KR20080067302A - Curable composition, color filter using the same and manufacturing method therefor, and solid image pickup element - Google Patents

Abstract

A curing composition, a color filter containing a colored pattern comprising the composition, a method for preparing the color filter, and a solid state image sensing device containing the color filter are provided to improve the sensitivity and storage stability of the composition and to enhance the adhesion to a substrate. A curing composition comprises a resin; an ethylenically unsaturated compound; and a photopolymerization initiator, wherein the resin is prepared by polymerizing a monomer having a dipole moment of 2.0 or more as a copolymerization component. Preferably the monomer having a dipole moment of 2.0 or more has at least one group selected from an ether, a cyano, an ester phosphate, a lactone, a urethane, an ester carbonate and an acetal group.

Description

Curable composition, color filter using the same, manufacturing method thereof, and solid-state imaging device {CURABLE COMPOSITION, COLOR FILTER USING THE SAME AND MANUFACTURING METHOD THEREFOR, AND SOLID IMAGE PICKUP ELEMENT}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition suitable for manufacturing color filters used in liquid crystal display devices (LCDs), solid state imaging devices (CCDs, CMOS, etc.), color filters formed from the curable compositions, and methods of manufacturing the same.

The color filter is an essential component of a liquid crystal display or a solid state image pickup device.

Liquid crystal displays are denser and comparable in performance or better than CRTs commonly used as display devices, and thus replace CRTs as television screens, personal computer screens and other display devices. In recent years, as a trend of the development of liquid crystal displays, there has been a change from conventional monitor applications with relatively narrow screens to television applications with large screens and high image quality.

As for color filters for liquid crystal displays (LCDs), substrate sizes have been enlarged for the production of large television sets. Curable compositions for use in the production of color filters using such large substrates require curing at low energy in order to improve productivity.

In addition, in comparison with those for monitor applications, liquid crystal displays for television applications require high image quality, i.e. improvement in contrast and color purity.

Regarding the curable composition for the use of color filter manufacture, it is required to use a colorant (organic pigment, etc.) having a fine particle size for the purpose of improving the contrast (see, for example, Japanese Patent Laid-Open No. 2006-30541). .

However, when a pigment having a small particle size is included in the curable composition, if the pigment adsorption property of the dispersant is improved for the purpose of improving dispersion stability, the pigment aggregation is promoted by crosslinking of the pigment by the dispersant, whereby storage stability such as dispersion stability is improved. There exists a tendency for developability to fall when it is reduced or when a pattern is formed using a curable composition.

In addition, since the surface area of the fine pigment is increased, the use of the fine pigment tends to increase the amount of dispersant for dispersing the pigment in the curable composition.

Moreover, when the acid value of the resin added at the time of dispersion is improved in order to ensure developability, there exists a tendency for aggregation of a pigment to be promoted by interaction, such as a hydrogen bond between acidic groups.

When dispersing a pigment and trying to obtain developability by adding resin to a curable composition, it is necessary to add a large amount of resin.

Moreover, for the purpose of the improvement of color purity, the curable composition used for color filter manufacture requires a higher content rate of the coloring agent (organic pigment) in solid content. However, when the coloring agent is contained in a high concentration in the curable composition, the content rate of the photopolymerization initiator and the photopolymerizable monomer in the curable composition is reduced, so that the curable composition needs to be curable at low energy, but it is difficult to obtain curability at the exposed portion. to be.

On the other hand, the curable composition for the use of manufacture of the color filter for solid-state image sensors is required to harden at low energy. In addition, with respect to the color filter for the use of the solid state image pickup device, the development of a thin film of a coloring pattern is promoted, whereby the pigment concentration in the composition is improved.

In addition, in the pigment type color filter, the content rate of the pigment dispersant in a curable composition increases with the trend of the fine pigment for reducing the color nonuniformity resulting from the fact that a pigment is a comparatively coarse particle. As in the case of the curable composition for the purpose of manufacturing LCD, increase in the content rate of the pigment dispersant in the curable composition tends to lower the storage stability such as dispersion stability, and developability when forming a pattern using the curable composition. It tends to reduce and harden | cure hardening | curing property, and this becomes a problem.

In addition, in order to cope with problems such as color unevenness in the formed colored pattern, a technique of using an organic solvent soluble dye instead of a pigment as a colorant has been proposed (see, for example, Japanese Patent Application Laid-Open No. 2-127602). . However, with respect to the dye-based color filters, problems of deterioration in storage stability such as polymerization inhibition effect derived from dyes and precipitation of dyes have become remarkable as the dye concentration is increased.

As described above, depending on the curable composition for the use of color filter manufacture, either in the case of liquid crystal display or in the case of a solid-state image sensor, the content of the photopolymerization initiator and the photopolymerizable monomer as an essential component for curing the curable composition. Since the colorant concentration is limited and the colorant concentration is increased, sufficient hardenability is not obtained due to the low sensitivity, insufficient adhesion to the substrate, development speed decreases or residues are generated in the unexposed portion, making it very difficult to form a desired pattern. Dispersion stability and developability worsen when a coloring agent is a pigment, and storage problems, such as precipitation of dye, become low when a coloring agent is a dye.

In order to cope with these problems, improvement in sensitivity by imparting polymerizability to resins introduced in order to mainly provide film formability, developability, and the like has been studied (for example, Japanese Patent Application Laid-Open No. 2000-321763). And 2003-029018). Also, paragraphs 85 to 87 of "Color Filter Latest Technique Trend" (published by Johokiko Co., Ltd.), and paragraphs 129 to 150 of "Process Technique and Chemicals for Latest Color Filter" (published by CMC Publishing Co., Ltd.) Technology is presented. However, even when these resins are used, satisfactory exposure sensitivity has not yet been obtained. In addition, due to insufficient exposure sensitivity, hardening is insufficient at deep portions such as near the substrate interface, and the problem of substrate adhesion deteriorates.

It is an object of the present invention to provide a curable composition that is cured with very high sensitivity and has good storage stability.

In addition, another object of the present invention is a high sensitivity formed by using the curable composition, there is little development residue of the uncured portion, excellent adhesion to the substrate of the cured portion, and also has a high resolution and a desired cross-sectional color pattern It is to provide a color filter having.

Still another object of the present invention is to provide a method of manufacturing the color filter with excellent productivity, and a solid state image pickup device having the color filter manufactured by the manufacturing method.

As a result of intensive studies from the viewpoint of the above environment, the present inventors have found that the problem can be solved and completed the present invention.

The present invention has been made in view of the above situation, and provides a curable composition, a color filter using the same, a method of manufacturing the same, and a solid state image pickup device.

The first aspect of the present invention

<1> A curable composition containing a resin, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, wherein the resin is prepared by polymerizing a monomer having at least a dipole moment of 2.0 or more as a copolymerization component. .

The second aspect of the present invention

<2> The color filter which has a coloring pattern formed from the curable composition of a 1st form which further contains a coloring agent or a sensitizer is provided.

The third aspect of the present invention

<3> Process of forming the colored layer which consists of curable composition by apply | coating the curable composition of the 1st form which further contains a coloring agent on a support body; It provides a method for producing a color filter comprising the step of exposing the colored layer through a mask and the step of forming a colored pattern by developing the post-exposure colored layer.

The fourth aspect of the present invention

<4> There is provided a solid state image pickup device comprising a color filter manufactured by the color filter manufacturing method according to the third aspect.

According to the present invention, even when the coloring agent is contained at a high concentration, the storage stability such as dispersion stability is good, it is cured with high sensitivity by exposure, the adhesion to the substrate surface is high in the hardened region, and the uncured portion in the uncured region. The curable composition which can form the pattern excellent in the removal property of can be provided.

In addition, according to the present invention, it is possible to provide a color filter having a color pattern having excellent resolution and adhesion to a support formed using the curable composition of the present invention, and a manufacturing method for forming the color filter with high productivity.

Hereinafter, the curable composition of this invention contains resin, the compound which has an ethylenically unsaturated double bond, and a photoinitiator, The said resin is manufactured by superposing | polymerizing the monomer whose dipole moment is 2.0 or more as a copolymerization component.

In addition, the resin preferably has an ethylenically unsaturated double bond in the side chain.

Moreover, it is preferable that the curable compound of this invention contains a coloring agent further.

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

<Resin (A)>

Resin of this invention is resin manufactured by superposing | polymerizing the monomer which has a dipole moment of 2.0 or more as a copolymerization component. It is preferable that the resin of this invention has an ethylenically unsaturated double bond in a side chain.

It is preferable that the said resin is a polymer compound which has group represented by following General formula (1)-(3) as said ethylenically unsaturated double bond.

In general formula, R <^1> -R <^11> represents a hydrogen atom or monovalent organic group each independently. X and Y each independently represent an oxygen atom, a sulfur atom or -NR ¹² , and Z represents an oxygen atom, a sulfur atom, -NR ¹² or a phenylene group. R ¹² represents a hydrogen atom or a monovalent organic group.

In the general formula (1), R ¹ to R ³ each independently represent a monovalent organic group. Examples of R ¹ include an alkyl group, an alkoxyl group, an alkoxy carbonyl group, and the like, which may have a hydrogen atom or a substituent. In particular, a hydrogen atom, a methyl group, a methyl alkoxy group, and a methyl ester group are preferable. R ^{2 and} R ³ are each independently a hydrogen atom, a halogen atom, an amino group, a dialkyl amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or an aryl which may have a substituent Group, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkyl amino group which may have a substituent, aryl amino group which may have a substituent, alkyl sulfonyl group which may have a substituent, and aryl which may have a substituent Sulfonyl groups and the like. In particular, the hydrogen atom, the carboxyl group, the alkoxy carbonyl group, the alkyl group which may have a substituent, and the aryl group which may have a substituent are preferable.

Here, as a substituent introduced, a methoxy carbonyl group, an ethoxy carbonyl group, an isopropoxyoxy carbonyl group, a methyl group, an ethyl group, a phenyl group, etc. can be mentioned.

X represents an oxygen atom, a sulfur atom or -NR ¹² . Here, as R <^12> , the alkyl group etc. which may have a substituent are mentioned.

In general formula (1), as an alkyl group, a C1-C30 linear or cyclic alkyl group can be mentioned. Alkyl groups having 1 to 20 carbon atoms are preferred, and alkyl groups having 1 to 10 carbon atoms are particularly preferred.

In the general formula (1), examples of the aryl group include those having 6 to 30 carbon atoms. It is preferable that they are 6-20 carbon atoms, and it is especially preferable that they are 6-10 carbon atoms.

In the said General formula (2), R <^4> -R <^8> represents a monovalent organic group each independently. Examples of R ⁴ to R ⁸ include a hydrogen atom, a halogen atom, an amino group, a dialkyl amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, and an aryl group which may have a substituent. , An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkyl amino group which may have a substituent, an aryl amino group which may have a substituent, an alkyl sulfonyl group which may have a substituent, an aryl sulfo which may have a substituent And the like may be mentioned. In particular, the hydrogen atom, the carboxyl group, the alkoxy carbonyl group, the alkyl group which may have a substituent, and the aryl group which may have a substituent are preferable. As a substituent introduced, what was listed by General formula (1) can be mentioned. Y represents an oxygen atom, a sulfur atom or -NR ¹² . As R <^12> , what was listed by General formula (1) can be mentioned. In General formula (2), what was enumerated by General formula (1) as an alkyl group and an aryl group can be enumerated, A preferable example is also applicable.

In the said General formula (3), R <^9> -R <^11> represents a monovalent organic group each independently. Specific examples of the organic group include a hydrogen atom, a halogen atom, an amino group, a dialkyl amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, and an aryl which may have a substituent. Group, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkyl amino group which may have a substituent, aryl amino group which may have a substituent, alkyl sulfonyl group which may have a substituent, and aryl which may have a substituent Sulfonyl groups and the like. In particular, the hydrogen atom, the carboxyl group, the alkoxy carbonyl group, the alkyl group which may have a substituent, and the aryl group which may have a substituent are preferable.

As a substituent introduced, what was listed by General formula (1) can be enumerated in the same manner.

Z represents an oxygen atom, a sulfur atom, -NR ¹² or a phenylene group. As R <^12> , what was listed by General formula (1) can be mentioned.

In General formula (3), as an alkyl group and an aryl group, what was listed by General formula (1) can be enumerated, and the same preferable example is applicable.

In the resin in the present invention, the polymer compound having a group represented by the general formula (1) can be produced by at least one of the following synthesis methods 1) and 2).

Synthesis Method 1)

A method of obtaining a desired polymer compound by synthesizing a polymer compound by copolymerizing at least one of the radically polymerizable compounds represented by the following general formula (12) with a specific monomer described later, removing protons using a base, and leaving Z. .

In formula (12), R ¹ to R ³ And X are the same as those in General Formula (1), respectively, and the same preferred examples can be applied.

In formula (12), Z represents an anionic leaving group. Q represents an oxygen atom, -NH- or -NR ^14- (wherein R ¹⁴ represents an alkyl group which may have a substituent). As R <^13> , a hydrogen atom, the alkyl group which may have a substituent, etc. are mentioned. In particular, a hydrogen atom, a methyl group, a methyl alkoxy group, and a methyl ester group are preferable. A represents a divalent organic linking group. The divalent organic linking group as A is not particularly limited, but is an alkylene group having 1 to 30 carbons in total (for example, methylene, ethylene, cyclohexylene), and an arylene group having 6 to 30 carbons in total (for example, phenylene). , Triylene, naphthalylene). Particularly preferred are alkylene having 1 to 10 total carbons and arylene having 6 to 15 total carbons.

In General formula (13), R <^1> -R <^3> is the same as that of General formula (1), and the same preferable example is applicable.

