JP4969189B2 - Curable composition for forming color filter for solid-state image sensor, color filter for solid-state image sensor, and method for producing the same - Google Patents

Description

The present invention is a solid-state imaging device (CCD, CMOS, etc.) suitable curable composition for producing a color filter used in, and a color filter formed by the curable composition, and a method for producing the same.

The color filter is an essential component for liquid crystal displays and solid-state image sensors.
Liquid crystal displays are more compact than CRTs that are widely used as display devices and have the same or better performance, so CRTs are being replaced as television screens, personal computer screens, and other display devices. Also, in recent years, the development trend of liquid crystal displays is moving from conventional monitor applications where the screen has a relatively small area to TV applications where a large screen and high image quality are required.

As for color filters for liquid crystal displays (LCDs), the substrate size is increasing due to the production of large TVs. A curable composition for use in color filter production using such a large substrate is desired to be cured with low energy in order to improve productivity.
In addition, liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor use. That is, improvement in contrast and color purity.

With respect to the curable composition for use in color filter production, a finer particle size is required as the particle size of the colorant (organic pigment or the like) used for improving contrast (see, for example, Patent Document 1).
However, in order to improve dispersion stability when pigments with small particle sizes are incorporated into the curable composition, if the pigment adsorbability of the dispersant is improved, the dispersant bridges the pigment and promotes pigment aggregation. However, the stability over time such as dispersion stability is lowered, and the developability when a pattern is formed using the curable composition tends to be lowered.
Moreover, since the surface area increases when the pigment is refined, the use of the refined pigment tends to increase the amount of dispersant added for dispersing the pigment in the curable composition.
Furthermore, when the acid value of the resin added at the time of dispersion is improved in order to ensure developability, there is a tendency to promote pigment aggregation due to interactions such as hydrogen bonding between acid groups.
In order to obtain developability by adding a resin to the curable composition after dispersion of the pigment, it is necessary to add a large amount of the resin.

  In addition, a curable composition for use in color filter production is required to have a higher colorant (organic pigment) content in the solid content in order to improve color purity. However, when the colorant is contained at a high concentration in the curable composition, the content of the photopolymerization initiator and the photopolymerizable monomer in the curable composition is decreased. While curability at low energy is desired, there is a problem that it is difficult to obtain curability at the exposed portion.

On the other hand, curing with low energy is also desired for curable compositions for use in the production of color filters for solid-state imaging devices. In addition, for color filters for solid-state imaging devices, the coloring pattern is becoming thinner, and accordingly, the pigment concentration in the composition is improved.
Furthermore, in the pigment-based color filter, the content of the pigment dispersant in the curable composition increases as the pigment is refined to reduce color unevenness due to the pigment being relatively coarse particles. There is a tendency. The increase in the content of the pigment dispersant in the curable composition is similar to the curable composition for LCD production, and the stability over time such as dispersion stability is reduced, or pattern formation is performed using the curable composition. When developing, there is a tendency that developability tends to decrease, and it is difficult to obtain curability.

  In order to cope with problems such as color unevenness in the formed coloring pattern, a technique using an organic solvent-soluble dye instead of a pigment as a colorant has been proposed (for example, see Patent Document 2). However, in dye-based color filters, with the increase in dye concentration, problems such as a polymerization-inhibiting effect derived from dyes and a decrease in stability over time, such as precipitation of dyes, have become prominent.

  As described above, in the case of a curable composition for use in manufacturing a color filter, in either case for a liquid crystal display or a solid-state imaging device, photopolymerization is an essential component for curing the curable composition. In addition to limiting the content of the colorant and the photopolymerizable monomer, the concentration of the colorant is high, so the sensitivity is low and sufficient curing cannot be obtained, the adhesion to the substrate is insufficient, unexposed The development rate is reduced and the generation of residues is observed. Desirable pattern formation is extremely difficult. Dispersion stability and developability are poor when the colorant is a pigment. Precipitation of dye when the colorant is a dye. Various problems such as low temporal stability have occurred.

In order to improve the substrate adhesion of the colored layer in the color filter, techniques for introducing a silane coupling agent into the colored curable composition used for forming the colored layer have been proposed (see, for example, Patent Documents 3 and 4). ). However, in the colored layer formed with these curable compositions, satisfactory substrate adhesion has not yet been obtained, and the adhesion between the colored layer and the substrate in the unexposed area has increased. There has also been a problem that the residue tends to remain in the exposed area. In addition, the introduction of a silane coupling agent alone cannot solve the problems such as a decrease in the developing speed of unexposed areas, a decrease in sensitivity, a decrease in dispersion stability when a pigment is used as a colorant, or the like. there were. Among them, as a measure for improving stability over time, such as improvement in developability and dispersion stability, introduction of a monomer having an alcoholic hydroxyl group into an organic pigment dispersion for color filters has been proposed (for example, patents). Reference 5), a sufficient effect is not obtained.
JP 2006-30541 A JP-A-2-127602 (Patent No. 2874091) (Japanese Patent Laid-Open No. 11-38226) JP-A-8-259876

The object of the present invention made in consideration of the problems in the prior art is that even when a colorant is contained in a high concentration, stability over time such as dispersion stability is good, and it is cured with high sensitivity by exposure. When applied to pattern formation on the surface of a hard substrate, a curable composition having a good pattern forming property that has high adhesion to the surface of a hard material in a cured region and excellent removability in an uncured region. It is to provide.
In addition, another object of the present invention is to provide a color filter having a coloring pattern that is formed using the curable composition of the present invention and has excellent resolving power and adhesion to the support, and high production of the color filter. It is in providing the manufacturing method which can be manufactured by property.

Means for solving the above problems are as follows.
<1> (A) A compound represented by the following general formula (I) having a plurality of ethylenically unsaturated double bonds and a secondary hydroxyl group, which is one or more selected from the following group (hereinafter referred to as “ A curable composition for forming a color filter for use in a solid-state imaging device, comprising: (B) a photopolymerization initiator that is an oxime-based compound; and (C) a colorant .
Et Chi glycol diglycidyl ether dimethacrylate propylene glycol diglycidyl ether diacrylate 1,6-hexanediol diglycidyl ether diacrylate of bisphenol A diglycidyl ether diacrylate of bisphenol A epoxy diacrylate oligomer <2> Further, (D) the (A ) Containing a compound having an ethylenically unsaturated double bond other than the compound represented by formula (I) having a plurality of ethylenically unsaturated double bonds and secondary hydroxyl groups <1 > A curable composition for forming a color filter for use in a solid-state imaging device.
< 3 > The curable composition for forming a color filter for use in a solid-state imaging device according to <1> or <2> , further comprising (E) a sensitizer.
< 4 > The content of the colorant (C) is 30% by mass or more and 85% by mass or less in the total solid content contained in the curable composition. <1> to < 3 > A curable composition for forming a color filter for use in any one of the solid-state imaging devices.
< 5 > The curable composition for forming a color filter for use in a solid-state imaging device according to any one of <1> to < 4 >, wherein the colorant (C) is a pigment.
< 6 > The curable composition for forming a color filter for use in a solid-state imaging device according to any one of <1> to < 4 >, wherein the colorant (C) is a dye.
< 7 > A color filter for use in a solid-state imaging device, having a colored pattern formed of the curable composition according to any one of <1> to < 6 > on a support.
< 8 > A colored layer forming step of applying a curable composition according to any one of <1> to < 6 > on a support to form a colored layer comprising the curable composition; A method for producing a color filter for use in a solid-state imaging device, comprising: an exposure step of exposing a colored layer through a mask; and a developing step of developing the colored layer after exposure to form a colored pattern.

