays such as televisions, personal computers, and mobile phones are required to have high image quality and high saturation, and in particular, for televisions, large screens are also required. At present, the mainstream of these displays is a liquid crystal display system, and in order to achieve the above-described high image quality, high saturation, and large screen, the technology of the color filter used therein has become very important. Specifically, it is a technique relating to a process for producing a color filter and a photocurable coloring composition adapted thereto.

With regard to high-definition color filters, it is necessary to form a pattern with high accuracy for pattern exposure and subsequent development in order to make the line width of the color filter pattern formation fine. In addition, in order to increase the saturation, it is essential to adjust the hue of the colorant and increase the density. However, in the curable composition to which the conventional pigment dispersion system is applied, there are problems such as color unevenness due to the pigment being relatively coarse particles, and it is difficult to further improve the resolution. It was not suitable for applications requiring a fine pattern such as a solid-state imaging device. Therefore, a technique using an organic solvent-soluble dye instead of a pigment as a colorant has been proposed (for example, see Patent Document 1).
Whether a dye or a pigment is used as the colorant, it is essential to increase the content of the colorant in the color curable composition for producing a color filter. On the other hand, the color curable composition The content of the photopolymerization initiator and photopolymerizable monomer, which are components necessary for curing the resin, is limited, or the exposure wavelength light for the effect is prevented from reaching the glass support interface. It is necessary to increase the sensitivity of the curable coloring composition and increase the adhesion to the support.

Furthermore, in recent years, with the increase in substrate size, it is indispensable to manufacture large-area color filters. However, if the conventional productivity is maintained without changing the energy cost in the process, the application time, exposure time, etc. Reduction is indispensable. For this reason, it is necessary to improve the wettability of the photocurable coloring composition to the glass support for achieving a high coating speed and to increase the sensitivity to cope with a short exposure time (small exposure amount). Yes.
In addition, when the screen is enlarged, minute defects after the color filter fabrication greatly influences the yield, and as a result, the heat resistance, light resistance, etc. of the curable composition that forms the colored pattern are also higher than before. Stabilization at a high level is required.

  Conventionally, as a curable composition for producing a color filter, for example, a radiation-sensitive composition in which a binder polymer containing a carboxyl group, a polyfunctional acrylate such as pentaerythritol hexaacrylate, and a photopolymerization initiator are combined. 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole as a highly sensitive photopolymerization initiator in such a radiation-sensitive composition, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and the like have been proposed (for example, see Patent Documents 2 and 3).

  In addition, as a photopolymerization initiator applicable to the curable composition, 2,2′-bis (2-chlorophenyl) is used as a photopolymerization initiator applicable to a radiation-sensitive composition used for a printing plate or a photoresist. ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- Tetra (trialkoxyphenyl) biimidazole has been proposed (see, for example, Patent Documents 4 and 5).

However, the sensitivity of any of the above curable compositions is not yet satisfactory, and it is necessary to irradiate with high energy radiation when curing. When a colored pattern of a color filter is formed using such a curable composition, if the irradiation amount is insufficient, problems such as missing or missing patterns, a remaining film rate or a decrease in pixel strength, etc. are caused. In the coloring pattern of the obtained color filter, there arises a problem that the resolution and the adhesion between the support and the support are lowered.
As described above, even when a colorant is contained in a high concentration, a curable coloring composition that cures with high sensitivity and has a good pattern forming property, and resolution and support obtained using the same Although a color filter having a colored pattern with excellent adhesion to the surface is desired, it has not been provided yet.
JP-A-2-127602 JP-A-6-75372 JP-A-6-75373, etc. Japanese Patent Publication No. 48-38403 JP-A-62-174204

The present invention has been made in view of the above-described problems, and an object thereof is to achieve the following objects.
That is, the object of the present invention is to cure with high sensitivity, excellent developability, good pattern forming property, developability and the glass support even when the colorant is contained in a high concentration. A photocurable coloring composition that can form a colored pattern excellent in both adhesion and useful for the production of a color filter, and the adhesion to a support with high resolution obtained using the same An object of the present invention is to provide a color filter having an excellent coloring pattern.

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

<1> A heterocycle-containing photopolymerization initiator selected from compounds represented by the following general formula (I) to general formula (IV), (A) a structural unit having a poly (meth) acrylate chain, and (B) a sulfone It has a poly (meth) acrylate chain in the side chain containing a structural unit having an alkali-soluble group that is a group selected from the group consisting of an acid group, a phosphate group, a carboxylic acid group, and a phenolic hydroxyl group. A photocurable coloring composition comprising a coloring pigment dispersed with an alkali-soluble graft polymer compound and a compound having an ethylenically unsaturated group capable of addition polymerization.

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

In general formula (II), Q represents a bromine atom or a chlorine atom. P _is, -CQ _3, -NH _2, represents -NHR, -N _{(R) 2,} or -OR, wherein, Q is as defined above, R represents a phenyl or alkyl group. W represents an aromatic group, a heterocyclic group, or a monovalent group represented by the following general formula (II-A). n represents 0, 1 or 2.

  In General Formula (II-A), Z is —O— or —S—, and R has the same meaning as in General Formula (II).

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

In General Formula (III-A), R ² represents a hydrogen atom or ORc, where Rc represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R ³ represents a bromine atom, a chlorine atom, an alkyl group, an alkenyl group, an aryl group, or an alkoxy group.

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

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

<2> before Kigu raft polymer compound is further described in comprising a structural unit having (C) an aromatic group as a copolymer component, and having an aromatic group in a side chain <1> Photocurable coloring composition.
<3> The photocurability according to <1> or <2>, wherein the content of the structural unit having the (A) poly (meth) acrylate chain in the graft polymer compound is 20 mol% to 70 mol%. Coloring composition.
<4> The photocurability according to <1> or <2>, wherein the content of the structural unit having the (A) poly (meth) acrylate chain in the graft polymer compound is 20 mol% to 40 mol%. Coloring composition.
<5> In the structural unit having the (A) poly (meth) acrylate chain, the connection structure connecting the poly (meth) acrylate chain and the main chain has one or more sulfur atoms (S). <4> The photocurable coloring composition according to any one of the above.
<6> The structural unit (B) having an alkali-soluble group in the graft polymer compound is at least one selected from (B-1) to (B-20) described later <1> to <5 > The photocurable coloring composition of any one of>.
On a <7> glass support, a layered product comprising a photocurable colored layer comprising the photocurable coloring composition according to any one of <1> to <6> is subjected to pattern exposure and photocured. A color filter comprising a colored pattern obtained by curing an exposed area of a colored layer and developing an unexposed area.