Synthesis Method 2)

A structure in which a stem polymer compound (polymer compound containing a main chain) is synthesized by copolymerizing at least one radical polymerizable compound having a functional group with a specific monomer described later, and the structure represented by the side chain functional group and the general formula (13) of the stem polymer compound. A method for obtaining a desired polymer compound by reacting a compound having a compound.

As a radically polymerizable compound represented by General formula (12), although the following compound can be enumerated as an example, it is not limited to this.

The radically polymerizable compound represented by General formula (12) can be easily obtained as a commercial item or by the synthesis method shown to the synthesis example mentioned later.

One or more of these radically polymerizable compounds, the specific monomers described below, and other radically polymerizable compounds, if necessary, are polymerized by a conventional radical polymerization method to synthesize a polymer compound, and the desired amount of base is cooled by a polymer solution. Or the group represented by General formula (1) can be introduce | transduced by carrying out reaction by dripping under heating conditions, and carrying out neutralization treatment with an acid as needed. For the production of the polymer compound, a conventionally known suspension polymerization method or solution polymerization method can be used.

As the base, either an inorganic compound or an organic compound can be used. Preferred inorganic bases include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen chloride, potassium carbonate, potassium hydrogen carbonate and the like. Examples of the organic base include metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, organic amine compounds such as triethyl amine, pyridine and diisopropyl ethyl amine.

In the synthesis method 2), as a functional group of the radically polymerizable compound which has a functional group used for synthesis | combination of a stem polymer compound, a hydroxyl group, a carboxyl group, a halogenated carboxylate group, a carboxylic anhydride group, an amino group, a halogenated alkyl group, an isocyanate group, Epoxy group etc. can be mentioned. As a radically polymerizable compound which has such a functional group, 2-hydroxyl ethyl acrylate, 2-hydroxyl ethyl methacrylate, 4-hydroxy butyl acrylate, 4-hydroxy butyl methacrylate, acrylic acid, methacrylic acid, Chloride acrylate, chloride methacrylate, methacrylic anhydride, N, N-dimethyl-2-amino ethyl methacrylate, 2-chloroethyl methacrylate, 2-ethyl isocyanate methacrylate, glycidyl acrylate, Glycidyl methacrylate, and the like.

At least 1 type of these radically polymerizable compounds and the specific monomer mentioned later are polymerized, and the stem polymer compound is synthesize | combined by copolymerizing with another radically polymerizable compound as needed, and it reacts with the compound which has group represented by General formula (13). By doing so, a desired polymer compound can be obtained.

Here, as an example of the compound which has a group represented by General formula (13), the compound enumerated as an example of the radically polymerizable compound which has the said functional group can be mentioned.

In the present invention, the polymer compound having a group represented by the general formula (2) can be produced by at least one of the synthesis methods 3) and 4) shown below.

Synthesis Method 3)

By polymerizing at least one of the radically polymerizable compounds having an unsaturated group represented by the general formula (2) and an ethylenically unsaturated group having higher polymerization property than the unsaturated group, the specific monomers described later and other radically polymerizable compounds as necessary Method of obtaining a polymer compound. This method uses the compound which has two or more ethylenically unsaturated groups with addition polymerization property to 1 molecule, such as allyl methacrylate.

Synthesis Method 4)

A polymer compound is synthesize | combined by copolymerizing 1 or more types of the radically polymerizable compound which has a functional group, and the specific monomer mentioned later, and reacting a side chain functional group and the compound which has a structure represented by following General formula (14) by General formula (2). How to introduce the displayed group.

In general formula (14), R <^4> -R <^8> is the same as that of general formula (2), and the same preferable example is applicable.

As a radically polymerizable compound which has the unsaturated group represented by General formula (2), and the ethylenically unsaturated group which is higher polymerization property than this unsaturated group, allyl acrylate, allyl methacrylate, 2-allyloxy ethyl acrylate, 2-allo Iloxy ethyl methacrylate, propargyl acrylate, propargyl methacrylate, allyl acrylate, allyl methacrylate, diallyl acrylate, diallyl methacrylate, N-allyl acrylamide, N-allyl methacrylamide And the like can be enumerated as examples.

Moreover, the example shown to the said synthesis method 2) can be mentioned as an example of the polymer compound obtained by superposing | polymerizing 1 or more types of the radically polymerizable compound which has a functional group.

Examples of the compound having a structure represented by Formula (14) include allyl alcohol, allyl amine, diallyl amine, 2-allyloxy ethyl alcohol, 2-chloro-1-butene and allyl isocyanate.

The polymer compound having a group represented by the general formula (3) according to the present invention can be produced by at least one of the synthesis methods 5) and 6) shown below.

Synthesis Method 5)

One or more of the radically polymerizable compounds having an unsaturated group represented by the general formula (3) and an ethylenically unsaturated group having higher polymerization property than this unsaturated group and a specific monomer described later are copolymerized, and other radically polymerizable compounds as necessary. A method of obtaining a polymer compound by copolymerizing with a.

Synthesis Method 6)

A method of introducing by reacting a compound having a structure represented by the side chain functional group with the general formula (15) after the polymer compound is synthesized by copolymerizing at least one of the radically polymerizable compounds having a functional group with a specific monomer described later.

As a radically polymerizable compound which has the unsaturated group represented by General formula (3), and the ethylenically unsaturated group which is higher polymerization property than this unsaturated group, vinyl acrylate, vinyl methacrylate, 2-phenyl vinyl acrylate, 2-phenyl Vinyl methacrylate, 1-propenyl acrylate, 1-propenyl methacrylate, vinyl acrylamide, vinyl methacrylamide, and the like can be enumerated as examples.

As a polymer compound obtained by copolymerization, the thing enumerated as the example in the said synthesis method 2) can be obtained.

In general formula (15), R <^9> -R <^11> is the same as that of general formula (3), and the same preferable example is applicable.

As a compound which has a structure represented by General formula (15), 2-hydroxy ethyl monovinyl ether, 4-hydroxy butyl monovinyl ether, diethylene glycol monovinyl ether, 4-chloromethyl styrene, etc. are mentioned as an example. Can be.

In addition to the general formula (12) used in the synthesis method 1) in the synthesis method 1), a synthesis method using one or more of the following general formulas (4) and (5) is also preferable.

In formula (4) or (5), R ⁵ _, R ⁶ _, R ⁷ represents hydrogen or a monovalent organic group, A ² represents an oxygen atom, a sulfur atom or -NR ^8- , G ¹ represents an organic linking group, R ⁸ represents hydrogen or a monovalent organic group, and n is 1 to 1 The integer of 10 is shown. R ¹ to R ³ are the same as those in General Formula (12), A ¹ is the same as X in General Formula (1), and X ¹ is the same as Z in General Formula (12).

R <^9> -R <^13> represents hydrogen or monovalent organic group, and at least 1 is group represented by following General formula (6). R <^14> -R <^16> represents hydrogen or monovalent organic group.

In general formula (4) or (5), a monovalent organic group is the same as the monovalent organic group in General formula (1), and the same preferable example is applicable.

In the general formula (6), G ² represents an organic linking group, m represents an integer of 1-10. R ¹ to R ³ _, A ¹ _{, and} X ¹ are the same as those in General Formula (4).

The following can be mentioned as a preferable specific example of a compound represented by the said General formula (4) or (5) (i-1-i-60).

In the synthesis of a compound having a group represented by the general formula (1) obtained by using the general formula (4) or (5) (hereinafter also referred to as a "polyvinyl polymer compound"), in addition to other general radically polymerizable compounds Copolymerization of a compound having a double bond by a leaving reaction as described above is also one embodiment of the present invention.

In the synthesis methods 1) to 6), other general radically polymerizable compounds may be copolymerized as necessary as described above. In the present invention, as a general radically polymerizable compound to be copolymerized, for example, acrylate, methacrylate, N, N-2 substituted acrylamide, N, N-2 substituted methacryl amide, styrene, acrylonitrile, methacryl Ronitrile and the like.

Specific examples include alkyl acrylates (preferably 1-20 carbon atoms in the alkyl group) (specifically, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl Acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-dimethyl hydroxyl propyl acrylate, 5-hydroxy pentyl acrylate, trimethylol propane monoacrylate, pentaerythritol monoacrylate, Acrylates such as glycidyl acrylate, benzyl acrylate, methoxy benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like), aryl acrylate (for example, phenyl acrylate and the like),

Alkyl methacrylate (preferably 1-20 carbon atoms in the alkyl group) (specifically, for example, methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate) Latex, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxy butyl methacrylate, 5-hydroxy pentyl methacrylate, 2,2 -Dimethyl-3-hydroxy propyl methacrylate, trimethylol propane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.), Aryl methacrylate (for example, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.); Methacrylate acids,

Styrene and alkyl styrenes (methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene , Ethoxy methyl styrene and acetoxy methyl styrene, etc.), alkoxy styrene (such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene), halogen styrene (chloro styrene, dichloro styrene, trichloro styrene, tetra Chloro styrene, pentachloro styrene, bromine styrene, dibrom styrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl styrene and 4-fluoro-3-trifluoromethyl Styrenes such as styrene), acrylonitrile and methacrylonitrile.

As a radically polymerizable compound containing carboxylic acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p-carboxy styrene, etc. can be mentioned, for example.

Moreover, as a solvent used when synthesize | combining the said polyvinyl type polymer compound, For example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, 2-methoxy ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethyl formamide, N, N-dimethyl acetoamide, dimethyl sulfoxide, Toluene, ethyl acetate, methyl lactate, ethyl lactate, 1-methyl-2-pyrrolidone and the like.

These solvents can be used alone or as a mixture of two or more thereof.

As described above, the resin in the present invention as a copolymer is a resin produced by polymerizing a monomer having a dipole moment of 2.0 or more (hereinafter, also referred to as a "specific monomer") as a copolymerization component. "Specific monomer" is monomers other than the monomer which has an alkali-soluble group mentioned later here.

As said dipole moment, the numerical value calculated by the following calculation method was used.

That is, CAChe6.1 (manufactured by Fujitsu Corp.) is used to optimize the structure of the specific monomer obtained by the calculation method AM1, and then calculate the dipole moment by the optimum structure.

According to the specific monomer as the copolymerization component of the resin in the present invention, the structure is not limited as long as the dipole moment calculated by the calculation method is 2.0 or more. In particular, from the viewpoint of sensitivity and storage stability, the value of the dipole moment is preferably 2.5 or more, more preferably 2.5 or more and 15 or less, still more preferably 3.0 or more and 10 or less, particularly preferably 3.5 or more and 9.0 or less, particularly 3.5 or more Most preferably, it is 8.0 or less.

Since the dipole moment of the said specific monomer exists in the range of 2.5 or more and 15 or less, it is preferable from a viewpoint of the ease of resin synthesis | combination, the sensitivity of the curable composition containing resin, developability, and storage stability.

Among the above examples, it is particularly preferred that the specific monomer has at least one group selected from the group consisting of ether groups, cyano groups, phosphate groups, lactone groups, urethane groups, carbonate groups and acetal groups.

The ether group contained in the specific monomer is preferably a straight chain, branched or cyclic ether group having 2 to 30 carbon atoms, and particularly preferably a straight chain, branched or cyclic ether group having 2 to 15 carbon atoms. Examples of ether group, 2-methoxyethyl, _{2-ethoxyethyl, MeOCH 2 CH 2 OCH 2 CH} 2 -, MeO (CH 2 CH 2 O) 2 CH 2 CH 2 -, oxetane-2-one, octanoic Cetane-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-2-yl, tetrahydro-2H-pyran-2-yl, octahydro-1H-isoclomen-3-yl, oxirane-2- Work and the like.

The lactone group contained in the specific monomer is preferably a lactone group having 3 to 30 carbon atoms, and more preferably a lactone group having 5 to 20 carbon atoms. As an example of a lactone group, the following structure can be enumerated. In the following structures, R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, wherein the alkyl group, cycloalkyl group or aryl group each independently has 1 to 20 carbon atoms.

The urethane group contained in a specific monomer is preferably a linear or cyclic urethane group having 1 to 30 carbon atoms, and a linear or cyclic urethane group having 1 to 20 carbon atoms is preferable.

As an example of a urethane group, although the following structure can be enumerated, it is not limited to this. In the following structures, R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, wherein the alkyl group, cycloalkyl group or aryl group each independently has 1 to 20 carbon atoms.

The carbonate group contained in the specific monomer is preferably a linear or cyclic carbonate group having 1 to 30 carbon atoms, and a linear or cyclic carbonate group having 1 to 20 carbon atoms is preferable.

As an example of a carbonate ester group, although the following structure can be enumerated, it is not limited to this.

The acetal group contained in the specific monomer is preferably a linear or cyclic acetal group having 1 to 30 carbon atoms, and a linear or cyclic acetal group having 1 to 20 carbon atoms is preferable. As an example of an acetal group, although the following structure can be enumerated, it is not limited to this. In the following structures, R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, wherein the alkyl group, cycloalkyl group or aryl group each independently has 1 to 20 carbon atoms.

The phosphate contained in the specific monomer is preferably a linear or cyclic phosphate group having 1 to 30 carbon atoms, and more preferably a linear or cyclic phosphate group having 1 to 20 carbon atoms. As an example of a phosphate group, the following structure is enumerated, but it is not limited to this.

As a specific example of the said monomer, although the following compound can be used preferably, it is not limited to this.