Although the effect | action of the curable composition of this invention is not clear, it estimates as follows.
The curable composition of the present invention contains (A) a compound (specific compound) having a plurality of ethylenically unsaturated double bonds and secondary hydroxyl groups as an essential component, and the specific compound is contained in the curable composition. High dispersion stability of the colorant by suppressing the aggregation of the colorant by intervening between the dispersed colorants (pigments, etc.) and suppressing the interaction between the colorants or between the dispersants covering the colorant Is considered to be demonstrated.
In addition, the specific compound contained in the curable composition of the present invention is due to the fact that the polarity is improved due to the secondary hydroxyl group and the hydrogen atoms adjacent to the secondary hydroxyl group are easily extracted. It is considered that the inhibition of polymerization by oxygen in the exposed area is suppressed, and the high sensitivity appears remarkably.
In addition, the specific compound improves the gel curing efficiency for the exposed part, while improving the removability (developability) by suppressing the aggregation of the pigment and the non-exposed part due to the secondary hydroxyl group, When the curable composition of the present invention is applied to pattern formation on the surface of a hard material, it is considered that excellent pattern formability is exhibited. Further, in the pattern formation using the curable composition, when a compound having a primary hydroxyl group is used, since the mobility of the hydroxyl group in the compound is high, development is performed not only on the unexposed area but also on the exposed area. Although it is susceptible to the influence of liquid etc., there is a concern about the decrease in film properties. However, the specific compound in the present invention has a secondary hydroxyl group, so that it exhibits excellent removability in the unexposed area but develops in the exposed area. The influence of liquid etc. can be suppressed. Therefore, in pattern formation using the curable composition of the present invention, it is considered that excellent curability in the exposed area and excellent removability in the unexposed area are compatible.
Furthermore, when the curable composition of the present invention is applied to the surface of a hard material having a polar group, the secondary hydroxyl group of the specific compound forms an interaction with the polar group on the surface of the hard material. From this, it is considered that the adhesion between the exposed portion and the hard material surface is also improved.

According to the present invention, even when the colorant is contained at a high concentration, the stability over time such as dispersion stability is good, and it is cured with high sensitivity by exposure and applied to pattern formation on the surface of a hard substrate. In the cured region, it is possible to provide a curable composition that can form a good pattern with high adhesion to the hard material surface of the cured portion in the cured region and excellent removability of the uncured portion in the uncured region. .
Furthermore, according to the present invention, a color filter that is formed using the curable composition of the present invention and has a colored pattern that is excellent in resolving power and adhesion between the support and the color filter with high productivity. A manufacturing method that can be manufactured can be provided.

  Hereinafter, the curable composition of the present invention, a color filter using the curable composition, and a production method thereof will be described in detail.

[Curable composition]
The curable composition of the present invention, (A) is at least one selected from the following group, the plurality of ethylenically unsaturated double bonds and that of compound having a the secondary hydroxyl group, (B) the oxime It is for forming a color filter for use in a solid-state imaging device containing a photopolymerization initiator which is a system compound and (C) a colorant.
Ethylene glycol diglycidyl ether dimethacrylate
Propylene glycol diglycidyl ether diacrylate
1,6-hexanediol diglycidyl ether diacrylate
Bisphenol A diglycidyl ether diacrylate
Bisphenol A epoxy diacrylate oligomer

  Hereinafter, each component contained in the curable composition of this invention is demonstrated one by one.

<(A) a plurality of ethylenically unsaturated double bonds and that of compound having a the secondary hydroxyl group>
The curable composition of the present invention, at least one selected from the following group, containing a plurality of ethylenically unsaturated double bonds and that of compound having a the secondary hydroxyl group of the (specific compound).
Ethylene glycol diglycidyl ether dimethacrylate
Propylene glycol diglycidyl ether diacrylate
1,6-hexanediol diglycidyl ether diacrylate
Bisphenol A diglycidyl ether diacrylate
Bisphenol A epoxy diacrylate oligomer
The number of ethylenically unsaturated double bonds in the particular compound, from the viewpoint of removability of sensitivity and unexposed portions (developing property), preferably from 2 to 100, more preferably from 2 to 50, 2 to 10 More preferably, 2 to 5 is most preferable. In addition, the number of secondary hydroxyl groups in the specific compound is preferably 1 to 100, more preferably 1 to 50, and still more preferably 1 to 10 from the viewpoints of sensitivity and removability (developability) of unexposed areas. 1-3 are most preferred.
Here, the secondary hydroxyl group means “a hydroxyl group linked to a carbon atom and having one hydrogen atom directly linked to the carbon atom”.

  The specific compound is preferably an epoxy acrylate having a plurality of (meth) acrylate groups. Here, in the present invention, (meth) acrylate represents acrylate or methacrylate.

Among the epoxy acrylate having a plurality of (meth) acrylate group is a specific compound is a compound represented by the following general formula (I).

  In general formula (I), X represents an n-valent organic group, R represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more. However, when n is 1, the organic group represented by X has at least one ethylenically unsaturated double bond in its structure.

  In general formula (I), X is not particularly limited as long as it is an n-valent organic group. Among them, the structure includes an oxygen atom, a nitrogen atom, a sulfur atom, a hydrocarbon ring structure having 3 to 20 carbon atoms, hetero 1 to C carbon atoms which may have a partial structure selected from the group consisting of a ring, an ester bond, a sulfonate bond, a phosphate bond, a urethane bond, a thiourethane bond, an amide bond, a urea bond and a thiourea bond Preferably, it has a partial structure selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a hydrocarbon ring structure having 3 to 10 carbon atoms. A linear or branched alkyl group having 1 to 40 carbon atoms which may be more preferable, and a linear or branched alkyl group having 1 to 40 carbon atoms which may have an oxygen atom in the structure thereof To be Preferred.