The photocurable coloring composition of the present invention (hereinafter appropriately referred to as a curable composition) has a specific photopolymerization initiator having a heterocycle in the molecule and a poly (meth) acrylate chain in the side chain. , A color pigment dispersed with an alkali-soluble graft polymer containing 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, and an ethylenically unsaturated compound capable of addition polymerization Contains compounds with groups.
Although the mechanism of action of the present invention is not clear, the photopolymerization initiator in the photocurable coloring composition is derived from its heterocyclic structure, and the poly (meth) acrylate is present in the side chain used as a pigment dispersant. Due to the side chain structure of the graft polymer compound having a chain, it forms a good interaction with silanol groups and metal ions present on the glass surface as the base material, thus improving pattern formation after exposure and development. Further, it is considered that the adhesion durability of the colored pattern in the color filter is improved. In addition, the alkali-soluble graft polymer compound having a poly (meth) acrylate chain in the side chain is excellent in pigment dispersibility, is uniformly dispersed without aggregation of the pigment, and the polymer compound side is disposed around the pigment. Since the chain structure is located radially and the affinity between the poly (meth) acrylate chain and the specific initiator having a heterocyclic structure is good, the pigment using this pigment dispersant is accompanied by a photopolymerization initiator. It is thought that it is uniformly dispersed in the system. Usually, photopolymerization initiators having a heterocyclic structure in the molecule are prone to self-aggregation, but specific initiators with high sensitivity are also uniformly dispersed by interaction with pigments using specific dispersants. Therefore, by photocuring uniformly by exposure, high sensitivity and an effect of improving adhesion to the support can be obtained, while in the unexposed area, the developer permeability becomes uniform, so that the coating film can be quickly formed. It is considered that it dissolves and exhibits excellent developability. The photocurable coloring composition of the present invention has also been confirmed by Examples described later that both the adhesion of the cured film to the glass support and excellent developability are compatible.

According to the present invention, even when the colorant is contained at a high concentration, it is cured with high sensitivity, has excellent developability, has good pattern forming properties, and developability and adhesion to a glass support. The photocurable coloring composition which can form the coloring pattern excellent in both of these, and is useful for preparation of a color filter can be provided.
Furthermore, by using the photocurable coloring composition of the present invention, it is possible to provide a color filter having a colored pattern with high resolution and excellent adhesion to a support.

Hereinafter, the photocurable coloring composition of the present invention and a color filter obtained using the same will be described in detail.
(Photocurable coloring composition)
The photocurable coloring composition of the present invention comprises (1) a heterocyclic-containing photopolymerization initiator selected from the compounds represented by the following general formulas (I) to (IV) (hereinafter referred to as “specific initiator” as appropriate). And (2) a group selected from the group consisting of (A) a structural unit having a poly (meth) acrylate chain and (B) a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and a phenolic hydroxyl group. A color pigment dispersed with an alkali-soluble graft polymer compound having a poly (meth) acrylate chain in the side chain, containing a structural unit having a certain alkali-soluble group as a copolymerization component, and (3) addition polymerization is possible It has a photocurable colored layer containing a compound having an ethylenically unsaturated group.
Hereinafter, each component contained in the photocurable coloring composition according to the present invention will be sequentially described.

<(1) Heterocycle-containing photopolymerization initiator selected from compounds represented by the following general formula (I) to general formula (IV) >
The curable colored layer of the present invention contains a specific photopolymerization initiator containing a heterocyclic structure in the molecule.

In general formula (I), W represents an aryl group, X represents a hydrogen atom, an alkyl group or an aryl group, and Y represents a fluorine atom, a chlorine atom or a bromine atom. n represents an integer of 1 to 3.
The aryl group and alkyl group may further have a substituent. Examples of the substituent that can be introduced include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, a carboalkoxy group, a carboaryloxy group, an acyl group. Group, nitro group, dialkylamino group, sulfonyl derivative and the like.
Specific examples of the compound represented by the general formula (I) include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1 , 3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, and the like.

  In addition, as a halomethyl-s-triazine compound which is a specific initiator preferably used in the present invention, a vinyl-halomethyl-s-triazine compound represented by the following general formula (II) described in JP-B-59-1281 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compounds represented by the following general formula (III) described in JP-A No. 53-133428 and the following general formula (IV) 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound represented by the formula:

In general formula (II), Q represents a bromine atom or a chlorine atom. P _is, -CQ _3, -NH _2, represents -NHR, -N _{(R) 2,} or -OR, wherein, Q is as defined above, R represents a phenyl or alkyl group. W represents an aromatic group, a heterocyclic group, or a monovalent group represented by the following general formula (II-A). n represents 0, 1 or 2.
In the general formula (II), the aromatic group and the heterocyclic group may further have a substituent. Examples of the substituent that can be introduced include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, Examples thereof include a carboalkoxy group, a carboaryloxy group, an acyl group, a nitro group, a dialkylamino group, and a sulfonyl derivative.

In General Formula (II-A), Z is —O— or —S—, and R has the same meaning as in General Formula (II).
Specific examples of the compound represented by the general formula (II) include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- ( 1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like.