In the present invention, the resin is a resin prepared by polymerizing the specific monomer as a copolymerization component, and has a partial structure which may or may be an ethylenically unsaturated double bond of the side chain of the resin (hereinafter, "provides a double bond of resin. Preferred is a resin prepared by polymerizing " copolymerizing component &quot;

In the present invention, as a combination of a copolymerization component providing a resin, that is, a combination of "specific monomer" and "copolymerization component providing a double bond of a resin", M-1, M-8, i-1, i-7, i Any of -8, i-10, i-16 and i-49 and M-9A, M-11A, M-12A, M-13A, M-14A, M-15A, M-9MA, M-11MA, Combinations of any one of M-12MA, M-13MA, M-14MA, M-15MA and M-16MA are preferred, and any of M-1, i-1, i-10, i-16 and i-49 And combinations of any one of M-11A, M-13A, M-14A, M-11MA, M-13MA and M-14MA are more preferable, and a combination of Exemplified Compound i-1 and Exemplified Compound M-14MA, Exemplary Compound Combination of i-1 and Exemplary Compound M-11MA, Combination of Exemplary Compound i-1 and Exemplary Compound M-13MA, Combination of Exemplary Compound M-1 and Exemplary Compound M-14MA, Exemplary Compound M-1 and Exemplary Compound M- Particular preference is given to combinations of 11MA and combinations of exemplary compound M-1 and exemplary compound M-13MA.

The said combination is preferable from a viewpoint of the ease of resin synthesis, the sensitivity and developability of curable composition containing resin, and storage stability.

In the present invention, the configuration of the resin may be a block copolymer, a random copolymer, a graft copolymer, or the like. In particular, a block copolymer is preferable in view of ease of resin synthesis.

In the present invention, the content of the copolymer component that provides the double bond of the resin is preferably 0.1 mol% to 95 mol%, more preferably 1 mol% to 85 mol%, and more preferably 5 mol% to 75 mol%. Is particularly preferred.

Here, the "content of the copolymerization component which provides the double bond of resin" specifically means the following.

That is, in the said synthesis method 1), "content in the copolymer of the radically polymerizable compound represented by General formula (12)" means, and in the said synthesis methods 2), 4), and 6), it is "radical polymerizable which has a functional group. Content in the copolymer as a copolymerization component after the reaction of any of the functional groups and the general formulas (13), (14) and (15) after copolymerization of the compound, and in the synthesis method 3) or 5), The content in the copolymer of the radically polymerizable compound which has the unsaturated group represented by (2) or (3) and the ethylenically unsaturated group which is higher polymerization property than the said unsaturated group "is meant.

Since content of the copolymerization component which provides the double bond of the said resin exists in the said range, since a sensitivity improves and adhesiveness with respect to a board | substrate is favorable, it is preferable.

In the resin of the present invention, the content of the specific monomer is preferably 1 mol% to 90 mol%, more preferably 3 mol% to 70 mol%, more preferably 5 mol% to 50 mol% as the copolymerization component. Particularly preferred.

Since content of the said specific monomer exists in the said range, since a sensitivity improves and adhesiveness with respect to a board | substrate is favorable, it is preferable.

In the said resin, it is preferable that the molar ratio of "content of the said specific monomer" and "content of the copolymerization component which provides the double bond of the said resin" in the said resin is 100: 1-1: 100, and 50: 1-1: 1: It is more preferable that it is 50, and it is especially preferable that it is 10: 1-1:10.

Since the component ratio of the copolymerization component which provides the double bond of the said specific monomer and the said resin is in the said range, since a sensitivity improves and adhesiveness with respect to a board | substrate is favorable, it is preferable.

In the present invention, the resin may be a resin produced by polymerization with a monomer containing an alkali-soluble group as a copolymerization component. Here, an "alkali soluble group" means a functional group which is decomposed by a developing solution used when forming a pattern and solubility in a developing solution (alkaline aqueous solution) is improved. The alkali-soluble group is preferably a functional group having a pKa of 11 or less in water at 25 ° C. As a functional group, a carboxyl group, a sulfo group, a sulfone amide group, a phosphoric acid group, a phenol type hydroxyl group, etc. are mentioned, for example. In particular, carboxyl groups are most preferred.

It is preferable that content as a copolymerization component of the monomer containing the said alkali-soluble group is 1 mol%-90 mol%, It is more preferable that it is 3 mol%-70 mol%, It is especially preferable that it is 5 mol%-50 mol%. .

Since content as a copolymerization component of the monomer containing the said alkali-soluble group exists in the said range, since a sensitivity improves and adhesiveness with respect to a board | substrate is favorable, it is preferable.

It is preferable that a weight average molecular weight (polystyrene conversion value in a GPC measurement method) is 500-100,000, It is more preferable that it is 1,000-50,000, It is especially preferable that it is 1,000-30,000. 3.0 or less are preferable and, as for molecular weight distribution (a ratio of a weight average molecular weight and a number average molecular weight), 2.0 or less are most preferable.

Although the specific example of resin in this invention is shown below with those weight average molecular weights, this invention is not limited to these.

According to the resin in the present invention, the total content (mol%) of the copolymerization component providing the double bond of the specific monomer and the resin is preferably 2 mol% to 98 mol%, preferably 5 mol% to 90 mol%. More preferably, it is especially preferable that they are 10 mol%-80 mol%.

Since the said total content exists in the said range, since a sensitivity improves and adhesiveness with respect to a board | substrate is favorable, it is preferable.

It is preferable that content of the said resin is 0.1 mass%-75 mass% with respect to the total solid of the curable composition of this invention, 1 mass%-50 mass% are more preferable, 2 mass%-40 mass% are especially preferable. . According to this range, good sensitivity and pattern formability can be obtained.

<(B) Photoinitiator>

The curable composition of this invention contains a photoinitiator (B) for the improvement of a sensitivity and pattern formation property.

The photoinitiator in this invention is a compound which decomposes | disassembles by light, starts and accelerates superposition | polymerization of the polymeric component in this invention, and it is preferable to have absorption in the range of 300-500 nm wavelength. In addition, a photoinitiator can be used individually or in combination of 2 or more types.

As a photoinitiator, an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide compound, an azo compound, a coumarin compound, an azide compound, a metallocene compound, for example , Hexaaryl biimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, acyl phosphine (oxide) compounds, alkyl amino compounds and the like.

Hereinafter, each compound is explained in full detail.

As the organic halogenated compound, specifically Wakabayashi et al. "Bull Chem. Soc Japan" 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281, Small 55-32070, Small 60 -239736, SO 61-169835, SO 61-169837, SO 62-58241, SO 62-212401, SO 63-70243, SO 63-298339, by MP Hutt, "Journal of Heterocyclic Chemistry And compounds disclosed in “1 (No 3), (1970)”, etc. In particular, oxazole compounds substituted with trihalomethyl groups and s-triazine compounds can be enumerated.

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, more specifically, for example, 2, 4,6-tris (monochloro methyl) -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 (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p -Chloro phenyl) -4,6-bis (trichloro methyl) -s-triazine, 2- [1- (p-methoxy phenyl) -2,4-butadienyl] -4,6-bis (trichloro Methyl) -s-triazine, 2-s Tyryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi- Propyloxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Naphthoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl thio-4,6-bis (trichloromethyl) -s-triazine, 2-benzyl thio-4 , 6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromo methyl) -s-triazine, 2,4,6-tris (tribromo methyl) -s- Triazine, 2-methyl-4,6-bis (tribromo methyl) -s-triazine, 2-methoxy-4,6-bis (tribromo methyl) -s-triazine and the like can be enumerated. have.

As the oxydiazole compound, 2-trichloro methyl-5-styryl-1,3,4-oxodiazole, 2-trichloro methyl-5- (cyano styryl) -1,3,4-oxodia Sol, 2-trichloro methyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloro methyl-5- (4-styryl) styryl-1,3, 4-oxodiazole, etc. can be mentioned.

Examples of the carbonyl compound include benzophenone, Michler's ketone, 2-methyl benzophenone, 3-methyl benzophenone, 4-methyl benzophenone, 2-chloro benzophenone, 4-bromo benzophenone, and 2-carboxy benzophenone. Benzophenone derivatives of 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenone, 1-hydroxy cyclohexyl phenyl ketone, α-hydromethoxy-2-methyl phenyl propanone, 1- Hydroxy-1-methyl ethyl- (p-isopropyl phenyl) ketone, 1-hydroxy-1- (p-dodecyl phenyl) ketone, 2-methyl (4 '-(methyl thio) phenyl) -2-mor Acetophenone derivatives such as polyno-1-propanone, 1,1,1-trichloro methyl- (p-butyl phenyl) ketone, and 2-benzyl-2-dimethyl amino-4-morpholino butyrophenone, Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4- Thioxanthone derivatives such as diisopropyl thioxanthone, p-dimethyl Mino ethyl benzoate, p- can be listed diethyl aminoethyl and the like, such as benzoin benzoin benzoate benzoate derivative.

As a ketal compound, benzyl methyl ketal, benzyl- (beta)-methoxy ethyl ethyl acetal, etc. can be mentioned.

Examples of the benzoin compound include m benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl benzoate and the like.

As an acridine compound, 9-phenyl acridine, 1,7-bis (9-acridinyl) heptane, etc. can be mentioned.

Examples of the organic peroxide compound include trimethyl cyclohexanone peroxide, acetyl acetone peroxide, 1,1-bis (tert-butyl peroxy) -3,3,5-trimethyl cyclohexane, 1,1-bis (tert -Butyl peroxy) cyclohexane, 2,2-bis (tert-butyl peroxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropyl benzene hydroperoxide, 2, 5-dimethyl hexane-2 , 5-dihydroperoxide, 1,1,3,3-tetramethyl butyl hydroperoxide, tert-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butyl Peroxy) hexane, 2,5-oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichloro benzoyl peroxide, diisopropyl peroxy dicarbonate, di-2-ethyl hexyl peroxy dicarbon , Di-2-ethoxy ethyl peroxy dicarbonate, dimethoxy isopropyl peroxy car Carbonate, di (3-methyl-3-methoxy butyl) peroxy dicarbonate, tert-butyl peroxy acetate, tert-butyl peroxy pivalate, tert-butyl peroxy neodecanoate, tert-butyl per Oxy octanoate, tert-butyl peroxy laurate, tesyl carbonate, 3,3 ', 4,4'-tetra- (t-butyl peroxy carbonyl) benzophenone, 3,3', 4,4 '-Tetra- (t-hexyl peroxy carbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropyl cumyl peroxy carbonyl) benzophenone, carbonyl di (t-butyl per Oxy diphthalate dihydrogen), carbonyl di- (t-hexyl peroxy diphthalate dihydrogen), and the like.

As an azo compound, the azo compound etc. which were described, for example in Unexamined-Japanese-Patent No. 8-108621 can be mentioned.

Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenyl coumarin and 3-chloro-5-diethyl amino-((s-triazine -2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethyl amino-((s-triazin-2-yl) amino) -3-phenyl coumarin, and the like.

Examples of the diazide compound include the organic azide compounds described in US Pat. Nos. 2,848,328, 2,852,379 and 2,940,853, and 2,6-bis (4-azide benzylidene) -4-ethyl cyclohexanone (BAC-E). And the like.

Examples of the metalocene compound include di-cyclopentadienyl-Ti-bisphenyl, G-cyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, and di-cyclopentadienyl-Ti. -Bis-2,4-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl- Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl , Di-methylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1 -Yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4, 5,6-pentafluorophenyl-1-yl, Japanese Patent Laid-Open Publication Nos. 59-152396, and 61-151197, such as the iron-arene complexes described in Japanese Patent Application Laid-open No. Hei 1-304453, and Japanese Patent Application Laid-Open No. Hei 1-52109. No. 63-41484, No. 2-249, No. 2-4705, and It can be exemplified by various titanocene compounds described in JP-5-83588 call.

As the hexaaryl biimidazole compound, for example, various compounds described in JP-A-6-29285, U.S. Patent Nos. 3,479,185, 4,311,783, 4,622,286, and the like, specifically, 2,2'-bis (o -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-bromophenyl)) 4,4', 5,5'-tetraphenyl biimidazole , 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxy phenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2 , 2'-bis (o-nitrophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'- Tetraphenyl biimidazole, 2,2'-bis (o-trifluoro phenyl) -4,4 ', 5,5'-tetraphenyl biimidazole and the like.

As an organic borate compound, for example, Unexamined-Japanese-Patent No. 62-143044, 62-150242, 9-988685, 9-188686, 9-188710, 2000-131837, and 2002-107916 Japanese Patent No. 2,764,769, Japanese Patent Application Laid-Open No. 2000-310808, and Kunz, Martin, organic borate described in "Rad Tech '98. Proceeding April 19-22, 1998, Chicago," Japanese Patent Application Laid-Open No. 6-157623 Organic sulphonium borate complexes or organic oxosulfonium borate complexes described in Japanese Patent Application Laid-Open Nos. 6-175564 and 6-175561, and the organic iodonium disclosed in Japanese Patent Application Laid-open Nos. Hei 6-175554 and 6-175553 Borate complex, organic phosphonium borate complex disclosed in Japanese Patent Laid-Open No. 9-188710, Japanese Patent Laid-Open No. 6-348011, Japanese Patent Laid-Open No. 7-128785, Japanese Patent Laid-Open No. 7-140589, Japanese Patent Laid-Open No. 7-306527 The organoboron mutated metal coordination complexes, such as 292014, etc. can be mentioned as a specific example.

As a disulfonic acid compound, the compound etc. which are described in the specification of Unexamined-Japanese-Patent No. 61-166544, the specification of Unexamined-Japanese-Patent No. 2002-238465, etc. can be mentioned.

Examples of oxime ester compounds include J. C. S. Perkin II (1979) 1653-1660), J. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and The compound described in Unexamined-Japanese-Patent No. 2000-66385, the compound of Unexamined-Japanese-Patent No. 2000-80068, the international patent application 2004-534797, etc. can be mentioned.