In the general formula (I), the organic group represented by X may further have a substituent when it can be introduced. Examples of the substituent that can be introduced into X include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a chain, branched or cyclic alkenyl group having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. Alkynyl group, C6-C20 aryl group, C1-C20 acyloxy group, C2-C20 alkoxycarbonyloxy group, C7-C20 aryloxycarbonyloxy group, C1-C20 Carbamoyloxy group, carbon number 1-20 carbonamido group, carbon number 1-20 sulfonamido group, carbon number 1-20 carbamoyl group, carbon number 0-20 sulfamoyl group, carbon number 1-20 alkoxy Group, aryloxy group having 6 to 20 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, N-acyl having 1 to 20 carbon atoms Rufamoyl group, N-sulfamoylcarbamoyl group having 1 to 20 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms, arylsulfonyl group having 6 to 20 carbon atoms, alkoxycarbonylamino group having 2 to 20 carbon atoms, carbon number 7-20 aryloxycarbonylamino group, C0-20 amino group, C1-20 imino group, C3-20 ammonio group, carboxyl group, sulfo group, hydroxy group, mercapto group, carbon C1-C20 alkylsulfinyl group, C6-C20 arylsulfinyl group, C1-C20 alkylthio group, C6-C20 arylthio group, C1-C20 ureido group, C2-C2 20 heterocyclic groups, an acyl group having 1 to 20 carbon atoms, a sulfamoylamino group having 0 to 2 carbon atoms, a silyl group having 2 to 20 carbon atoms, Isocyanate group, an isocyanide group, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom), a cyano group, a nitro group, an onium group, and a group having an ethylenically unsaturated double bond. Among them, a chain, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable from the viewpoint of availability of raw materials, and from the viewpoint of sensitivity and developability, a carboxyl group, a sulfo group, a hydroxy group, a mercapto group, A group having an ethylenically unsaturated bond is preferred. Moreover, a carboxyl group and a hydroxy group are most preferable from the viewpoint of balance between sensitivity and developability.
However, when n in the general formula (I) is 1, the organic group represented by X has at least one ethylenically unsaturated double bond in its structure.

The ethylenically unsaturated double bond is introduced by an esterification reaction or an amidation reaction with an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.). An ethylenically unsaturated double bond is mentioned.
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 Examples also include an ethylenically unsaturated double bond introduced by a dehydration condensation product with a functional carboxylic acid. 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 Ethylenically unsaturated double groups introduced by substitution reaction of unsaturated carboxylic acid esters or amides having a leaving substituent such as tosyloxy group with monofunctional or polyfunctional alcohols, amines, thiols There are also bonds. As another example, it is possible to replace the unsaturated carboxylic acid with an unsaturated phosphonic acid, styrene, vinyl ether or the like. More preferable examples of the ethylenically unsaturated double bond include an ethylenically unsaturated double bond introduced by a (meth) acryl group or a vinyl ether group from the viewpoint of sensitivity and ease of synthesis.

  In general formula (I), R represents a hydrogen atom or a methyl group, and is more preferably a hydrogen atom from the viewpoint of exposure sensitivity.

  In general formula (I), n represents an integer greater than or equal to 1, 1-30 are preferable from a viewpoint of the sensitivity and the availability of a synthetic raw material, 1-15 are more preferable, and 2-10 are the most preferable.

  As a molecular weight of a specific compound, 170-10000 are preferable, 170-5000 are more preferable, 180-3000 are still more preferable, 180-1500 are the most preferable.

  Specific examples of the specific compound (Exemplary Compounds (1) to (5)) are shown below, but the specific compound in the present invention is not limited thereto.

  Commercially available products can also be used as the specific compound, and preferred examples thereof include TCR-1310H, TCR-1025, TCR-1064, TCR-1286, PCR-1069, K-48C, PCR-1157H, CCR-1105. , CCR-1115, CCR-1159H, ZAR-1395H, ZFR-1401H, ZFR-1122, ZFR-1124, ZFR-1185, EAM-2160, EAM-2300, R-130, R-190, EA-2320, R -205, R-280, CN series (CN-104, CN-104A80, CN-104B80, CN-111, CN-112C60, CN-116, CN-118, CN-120, CN-120A60, CN-120A75, CN-120B60, CN-120B8 CN-120C60, CN-120C80, CN-120D80, CN-120E50, CN-120M50, CN-124, CN-124A80, etc. (above, manufactured by Nippon Kayaku Co., Ltd.), Ebecryl series (Ebecryl600, Ebecryl601, Ebecryl604, Ebecryl605, Ebecryl607, Ebecryl608, Ebecryl609, Ebecryl650 / 25TO, Ebecryl616, Ebecryl645, Ebecryl648, Ebecryl860, Ebecryl1606, Ebecryl1608, Ebecryl1629, Ebecryl1940, Ebecryl2952, Ebecryl3201, Ebecryl3404, Ebecryl3411, Ebe ryl3412, Ebecryl3415, Ebecryl3502, Ebecryl3600, Ebecryl3603, Ebecryl3604, Ebecryl3605, Ebecryl3608, Ebecryl3700, Ebecryl3700-20H, Ebecryl3700-20T, Ebecryl3700-25R, Ebecryl3701, Ebecryl3701-20T, Ebecryl3703, Ebecryl3702, Ebecryl3708, Ebecryl RDX63182, Ebecryl6040, Ebecryl IRR419, Etc.) (above, manufactured by Daicel Cytec Co., Ltd.), Bremer GMR-H, GMR-R, GAM, GAM-R (above, manufactured by NOF Corporation) Light Ester G-101P G-201P, Epoxy ester series (Epoxy ester 40EM, Epoxy ester 70PA, Epoxy ester 200PA, Epoxy ester 80MFA, Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 3000M, Epoxy ester 3000A, etc.) (above, Kyoeisha Chemical Co., Ltd.) Manufactured), V # 540 (manufactured by Osaka Organic Chemical Co., Ltd.), CN series (CN104, CN104A, CN104B80, CN111, CN112C60, CN115, CN116, CN118, CN120, CN120A60, CN120A75, CN120B60, CN120B80, CN120C60, C120 , CN120D80, CN120E50, CN120M50, CN124, CNUVE151, (NUVE151 / 80, CN151, etc.) (manufactured by Sartomer), NK ester 701, 701A, NK oligo EA-1020, EA-1025, EA-1026, EA-1028, EA-5520, EA-5521, EA- 5821, EA-5921, EA-6310, EA-6320, EA-6340, EA-7120, EA-7140, EA-7420, EA-7440 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  Examples of the synthesis method of the specific compound include a reaction between an epoxy compound and an unsaturated carboxylic acid, an epoxy compound having an ethylenically unsaturated bond, and a compound containing an active hydrogen capable of reacting with an epoxy group of an approximate compound. Reaction, a reaction between a polyol having a secondary hydroxyl group and an unsaturated carboxylic acid or unsaturated acid halide is preferably used, but is not limited thereto.