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

In General Formula (III-A), R ² represents a hydrogen atom or ORc, where Rc represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R ³ represents a bromine atom, a chlorine atom, an alkyl group, an alkenyl group, an aryl group, or an alkoxy group.
The alkyl group, alkenyl group, aryl group, and alkoxy group may further have a substituent. Examples of the substituent that can be introduced include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, a carboalkoxy group, Examples thereof include a carboaryloxy group, an acyl group, a nitro group, a dialkylamino group, and a sulfonyl derivative.
Specific examples of the specific initiator represented by the general formula (III) include 2- (naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphtho-). 1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4- Butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl- s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphtho 1-yl] -4,6-bisto Chloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) ) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphtho) -1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl- s-tria Emissions, and the like.

In general 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 general formula (IV-A) or (IV-B). R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. X and Y each independently represent a chlorine atom or a bromine atom. m and n each independently represents 0, 1 or 2.
The alkyl group, aryl group, and alkoxy group may further have a substituent. Examples of the substituent that can be introduced include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, a carboalkoxy group, and a carboaryloxy group. Group, acyl group, nitro group, dialkylamino group, sulfonyl derivative and the like.

In general formulas (IV-A) and (IV-B), R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group or an aryl group.
The alkyl group and the aryl group may further have a substituent. Examples of the substituent that can be introduced include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, a carboalkoxy group, a carboaryloxy group, Examples include an acyl group, a nitro group, a dialkylamino group, and a sulfonyl derivative.

In the general formula (IV), R ¹ and R ² may form a heterocycle composed of a nonmetallic atom together with the nitrogen atom bonded thereto, and in this case, examples of the heterocycle include those shown below. It is done.

  Specific examples of the specific initiator represented by the general formula (IV) include 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine. 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N-di (chloroethyl) ) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine, 4- (p-N-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di Trichloromethyl) -s-triazine, 4- [p-N, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (p-N-chloroethylcarbonylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [MN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine ,

4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o- Chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN- Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 (O-FLUORO -p-N-chloroethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine, and the like.

These specific initiators are characterized in that they have a radical generation site and a heterocyclic structure in the molecule, and this heterocyclic ring contains 2 nitrogen atoms from the viewpoint of interaction formation with the glass support described later. From the same viewpoint, compounds having a triazine skeleton containing three nitrogen atoms, specifically, compounds represented by general formula (II) to general formula (IV) are preferable. Further preferred. Among these, a preferred embodiment is a compound represented by the general formula (IV), and most preferred is a compound represented by the general formula (IV) wherein at least one of R ³ and R ⁴ is a halogen atom. Can be mentioned.
The heterocycle may have a substituent, and examples of the substituent that can be introduced include an alkyl group, a phenyl group, and a halogenated alkyl group. Among them, a halogenated alkyl group is preferable, and a heterocycle Particularly preferred are those in which a halogenated alkyl group is directly bonded to the triazine ring.

A specific initiator can be used individually or in combination of 2 or more types.
It is preferable that content of the specific initiator in a photocurable coloring composition is the range of 0.1-15.0 mass% in conversion of solid content, More preferably, it is 0.5-10.0 mass%. In this range, the polymerization reaction proceeds efficiently, and the strength of the obtained cured film is excellent.

(Other photopolymerization initiators)
In addition, in a curable composition, in addition to the said specific initiator, unless the effect of this invention is impaired, photoinitiators other than this can be used together.
The photopolymerization initiator that can be used here is a compound that is decomposed by light and starts and accelerates polymerization of a compound having an ethylenically unsaturated group capable of addition polymerization, which will be described later, and has absorption in a wavelength region of 300 to 500 nm. It is preferable.

Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, biimidazoles. Compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.
Among these, from the viewpoint of increasing sensitivity, at least one compound selected from the group consisting of trihalomethyltriazine compounds, biimidazole compounds, and oxime compounds is most preferable, and biimidazole compounds are most preferable.

The content of the photopolymerization initiator that can be used in combination is preferably 75% by mass or less, more preferably in the range of 0 to 50% by mass with respect to the specific initiator.
Further, the total amount of the specific initiator and the other photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, and particularly preferably 0.1 to 30% by mass with respect to the total solid content of the composition. Preferably it is 0.3-20 mass%. Within this range, good sensitivity and pattern formability can be obtained.

(Sensitizer)
A sensitizer can be used in combination with these specific initiators.
The sensitizer that can be used in the present invention is preferably a sensitizer that sensitizes a radical initiator by an electron transfer mechanism or an energy transfer mechanism.
Specific examples of the sensitizer include, for example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, Rhodamine B, rose bengal), thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines ( For example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquino) ), Squalium (eg, squalium), coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, etc. Examples include aromatic ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

Such sensitizers can be further subjected to various chemical modifications for improving the properties of the curable composition.
For example, by combining a sensitizer and an addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, the exposure film can be increased in strength or exposed. It is possible to suppress unnecessary precipitation of the specific sensitizer from the subsequent film.
In addition, partial structures having radical generating ability in the sensitizer and the photopolymerization initiator (for example, reductive decomposable sites such as alkyl halide, onium, peroxide, biimidazole, onium, biimidazole, borate, amine) , Trimethylsilylmethyl, carboxymethyl, carbonyl, imine, and other oxidatively cleavable moieties) can significantly increase the photosensitivity particularly in a low concentration of the starting system.

A sensitizer may be used individually by 1 type, or may use 2 or more types together.
The content of the sensitizer is preferably 0.1% by mass to 20% by mass and more preferably 0.2% by mass to 20% by mass in the total solid content of the curable composition.
When the concentration of the colorant in the curable composition is very high and the light transmittance of the formed color pattern (photosensitive layer) becomes extremely low, specifically, these sensitizers are used. By adding it when the light transmittance of 365 nm of the photosensitive layer when not added is 10% or less, the effect is remarkably exhibited.