As an onium salt compound, it is S.I. Schlesinger, Photogr. Sci. Diazonium salts disclosed in Eng., 18, 387 (1974) and in T. S. Bal et al, Polymer, 21, 423 (1980), in the specification of US Pat. No. 4,069,055, and in JP-A-4-365049. Ammonium salts, phosphonium salts disclosed in U.S. Patent Nos. 4,069,055 and 4,069,056, European Patent Nos. 104,143, U.S. Patents 339,049 and 410,201, and Japanese Patent Laid-Open Nos. 2-150848 and 2-296514. Listed iodonium and the like.

The iodonium salt preferably used in the present invention is a diaryl iodonium salt. From the standpoint of stability, it is preferable that two or more electron donating groups such as an alkyl group, an alkoxy group and an aryloxy group are substituted.

As sulfonium salts preferably used in the present invention, European Patent Nos. 370,693, 390,214, 233,567, 297,443 and 297,442, US Patents 4,933,377, 161,811, 410,201 and 339,049 And sulfonium salts disclosed in US Pat. Nos. 4,760,013, 4,734,444 and 2,833,827, and German Patents 2,904,626, 3,604,580 and 3,604,581. It is preferable to substitute by the electron-withdrawing group from the point of stability. It is preferable that the electron-withdrawing group has a hammit value exceeding zero. As a preferable electron withdrawing group, a halogen atom, carboxylic acid, etc. can be mentioned.

Moreover, as another preferable sulfonium salt, the sulfonium salt which has one substituent of a triaryl sulfonium salt has a coumarin and anthraquinone structure, and has absorption in 300 nm or more. As another preferable sulfonium salt, the sulfonium salt which triaryl sulfonium salt has an allyloxy group and an arylthio group as a substituent, and has absorption in 300 nm or more is mentioned.

Moreover, as an onium salt compound, J. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977, J. V. Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 ( Onium salts, such as the selenium salt of 1979), and the arsonium salt of C. S. Wen et al, Tech, Proc, Conf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), etc. can be mentioned.

As an acyl hosepin (oxide) compound, Ciba Specialty Chemicals Corp. Products include IRUGACURE 819, DAROCURE 4265, and DAROCURE TPO.

As the alkyl amino compound, for example, a compound or alkyl having a dialkylamino phenyl group disclosed in Japanese Patent Laid-Open No. 9-281698, Japanese Patent Laid-Open No. 6-19240 and Japanese Patent Laid-Open No. 6-19249 or the like Amine compounds may be enumerated. Specifically, examples of the compound having a dialkyl amino phenyl group include compounds such as p-dimethyl amino benzoate, and dialkyl amino phenylcarboxes such as p-diethyl amino benzcarbaldehyde and 9-julloydyl carbaldehyde. The aldehyde can be enumerated, and examples of the alkyl amine compound include triethanol amine, diethanol amine, triethyl amine and the like.

<Photoinitiator (B)>

From the viewpoint of exposure sensitivity, the photopolymerization initiator (B) used in the present invention is a triazine compound, an alkyl amino compound, a benzyl gimethyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an acyl phosphine compound, or a phosph Fin oxide compounds, metalocene compounds, oxime compounds, biimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes And a salt, a halomethyl oxadiazole compound, and a compound selected from the group consisting of a 3-aryl substituted coumarin compound.

Triazine compounds, alkyl amino compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, oxime compounds, biimidazole compounds, onium compounds, benzophenone compounds or acetophenone compounds desirable. At least one compound selected from the group consisting of a triazine compound, an alkyl amino compound, an oxime compound and a biimidazole compound is more preferable.

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

<Compound (C) having an ethylenically unsaturated double bond>

The curable composition of this invention can contain the compound which has an ethylenically unsaturated double bond other than the said resin (henceforth a "compound which has an ethylenically unsaturated double bond").

The compound having an ethylenically unsaturated double bond used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond in addition to the resin, and has at least one, preferably two or more terminal ethylenically unsaturated bonds. It is selected from the compound having. Such groups of compounds are well known in the industry and can therefore be used without any limitation in the present invention. These have, for example, the chemical forms of monomers, prepolymers, ie oligomers having dimers or trimers, mixtures thereof and copolymers thereof. As an example of a monomer and its copolymer, unsaturated carboxylic acid (acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), its ester, and an amide can be mentioned. Preferably, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds and amides of unsaturated carboxylic acids and aliphatic polyamine compounds can be used. In addition, dehydration of unsaturated carboxylic acid esters or amides having polynuclear substituents such as hydroxyl groups, amino groups and mercapto groups with addition reactions of monofunctional or polyfunctional isocyanates or epoxy or monofunctional or polyfunctional carboxylic acids Condensation reactants can also be preferably used. Further, unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups and addition reaction products of monofunctional or polyfunctional alcohols, amines or thiols, and also leavingable substituents such as halogen groups and tosyloxy groups Preference is also given to substitution reactions of unsaturated carboxylic acid esters or amides with monofunctional or polyfunctional alcohols, amines or thiols. As another example, a compound group in which the above unsaturated carboxylic acid is substituted with unsaturated phosphonic acid, styrene, vinyl ether, or the like may be used.

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

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-hydroxypropoxy) phenyl] dimethylmethane and bis- [p- (methacryloxyethoxy) phenyl] Methacrylic acid esters such as dimethylmethane.

Ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butane diol diitaconate, 1,4-butane diol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate and sorbitol tetraitaconate, etc. Itaconic acid esters. Crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate and sorbitol tetradicrotonate. Isocrotonic acid esters such as ethylene glycol diisocrotonate and pentaerythritol diisocrotonate. Maleic esters such as ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate and sorbitol tetramaleate.

As examples of other esters, for example, the aliphatic alcohol esters described in Japanese Patent Application Laid-Open No. 51-47334 and Japanese Patent Application Laid-open No. 57-196231, or Japanese Patent Publication No. 59-5240, No. 59-5241, and Esters having an aromatic skeleton described in Japanese Patent Application Laid-Open No. 2-226149 and esters having an amino group described in Japanese Patent Application Laid-Open No. Hei 1-65613 are also preferably used. In addition, the above-mentioned ester monomer can be used also as a mixture.

Moreover, as an example of the monomer of the amide of an aliphatic polyhydric amine compound and unsaturated carboxylic acid, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylenebis- acrylamide, 1, 6- hexamethylene bis Methacrylamide, diethylenetriaminetrisacrylamide, xylenebisacrylamide and xylenebismethacrylamide. Examples of other preferred amide monomers include monomers having a cyclohexylene structure described in JP-A-54-21726.

Moreover, the urethane type addition polymeric compound manufactured using addition reaction of an isocyanate and hydroxyl group is also preferable. As a specific example, the hydroxyl group of the compound represented by the following general formula (A) to the polyisocyanate compound which has 2 or more isocyanate groups in 1 molecule etc. which are described, for example in Unexamined-Japanese-Patent No. 48-41708, etc. The vinyl urethane compound etc. which have two or more polymerizable vinyl groups in the molecule | numerator to which the vinyl monomer which has is added are mentioned.

CH ₂ = C (R ¹⁰ ) COOCH ₂ CH (R ¹¹ ) OH General formula (A)

(Wherein R ¹⁰ and R ¹¹ represent H or CH ₃ ).

In addition, the urethane acrylates described in Japanese Patent Laid-Open Nos. 51-37193, Japanese Patent Laid-Open Nos. 2-32293 and 2-16765 and Japanese Patent Laid-Open Nos. 58-49860, 56-17654, and Also preferred are urethane compounds having an ethylene oxide-based backbone described in 62-39417 and 62-39418. Moreover, the photopolymerizable composition which was very excellent in the photosensitive rate by using the addition polymeric compound which has an amino structure or a sulfide structure in the molecule | numerator of Unexamined-Japanese-Patent No. 63-277653, 63-260909, and 1-105238 is used. Can be obtained.

Another example is the reaction of polyester acrylate and epoxy resins described in each specification of Japanese Patent Application Laid-Open Nos. 48-64183, 49-43191 and 52-30490 to the reaction of (meth) acrylic acid. Polyfunctional acrylates and methacrylates, such as obtained epoxy acrylate, are mentioned. Moreover, the specific unsaturated compound of Unexamined-Japanese-Patent No. 46-43946, 1-40337, 1-40336, and the vinyl phosphonic acid type-compound of Unexamined-Japanese-Patent No. 2-25493 are mentioned. The structure which has a perfluoroalkyl group of Unexamined-Japanese-Patent No. 61-22048 may be used preferably. In addition, Adhesion Society of Japan, vol. 20, No. 7, p. Compounds introduced as photocurable monomers and oligomers in the journals 300 to 308 (1984) can also be used.

The details of the structure of these addition-polymerizable compounds, used alone or in combination, and the amount of addition can be arbitrarily set according to the performance design of the curable composition. For example, it can select from the following viewpoint.

In view of sensitivity, a structure containing a large amount of unsaturated group per molecule is preferable. In most cases, more than bifunctional is preferable. Moreover, in order to improve the intensity | strength of an image part, ie, a cured film, a trifunctional or more thing is preferable. Moreover, the method of adjusting both a sensitivity and intensity | strength is also effective by using the combination of another functional water and another polymerizable group (for example, acrylic ester, methacrylic ester, styrene type compound, and vinyl ether type compound). From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably to use a compound containing three or more, and to use a compound containing four or more. Most preferred. In addition, it is preferable to contain an EO-modified substance from a 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 strength.

The addition and use of the addition polymerizable compound are also important factors in terms of compatibility and dispersibility with other components (resin, photopolymerization initiator and pigment) and the like in the curable composition. For example, the use of low purity compounds or the use of two or more combinations can improve compatibility. Moreover, a specific structure can also be selected in order to improve adhesiveness with a board | substrate.

In view of the above, bisphenol A diacrylate, bisphenol A diacrylate EO-modified substance, trimethylol propane triacrylate, trimethylol propane tri (acryloyloxy propyl) ether, trimethylol ethane triacrylate, tetraethylene glycol Diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetra Acrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy ethyl) isocyanurate, pentaerythritol tetraacrylate EO-modified material, dipentaerythritol hexaacrylate EO-modified material As the preferred examples can be exemplified. Moreover, as a commercial item, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp Corp.), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH- 600, T-600, AI-600 (manufactured by Kyoeisha Chemical CO., Ltd.), and UA-7200 (manufactured by Shin-Nakamura Chemical. Co., Ltd.) are preferred.

Among them, EO-modified bisphenol A diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanuret , EO-modified pentaerythritol tetraacrylate and EO-modified dipentaerythritol hexaacrylate are more preferred. Commercially available products include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical CO., LTD.) This is more preferable.

Content of the compound which has ethylenically unsaturated double bond other than resin (C) in this invention is; It is preferable that the said resin (A) in solid content of the curable composition of this invention is 1 mass%-90 mass%, It is more preferable that it is 5 mass%-80 mass%, It is further more preferable that it is 10 mass%-70 mass%. Do.

When using the curable composition of this invention especially for formation of the coloring pattern of a color filter, it is preferable that content of the compound which has ethylenically unsaturated double bonds other than (C) resin is 5 mass%-50 mass% in the said range. It is more preferable that they are 7 mass%-40 mass%, and it is still more preferable that they are 10 mass%-35 mass%.

Moreover, from a viewpoint of a sensitivity and the removability (developability) of an unexposed part, content ratio (mass ratio) of the said resin (A) and (C); 0.001-100 (A) / (C) is preferable, 0.005-50 are more preferable, and 0.01-10 are more preferable for compounds which have ethylenically unsaturated double bonds other than resin (A).

<Colorant (D)>

It is preferable that the curable composition of this invention contains a coloring agent (D).

There is no restriction | limiting in particular in the coloring agent contained in the curable composition of this invention, The conventionally well-known various dye and pigment can be used as 1 type, or 2 or more types of mixtures. It is preferable that a coloring agent is a pigment from a viewpoint of durability, such as heat resistance and light resistance.

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

Examples of the inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and composite oxides of the metals may be enumerated.

As the 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;

Carbon black and the like.

In the present invention, those having a basic N atom in the structural formula of the pigment can be particularly preferably used. Pigments having these basic N atoms exhibit advantageous dispersibility in the compositions of the present invention. Although the cause is not elucidated sufficiently, it is presumed that the favorable affinity of the photosensitive polymerization component and a pigment has influenced.

As the pigment preferably used in the present invention, the following may be mentioned. However, the present invention is not limited thereto:

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 individually or in combination of these in order to improve color purity. The specific example of the said combination is shown below. For example, an anthraquinone pigment, a perylene pigment, or a diketopyrrolopyrrole pigment alone, or one or more thereof, and an azo yellow pigment, an isoindolin yellow pigment, a quinophthalone yellow pigment, or the like as a red pigment. Mixtures of perylene-based red pigments can be used. For example, C.I. Pigment Red 177 is listed as an anthraquinone pigment, C.I. Pigment Red 155 and C.I. Pigment Red 224 are listed as perylene pigments, and diketopyrrolopy C. I. pigment red 254 is mentioned as a roll pigment. From the viewpoint of color reproducibility, a mixture with C. Pigment Yellow 139 is preferable. As for the mass ratio of a red pigment and a yellow pigment, 100: 5-100: 50 are preferable. If this ratio is 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm-500 nm, and color purity may not be improved. If the ratio is 100: 51 or more, the dominant wavelength may be closer to the shorter wavelength, which may increase the deviation from the NTSC target color. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of the combination of a red pigment, a ratio can be adjusted according to chromaticity.

As the green pigment, a halogenated phthalocyanine pigment alone or a mixture of an azo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin yellow pigment can be used. For example, C.I. Pigment Green 7, 36, 37 and C. I. Pigment Yellow 83, C. I. Pigment Yellow 138, C. I. Pigment Yellow 139, C. I Pigment Yellow 150, C. I. Pigment Yellow 180 or C. I. Pigment Yellow 185 is a mixture of preferred. As for the mass ratio of a green pigment and a yellow pigment, 100: 5-100: 150 are preferable. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

As a blue pigment, a phthalocyanine type pigment can be used individually or a mixture of this and a dioxazine type purple pigment can be used. For example, a mixture of C. Pigment Blue 15: 6 and C. Pigment Violet 23 is preferable. As for mass ratio of a blue pigment and a purple pigment, 100: 0-100: 30 are preferable, More preferably, it is 100: 10 or less.