  The method for synthesizing the epoxy compound used in the method for synthesizing the specific compound is not particularly limited. From the viewpoint of ease of synthesis, yield, etc., for example, the reaction of a compound having an alcoholic or phenolic hydroxy group with epichlorohydrin. A preferred example is the reaction of glycidol with an acid halide. Preferred examples of the epoxy compound include 1,4-butanediol diglycidyl ether, 3- [bis (glycidyloxymethyl) -methoxy] -1,2-propanediol, 1,4-cyclohexanedimethanol diglycidyl ether. , Allyl glycidyl ether, tris (2,3-epoxypropyl) isocyanurate, and commercially available products such as EPOlite 40E, 100E, 200E, 400E, 70P, 200P, 400P, 1500NP, 1600, 80MF, 100MF, 4000, 3002 (or more , Manufactured by Kyoeisha).

  As content of a specific compound, 0.01 mass%-80 mass% are preferable with respect to the total solid contained in the curable composition of this invention, and 0.05 mass%-60 mass% are more preferable. 0.1% by mass to 40% by mass is more preferable, and 0.3% by mass to 20% by mass is most preferable.

<(B) Photopolymerization initiator>
The curable composition of the present invention contains (B) a photopolymerization initiator (hereinafter referred to as “photopolymerization initiator” as appropriate ) which is an oxime compound .
The photopolymerization initiator in the present invention is a compound that is decomposed by light and starts and accelerates the polymerization of the component (A) and the component (D) described later, and has absorption in the wavelength region of 300 to 500 nm. It is preferable that Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Hut "Journal of Heterocyclic Chemistry" 1 (No3), (1970) "The compound described in a brush is mentioned, Especially, the oxazole compound substituted by the trihalomethyl group and s-triazine compound are mentioned.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include mbenzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate, and the like.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. 18, 387 (1974), T .; S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  Examples of the alkylamino compound include compounds having a dialkylaminophenyl group described in paragraph No. [0047] of JP-A-9-281698, JP-A-6-19240, JP-A-6-19249, and the like. An amine compound is mentioned. Specifically, compounds having a dialkylaminophenyl group include compounds such as ethyl p-dimethylaminobenzoate, and dialkylaminophenyl carbaldehydes such as p-diethylaminobenzcarbaldehyde and 9-julolidylcarbaldehyde. Examples of the amine compound include triethanolamine, diethanolamine, and triethylamine.

The photopolymerization initiator (B) used in the present invention, from the viewpoint of exposure sensitivity, a oximes compound.

  (B) It is preferable that content of a photoinitiator is 0.1 mass%-50 mass% with respect to the total solid of the curable composition of this invention, More preferably, 0.5 mass%-30 % By mass, particularly preferably 1% by mass to 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

<(C) Colorant>
The curable composition of the present invention contains (C) a colorant.
There is no restriction | limiting in particular in the coloring agent contained in the curable composition of this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types. The colorant is preferably a pigment from the viewpoint of durability such as heat resistance and light resistance.

  As the pigment that can be contained in the curable composition of the present invention, various conventionally known inorganic pigments or organic pigments can be used, and high transmittance is preferable.

  Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal oxides of the above metals.

As an organic pigment, for example,
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. 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.

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

When used for a color filter, the primary particle diameter of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The primary particle diameter of the pigment is more preferably 5 to 75 nm, still more preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
The primary particle diameter of the pigment can be measured by a known method such as an electron microscope.

  Among these, the pigment is preferably a pigment selected from anthraquinone, azomethine, benzylidene, cyanine, diketopyrrolopyrrole, and phthalocyanine.

Moreover, when using the composition of this invention for color filters, it is preferable to use the dye which melt | dissolves uniformly in a composition from a viewpoint of uneven color and contrast.
The dye that can be used as the colorant contained in the curable composition of the present invention is not particularly limited, and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In addition, after pattern exposure of the curable composition and curing of the exposed portion, unexposed portions are removed by water or alkali development to form a pattern, for example, when a colored pattern of a resist or a color filter is formed. From the viewpoint of completely removing the binder, dye, and the like in the non-light-irradiated part due to the acid dye, an acid dye and / or a derivative thereof may be suitably used.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

  The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, and other components in the composition. It is selected in consideration of all required performance such as interaction with components, light resistance, heat resistance and the like.

Hereinafter, although the specific example of an acidic dye is given, in this invention, it is not limited to these. For example,
acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95107, 108, 169, 173;

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119,137,149,150,153,155,156,158,159,160,161,162,164,166,167,170,171,172,173,188,189,190,192,193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;
Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the acid dyes mentioned above, acid black 24;
acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;
acid orange 8, 51, 56, 74, 63;
acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
acid violet 7;
acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 111, 112, 114, 116, 134, 155, 169, 172, 184, 220, 228, 230, 232, 243;
Dyes such as Acid Green 25 and derivatives of these dyes are preferred.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Acid dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110, and derivatives of these dyes are also preferably used.

  Among them, as the colorant (D), triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo A colorant selected from pyrazole azo, anilino azo, pyrazolotriazole azo, pyridone azo, and anthrapyridone is preferable.

  The content of the colorant in the curable composition of the present invention is preferably 30% by mass or more and 85% by mass or less, including the case where it is used for forming a color filter color pattern, and is 40% by mass or more and 80% by mass or less. More preferably, it is more preferable that it is 50 mass% or less and 75 mass% or less.

<(D) Compound containing ethylenically unsaturated double bond>
The curable composition of the present invention includes a compound containing an ethylenically unsaturated double bond other than the specific compound (hereinafter, sometimes simply referred to as “compound containing an ethylenically unsaturated double bond”). It is preferable to contain.

  The compound containing an ethylenically unsaturated double bond that can be used in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond other than the specific compound, and having terminal ethylene. Selected from compounds having at least one, preferably two or more, unsaturated unsaturated bonds. 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 hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. 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. Containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group in the compound represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Vinyl urethane compounds to be used.

^{_{CH 2 = C (R 10)}} COOCH 2 CH (R 11) OH formula (A)
(However, R ¹⁰ and R ¹¹ 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 photopolymerizable composition excellent in the 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 methods such as the structure, single use or combined use, addition amount and the like can be arbitrarily set according to the 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 image area, that is, the cured film, those having three or more functionalities are preferable. A method of adjusting both sensitivity and strength by using a compound) is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.
In addition, the selection and use method of the addition polymerization compound is an important factor for the compatibility and dispersibility with other components (for example, resin, photopolymerization initiator, pigment) in the curable composition, 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 the adhesion with a substrate or the like.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Manufactured), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei), UA-7200 (Shin Nakamura Chemical Co., Ltd.) Product).

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Examples of commercially available modified products such as pentaerythritol hexaacrylate EO include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha) is more preferable.

(D) The content of the compound containing an ethylenically unsaturated double bond other than the specific compound is preferably 1% by mass to 90% by mass in the solid content of the curable composition of the present invention. It is more preferably from 80% by mass to 80% by mass, and further preferably from 10% by mass to 70% by mass.
In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the compound containing an ethylenically unsaturated double bond other than the specific compound (D) is 5 mass in the above range. % To 50% by mass, more preferably 7% to 40% by mass, and still more preferably 10% to 35% by mass.