<(2) An alkali-soluble group which is a group selected from the group consisting of (A) a structural unit having a poly (meth) acrylate chain and (B) a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and a phenolic hydroxyl group. A coloring pigment dispersed with an alkali-soluble graft polymer compound having a poly (meth) acrylate chain in the side chain, which contains a structural unit having a copolymer component as a copolymer component>
The colorant used in the present invention is a group selected from the group consisting of (A) a structural unit having a poly (meth) acrylate chain and (B) a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and a phenolic hydroxyl group. Coloring dispersed with an alkali-soluble graft polymer compound having a poly (meth) acrylate chain in the side chain (hereinafter referred to as a specific dispersant as appropriate), which contains a structural unit having a certain alkali-soluble group as a copolymerization component Pigment.
(Specific polymer dispersant)
First, the specific dispersant will be described. The specific dispersant is an alkali-soluble graft polymer compound characterized by having a poly (meth) acrylate chain in the side chain, and therefore (B) in the molecule together with (A) the poly (meth) acrylate chain. It is necessary to include as a copolymerization component a structural unit having an alkali-soluble group (-Acid) which is 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. Is preferably present at the end of the side chain in the structural unit having an alkali-soluble group (B) from the viewpoint of developability. Further, in a preferred embodiment, the side chain structure has (C) an aromatic group (—Ar), that is, (C) a structural unit having an aromatic group (—Ar) is included as a copolymerization component. is there.
The main chain structure of the specific dispersant (polymer dispersant) is not particularly limited, but preferred examples include polymethacrylate, polyacrylate, polymethacrylamide, polyacrylamide, polystyrene and the like, and constitutes these polymers. Likewise preferred are copolymers containing two or more selected from structural units.
Among these, more preferable examples include polymethacrylate, polystyrene, and a copolymer containing methacrylic acid and styrene as structural units.
The specific dispersant in the present invention is a group selected from the group consisting of (A) poly (meth) acrylate chain as a graft chain, (B) sulfonic acid group, phosphoric acid group, carboxylic acid group, and phenolic hydroxyl group. It is obtained by copolymerizing monomers capable of forming a structural unit each having an alkali-soluble group and, preferably, (C) an aromatic group. Next, structural units suitable for constituting the specific dispersant in the present invention will be sequentially described.

<(A) Structural unit having a poly (meth) acrylate chain>
Examples of the poly (meth) acrylate chain that the specific polymer dispersant in the present invention has as a graft chain include polymethacrylate, polyacrylate, and a copolymer containing them as a main component. As the side chain of the structural unit, the specific dispersing agent is constituted by copolymerizing structural units linked through an appropriate linking group.
Specific examples of the graft chain that can be introduced include polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polybenzyl methacrylate, polymethyl acrylate, and polyethyl acrylate. A chain structure formed by polymerization is also preferable.
The structure of the linking group that connects the graft chain and the main chain is not particularly limited, but a structure having one or more sulfur atoms (S) in the linking structure is preferable from the viewpoint of production simplicity.
Examples of the linking group include those in which an alkylene group, a phenylene group, —O—, —S—, —OC (═O) —, or the like are linked singly or in combination. The number of atoms between the main chain structure and the poly (meth) acrylate chain (the total number of atoms used only for connecting the main chain and the poly (meth) acrylate chain) is preferably from 3 to 15. . The linking group can have a hydroxyl group, an ester group, or the like as a substituent.
The chain length of the poly (meth) acrylate chain is preferably 30 to 1000 linked (meth) acrylate structural units, more preferably 50 to 500.
Specific examples [(A-1) to (A-7)] of structural units having a (A) poly (meth) acrylate chain in the side chain suitable for constituting the specific dispersant according to the present invention are shown below. , Together with the weight average molecular weight (Mw) of the structural unit, the present invention is not limited thereto.

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

<(B) Structural unit having an alkali-soluble group (-Acid) which is 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 >
It is preferable that (B) alkali-soluble group (-Acid) which the specific dispersing agent which concerns on this invention has is an acid group of pKa1-11.
The acid group, scan sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a carboxylic acid group, or include phenolic hydroxyl acid group, more preferably a phosphoric acid group, a phosphonic acid group, or carboxylic acid groups It is.
The phenolic hydroxyl acid group may be one having a substituent, examples of the substituent which can be introduced, preferably a halogen atom, a carboxylic acid group, a hydroxyl group, an amide group, an alkoxy having 1 to 10 carbon atoms Groups, 1 to 10 alkoxycarbonyl groups.
Specific examples ((B-1) to (B-20)) of structural units having (B) an alkali-soluble group at the end of the side chain, which are suitable for constituting the specific dispersant according to the present invention, are given below. However, the present invention is not limited to these.

  The structural unit is preferably contained in an amount of 5 to 80 mol%, more preferably 5 to 60 mol%, based on the specific dispersant.

<(C) Structural Unit Having Aromatic Group (—Ar)>
The specific dispersant according to the present invention preferably has (C) an aromatic group (—Ar) in addition to the above essential components. Here, (C) the aromatic group represents 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.
Preferable specific examples of the aromatic group include a furan ring group, a thiophene ring group, a pyrrole ring group, an indolenine ring group, a pyridine ring group, a quinoline ring group, a phenyl group, a naphthyl group, and an anthracene ring group. These aromatic groups may have a substituent. Examples of the substituent that can be introduced include a halogen atom, a carboxylic acid group, a hydroxyl group, an amide group, an alkyl group having 1 to 12 carbon atoms, and a carbon number. A 6-20 aryl group, a C1-C10 alkoxy group, a C1-C10 alkoxycarbonyl group, etc. are mentioned.
More preferably, a phenyl group and a naphthyl group are mentioned.
Specific examples ((C-1) to (C-16)) of structural units having an aromatic group (C) at the end of the side chain, which are suitable for constituting the specific dispersant according to the present invention, are given below. However, the present invention is not limited to these.

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

The preferred weight average molecular weight of the specific dispersant obtained by copolymerizing each structural unit having the functional group represented by (A), (B) and (C) at the side chain end as desired is 3000 to 200000. Yes, more preferably in the range of 3000-50000, most preferably 3000-10000.
Hereinafter, specific examples [(P-1) to (P-11)] of the specific dispersant used in the present invention, the structural unit constituting the specific dispersant, the polymerization molar ratio, and the weight average molecular weight (Mw) thereof. Indicated by The structural units (A-O), (B-O), and (C-O) shown below represent reference numerals of specific examples displayed in the description of the structural units having the functional groups (A) to (C). .
In addition, this invention is not limited to these exemplary compounds.