As the pigment for the black matrix, carbon, titanium carbon, iron oxide, and titanium oxide are used alone or in a mixture thereof. Combinations of carbon and titanium carbon are preferred. The mass ratio of carbon and titanium carbon is preferably in the range of 100: 0 to 100: 60.

When used for color filters, the average particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and more preferably 5 nm or more from the viewpoint of dispersion stability. As for the average particle size of a pigment, 5-75 nm is more preferable, More preferably, it is 5-55 nm, Especially preferably, it is 5-35 nm.

The average particle size of a pigment can be measured by well-known methods, such as an electron microscope.

In particular, the pigment is preferably a pigment selected from anthraquinone series, azomethine series, benzylidene series, cyanine series, diketopyrrolopyrrole series and phthalocyanine series.

In addition, when using the composition of this invention for a color filter, it is preferable to use the dye which melt | dissolves uniformly in a composition from a viewpoint of color nonuniformity and contrast.

The dye 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, JP-A-64-90403, JP-64-91102, JP 1-94301 and JP 6-11614, JP 2,592,207, JP 4,808,501, 5,667,920, and No. 5,059,500, Japanese Patent Application Laid-Open No. 5-333207, No. 6-35183, No. 6-51115, No. 6-194828, No. 8-211599, No. 4-249549, No. 10-123316, No. 11-302283, Flat 7-286107, 2001-4823, Flat 8-15522, Flat 8-29771, Flat 8-146215, Flat 11-343437, Flat 8-62416, 2002-14220 , 2002-14221, 2002-14222, 2002-14223, Hei 8-302224, Hei 8-73758, Hei 8-179120 and Hei 8-151531 can be used.

Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthripyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, phenothiazine and pi Loropyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In addition, after the pattern exposure of the curable composition and the curing of the exposed part, the unexposed part is removed by water or alkali development to form a pattern, for example, in the case of forming a colored pattern of a resist or a color filter, the unexposed part obtained from development From the viewpoint of completely removing the binder and the dye, the acid dye and / or its derivative may be appropriately used in some cases.

In addition, direct dyes, basic dyes, mordant dyes, acidic mordant dyes, azoic dyes, disperse dyes, oil soluble dyes, food dyes and / or derivatives thereof may also be suitably used.

The acidic dye is not particularly limited as long as it has acidic groups such as sulfonic acid and carboxylic acid, solubility in an organic solvent or developer, salt formation with basic compounds, absorbance, interaction with other components in the composition, light resistance and heat resistance, and the like. This can be chosen by considering the required performance.

The following are examples of acidic dyes, but the present invention is not limited thereto. For example:

Acid alizarin violet N;

Acidic blacks 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;

Acidic chromium violet K;

Acidic fuchsin;

Acidic greens 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109;

Acidic oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

Acidic 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;

Acidic 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, 163, 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;

Yellow yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;

Mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Mordant 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;

Mordant violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

Mordant 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;

Mordant 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, acid black 24;

Acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1;

Acidic oranges 8, 51, 56, 74,63;

Acidic red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217, 249;

Acidic 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 acidic green 25 and derivatives of these dyes are preferred.

In addition to the above dyes, acid dyes of azo, xanthene and phthalocyanine are also preferable, and C.I. Solvent Blue 44, 38; C．I．Solvent Orange 45; Acid dyes such as Rhodamine B and Phodamine 110 and derivatives of these dyes are also preferably used.

Among these, the coloring agent (D) is triallyl methane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzo Preference is given to a colorant selected from pyran, indigo, pyrazoloazo, anilinoazo, pyrazoletriazole azo, pyridoneazo and anthrapyridone.

It is preferable that content of a coloring agent in the curable composition of this invention is 30 mass% or more and 85 mass% or less including the case where it uses for formation of the coloring pattern of a color filter, It is more preferable that they are 40 mass% or more and 80 mass% or less, 50 mass It is most preferable that they are% or more and 75 mass% or less.

<Binder polymer (E)>

The curable composition of this invention may contain a binder polymer (E) in the range which does not impair the effect of this invention for the purpose of the improvement of a coating film, etc ..

It is preferable to use a linear organic polymer as a binder polymer. As such a "linear organic polymer", those conventionally known can be arbitrarily used. Preferably, in order to enable water development or weakly alkaline water development, a linear organic polymer soluble or swellable in water or weakly alkaline water is selected. The linear organic polymer is selected and used not only as a coating film forming agent but also as a water, weak alkaline water or an organic solvent developer. For example, the use of water soluble organic polymers enables water development. Examples of such linear organic polymers include Japanese Patent Application Laid-Open Nos. 59-44615, Japanese Patent Publication Nos. 54-34327, 58-12577 and 54-25957, and Japanese Patent Publication Nos. 54-92723 and 59- Hydrolysis, half-esterification of resins obtained by polymerizing or copolymerizing monomers having carboxyl groups, polymerized or copolymerizing monomers having acid anhydrides, described in US Pat. The radical polymer which has a carboxylic acid group in side chains, such as epoxy acrylate obtained by modifying the resin obtained by half-amidation and an epoxy resin with unsaturated monocarboxylic acid and an acid anhydride, can be mentioned. Examples of the monomer having a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxy styrene, and the like. As a monomer which has an acid anhydride, maleic anhydride etc. can be mentioned.

Similarly, there are acidic cellulose derivatives having a carboxylic acid group in the side chain. It is also useful to add cyclic acid anhydride to a polymer having a hydroxyl group.

When using the said binder polymer as alkali-soluble copolymer, you may use monomers other than the above as a compound to copolymerize. 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 meta Acrylic acid esters and methacrylic acid esters which have aliphatic hydroxyl groups, such as a acrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate.

(2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate 2-chloroethyl Acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate and Alkyl acrylates, such as propargyl acrylate.

(3) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate Acrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1- Alkyl methacrylates, such as propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.

(4) Acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide , N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide and Acrylamide and methacrylamide, such as allyl methacrylamide.

(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) Styrene, such as styrene, (alpha) -methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxy styrene.

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

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

(10) N-vinyl pyrrolidone, acrylonitrile, methacrylonitrile and the like;

(11) unsaturated imides such as maleimide, N-acryloyl acrylamide, N-acetyl methacryl amide, N-propionyl methacryl amide, and N- (p-chlorobenzoyl) methacryl amide.

(12) Methacrylic acid monomers in which a hetero atom is bonded to the α-position, such as the compounds described in JP-A-2000-309057 and 2002-311569.

Among these examples, (meth) acrylic resins having allyl groups or vinyl ester groups and carboxyl groups in the side chains, alkali-soluble resins having double bonds in the side chains described in Japanese Patent Laid-Open Nos. 2000-187322 and 2002-62698 and Japanese Patents Alkali-soluble resins having an amide group in the side chain described in Japanese Patent Application Laid-Open No. 2001-242612 are preferable for their excellent film strength, sensitivity and balance of developability.

In addition, Japanese Patent Publication Nos. 7-12004, 7-120041, 7-120042, 8-12424, Japan Patent Publication No. 63-287944, 63-287947, and 1-271741 The urethane-based binder polymer having an acidic group described in Japanese Patent Application Laid-open No. Hei 10-116232, and the urethane-based binder polymer having an acidic group and a double bond in the side chain described in Japanese Patent Application Laid-Open No. 2002-107918 have high strength. Since it is very excellent, it is advantageous at the point of low exposure amount aptitude.

Acetal-modified polyvinyl alcohol-based binder polymers having acidic groups described in European Patent Nos. 993966, EP 1204000 and JP 2001-318463 A are suitable because of their excellent balance between film strength and developability.

Also useful as water-soluble linear organic polymers are polyvinylpyrrolidone and polyethylene oxide. In addition, in order to improve the strength of the cured film, alcohol-soluble nylon and polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.

3,000 or more are preferable and, as for the weight average molecular weight of a binder polymer (E), the inside of the range of 5,000-300,000 is more preferable. 1,000 or more are preferable and, as for a number average molecular weight, the inside of the range of 2,000-250,000 is more preferable. 1 or more are preferable, and, as for polydispersity (weight average molecular weight / number average molecular weight), it exists in the range of 1.1-10 more preferably.

These binder polymers may be any of random polymers, block polymers, graft polymers, and the like.

The binder polymer (E) can be synthesized by a conventionally known method. As a solvent used at the time of synthesis, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy ethyl Acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethyl formamide, N, N-dimethyl acetoamide, toluene, ethyl acetate, methyl lac Tate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents can be used alone or as a mixture of two or more thereof.

As a radical polymerization initiator used when synthesize | combining the binder polymer used by this invention, well-known compounds, such as an azo initiator and a peroxide initiator, can be mentioned.

From the viewpoint of the balance of pigment dispersion stability and developability over time, when the curable composition of the present invention is used to form a color pattern of a color filter, the content of the binder polymer (E) is 5% by mass relative to the total solids of the curable composition of the present invention. It is preferable that it is -60 mass%, It is more preferable that it is 7 mass%-50 mass%, It is most preferable that it is 10 mass%-40 mass%.

The curable composition of this invention contains the following component further demonstrated in detail as needed.

<(F) Dispersant>

When the curable composition of this invention contains a pigment as a coloring agent (D), it is preferable to add (F) dispersing agent from a viewpoint of improving the dispersibility of a pigment.

As a dispersing agent (pigment dispersing agent) used for this invention, a polymer dispersing agent [polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acryl Latex, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate, and the like] and polyoxy ethylene alkyl phosphate ester, polyoxy ethylene alkyl amine, alkanol amine, pigment derivative and the like.

Polymeric dispersants can be further classified into linear polymers, terminal modified polymers, and graft polymers in terms of their structure.

The polymer dispersant functions to adsorb on the surface of the pigment to prevent reagglomeration. Therefore, terminal modified polymers, graft polymers, and block polymers having anchor moieties as the pigment surface can be listed as preferred structures. On the other hand, pigment derivatives provide the effect of promoting the adsorption of polymer dispersants by improving the pigment surface.

Specific examples of the pigment dispersant used in the present invention include BYK Chemie Corp. Products "Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer comprising acidic groups), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 ( Polymer copolymer "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA4047, 4050, 4010, 4165 (polyurethane-based), EFKA4330, 4340 (block copolymer), 4400, manufactured by EFKA Corp. 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester, 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Fan Techno Corp. Products "AJISPER PB821, PB822", "FROREN TG-710 (urethane oligomer)" from Kyoeisha Chemical Co., Ltd., "POLYFLOW No. 50E, No. 300 (acrylic copolymer)", "DISPERON" manufactured by Kusumoto Kasei Corp. KS-860, 873N, 874, # 2150 (aliphatic polyvaleic acid carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 ", Ka o Corp. products "DEMOL RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)," HOMOGENOL L-18 (polymeric polycarboxylic acid), "EMARGEN 920, 930 , 935, 985 (polyoxy ethylene nonyl phenyl ether), "ACETAMINE 86 (stearyl amine acetate)", "SOLSPACE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine) from RUBERESOL Corp. , 3000, 17000, 27000 (Polymer with Functional at End), 24000, 28000, 32000, 38500 (Graft Polymer) ", NIKKO CHEMICAL Corp. Products such as "NIKKOL T106 (polyoxy ethylene sorbitan monooleate), MYS-IEX (polyoxy ethylene monostearate), and the like.

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

In this invention, it is preferable that content of a dispersing agent is 1 mass%-100 mass% with respect to a pigment, 3 mass%-100 mass% are more preferable, 5 mass%-80 mass% are more preferable.

When using a polymer dispersing agent, the range of 5 mass%-100 mass% is preferable with respect to a pigment, and, specifically, the range of 10 mass%-80 mass% is more preferable. Moreover, when using a pigment derivative, it is preferable that the usage-amount exists in the range of 1 mass%-30 mass% with respect to a pigment, It is more preferable to exist in the range of 3 mass%-20 mass%, and 5 mass%-15 mass mass It is especially preferable to exist in the range of%.

In this invention, when using a pigment and a dispersing agent, it is preferable that the sum total of a pigment and a dispersing agent is 35 mass%-90 mass% with respect to the total solid of a curable composition from a viewpoint of a cure sensitivity and a color density, and 45 mass% It is more preferable that it is -85 mass%, and it is still more preferable that it is 50 mass%-80 mass%.

<(G) sensitizer>

It is preferable that the curable composition of this invention contains a (G) sensitizer for the purpose of the improvement of the radical generation efficiency of a polymerization initiator, and the long wavelength of a photosensitive wavelength. As a sensitizer used for this invention, it is preferable that the said photoinitiator can be sensitized by an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizer used in the present invention include those belonging to the compounds listed below and those having an absorption wavelength in the wavelength range of 300 nm to 450 nm.

Preferable sensitizers include those belonging to the following compounds and those having an absorption wavelength in the wavelength region of 330 nm to 450 nm.