  In addition, the content ratio (mass ratio) between the (A) specific compound and the (D) compound containing an ethylenically unsaturated double bond other than the specific compound is sensitivity and removability of unexposed areas (developability). In view of the above, (A) / (D) is preferably 0.001 to 100, more preferably 0.005 to 50, and still more preferably 0.01 to 10.

<(E) Resin>
The curable composition of the present invention may contain (E) a resin (hereinafter, appropriately referred to as “binder polymer”) for the purpose of improving film properties.
It is preferable to use a linear organic polymer as the binder polymer. 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 (12).

(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 very excellent in strength, and is advantageous in terms of 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.

(E) The weight average molecular weight of the resin 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 in 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 resins may be any of random polymers, block polymers, graft polymers and the like.

(E) The resin 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.

  (E) When the curable composition of the present invention is used for forming a color pattern of a color filter, the content of the resin is determined by the curing of the present invention from the viewpoint of the balance between pigment dispersion stability with time and developability. It is preferably 5% by mass or more and 60% by mass or less, more preferably 7% by mass or more and 50% by mass or less, and more preferably 10% by mass or less and 40% by mass or less based on the total solid content of the composition. Is most preferred.

  The curable composition of this invention may further contain the arbitrary components explained in full detail as needed.

<(F) Dispersant>
When a pigment is contained as the (C) colorant in the curable composition of the present invention, it is preferable to add the (F) dispersant from the viewpoint of improving the dispersibility of the pigment.

Dispersants (pigment dispersants) that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified polymers. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
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.

  These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

As content of the dispersing agent in this invention, it is preferable that it is 1 mass%-100 mass% with respect to a pigment, 3 mass%-100 mass% are more preferable, 5 mass%-80 mass% are still more preferable. .
Specifically, when a polymer dispersant is used, the amount used is preferably in the range of 5% by mass to 100% by mass and more preferably in the range of 10% by mass to 80% by mass with respect to the pigment. preferable. In the case of using a pigment derivative, the amount used is preferably in the range of 1% by mass to 30% by mass with respect to the pigment, and more preferably in the range of 3% by mass to 20% by mass. It is preferably in the range of 5% by mass to 15% by mass.

  In the present invention, when a pigment and a dispersant are used, the total content of the pigment and the dispersant is 35% by mass or more based on the total solid content constituting the curable composition from the viewpoint of curing sensitivity and color density. It is preferably 90% by mass or less, more preferably 45% by mass or more and 85% by mass or less, and further preferably 50% by mass or more and 80% by mass or less.

<(G) Sensitizer>
The curable composition of the present invention may contain (G) a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.

Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
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 (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , 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 and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.
Further, European Patent No. 568,993, US Patent No. 4,508,811, No. 5,227,227, JP-A-2001-125255, JP-A-11- And the compounds described in Japanese Patent No. 271969.

  More preferable examples of the sensitizer include compounds represented by the following general formulas (i) to (iv).

In general formula (i), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents the basic nucleus of the dye in combination with adjacent A ¹ and the adjacent carbon atom. Represents a non-metallic atomic group to be formed, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. Also good. W represents an oxygen atom or a sulfur atom.

In General Formula (ii), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (i).

In the general formula (iii), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with an adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In general formula (iv), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, wherein R ⁶³ and R ⁶⁴ each independently represent a substituted or unsubstituted alkyl group, substituted Or an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye together with adjacent A ³ , A ⁴ and an adjacent carbon atom; ⁶⁰ and R ⁶¹ are each independently a monovalent non-metallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring.

  Moreover, as a preferable sensitizer which can be contained in the curable composition of this invention, at least 1 type selected from the compound represented by the following general formula (IV)-(VI) other than the above thing is mentioned. These may be used individually by 1 type, and may use 2 or more types together.

In general formula (IV) or general formula (V), R ¹ and R ² each independently represent a monovalent substituent, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or Represents a monovalent substituent. n represents an integer of 0 to 5, n ′ represents an integer of 0 to 5, and n and n ′ are not both 0. When n is 2 or more, a plurality of R ¹ may be the same or different. When n ′ is 2 or more, a plurality of R ² may be the same or different.

  As a compound represented by general formula (IV), it is preferable that it is a compound represented by the following general formula (IV-1) from a viewpoint of the colorability in the case of containing a sensitivity and a pigment.

In general formula (IV-1), R ¹ and R ² each independently represents a monovalent substituent. n represents an integer of 0 to 5, and n ′ represents an integer of 1 to 5. When n is 2 or more, a plurality of R ¹ may be the same or different, and when n ′ is 2 or more, a plurality of R ² are the same or different. Also good.

In the general formula (IV-1), the monovalent substituent represented by ^{R 1} and ^{R 2} are synonymous with the monovalent substituent represented by ^{R 1} and ^{R 2} in the general formula (IV) The preferable range is also the same.

The general formula (IV) or general formula (V) compounds represented by is preferably a molar extinction coefficient epsilon at a wavelength of 365nm is ^{500mol -1} · L · ^cm -1 or more, epsilon at a wavelength of 365nm is 3000 mol ^- more preferably ¹ · L · ^{cm -1} or more, and most preferably ε at a wavelength of 365nm is 20000mol ^-1 · L · ^{cm -1} or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.
Here, the molar extinction coefficient ε is obtained by measuring a transmission spectrum of a sample at 365 nm using a dye solution adjusted to a concentration of 0.01 g / l in a 1-methoxy-2-propanol solution as a sample, and UV-visible absorption of the sample. It is obtained by determining the absorbance from the spectrum. The measurement apparatus used was a Varian UV-Vis-MR Spectrophotometer Cary 5G type spectral altimeter.

Although the preferable specific example of a compound represented by general formula (IV) or general formula (V) is illustrated below, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group. In the following specific examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, n-Bu represents an n-butyl group, and Ph represents a phenyl group.

In general formula (VI), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom, a sulfur atom, or —N (R ³ ) —, Y represents an oxygen atom, A sulfur atom or -N (R < ³ >)-is represented. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ¹ , R ² , and R ³ are each bonded to each other to form an aliphatic group Or you may form an aromatic ring.

In the general formula (VI), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group. When R ¹ , R ² and R ³ represent a monovalent nonmetal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group It is preferably a heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxy group, or a halogen atom.

In the compound represented by the general formula (VI), Y is preferably an oxygen atom or —N (R ³ ) — from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. R ³ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group. Furthermore, Y is most preferably —N (R ³ ) —.