The specific polymer dispersant that can be used in the present invention can be synthesized by a conventionally known method.
Specifically, the monomer of each unit can be obtained by thermal polymerization with an azo initiator in a solvent.

(Color pigment)
There is no restriction | limiting in particular in the color pigment disperse | distributed with this specific dispersing agent, According to the objective, 1 type, or 2 or more types can be mixed and used suitably for a color filter use.
As the pigment that can be used in the photocurable coloring composition according to the present invention, various conventionally known inorganic pigments or organic pigments can be used. In addition, it is preferable to use a pigment having a particle size as small as possible considering that it is preferable that the formed photocurable colored layer has a high light transmittance regardless of whether it is an inorganic pigment or an organic pigment. In consideration of handling properties, the average particle size of the pigment is preferably 0.01 μm to 0.1 μm, and more preferably 0.01 μm to 0.05 μm. Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc And metal oxides such as antimony, and composite oxides of the above metals.

As an organic pigment, 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;
Examples thereof include carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the photosensitive polymerization component and the pigment has an influence.

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present 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 alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. When the ratio is 100: 51 or more, the dominant wavelength is shorter than the short wavelength, and the deviation from the NTSC target hue may be large. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 nm to 450 nm, and the color purity may not be improved. When the ratio exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue may increase. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Further, as the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium carbon is preferable. The mass ratio of carbon to titanium carbon is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, the dispersion stability may decrease.

The pigment in the present invention preferably has an average particle diameter r (unit: nm) satisfying 20 ≦ r ≦ 300, preferably 125 ≦ r ≦ 250, particularly preferably 30 ≦ r ≦ 200. By using such a pigment having an average particle diameter r, red and green pixels having a high contrast ratio and a high light transmittance can be obtained. The “average particle diameter” as used herein means the average particle diameter of secondary particles in which primary particles (single microcrystals) of the pigment are aggregated.
In addition, the particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of the secondary particles falling within (average particle size ± 100) nm. As mentioned above, it is desirable that it is 80 mass% or more.

(Adjustment of pigment dispersed with dispersant)
The pigment having the above average particle size and particle size distribution is obtained by mixing a commercially available pigment with the specific dispersant and solvent together with other pigments used as desired (average particle size is usually over 300 nm). The pigment mixture can be prepared by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

  The specific polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. The specific dispersant is a graft type polymer having an anchor site to the pigment surface. In order to promote the adsorption of such a polymer dispersant, it is also preferable to use a pigment derivative. As a method for such surface modification, the above pigment derivative (in which a functional group such as an amino group, an amide group, a sulfonic acid group, a carboxylic acid group, a hydroxyl group, or an ester group is introduced into the dye matrix forming the pigment) ) May be mixed at the time of pigment formation. The mixing ratio of the pigment derivative is 3 to 20% by mass, preferably 5 to 10% by mass. In the present invention, it is preferable to use a combination of a surface-modified pigment derivative and a specific dispersant.

The specific dispersant of the present invention may be used alone or in combination of two or more. Further, depending on the purpose, other known dispersants can be used in combination as long as the effects of the present invention are not impaired.
As content of the specific dispersing agent in the curable composition concerning this invention, it is preferable that it is 1-80 mass% with respect to a pigment, 5-70 mass% is more preferable, 10-60 mass% is still more. preferable. In addition, when using a pigment derivative with improved dispersant adsorptivity, the amount used is preferably in the range of 1 to 30% by weight, preferably 3 to 20% by weight with respect to the pigment derivative. More preferably, it is in the range, and particularly preferably in the range of 5 to 15% by mass.

<Other pigment dispersants that can be used in combination>
In the present invention, as a dispersant (other pigment dispersant) that can be used in combination with the specific dispersant, a polymer dispersant (for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, Modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment Derivatives and the like can be mentioned.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) "Adisper PB821, PB822" manufactured by Ajinomoto Fan Techno Co., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "Polyflow No. 50E, No. 300 (acrylic copolymer)", “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.

  When these dispersants are used in combination, they may be used alone or in combination of two or more. 75 mass% or less is preferable with respect to the specific dispersant, and, as for the addition amount with respect to the said specific dispersant of another polymer dispersing agent, it is more preferable that it is the range of 0-50 mass%.

In the present invention, the content of the color pigment dispersed in (2) the specific dispersant in the photocurable color composition of the present invention is the sum of the content of the color pigment and the specific dispersant from the viewpoint of curing sensitivity and color density. As, it is preferable that it is 30 to 90 mass% with respect to the total solid which comprises a curable composition, It is more preferable that it is 40 to 85 mass%, 50 to 80 mass% More preferably, it is% or less.
When there are too few coloring pigments, when a color filter is produced with the curable composition of the present invention, there is a tendency that an appropriate chromaticity cannot be obtained. On the other hand, if the amount is too large, the photocuring does not proceed sufficiently and the strength as a film is lowered, or the development latitude during alkali development tends to be narrow, but the specific sensitizer according to the present invention has a light absorption efficiency. Since it is high, even if it is a case where a coloring agent is contained in a high concentration in a curable composition, the sensitivity improvement effect is exhibited notably.

<(3) Compound having an ethylenically unsaturated group capable of addition polymerization>
A compound having an addition-polymerizable ethylenically unsaturated group that can be used in the present invention (hereinafter appropriately referred to as a polymerizable compound) is an addition-polymerizable compound having at least one ethylenically unsaturated double bond. , 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 field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (A)
(In the general formula (A), R ⁴ and R ⁵ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photocurable coloring composition having an excellent photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the curable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
In addition, the compatibility of the addition polymerization compound with other components (for example, photopolymerization initiators, colorants (pigments, dyes, etc.), binder polymers, etc.) contained in the curable composition is also improved. The selection / use method is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion with a substrate or the like.