For example, polynuclear aromatic groups (phenanthrene, anthracene, pyrene, perylene, triphenylene, and 9,10-dialkoxy anthracene, etc.), xanthenes (fluorescein, eosin, erythrosin, rhodamine B and rose) Bengal, etc.), thioxanthones (isopropyl thioxanthone, diethyl thioxanthone, chlorothioxanthone, etc.), cyanines (such as thiacarbocyanine and oxacarbocyanine), merocyanine (merocyanine , Carbomerocyanine, etc.), phthalocyanines, thiazines (such as thionine, methylene blue and toluidine blue), acridines (such as acridine orange, chloroflavin and acriflavin), anthraquinones (anthra Quinones), squalariums (such as scallium), acridine orange, coumarins (such as 7-diethyl amino-4-methyl coumarin), ketocoumarin, phenothiazine, phenazine, styryl benzene, Azo compound, diphenyl methane, triphenyl methane, distyryl benzene, carbazoles, porphyrin, spiro Compound, quinacridone, indigo, styryl, pyryllium compound, pyrromethene compound, pyrazorothiazole compound, benzothiazole compound, barbitalic acid derivative, thiobarbital acid derivative, acetophenone, benzophenone, thioxanthone, mi Aromatic ketone compounds, such as a healer ketone, Heterocyclic compounds, such as N-aryl oxazolidinone, etc. can be mentioned. In addition, the compounds described in European Patent Nos. 568,993, U.S. Patent Nos. 4,508,811 and 5,227,227, Japanese Patent Laid-Open Nos. 2001-125255 and 11-271969 can be cited.

As an example of a more preferable sensitizer, the compound represented by the following general formula (i)-(i) can be enumerated.

In general formula (i), A ¹ is a sulfur atom or NR ⁵⁰ , R ⁵⁰ is an alkyl group or an aryl group, L ² is a nonmetallic atom group which forms a basic nucleus of the pigment in combination with adjacent A ¹ and adjacent carbon atoms, and R ⁵¹ and R ⁵² are each independently a hydrogen atom or a monovalent nonmetallic atom group, and may be bonded to each other to form an acidic nucleus of the pigment. W is an oxygen atom or a sulfur atom. As said alkyl group of R <^50>, the alkyl group of 1-30 carbon atoms can be enumerated, The alkyl group of 1-20 carbon atoms is preferable, and the alkyl group of 1-10 carbon atoms is the most preferable. As said aryl group of R <^50>, the aryl group of 6-30 carbon atoms can be mentioned, The aryl group of 6-20 carbon atoms is preferable, The aryl group of 6-10 carbon atoms is the most preferable.

In formula (ii), Ar ¹ and Ar ² are each independently an aryl group and are connected via a bond by -L ^3- . Where L ³ is -O- or -S-. In addition, W is the same as what was shown to General formula (i). Although the aryl group of 6-30 carbon atoms can be mentioned as an aryl group of Ar <^1> , The aryl group of 6-20 carbon atoms is preferable, The aryl group of 6-10 carbon atoms is the most preferable. Although the aryl group of 6-30 carbon atoms can be enumerated as said aryl group of Ar <^2> , The aryl group of 6-20 carbon atoms is preferable, The aryl group of 6-10 carbon atoms is the most preferable.

In general formula, A ² is a sulfur atom or NR ⁵⁹ , L ⁴ is a nonmetallic atom group which forms a basic nucleus of a dye in association with an adjacent A ² and carbon atom, and is also R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ are each independently a monovalent nonmetallic atom group, and R ⁵⁹ is an alkyl group or an aryl group. ^Examples of the alkyl group for R ⁵⁹ include alkyl groups having 1 to 30 carbon atoms, but alkyl groups having 1 to 20 carbon atoms are preferred, and alkyl groups having 1 to 10 carbon atoms are most preferred. ^Examples of the aryl group for R ⁵⁹ include an aryl group having 6 to 30 carbon atoms, but an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is most preferable.

In formula (i), A ³ and A ⁴ are each independently -S-, -NR ⁶² -or -NR ^63- , and R ⁶² , R ⁶³ are each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted group. Is a substituted aryl group, L ⁵ , L ⁶ are each independently a nonmetallic atom group which forms a basic nucleus of the pigment in combination with adjacent A ³ , A ⁴ or adjacent carbon atoms, and R ⁶⁰ , R ⁶¹ are each independently a monovalent nonmetal It may be an atomic group, or may combine with each other to form an aliphatic or aromatic ring. Although the alkyl group of R <^62> , R <^63> can ^mention the alkyl group of 1-30 carbon atoms, the alkyl group of 1-20 carbon atoms is preferable, and the alkyl group of 1-10 carbon atoms is the most preferable. ^Examples of the aryl group for R ⁶² and R ⁶³ include an aryl group having 6 to 30 carbon atoms, but an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is most preferable. In the case of substitution, as a substituent, an alkyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxyl group, an alkoxycarbonyl group, an acyl group, a hydroxyl group, and an amino group are preferable. 1-30 are preferable, as for the number of carbon atoms of these substituents, 1-20 are more preferable, and 1-10 are the most preferable.

Moreover, as a preferable sensitizer contained in the curable composition of this invention, 1 or more types chosen from the group which consists of a compound represented by the following general formula (IV)-(VI) besides the above can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.

In formula (IV) or (V), R ¹ and R ² are each independently a monovalent substituent, and R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent substituent. n is an integer of 0-5, n 'is an integer of 0-5, where n and n' are not zero at the same time. When n is two or more, two or more R <^1> may be same or different. When n 'is two or more, two or more R <^2> may be same or different, respectively. As said monovalent substituent, an alkyl group, a halogen atom (fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkoxyl group, an alkoxycarbonyl group, an acyl group, a hydroxyl group, and an amino group are preferable. 1-30 are preferable, as for the number of carbon atoms of these substituents, 1-20 are more preferable, and 1-10 are the most preferable.

As for the compound represented by general formula (IV), the compound represented by the following general formula (IV-1) is preferable from a viewpoint of the coloring property and a sensitivity in the case of containing a coloring agent.

In General Formula (IV-1), R ¹ and R ² are each independently a monovalent substituent. n is an integer of 0-5, n 'is an integer of 1-5. When n is two or more, two or more R <^1> may be same or different, respectively. When n 'is two or more, two or more R <^2> may be same or different.

In the general formula (Ⅳ-1), R 1 is a substituent represented by ¹ and R ² are monovalent substituents represented by R ¹ and R ² in the general formula (Ⅳ), to apply the same preferred range.

As a compound represented by general formula (IV) or general formula (V), it is preferable that molar extinction coefficient (epsilon) in 365 nm is 500 mol <^-1> L * cm <^-1> or more, and (epsilon) in 365 nm wavelength is 3,000 mol <^-1>. more preferably at least L · cm ^-1, and most preferably the ε at 365nm wavelength of less than 20,000mol ^-1 · L · cm ^-1. Since the value of the molar extinction coefficient (epsilon) in each wavelength is in the said range, since a sensitivity improvement effect is high, it is preferable from a viewpoint of light absorption efficiency.

Here, the molar extinction coefficient ε is determined from the UV-visible absorption spectrum of the sample by measuring the transmission spectrum of the sample at 365 nm using a sample of the dye solution adjusted to 0.01 g / l concentration in the 1-methoxy-2-propanol solution. It can obtain by calculating absorbance. As a measuring device, Varian Corp. A UV-Vis-MR spectrophotometer, a Cary5G type spectrophotometer, was used.

Although the preferable specific example of a compound represented by general formula (IV) or (V) is shown below, this invention is not limited to this.

General formula can be represented by a simple structural formula here, The solid line etc. which do not specify an element or a substituent among these represent a hydrocarbon group. In addition, in the following specific example, 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 formula (VI), A is an aromatic or heterocyclic ring which may have a substituent, X is an oxygen atom, a sulfur atom or -N (R ³ )-, and Y is an oxygen atom, sulfur atom or -N (R ³ ) -to be. R ¹ , R ² and R ³ are each independently a hydrogen atom or a monovalent nonmetallic atom group. A, R ¹ , R ² and R ³ may be bonded to each other to form an aliphatic or aromatic ring.

In formula (VI), when R ¹ , R ² and R ³ are monovalent nonmetallic atom groups, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aromatic heterocycle It is preferable that it is a residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

The alkyl group is preferably an alkyl group having 1 to 30 linear, branched or cyclic carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 15 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso-butyl group, tert-butyl group, n-octyl group, n-dodecyl group, cyclopentyl group, cyclopentyl group, benzyl group , Bicyclo [2,2,1] -heptan-2-yl, and the like.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 15 carbon atoms. For example, a phenyl group, a naphthyl group, etc. can be mentioned.

As said alkenyl group, the alkenyl group which has 1-30 carbon atoms of a linear, branched or cyclic | annular form is preferable, It is more preferable that it is 1-20 carbon atoms, It is especially preferable that it is 1-15 carbon atoms. For example, vinyl, allyl, cyclohexenyl, geranyl, etc. can be mentioned.

The aromatic heterocyclic moiety is preferably a 5-7 membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed ring aromatic heterocyclic moiety. More preferred are aromatic heterocyclic moieties having a heteroatom of at least one of a nitrogen atom, an oxygen atom and a sulfur atom, having a cyclic atom selected from the group consisting of carbon atoms, nitrogen atoms and sulfur atoms. More preferred are 5 or 6 membered aromatic heterocyclic moieties having 3 to 30 carbon atoms. Examples include 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl, imidazol-2-yl and the like.

As said alkoxyl group, the linear, branched or cyclic alkoxyl group of 1-30 carbon atoms is preferable, It is more preferable that it is 1-20 carbon atoms, It is especially preferable that it is 1-10 carbon atoms. For example, methoxy, ethoxy, n-propoxy, isobutoxy, n-butoxy, isobutoxy, tert-butoxy, etc. can be mentioned.

As said alkyl thi group, the linear, branched or cyclic alkyl thi group of 1-30 carbon atoms is preferable, It is more preferable that it is 1-20 carbon atoms, It is especially preferable that it is 1-10 carbon atoms. For example, methyl thio, ethyl thio, n-decyl thio group, etc. can be mentioned.

The monovalent nonmetallic atom group may be substituted as described above. Examples of the substituent include alkyl group, alkenyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, alkoxy group, alkoxycarbonyl group, acyl group, hydroxy group, alkyl thi group, aryl thi group and the like. When these substituents have carbon, 1-30 are preferable, as for total carbon number, 1-20 are more preferable, and 1-10 are the most preferable.

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

Hereinafter, although preferable specific example (VI1)-(VI124) of a compound represented by general formula (VI) is shown, this invention is not limited to this. In addition, the isomer by the double bond which connects an acidic nucleus and a basic nucleus is not clear, and this invention is not limited to any one isomer.

The compound represented by the general formula (VI) according to the present invention may further perform various chemical modifications for improving the properties of the curable composition.

For example, the strength of the exposure film is increased by combining a sensitizer (hereinafter also referred to as "sensitizing dye") and an addition polymer compound structure (such as acryloyl group and methacryloyl group) by covalent bonding, ionic bonding, hydrogen bonding, or the like. And unnecessary precipitation of the sensitizing dye from the post-exposure film can be suppressed.

In addition, partial sensitization dyes and partial structures (such as halogenated alkyls, oniums, peroxides and biimidazoles) which have radical generating ability in the photosensitive initiator and the photopolymerization initiator, and borate, amine, trimethyl silyl methyl, carboxymethyl, carbonyl and amine, etc. Binding to the oxidative cleavage site) significantly improves the photosensitivity, particularly in the state of low concentration of the initiator.

In the curable composition of this invention, the compound represented by general formula (IV)-(VI) may be used individually by 1 type or in combination of 2 or more types.

When the light transmittance of the coloring pattern (photosensitive layer) formed because the density | concentration of the coloring agent (pigment etc.) in a curable composition is very high is specifically, the light transmittance of 365 nm of the photosensitive layer formed without adding a sensitizing dye is 10. When it becomes% or less, the effect which improves photosensitivity is remarkably exhibited by adding the compound represented by said general formula (IV)-(VI). In particular, among the general formulas (IV) to (VI), the compound represented by general formula (VI) is most preferred. Specifically, the compounds of (VI56) to (VI122) are most preferred.

You may use a sensitizer individually or in combination of 2 or more types.

As for content of a sensitizer in the curable composition of this invention, 0.1 mass%-20 mass% are preferable with respect to the total solid of a curable composition from a viewpoint of the light absorption efficiency and initiation decomposition efficiency in a core part, and 0.5 mass%-15 mass mass % Is more preferable. The above range is preferable because the light absorption efficiency at the deep portion of the curable composition is increased and the onset decomposition efficiency is good.

<(H) Notary sensitizer>

The curable composition of the present invention may contain a sensitizer. In the present invention, the co-sensitizer further acts to improve the sensitivity of the sensitizing dye or photopolymerization initiator to active radiation, or to inhibit the polymerization inhibition of the polymerizable compound by oxygen.

Examples of such donor sensitizers include M. R. Sander et al. "Journal of Polymer Society" vol. 10, page 3,173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, 52-234692, 59-138205, 60-84305, 62-18537 and Amine, such as the compound of Unexamined-Japanese-Patent No. 64-33104 and Research Disclosure No.33825, is mentioned. Specifically, triethanolamine, p-dimethyl amino ethyl ester benzoate, p-formyl dimethyl aniline, p-methyl thio dimethyl aniline, etc. can be mentioned.

Other examples of the co-sensitizer include thiols and sulfides, for example, thiol compounds described in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, and Japanese Patent Application Laid-Open No. 5-142772, and Japanese Patent. Disulfide compounds of JP-A-56-75643, specifically 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quina Sleepy and β-mercaptonaphthalene are listed.

Other examples of the co-sensitizer include amino acid compounds (e.g., N-phenylglycine), organometallic compounds (e.g., tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-42965, Japan The hydrogen donor compound described in Unexamined-Japanese-Patent No. 55-34414, and the sulfur compound (for example, trithiane etc.) of Unexamined-Japanese-Patent No. 6-308727 are mentioned.