  Hereinafter, preferred specific examples (VI1) to (VI124) of the compound represented by the general formula (VI) are shown, but the present invention is not limited thereto. Further, it is not clear about an isomer by a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

The compound represented by the general formula (VI) according to the present invention can be further subjected to various chemical modifications for improving the properties of the curable composition.
For example, the sensitizing dye and an addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) are bonded by a method such as covalent bond, ionic bond, hydrogen bond, etc. Unnecessary precipitation suppression of the sensitizing dye from the film after exposure can be performed.
Further, the coupling between the portion structure having radical generating ability of the photopolymerization initiator described above with the sensitizing dye, in particular significantly increase the photosensitivity in a state of low concentration of the initiator system.

  In the curable composition of the present invention, the compounds represented by the general formulas (IV) to (VI) may be used alone or in combination of two or more.

  The compounds represented by the above general formulas (IV) to (VI) have a very high pigment concentration in the curable composition, and the light transmittance of the formed colored pattern (photosensitive layer) becomes extremely low. In this case, specifically, when the light transmittance of 365 nm of the photosensitive layer when formed without adding a sensitizing dye is 10% or less, the effect is remarkably exhibited. The In particular, among the above general formulas (IV) to (VI), the compound represented by the general formula (VI) is most preferable, and specifically, the compounds of (VI56) to (VI122) are most preferable.

A sensitizer may be used individually by 1 type and may use 2 or more types together.
The content of the sensitizer in the curable composition of the present invention is 0.1% by mass to 20% with respect to the total solid content of the curable composition from the viewpoint of light absorption efficiency into the deep part and initiation decomposition efficiency. It is preferable that it is mass%, and 0.5 mass%-15 mass% are more preferable.

<(H) Co-sensitizer>
The curable 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 the co-sensitizer is in the range of 0.1% by mass 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 the polymerization growth rate and the chain transfer. Is preferable, the range of 0.5 mass% to 25 mass% is more preferable, and the range of 1.0 mass% to 20 mass% is still more preferable.

<(I) 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.

  (H) The addition amount of the 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.

<Other additives>
Furthermore, in the present invention, in order to improve the physical properties of the cured film, known additives such as inorganic fillers, plasticizers, and sensitizers that can improve the ink inking property on the surface of the photosensitive layer, substrate adhesion You may add the board | substrate adhesion agent which can improve this.
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 binder.

When the curable composition of the present invention is applied to the surface of a hard material such as a substrate, an additive for improving the adhesion to the surface of the hard material (hereinafter referred to as “substrate adhesion agent”) is added. May be.
As the substrate adhesion agent, known materials can be used, but it is particularly preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum 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-aminopropyltri Ethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.

  Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldi Methacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, Li isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

  The content of the substrate adhesion agent is 0.1% by mass or more and 30% by mass with respect to the total solid content of the curable composition of the present invention from the viewpoint of leaving no residue in the unexposed part of the curable composition. % Or less, more preferably 0.5% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less.

  The curable composition of the present invention is cured with high sensitivity and has good storage stability. Moreover, the high adhesiveness to hard material surfaces, such as a board | substrate which applies a curable composition, is shown. Accordingly, the curable composition of the present invention can be preferably used in the fields of image forming materials such as three-dimensional stereolithography, holography, and color filters, inks, paints, adhesives, and coating agents.

[Color filter and manufacturing method thereof]
Next, the color filter of the present invention and the manufacturing method thereof are described.
The color filter of the present invention is characterized by having a colored pattern formed using the curable composition of the present invention on a support.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

A colored layer forming step of forming a colored layer comprising the curable composition by applying the curable composition of the present invention on the support, and exposure for exposing the colored layer through a mask And a developing step of developing the colored layer after exposure to form a colored pattern.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Colored layer forming step>
In the colored layer forming step, the curable composition of the present invention is applied on the support to form a colored layer comprising the curable composition.

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like obtained by attaching a transparent conductive film to these, an image sensor, etc. 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 of 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 film thickness immediately after application of the curable composition is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, from the viewpoint of film thickness uniformity of the coating film and ease of drying of the coating solvent. 0.2-3 micrometers is more preferable.

  The colored layer (curable composition layer) applied on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, oven, or the like.

The coating film thickness after drying of the curable composition (hereinafter referred to as “dry film thickness” as appropriate) can be used for LCD color filters and can be used for LCD thinning, from the viewpoint of securing color density. 0.1 μm or more and less than 2.0 μm is preferable, 0.2 μm or more and 1.8 μm or less is more preferable, and 0.3 μm or more and 1.75 μm or less is particularly preferable.
In addition, in order to use it as an IS color filter, the light in the oblique direction does not reach the light receiving unit from the viewpoint of securing the color density, and the difference in the light collection rate between the end and the center of the device becomes remarkable. From the viewpoint of reducing defects, it is preferably 0.05 μm or more and less than 1.0 μm, more preferably 0.1 μm or more and 0.8 μm or less, and particularly preferably 0.2 μm or more and 0.7 μm or less.

<Exposure process>
In the exposure step, the colored layer (curable composition layer) formed in the colored layer forming step is exposed through a mask having a predetermined mask pattern.
In this step, the pattern of the coating film is exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured, developed with a developer, and each color (three colors or four colors). This can be done by forming a pattern-like film consisting of these pixels. As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.
If the color filter of the present invention is a liquid crystal display device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter of the present invention is for a solid-state imaging device, more preferably 30~1500mJ / cm ² is preferably 50~1000mJ / cm ² within the above range, and most preferably 80~500mJ / cm ^2.

<Development process>
Subsequently, by performing an alkali development process (development process), the light non-irradiated part is eluted in the alkaline aqueous solution by the exposure, and 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 alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and the like, and these alkaline agents are added with pure water so that the concentration becomes 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. A diluted alkaline aqueous solution is preferably used as the developer. 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.
Next, excess developer is washed away and dried.

  In the production method of the present invention, the colored pattern formed is cured by heating (post-baking) and / or exposure as necessary after performing the above-described colored layer forming step, exposure step, and development step. A curing step may be included.

The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicon substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

  By repeating the colored layer forming step, the exposure step, and the developing step (and, if necessary, the curing step) described above for the desired number of hues, a color filter having a desired hue is produced.

  The application of the curable composition of the present invention has been described mainly with respect to the application to the pixels of the color filter, but it goes without saying that it can also be applied to a black matrix provided between the pixels of the color filter. The black matrix is subjected to pattern exposure and alkali development in the same manner as in the above pixel production method except that a black pigment such as carbon black or titanium black is added to the curable composition of the present invention as a colorant. Further, after that, post-baking can be performed to promote the curing of the film.

  Since the color filter of the present invention uses the curable composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition has excellent development resistance. It is possible to form a high-resolution pattern that is excellent in sensitivity, has good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. 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.

[ Reference Example 1]
[A1. Preparation of curable composition]
Here, an example in which a curable composition containing a pigment is prepared for forming a color filter for use in a liquid crystal display element will be described.