  The photocurable coloring composition of the present invention has (1) a specific initiator, (2) a colored pigment dispersed by a specific dispersant, and (3) an ethylenically unsaturated group capable of addition polymerization. In addition to the compound and a sensitizer used as desired, an optional component described in detail below may be further contained as necessary. Hereinafter, optional components that can be used in the present invention will be described.

<Binder polymer>
In the photocurable coloring composition of the present invention, a binder polymer can be used in combination as necessary for the purpose of improving the properties of the formed film.
It is preferable to use a linear organic polymer as the binder. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  When an alkali-soluble resin is used as a copolymer, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (13).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(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- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(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) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups described in No. 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the binder polymer that can be used in the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more. More preferably, it is the range of 2,000-250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, 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. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used in synthesizing the binder polymer that can be used in the present invention include known compounds such as an azo initiator and a peroxide initiator.
When such other binder polymer is used, the content is preferably 0 to 50% by mass, and more preferably 0 to 30% by mass.

<Co-sensitizer>
The photocurable coloring composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and initiator to actinic radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is in the range of 0.1 to 30% by mass with respect to the mass of the total solid content of the curable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. Preferably, the range of 1-25 mass% is more preferable, and the range of 0.5-20 mass% is still more preferable.

<Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor may be added in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the curable composition. desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Adhesion improver>
In the present invention, it is preferable to add an adhesion improver in order to improve adhesion to a hard surface (substrate) as a base material. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is most preferable.
0.5-30 mass% is preferable in the total solid of a curable composition, and, as for the addition amount of a contact | adherence improving agent, 0.7-20 mass% is more preferable.

<Other additives>
Furthermore, in the present invention, a known additive such as an inorganic filler, a plasticizer, or a sensitizer capable of improving the ink inking property on the surface of the photosensitive layer may be added to improve the physical properties of the cured film. Good.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

<Diluent>
The photocurable coloring composition of the present invention may be used by dissolving it in various organic solvents when it is applied on a support in the production of a color filter.
The organic solvent used here is acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 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 sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like.
These solvents can be used alone or in combination. The concentration of the solid content in the organic solvent is preferably 2 to 60% by mass.

[Color filter]
Next, the color filter of the present invention will be described.
In the color filter of the present invention, a photocurable colored layer made of a photocurable coloring composition is formed on the surface of a glass support, and pattern exposure is performed by means such as through a mask. It develops and forms by forming a coloring pattern in the glass support surface.
The photocurable coloring layer may be formed by applying a photocurable coloring composition to a glass support and drying it, or by laminating a sheet prepared in advance with the photocurable coloring composition. You may form in close contact on a support body.

<Glass support>
As the support that can be used in the present invention, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, and imaging elements and the like used for liquid crystal display elements and the like are used. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

As a coating method of the curable composition according to the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied. .
The curable composition applied 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.

  As a coating film thickness after drying of a curable composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is further more preferable.

  The photocurable coloring composition according to the present invention is cured with high sensitivity by exposure, is excellent in developability of an unexposed portion after exposure, and is high on the surface of a glass support to which the photocurable coloring composition is applied. Shows adhesion.

The color filter of the present invention is characterized by having a colored pattern formed as described above on a glass support.
Specifically, the photocurable colored layer made of the photocurable coloring composition of the present invention is subjected to pattern exposure through a predetermined mask pattern or by scanning exposure, and a coating film portion irradiated with light. By curing only this and developing the uncured area with a developing solution, a patterned film composed of pixels of each color (3 colors or 4 colors) is formed, and the color filter of the present invention is produced.

<Exposure process>
In the exposure step, the photocurable colored layer is subjected to pattern exposure, for example, by exposure through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, particularly ultraviolet rays such as g-line and i-line are preferably used, and a high-pressure mercury lamp is more preferably used. Exposure is preferably ^{5mJ / cm 2 ~1500mJ / cm 2} , more preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~800mJ / cm 2 being most preferred.

<Development process>
Subsequent to the exposure step, an alkali development treatment is performed to elute the light non-irradiated portion in the exposure step into an aqueous alkali solution. Thereby, only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

  Examples of the alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0. ] -7- An alkaline aqueous solution obtained by diluting an organic alkaline compound such as undecene with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  In the production method of the present invention, after performing the above-described curable composition layer forming step, exposure step, and development step, if necessary, the formed colored pattern is cured by heating and / or exposure. A process may be included.

  Thereafter, a photocurable colored layer of another hue is formed, and a color filter having a desired hue is produced by repeating the exposure process and the development process (and, if necessary, the curing process) for the desired number of hues. .

  Since the color filter of the present invention is produced using a laminate having a layer made of a photocurable coloring composition capable of forming an interaction with glass on a glass support, it is excellent in pattern formability and formed. The colored pattern shows high adhesion to the support substrate, and in the unexposed area, the film structure made of the curable composition has excellent uniformity and suppresses the developer permeability. In addition, there is no concern about the occurrence of agglomerates of photopolymerization initiators, and the penetration of the developer is uniform and promptly progresses to show high developability. Therefore, the exposure sensitivity is excellent and the adhesion between the exposed portion and the substrate is good. It is possible to form a high-resolution pattern that has no residual film. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.
[Example 1]
Here, an example in which a photocurable coloring composition α-1 containing a colorant (pigment) is prepared and a color filter for use in a liquid crystal display element is produced using the curable composition α-1 will be described. .

[1. Preparation of photocurable coloring composition α-1]
1-1. Preparation of pigment dispersion (Q1): Green pigment I. Pigment Green 36 and C.I. I. 40 parts by mass of a 30/70 (mass ratio) mixture with CI Pigment Yellow 219, and 7 parts by mass of BYK2001 (Disperbyk: manufactured by Big Chemie (BYK), solid content concentration: 45.1% by mass) as a dispersant. 51 parts by mass), a mixed liquid consisting of 3 parts by mass of the specific dispersant [Exemplary Compound (P-1)] according to the present invention and 150 parts by mass of ethyl 3-ethoxypropionate as a solvent was mixed and dispersed by a bead mill for 20 hours. Thus, a pigment dispersion (Q1) was prepared.
With respect to the obtained pigment dispersion (Q1), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 170 nm.