From the viewpoint of improving the curing rate according to the balance between the polymerization growth rate and the chain transfer, the content of the co-sensitizer to the mass of the total solid of the curable composition is preferably in the range of 0.1% by mass to 30% by mass, and is preferably 0.5% by mass to 25%. The inside of the range of mass% is more preferable, and the inside of the range of 1.0 mass%-20 mass% is still more preferable.

<(I) polymerization inhibitor>

In the present invention, it is preferable to add a small amount of thermal polymerization inhibitor in order to inhibit unnecessary thermal polymerization of the compound having a polymerizable ethylenically unsaturated double bond during preparation or storage of the curable composition.

As the thermal polymerization inhibitor used in the present invention, hydroquinone, p-methoxy phenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis (3 -Methyl-6-t-butyl phenol), 2,2'-methylene bis (4-methyl-6-t-butyl phenol), N-nitrosophenyl hydroxy amine trickle salt, etc. can be mentioned.

As for the addition amount of a polymerization inhibitor, about 0.01 mass%-about 5 mass% are preferable with respect to the mass of a total composition. If necessary, in order to prevent the inhibition of polymerization by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide may be added to disperse unevenly on the surface of the photosensitive layer during the drying step 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>

Moreover, in this invention, even if it adds well-known additives, such as an inorganic filler for improving the physical property of a cured coating film, a plasticizer, and a sensitizer for improving the ink property of the photosensitive layer surface, and a board | substrate adhesive agent for improving board | substrate adhesiveness, good.

Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol, and the like. When using a coupling agent, it can add at 10 mass% or less with respect to the total mass of a compound and an coupling agent which have an ethylenically unsaturated double bond.

When using the curable composition of this invention with respect to hard material surfaces, such as a board | substrate, you may add the additive (henceforth "substrate adhesive agent") for improving adhesiveness with respect to a hard material surface.

As a board | substrate adhesive agent, a well-known material can be used. In particular, it is preferable to use a silangue coupling agent, a titanate coupling agent, or an aluminum coupling agent.

Examples of silane coupling agents include γ- (2-amino ethyl) amino propyl trimethoxy silane, γ- (2-amino ethyl) amino propyl dimethoxy silane, β- (3,4-epoxy cyclohexyl) ethyl trimeth Oxy silane, γ-amino propyl trimethoxy silane, γ-amino propyl triethoxy silane, γ-methacryloxy propyl trimethoxy silane, γ-methacryloxy propyl triethoxy silane, γ-acryloxy propyl trimethoxy Oxy silane, γ-acryloxy propyl triethoxy silane, γ-isocyanate propyl trimethoxy silane, γ-isocyanate propyl triethoxy silane, N-β- (N-vinyl benzyl amino ethyl) -γ-amino propyl trimeth Methoxy silane hydrochloride, γ- glycidoxy propyl trimethoxy silane, γ- glycidoxy propyl ethoxy silane, amino silane, γ- mercapto propyl trimethoxy silane, γ- mercapto propyl triethoxy silane, methyl T Methoxy silane, methyl triethoxy silane, vinyl triacetoxy silane, γ-chloro propyl trimethoxy silane, hexamethyl disilazane, γ-anilino propyl trimethoxy silane, vinyl trimethoxy silane, vinyl trie Methoxy silane, vinyl tris (β-methoxy ethoxy) silane, octadecyl dimethyl [3- (trimethoxy silyl) propyl] ammonium chloride, γ-chloro propyl methyl dimethoxy silane, γ-mercapto propyl methyl dimethoxy silane , Methyl trichloro silane, dimethyl dichloro silane, trimethyl chloro silane, 2- (3,4-epoxy cyclohexyl) ethyl trimethoxy silane, bisallyl trimethoxy silane, tetraethoxy silane, bis (trimethoxy silyl) Hexane, phenyl trimethoxy silane, N- (3-acryloxy-2-hydroxy propyl) -3-amino propyl triethoxy silane, N- (3-methacryloxy-2-hydroxy propyl) -3- Amino propyl triethoxy silane, (meta Reel yloxymethyl) can be enumerated, methyl diethoxy silane, and (acryloxypropyl) methyl dimethoxysilane.

In particular, γ-methacryloxy propyl trimethoxy silane, γ-methacryloxy propyl triethoxy silane, γ-acryloxy propyl trimethoxy silane, γ-acryloxy propyl triethoxy silane, γ-mercapto propyl tri Preferred are methoxy silane, γ-amino propyl triethoxy silane and phenyl trimethoxy silane, with γ-methacryloxy propyl trimethoxy silane being most preferred.

Examples of titanate-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tridecyl benzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) Titanate, tetraoctyl bis (ditolyldecyl phosphite) titanate, tetra (2,2-diallyloxymethyl) bis (di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate , Bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, triisopropyl tri (dioctyl Phosphate) Titanate, Isopropyl Tricumyl Phenyl Titanate, Isopropyl Tri (N-amide Ethyl Ami No ethyl) titanate, dicumyl phenyloxy acetate titanate and diisostearoyl ethylene titanate.

Examples of aluminum coupling agents include acetoalkoxy aluminum diisopropylate.

From the viewpoint of preventing residue residue on the unexposed portion when the curable composition is exposed, the content of the substrate adhesive to the total solid content of the curable composition of the present invention is preferably 0.1% by mass to 30% by mass, and 0.5% by mass. It is more preferable that it is -20 mass%, and it is especially preferable that it is 1 mass%-10 mass%.

According to the said structure, the curable composition of this invention can be hardened with high sensitivity, and storage stability is also preferable. Moreover, the curable composition of this invention shows high adhesiveness with respect to the surface of materials (hard materials, such as a board | substrate) to be used. Therefore, the curable composition of the present invention can be preferably used in the field of image forming materials such as three-dimensional light sculptures, holography and color filters, or inks, paints, adhesives, coatings and the like.

[Color filter and its manufacturing method]

Next, the color filter of this invention and its manufacturing process are demonstrated.

The color filter of this invention has a coloring pattern using the curable composition of this invention on a support body, It is characterized by the above-mentioned.

Next, the color filter of this invention is demonstrated in detail with reference to the manufacturing process (process of manufacturing the color filter of this invention).

The method of manufacturing a color filter of the present invention is a color layer forming step of forming a colored layer made of a curable composition by applying the curable composition of the present invention on a support member, an exposure step of exposing the colored layer through a mask and coloring after exposure And developing the layer to form a colored pattern.

Hereinafter, each step in the production method of the present invention will be described.

<Coloring layer forming process>

In the colored layer forming step, the colored layer made of the curable composition is formed by applying the curable composition of the present invention onto the support member.

Examples of the support that can be used in this step include soda glass, Pyrex (registered trademark) glass, quartz glass and glass with a transparent conductive film attached thereto, and photoelectric conversion element substrates used in imaging devices. Examples include silicon substrates and complementary metal oxide semiconductors (CMOS). On these substrates, black stripes may be formed to separate the pixels.

If necessary, a lower coating layer may be formed on these supports in order to improve adhesion to the upper layer, to prevent diffusion of materials, and to planarize the surface of the substrate.

As the method of applying the curable composition of the present invention to the support member, various coating methods such as slit coating, inkjet coating, rotary coating, cast coating, roll coating and screen coating can be used.

From the viewpoint of the coating film uniformity of the coating film and the ease of drying of the coating solvent, the film thickness of the curable composition is preferably 0.1 to 10 µm, more preferably 0.2 to 5 µm, further preferably 0.2 to 3 µm, immediately after application.

The colored layer (curable composition layer) coated on the substrate may be dried (prebaked) at 50 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 also referred to as "dry film thickness") is preferably 0.1 µm or more and less than 2.0 µm in view of securing compatibility and color density for LCDs for use as color filters for LCDs, 0.2 micrometer or more and 1.8 micrometer or less are more preferable, and 0.3 micrometer or more and 1.75 micrometer or less are especially preferable.

In addition, in order to use as a color filter for IS, the thickness is preferably 0.05 µm or more and less than 1.0 µm in view of securing color density and reducing problems such as a remarkable difference in light collection ratio between the distal end and the center of the device. 0.1 micrometer or more and 0.8 micrometer or less are more preferable, and 0.2 micrometer or more and 0.7 micrometer or less are especially preferable.

Exposure stage

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.

According to the exposure in this step, the pattern exposure of the coating film can be performed by exposing through a predetermined mask pattern by light irradiation in order to cure only the coating film portion. Ultraviolet rays, such as g line | wire and i line | wire, can be used suitably as radiation used at the time of exposure. Dose is 5 ~ 1,500mJ / cm ² is preferable, and 10 ~ 1,000mJ / cm ^2, and more preferred, most preferred 10 ~ 500mJ / cm ^2.

When the color filter of this invention is for liquid crystal display elements, 5-200mJ / cm <^2> is preferable in the said range, 10-150mJ / cm <^2> is more preferable, 10-100mJ / cm <^2> is the most preferable. Further, when the color filter the solid-state image sensor of the present invention tolerate, is 30 ~ 1,500mJ / cm ² from the above-mentioned range is preferable, and, and is 50 ~ 1,000mJ / cm ² and more preferably 80 ~ 500mJ / cm ² is most preferably .

Development stage

Then, by performing an alkali developing step (development step), only the portion with the tailings irradiated part eluted with the aqueous alkali solution with respect to photocuring by the exposure remains. By developing with a developing solution, it can carry out by forming the pattern coating film which has each color (3 or 4 colors). As the developer, an organic alkali developer having no risk of damaging the basic circuit is preferable. The developing temperature is usually 20 to 30 ° C, and the developing time is 20 to 90 seconds.

Examples of the alkaline agent used as the developer include ammonia water, ethyl amine, diethyl amine, dimethyl ethanol amine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo Organic alkaline compounds, such as-[5,4,0] -7-undecene, and inorganic compounds, such as sodium hydroxide, potassium hydroxide, sodium hydrogen chloride, and potassium hydrogencarbonate, are mentioned. The aqueous alkali solution obtained by diluting these alkali chemicals in pure water so that a density | concentration may be 0.001 mass%-10 mass%, Preferably 0.01 mass%-1 mass% can be used preferably. In the case of using a developer composed of such an aqueous alkali solution, it is generally washed (rinsed) with pure water after development.

Then, it is dried after washing to remove excess developer.

The manufacturing method of the present invention includes a curing step of curing the colored pattern formed by heating (post-baking) and / or exposure after performing the colored layer forming step, the exposure step and the developing step as described above.

Post-baking is post-development heat processing to complete hardening, and usually heat-processes at 100-240 degreeC. In the case where the substrate is a glass substrate or a silicon substrate, 200 to 240 ° C is preferred within the above temperature range.

This post-baking process can be performed continuously or batchwise using heating means, such as a hotplate, a convection oven (hot air circulation dryer), and a high frequency heater, so that a coating film may become the said conditions after image development.

The color filter having a desired color can be produced by repeating the above-described colored layer forming step, exposure step and developing step (moreover, curing step if necessary) with only the desired number of colors.

The use of the curable composition of the present invention was mainly described for the use of the color filter as a pixel; Needless to say, it is also applicable to the black matrix provided between the pixels of the color filter. The black matrix is the above-described method for producing a pixel by promoting the curing of the film by pattern exposure, alkali development, and then post-baking, except that a colorant having a black pigment such as carbon black or titanium black is used as the curable composition of the present invention. It can form in the same way as a method.

Since the color filter of the present invention is manufactured using the curable composition of the present invention having excellent exposure sensitivity, the composition cured in the exposed portion is excellent in adhesion and development resistance to the substrate, and the colored pattern formed is high in relation to the support member substrate. The pattern which has adhesiveness and also provides a desired cross-sectional shape has a high resolution.

Further, the solid state image pickup device of the present invention includes the color filter of the present invention manufactured by the method of manufacturing the color filter of the present invention.

Therefore, specifically, the color filter of the present invention can be preferably used for solid-state image pickup devices such as liquid crystal display devices and CCDs, and particularly preferably for high-resolution CCD devices or CMOSs exceeding 1,000,000 pixels. The color filter of this invention can be used as a color filter arrange | positioned between the light receiving part of each pixel containing a CCD element, and a micro lens for condensing.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1

<Synthesis of Compound (i-1)>

58.6 g of 2-hydroxyethyl methacrylate was placed in a 500 ml three-neck flask, and 250 ml of acetone was added thereto and stirred. After adding 39.2 g of pyridine and 0.1 g of p-methoxy phenol, it was cooled in an ice bath containing ice water. After the liquid mixture temperature became 5 degrees C or less, 114.9 g of 2-bromo isobutanoic acid bromide was dripped at the dropping funnel for 3 hours. After completion of the dropping operation, the ice bath was removed and further stirred for 3 hours. The reaction mixture was poured into 750 ml of water, and then stirred for 1 hour. The water mixture was extracted three times with 500 ml of ethyl acetate using a separatory funnel. The organic layer was washed sequentially with 500 ml of 1 M hydrochloric acid, 500 ml of saturated aqueous sodium hydrogen carbonate solution and 500 ml of saturated saline. 100 g of magnesium sulfate was added to the organic layer, followed by dehydration drying and filtration of this. The vacuum removal of the solvent gave 120.3 g of residue.

The obtained residue was confirmed to be compound (i-1) from ¹ H-NMR, IR, and mass spectrometry. In addition, the purity was 95% from HPLC.

(1) Synthesis of Resin (I)

86 g of 1-methyl-2-pyrrolidone placed in a 1,000 ml three-neck flask was heated to 90 ° C. in a nitrogen stream. 55 g of compound (i-1), 47 g of exemplary compound M-14MA, 13 g of methacrylic acid and 2,2'-azobis (2-methyl propionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 8.2 A solution of g and 86 g of 1-methyl-2-pyrrolidone was added dropwise over 2 hours. After completion of the dropping operation, this was further stirred for 2 hours. After cooling the reaction liquid to room temperature, this was poured into 7 L of water to precipitate a polymer compound. The precipitated polymer compound was filtered, washed with water and dried to obtain 110 g of the polymer compound.