A1-1. Preparation of pigment dispersion Preparation of pigment dispersion
As a pigment, C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 30/70 (mass ratio) mixture 40 parts by mass (primary grain size 32 nm), BYK2001 (Disperbyk: manufactured by BYK) (solid content concentration 45.1% by mass) 50 parts by mass (as a dispersant) A pigment dispersion (P1) was prepared by mixing and dispersing a mixed solution consisting of about 22.6 parts by mass in terms of solid content) and 110 parts by mass of ethyl 3-ethoxypropionate as a solvent with a bead mill for 15 hours.
For the pigment dispersion (P1), the average particle diameter of the pigment was measured by a dynamic light scattering method (measured without further dilution of P1 using Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)). Met.

A1-2. Preparation of curable composition (coating liquid) A curable composition solution was prepared by stirring and mixing the pigment dispersion liquid P1 subjected to the dispersion treatment so as to have the following composition ratio.
-(C) Colorant (Pigment dispersion (P1)) 600 parts by mass-(A) Specific compound (Epoxy ester 40EM (Kyoeisha Chemical Co., Ltd.)) 10 parts by mass , 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole) 30 parts by mass (D) 50 parts by mass of dipentaerythritol hexaacrylate (E ) Alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10000) 10 parts by mass / solvent: 900 parts by mass of PGMEA / substrate adhesion agent (3-methacryloxy) Propyltrimethoxysilane) 1 part by mass (G) Sensitizer (compound α below) 15 parts by mass (H) co-sensitizer (2-mercaptobenzoimidazo Le) 15 parts by weight

[A2. (Production of color filter)
A2-1. Formation of the curable composition layer The curable composition containing the pigment as a resist solution was slit-coated on a 550 mm × 650 mm glass substrate under the following conditions, and then allowed to stand for 10 minutes, followed by vacuum drying and pre-baking ( prebake) (100 ° C., 80 seconds) to form a curable composition coating film (curable composition layer).

(Slit application conditions)
・ Gap at the opening of the coating head tip: 50 μm
・ Application speed: 100 mm / second ・ Clearance between substrate and application head: 150 μm
・ Dry film thickness 1.75μm
・ Application temperature: 23 ℃

A2-2. Exposure and development Thereafter, the photocurable coating film is exposed in a pattern using a test mask with a line width of 20 μm using a 2.5 kW ultra-high pressure mercury lamp, and after the exposure, the entire surface of the coating film is organically developed. The sample was covered with a 10% aqueous solution (trade name: CD, manufactured by FUJIFILM Electronics Materials Co., Ltd.) and left still for 60 seconds.

A2-3. 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). Thereby, the color filter formed by forming a curable composition coating film (colored layer) on the glass substrate was obtained.

[A3. (Performance evaluation)
Storage stability of the coating liquid comprising the curable composition prepared above, exposure sensitivity of the curable composition coating film (colored layer) formed on the glass substrate using the curable composition composition, substrate The adhesion, developability, and pattern cross-sectional shape were evaluated as follows. The results are shown in Table 1.

A3-1. Stability over time of curable composition After the curable composition (coating solution) prepared above was stored at room temperature for 1 month, the viscosity of the solution was measured and evaluated according to the following criteria.
-Evaluation criteria-
○: No increase in viscosity was observed.
Δ: An increase in viscosity of 5% or more and less than 10% was observed.
X: An increase in viscosity of 10% or more was observed.

A3-2. Exposure sensitivity of curable composition coating film (colored layer),
The curable composition coating film was exposed by changing the exposure dose to various exposure doses of 10 to 100 mJ / cm ² , and the exposure dose at which the pattern line width after post-baking was 20 μm was evaluated as exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

A3-3. Developability, pattern cross-sectional shape, and substrate adhesion The developability, pattern cross-sectional shape, and substrate adhesion were evaluated by confirming the substrate surface and cross-sectional shape after post-baking with an optical microscope and SEM photograph observation. Details of the evaluation method and evaluation criteria are as follows.

<Developability>
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability.
-Evaluation criteria-
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but it was practically unproblematic.
X: Residue was remarkably confirmed in the unexposed part.

<Pattern cross-sectional shape>
The cross-sectional shape of the formed pattern was observed. The pattern cross-sectional shape is most preferably a forward taper, and a rectangular shape is next preferred. Reverse taper is not preferred.

<Board adhesion>
The evaluation of the substrate adhesion was performed by observing whether or not a pattern defect occurred. The evaluation criteria are as follows.
-Evaluation criteria-
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

[ Reference Examples 2 to 10, Comparative Examples 1 and 2]
In the curable composition prepared in Reference Example 1, a color filter was prepared in the same manner as in Reference Example 1 except that (A) epoxy ester 40EM, which is a specific compound, was replaced with the compound shown in Table 1 below. The same evaluation as in Reference Example 1 was performed. The results are shown in Table 1.

From the results of Table 1, it can be seen that the curable compositions of the respective reference examples containing the specific compound are excellent in storage stability in the solution state. In addition, when a colored pattern is formed on a support using this curable composition, the exposure sensitivity is high and the developability is excellent for each comparative example not using a specific compound, and the substrate adheres to the substrate. It can be seen that an excellent color filter is obtained in both the properties and the pattern cross-sectional shape.

[Example 11]
Hereinafter, an example of preparing a curable composition containing a colorant (pigment) for forming a color filter for use in a solid-state imaging device will be described.

[B1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
<Composition of resist solution>
Propylene glycol monomethyl ether acetate 19.20 parts by mass (PGMEA: solvent)
-Ethyl lactate 36.67 parts by mass-Resin (40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18)) 30.51 parts by mass Ethylenically unsaturated double bond-containing compound (dipentaerythritol hexaacrylate) 12.20 parts by mass Polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass Fluorosurfactant (F-475, Dainippon Ink) 0.83 parts by mass / photopolymerization initiator (trihalomethyltriazine photopolymerization initiator) 0.586 parts by mass (TAZ-107, manufactured by Midori Chemical Co., Ltd.)

[B2. Production of silicon substrate with undercoat layer]
A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A silicon wafer substrate with an undercoat layer Got.

[B3. Preparation of pigment dispersion
As a pigment, C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 30/70 (mass ratio) mixture 40 parts by mass (primary grain size 32 nm), BYK2001 (Disperbyk: manufactured by BYK) (solid content concentration 45.1% by mass) 50 parts by mass (as a dispersant) A pigment dispersion (P1) was prepared by mixing and dispersing a mixed solution consisting of about 22.6 parts by mass in terms of solid content) and 110 parts by mass of ethyl 3-ethoxypropionate as a solvent with a bead mill for 15 hours.
With respect to the pigment dispersion (P1), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 200 nm.