1-2. Preparation of Photocurable Coloring Composition α-1 (Coating Liquid) Components of the following composition α-1 were mixed and dissolved to prepare a curable composition A-1.
<Composition α-1>
Pigment dispersion (Q1) 600 parts by mass Alkali-soluble resin (benzyl methacrylate / methacrylic acid copolymer, molar ratio: 70/30,
Mw: 10000) 190 parts by mass Dipentaerythritol hexaacrylate [polymerizable compound] 60 parts by mass Compound 1 (the following structure) [specific photopolymerization initiator] 60 parts by mass Michler ketone [sensitizer] 40 parts by mass Sensitizer: 40 parts by mass of 2-mercaptobenzothiazole-Surfactant: (trade name: Tetranic 150R1, BASF) 1 part by mass-Solvent: 1000 parts by mass of propylene glycol monomethyl ether acetate-γ-methacryloxypropyltriethoxy Silane 10 parts by mass

[2. (Production of color filter)
2-1. Formation of the curable composition layer The photocurable coloring composition α-1 containing the pigment obtained as described above was applied as a resist solution to a 550 mm × 650 mm glass substrate by slit coating under the following conditions, and then left as it was for 10 minutes. Then, vacuum drying and prebaking (100 ° C., 80 seconds) were performed to form a photocurable colored layer.

(Slit application conditions)
Gap at the opening at the tip of the coating head: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C

2-2. Exposure and development Thereafter, the surface of the photocurable colored layer is exposed in a pattern through a mask using a 2.5 kW ultra-high pressure mercury lamp. After the exposure, the entire surface of the coating film is an organic developer (trade name: CD The film was covered with a 10% aqueous solution of Fuji Film Arch Co., Ltd. and allowed to stand for 60 seconds.

2-3. Heat treatment After standing still, pure water was sprayed in a shower to wash away the developer, and the coating film subjected to the photocuring treatment and development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). As a result, a colored pattern was formed on the glass substrate to obtain a color filter.

[3. (Performance evaluation)
Exposure pattern formability in the photocurable coloring layer of the color filter laminate formed on the glass substrate using the photocurable coloring composition α-1 (coating liquid) prepared above, and further coloring in the color filter The substrate adhesion of the pattern was evaluated as follows. 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 coated on a glass substrate and dried to a film thickness of 1.0 μm. The spin coating conditions were 300 rpm for 5 seconds, 800 rpm for 20 seconds, and the drying conditions were 100 ° C. for 80 seconds. Next, using a test photomask having a line width of 10 μm, for a colored layer using the pigment dispersions Q1 to Q3, 50 mJ / cm ² , and for a colored layer using the pigment dispersion Q4, It exposed with the exposure amount of 200 mJ / cm < ² >. Next, development was performed using a 60% CD-2000 (produced by Fuji Film Electronics Materials) at 25 ° C. until the remaining film in the unexposed area disappeared completely. This was done by checking the remaining condition in the dark field of an optical microscope). Then, after rinsing with running water for 20 seconds, spray drying was performed to complete patterning. The film thickness after development of the area irradiated with light in the exposure process was measured, and the film reduction with respect to 100% of the film thickness before exposure was evaluated according to the following criteria. The smaller the film loss, the higher the exposure sensitivity and the shorter the development time required to reach a state where there is no residual film (excellent developability), indicating that the pattern forming properties are better due to these compatibility.
○: 95% or more Δ: less than 95 to 85% or more ×: less than 85%

3-2. Substrate adhesion The substrate adhesion was evaluated by confirming the coloring pattern in the color filter after post-baking by an ordinary method using an optical microscope and SEM photograph observation. Details of the evaluation method are as follows.

<Board adhesion>
As an evaluation of substrate adhesion, it was observed whether a pattern defect or a gap with the substrate occurred. These evaluation items were evaluated based on the following criteria. If it is (circle) and (triangle | delta), it is a level which is satisfactory practically.
○: No pattern defect and no gap with the substrate were observed.
(Triangle | delta): Although a pattern defect | defect is not observed and there exists an area | region where a clearance gap is seen with a board | substrate, it was a level which is satisfactory practically.
X: A pattern defect was clearly observed, and it was a practically unusable level.

[Examples 2 to 7, 9 to 16]
In Example 1, when preparing the specific initiator (compound 1), the pigment dispersion (Q1), and the pigment dispersion in the composition α-1 used for the preparation of the photocurable coloring composition α-1. In the same manner as in Example 1 except that at least one of the specific dispersants used was changed to that shown in Table 1 below, the photocurable coloring compositions α-2 to α-7, α- 9- α-12 was prepared. Using these, color filters having a colored pattern were obtained in the same manner as in Example 1. Furthermore, the same evaluation as in Example 1 was performed. The results are shown in Table 1.
Moreover, the structure of the specific initiator (compound 2-compound 4 ) used here is shown below. The specific dispersant is selected from the exemplified compounds [(P-2) to (P-11)].

Preparation of pigment dispersion (Q2): red I. Pigment red 254 and C.I. I. 40 parts by mass of an 80/20 (mass ratio) mixture with CI Pigment Red 177, and 10 parts by mass (about 4% by solids conversion) of BYK2001 (Disperbyk: manufactured by Big Chemie (BYK), solid concentration 45.1% by mass) as a dispersant. 51 parts by mass), a mixed liquid consisting of 150 parts by mass of ethyl 3-ethoxypropionate as a solvent of 3 parts by mass of the specific dispersant (P-1) according to the present invention is mixed and dispersed for 20 hours by a bead mill, and a pigment dispersion (P2) was prepared.
With respect to the obtained pigment dispersion (Q2), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 150 nm.