[B4. Preparation of curable composition (coating liquid)]
A curable composition solution was prepared by stirring and mixing the pigment dispersion P1 subjected to the dispersion treatment so as to have the following composition ratio.
-(C) Colorant (pigment dispersion (P1)) 600 parts by mass-(A) Specific compound (epoxy ester 40EM, manufactured by Kyoeisha Chemical Co., Ltd.) 8 parts by mass-(B) Photopolymerization initiator (oxime type) Photopolymerization initiator)
(CGI-124, manufactured by Ciba Specialty Chemicals) 30 parts by mass (D) TO-1382 (manufactured by Toagosei Co., Ltd.) 61 parts by mass, solvent (PGMEA) 900 parts by mass, substrate adhesion agent (3-methacrylic) Roxypropyltrimethoxysilane) 1 part by mass

[B5. Preparation and evaluation of color filter with curable composition]
<Evaluation of pattern formation and sensitivity>
The curable composition prepared as described above was prepared using the B2. The colored layer (coating film) was formed by coating on the undercoat layer of the silicon wafer with the undercoat layer obtained in (1). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at various exposure doses of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

The silicon wafer on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying.
Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure dose at which the pattern line width was 2 μm was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity. The measurement results are shown in Table 2 below.

<Developability>
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability.
-Evaluation criteria-
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but it was practically unproblematic.
X: Residue was remarkably confirmed in the unexposed part.

<Pattern formability>
The cross-sectional shape of the formed pattern was observed. The pattern cross-sectional shape is preferably rectangular, and reverse taper is not preferable.

<Board adhesion>
As an evaluation of substrate adhesion, it was observed whether or not a pattern defect occurred. These evaluation items were evaluated based on the following criteria: -Evaluation criteria-
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

<Stability over time of curable composition>
B4. After the curable composition (coating solution) prepared in 1 was stored at room temperature for 1 month, the viscosity of the solution was measured and evaluated according to the following criteria.
-Evaluation criteria-
○: No increase in viscosity was observed.
Δ: An increase in viscosity of 5% or more and less than 10% was observed.
X: An increase in viscosity of 10% or more was observed.

[Examples 12 to 15, Comparative Examples 3 and 4]
In the curable composition prepared in Example 11, a colored pattern was formed in the same manner as in Example 11 except that (A) the epoxy ester 40EM as the specific compound was replaced with the compound shown in Table 2 below. A color filter was obtained and evaluated in the same manner as in Example 11.
The results are shown in Table 2.

From the results in Table 2, the curable compositions (pigment systems) of each Example containing specific compounds used for forming color filters for solid-state imaging devices were excellent in storage stability in the solution state. I know that there is. In addition, when a colored pattern is formed on a support using this curable composition, the exposure sensitivity is high and the developability is excellent for each comparative example not using a specific compound, and the substrate adheres to the substrate. It can be seen that an excellent color filter is obtained in both the properties and the pattern cross-sectional shape.
From these results, the curable compositions of the examples achieved excellent pattern formability even when producing color filters for solid-state imaging devices, as in the case of producing color filters for liquid crystal display devices. I found out that

[Example 16]
Hereinafter, an example of preparing a curable composition containing (dye) for forming a color filter for use in a solid-state imaging device will be described.

[C1. Preparation of resist solution and production of silicon substrate with undercoat layer]
[B1. Preparation of resist solution] and [B2. A silicon substrate with an undercoat layer was produced in the same manner as in [Preparation of silicon substrate with undercoat layer].

[C2. Preparation of curable composition (coating liquid)]
The compound of the following composition was mixed and melt | dissolved and the colored photosensitive resin composition was prepared.
-Cyclohexanone (solvent) 80 parts by mass-(C) Varifast Yellow 1101 (dye) 6.0 parts by mass-(C) Acid Red 57 (dye) 6.0 parts by mass-(D) Dipentaerythritol hexaacrylate 4.0 Parts by mass (A) specific compound (epoxy ester 40EM, manufactured by Kyoeisha Chemical Co., Ltd.) 2.0 parts by mass (B) oxime photopolymerization initiator 2.0 parts by mass (CGI-124, Ciba Specialty Chemicals) (Made by company)

[C3. Preparation and evaluation of color filter with curable composition]
[B5. Preparation and evaluation of a color filter were carried out in the same manner as in [Preparation and evaluation of color filter by colored photosensitive resin composition]. The results are shown in Table 3.

[Examples 17 to 20, Comparative Examples 5 and 6]
Example 16 A color in which a colored pattern was formed in the same manner as in Example 16 except that (A) the epoxy ester 40EM, which is a specific compound, was replaced with a compound shown in Table 2 below. A filter was obtained and evaluated in the same manner as in Example 16.
The results are shown in Table 3.

From the results of Table 3, the curable compositions (dye systems) of each Example containing a specific compound used for forming a color filter for solid-state imaging devices were excellent in storage stability in the solution state. I know that there is. In addition, when a colored pattern is formed on a support using this curable composition, the exposure sensitivity is high and the developability is excellent for each comparative example not using a specific compound, and the substrate adheres to the substrate. It can be seen that an excellent color filter is obtained in both the properties and the pattern cross-sectional shape.
From these results, the curable compositions of the examples achieved excellent pattern formability even when producing color filters for solid-state imaging devices, as in the case of producing color filters for liquid crystal display devices. I found out that

Claims (8)

(A) is from 1 or more selected the following group, the plurality of ethylenically unsaturated double bonds and secondary hydroxyl groups and Yusuke that of compound a photopolymerization initiator which is (B) an oxime-based compound, And (C) a curable composition for forming a color filter for use in a solid-state imaging device, comprising a colorant.
Ethylene glycol diglycidyl ether dimethacrylate
Propylene glycol diglycidyl ether diacrylate
1,6-hexanediol diglycidyl ether diacrylate
Bisphenol A diglycidyl ether diacrylate
Bisphenol A epoxy diacrylate oligomer Furthermore, a feature in that it contains a compound having a (D) wherein (A) other than the plurality of ethylenically unsaturated double bonds and that of compound having a the secondary hydroxyl group, an ethylenically unsaturated double bond The curable composition for color filter formation of the solid-state image sensor use of Claim 1 . Furthermore, (E) sensitizer is contained, The curable composition for color filter formation of the solid-state image sensor use of Claim 1 or Claim 2 characterized by the above-mentioned. Wherein (C) the content of the coloring agent in the total solid content contained in the curable composition, to one of the claims 1 to 3, characterized in that at most 85% by weight to 30% by weight A curable composition for forming a color filter for use in the described solid-state imaging device. The curable composition for forming a color filter for use in a solid-state imaging device according to any one of claims 1 to 4 , wherein the colorant (C) is a pigment. The curable composition for forming a color filter for use in a solid-state imaging device according to any one of claims 1 to 4 , wherein the colorant (C) is a dye. A color filter for use in a solid-state imaging device, comprising a colored pattern formed on the support by the curable composition according to any one of claims 1 to 6 . A colored layer forming step of applying a curable composition according to any one of claims 1 to 6 on a support to form a colored layer comprising the curable composition; and A method for producing a color filter for use in a solid-state imaging device, comprising: an exposure step of exposing through a mask; and a development step of developing a colored layer after exposure to form a colored pattern.