Preparation of pigment dispersion (Q3): Blue I. Pigment blue 15: 6 and C.I. I. 35 parts by weight of a 90/10 (mass ratio) mixture with Pigment Violet 23, and 10 parts by weight (solid content conversion: about 4.4% by solid mass concentration 45.1% by mass, manufactured by BYK2001 (Disperbyk: BYK)) as a dispersant. 51 parts by mass), 3 parts by mass of the specific dispersant (P-1) according to the present invention and 150 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed and dispersed by a bead mill for 20 hours to disperse the pigment. A liquid (Q3) was prepared.
With respect to the obtained pigment dispersion (Q3), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 170 nm.

Preparation of Pigment Dispersion (Q4): Black As a pigment, Legal (carbon black manufactured by Cabot, particle size 31 nm, pH 9, DBP oil supply amount 42 ml / 100 parts, blackness My value 235) 27 parts by mass, benzyl methacrylate / methacrylic acid A mixture comprising 6 parts by mass of an acid copolymer (copolymerization ratio 70/30 molar ratio, weight average molecular weight 30000), 2 parts by mass of the specific dispersant (P-1) according to the present invention, and 65 parts by mass of propylene glycol monomethyl ether acetate. The liquid was mixed and dispersed by a bead mill for 20 hours to prepare a pigment dispersion (Q4).
With respect to the obtained pigment dispersion (Q4), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 100 nm.

[Comparative Examples 1-11, 13-16 ]
When forming a photocurable coloring layer using the photocurable coloring composition α-1 prepared in Example 1, the specific photopolymerization initiator having the composition α-1 used for the preparation, a pigment dispersion (Q1) And at least one of the specific dispersants used in preparing the pigment dispersion is changed to other compounds shown in Table 1 or comparative compounds, compositions β-1 to β-11, β-13 to β-16. Other than that, in the same manner as in Example 1, comparative photocurable coloring compositions β-1 to β-11, β-13 to β-16 were prepared, and a colored pattern was formed using them. A color filter was obtained. Furthermore, the same evaluation as in Example 1 was performed. The results are shown in Table 1.
The structures of the comparative photopolymerization initiators [Comparative Compound 1 to Comparative Compound 4] and Comparative Polymer Compounds [(Y-1) to (Y-6)] used in Comparative Examples are shown below. The structure of the comparative polymer compound is indicated by the structural unit constituting the polymer compound, the polymerization molar ratio, and its weight average molecular weight (Mw). The structural units (A-O), (B-O), and (C-O) shown below represent symbols of specific examples of the structural units displayed in the description of the functional groups (A) to (C).

From the results of Table 1, the color filters of Examples 1 to 7 and 9 to 12 produced using a photocurable coloring composition containing a specific initiator and a specific polymer compound are excellent in pattern formability, Substrate adhesion of the formed colored pattern is good, and by using the photocurable coloring composition of the present invention, the exposure sensitivity is high, the developability and the pattern formability are excellent, and the substrate of the formed colored pattern It can be seen that a color filter having excellent adhesion can be obtained.
On the other hand, Comparative Examples 5 to 8 using comparative compounds outside the scope of the present invention as photopolymerization initiators, or Comparative Examples 1 to 4 using only the comparative dispersing agents outside the scope of the present invention for adjusting the pigment dispersion. 9 to 11 and 13 to 16 are inferior in pattern formation and adhesion to the substrate as compared with Examples, and contain both a specific initiator and a color pigment dispersed by a specific dispersant. It turns out that the outstanding effect of this invention is acquired for the first time by using the photocurable coloring composition of this invention.

Claims (7)

A heterocycle-containing photopolymerization initiator selected from compounds represented by the following general formula (I) to general formula (IV), (A) a structural unit having a poly (meth) acrylate chain, and (B) a sulfonic acid group, An alkali-soluble component having a poly (meth) acrylate chain in the side chain, which includes, as a copolymerization component, a structural unit having an alkali-soluble group which is a group selected from the group consisting of a phosphate group, a carboxylic acid group, and a phenolic hydroxyl group . A photocurable coloring composition comprising a color pigment dispersed with a graft polymer compound and a compound having an ethylenically unsaturated group capable of addition polymerization.

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

In general formula (II), Q represents a bromine atom or a chlorine atom. P _is, -CQ _3, -NH _2, represents -NHR, -N _{(R) 2,} or -OR, wherein, Q is as defined above, R represents a phenyl or alkyl group. W represents an aromatic group, a heterocyclic group, or a monovalent group represented by the following general formula (II-A). n represents 0, 1 or 2.

In General Formula (II-A), Z is —O— or —S—, and R has the same meaning as in General Formula (II).

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

In General Formula (III-A), R ² represents a hydrogen atom or ORc, where Rc represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. R ³ represents a bromine atom, a chlorine atom, an alkyl group, an alkenyl group, an aryl group, or an alkoxy group.

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

In general formulas (IV-A) and (IV-B), R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group or an aryl group.   2. The photocurable coloring composition according to claim 1, wherein the graft polymer compound further includes (C) a structural unit having an aromatic group as a copolymerization component and has an aromatic group in a side chain. object.   The photocurable coloring composition according to claim 1 or 2, wherein the content of the structural unit having the (A) poly (meth) acrylate chain in the graft polymer compound is 20 mol% to 70 mol%. .   The photocurable coloring composition according to claim 1 or 2, wherein a content of the structural unit (A) having a poly (meth) acrylate chain in the graft polymer compound is 20 mol% to 40 mol%. .   The structural unit having the (A) poly (meth) acrylate chain has at least one sulfur atom (S) in the connecting structure connecting the poly (meth) acrylate chain and the main chain. The photocurable coloring composition of any one of these. The structural unit having an alkali-soluble group (B) in the graft polymer compound is at least one selected from the following (B-1) to (B-20). Item 1. The photocurable coloring composition according to item 1.
  The laminated body which has a photocurable colored layer which consists of a photocurable coloring composition of any one of Claims 1-6 on a glass support body is subjected to pattern exposure, pattern exposure is carried out, and it is photocurable. A color filter comprising a colored pattern obtained by curing an exposed area of a colored layer and developing an unexposed area.