The weight average molecular weight of the polymer compound obtained by gel permeation chromatography (GPC) using polystyrene as a standard was measured, which was 13,100. Moreover, as a result of measuring the acid value by titration, it was 1.25 meq / g (output value 1.30 meq / g), and it confirmed that superposition | polymerization was normally performed.

110 g of the obtained polymer compound, 0.1 g of p-methoxy phenol, and 470 g of 1-methyl-2-pyrrolidone were added to a 1,000 ml three neck flask flask, and the mixture was cooled in an ice bath containing ice water. After the liquid mixture temperature became 5 degrees C or less, 100 g of 1,8- diazabicyclo [5.4.0] -7-undecene (DBU) was dripped here over 1 hour using the dropping funnel. After completion of the dropping operation, the ice bath was removed and stirred for further 8 hours. Concentrated hydrochloric acid was added to the reaction solution to pH 7, and this was added to 7 L of water to precipitate Resin (I) of the polymer compound. 95 g of the polymer compound was obtained by filtering the precipitated polymer compound, wash | cleaning this with water, and drying.

According to ¹ H-NMR measurement of the obtained polymer compound, it was confirmed that 100% of the side chain groups derived from compound (i-1) were converted to ethylene methacrylate groups. Moreover, it was 12,100 when the mass mean molecular weight was measured by the gel permeation chromatography method (GPC) which used polystyrene as a reference material. Moreover, the acid value was measured by titration and found to be 1.45 meq / g (calculated value 1.51 meq / g).

Example 1

[A1. Preparation of Curable Composition]

Here, the manufacturing example of the curable composition containing the pigment for forming the color filter for liquid crystal display element uses is demonstrated and demonstrated.

A1-1. Preparation of Pigment Dispersion

Preparation of Pigment Dispersion

40 parts by mass of 30/70 (mass ratio) mixture of C. I. Pigment Green 36 and C. I. Pigment Yellow 219 (average particle size 61 nm) as a pigment, (Disperbyk: Bic Chemie (BYK) Corp., 50 parts by mass of BYK2001 (about 22.6 parts by mass based on solids), 5 parts by mass of the above-mentioned resin (I) in the present invention, and 110 parts by mass of 3-ethoxy ethyl propionate as a solvent. Pigment dispersion (P1) was prepared by mixing and dispersing with a bead mill for 15 hours.

The average particle size of the pigment was measured by dynamic light scattering method using Microtrac Nanotrac UPA = EX150 (manufactured by Nikkisou Co., Ltd.) without further diluting P1 with respect to the pigment dispersion (P1), which was 32 nm.

A1-2. Preparation of curable composition (coating liquid)

The curable composition solution was manufactured by stirring and mixing so that it may become the following composition ratio using the said pigment dispersion liquid P1 which carried out the dispersion process.

600 parts by mass of a coloring agent (D) (the pigment dispersion (P1))

Photopolymerization initiator (B)

30 parts by mass of (2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole)

(C) 50 parts by mass of pentaerythritol tetraacrylate

(E) Alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyl ethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10,000) 5 parts by mass

Solvent: 900 parts by mass of PGMEA

1 part by mass of a substrate adhesive (3-methacryloxy propyl trimethoxy silane)

(F) 15 parts by mass of sensitizer (following compound α)

(G) 15 parts by mass of a sensitizer (2-mercapto benzoimidazole)

                General formula α

[A2. Production of Color Filter]

A2-1. Formation of Curable Composition Layer

The curable composition containing the pigment was applied to a 550 mm x 650 mm glass substrate as a resist solution by slit coating under the following conditions, left as it is for 10 minutes, and subjected to vacuum drying and prebaking (80 seconds at 100 ° C.). The curable composition coating film (curable composition layer) was formed.

(Slit application condition)

Spacing of openings at the tip of coating head: 50 μm

Coating speed: 100 mm / s

Clearance between substrate and application head: 150 μm

Dry film thickness: 1.75 mu m

Coating temperature: 23 ℃

A2-2. Exposure, development

Thereafter, the curable composition coating film was exposed in a pattern using a 20 µm line width photo mask using a 2.5 kW ultrahigh pressure mercury lamp. After the exposure, the entire surface of the coating film was covered with a 10% aqueous solution of an organic developer (trade name: CD, manufactured by Fuji Film Electronics Materials Corp.), and left for 60 seconds.

A2-3. Heat treatment

After standing, pure water was sprayed onto the shower to wash the developer, and the exposed (photocured) treated and developed coating film was heated in an oven at 220 ° C. for 1 hour (post-baking). This obtained the color filter which has a curable composition coating film (colored layer) formed on the glass substrate.

[A3. Performance evaluation]

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

A3-1. Storage Stability of Curable Compositions

After storing the curable composition (coating solution) prepared above for 1 month at room temperature, the viscosity of the solution was measured and evaluated according to the following criteria.

-Evaluation standard-

A: No viscosity increase

B: viscosity increase of 5% or more but less than 10%

C: viscosity rise of 10% or more

A3-2. Exposure sensitivity of curable composition coating film (color layer)

The curable composition coating film was exposed with the exposure amount changed into various exposure amounts of 10-100 mJ / cm <^2> , and the exposure amount which the pattern line width after postbaking becomes 20 micrometers was evaluated as exposure sensitivity. The smaller the exposure sensitivity value, the higher the sensitivity.

A3-3. Developability, pattern cross-sectional shape, substrate adhesion

Developability, pattern cross-sectional shape, and board | substrate adhesiveness were evaluated by observing the board | substrate surface and its cross-sectional shape after post-baking by optical microscope and SEM photograph observation. The detail of an evaluation method and an evaluation standard is as follows.

<Developing>

The development was evaluated by observing the presence of a residue in an area (unexposed part) to which light was not irradiated in the exposure step.

-Evaluation standard-

A: No residue is found in the unexposed areas.

B: Slightly confirmed so that the residue does not cause practical problems in the unexposed part

C: The residue was remarkably confirmed in the unexposed part.

<Pattern cross-sectional shape>

The cross-sectional shape of the formed pattern was observed. As for the pattern cross-sectional shape, a forward taper is most preferable, and a rectangle is preferable next. Reverse taper is undesirable.

<Board adhesion>

Substrate adhesiveness was evaluated according to observation of whether the pattern was missing. Evaluation criteria are as follows.

-Evaluation standard-

A: No pattern defect was observed at all.

B: Almost no pattern defects were observed, but some defects were observed.

C: A pattern defect is remarkably observed.

Comparative Example 1

A color filter was produced in the same manner as in Example 1 except that the resin (I) was not used in the curable composition prepared in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

EXAMPLES 2-10

A color filter was produced in the same manner as in Example 1 except that the resin shown in Table 2 was used in place of the resin (I) in the curable composition prepared in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 2.

Example 11, Comparative Example 2

Color filter in the same manner as in Example 1, except that the curable composition prepared in Example 1 used the following resin (II) and resin (III) synthesized in the same manner as the resin (I) instead of the resin (I). Was produced and evaluation similar to Example 1 was performed. The dipole moment of the monomer used for resin (II) was computed as 2.48. In addition, the dipole moment of n-butyl acrylate used for resin (III) was computed as 1.58. The results are shown in Table 2.

From the result of Table 2, it turns out that the curable composition of the Example containing resin of this invention has stable storage stability in a solution state. In addition, when the coloring pattern is formed on the support member using this curable composition, the exposure sensitivity is high and developability is excellent with respect to the comparative example without using the resin of the present invention, and the substrate adhesion and pattern cross-sectional shape It can be seen that this excellent color filter is obtained.

Example 12

Hereinafter, the example which manufactures the curable composition containing the coloring agent (pigment) for formation of the color filter for solid-state image sensor use is demonstrated.

[B1. Preparation of Resist Solution]

The resist solution was prepared by mixing and dissolving the component of the following composition.

<Composition of Resist Solution>

19.20 parts by mass of propylene glycol monomethyl ether acetate

(PGMEA: solvent)

Ethyl lactate 36.67 parts by mass

30.51 parts by mass of (E) resin (40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxy ethyl copolymer (molar ratio = 60/22/18))

(C) 12.20 parts by mass of ethylenically unsaturated double bond-containing compound (dipentaerythritol hexaacrylate)

0.0061 parts by mass of a polymerization inhibitor (p-methoxy phenol)

Fluorine-based surfactants (F-475, Dainippon Ink Chemical Industry, Corp.)

                                                                   0.83 parts by mass

0.586 mass parts of photoinitiators (B) (trihalomethyl triazine type photoinitiator)

(TAZ-107, product of Midori Kagaku Co., Ltd.)

[B2. Fabrication of Silicon Substrate with Base Coating Layer]

The 6 inch silicon wafers were heated in an oven at 200 ° C. for 30 minutes. Then, the resist solution was applied onto the silicon wafer so that the dry film thickness was 1.5 占 퐉, and heated and dried in an oven at 220 ° C. for 1 hour to form a base coating layer to form a silicon wafer substrate having a base coating layer. Got it.

[B3. Preparation of Pigment Dispersion]

40 parts by mass of 30/70 (mass ratio) of C. I. Pigment Green 36 and C. I. Pigment Yellow 150 as pigments (average particle size 65 nm), as a dispersant (Disperbyk: BYK Chemi (BYK) Corp. 50 parts by mass (by about 22.6 parts by mass based on solids) of BYK2001, a solid content concentration of 45.1% by mass), 10 parts by mass of the resin (I) in the present invention, and 110 parts by mass of a propylene glycol monomethyl ether as a solvent. Pigment dispersion (P2) was prepared by mixing and dispersing for 15 hours.

With respect to the pigment dispersion (P2), the average particle size of the pigment was measured in the same manner as in Example 1 by the dynamic light scattering method, which was 32 nm.

[B4. Preparation of Curable Composition (Coating Liquid)]

The curable composition solution was manufactured by stirring and mixing so that it may become the following composition ratio using the said pigment dispersion liquid P2 which carried out the dispersion process.

600 parts by mass of coloring agent (D) (pigment dispersion (P2))

30 mass parts of photoinitiators (B) (oxime system photoinitiator)

(CGI-124, manufactured by Chiba Specialty Chemicals, Corp.)

25 parts by mass of (C-1) TO-1382 (manufactured by Toa Gosei Corp.)

30 parts by mass of (C-1) dipentaerythritol hexaacrylate

900 parts by mass of solvent (PGMEA)

1 mass part of substrate adhesive (3-methacryloxy propyl trimethoxy silane)

[B5. Preparation and Evaluation of Color Filter by Curable Composition]

<Pattern formation and sensitivity evaluation>

The colored layer (coating film) was formed by apply | coating the curable composition manufactured as mentioned above to the base coating layer of the silicon wafer with a base coating layer obtained at the said process B2. Then, heat processing (prebaking) was performed for 120 second using the 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 0.7 micrometer.

Then, the i-ray stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) was exposed at various exposure doses of 50 to 1,200 mJ / cm ² through an island pattern mask having a pattern of 2 탆 square at a wavelength of 365 nm.

Thereafter, the silicon wafer substrate on which the irradiated coating film was formed was placed on a horizontal rotating table of a spin-shower developer (DW-30, manufactured by Chemitronics Corp.), and CD-2000 (manufactured by Fuji Film Electronics Materials, Corp.) was used. To paddle development at 23 ° C. for 60 seconds to form a colored pattern on the silicon wafer substrate.

The pure water is supplied from the spray nozzle to the shower image while the silicon wafer substrate is rotated at a rotational speed of 50 rpm by a rotating device which fixes the silicon wafer on which the colored pattern is formed on the horizontal rotating table by a vacuum chuck method. After rinsing, spray drying was performed.

Then, the magnitude | size of the coloring pattern was measured using length measurement SEM "S-9260A" (made by Hitachi High Technologies Corp.). The exposure amount whose pattern line width becomes 2 micrometers was evaluated as exposure sensitivity. The smaller the exposure sensitivity value, the higher the sensitivity. The measurement results are shown in Table 2 below.

<Developing>

The development was evaluated by observing the presence of a residue in an area (unexposed part) to which light was not irradiated in the exposure step.

-Evaluation standard-

A: No residue is found in the unexposed areas.

B: Slightly confirmed so that the residue does not cause practical problems in the unexposed part

C: The residue was remarkably confirmed in the unexposed part.

<Pattern formability>

The cross-sectional shape of the formed pattern was observed. As for the pattern cross-sectional shape, a forward taper is most preferable, a rectangle is next, and a reverse taper is not preferable.

<Board adhesion>

For substrate adhesion, it was observed whether the pattern was missing. These evaluation items were evaluated according to the following evaluation criteria.

-Evaluation standard-

A: No pattern defect was observed at all.

B: Almost no pattern defects were observed, but some defects were observed.

C: A pattern defect is remarkably observed.

<Storage stability of the curable composition>

After storing the curable composition (coating solution) prepared in step B4 for 1 month at room temperature, the viscosity of the solution was measured and evaluated according to the following criteria.

-Evaluation standard-

A: No viscosity increase

B: viscosity increase of 5% or more but less than 10%

C: viscosity rise of 10% or more

<Color unevenness>

The color nonuniformity was evaluated by analyzing the luminance distribution by the following method, and obtaining and evaluating the ratio of the pixel which the deviation from the average is within ± 5% to the total number of pixels. Evaluation criteria are as follows.

The measuring method of luminance distribution is demonstrated. First, the curable composition was apply | coated on the base coating layer of the glass plate with a base coating layer obtained by the method similar to the said step B2, and the coloring layer (coating film) was formed. The heat treatment (prebaking) was performed for 120 second using the 100 degreeC hotplate so that the dry film thickness of this coating film might be set to 0.7 micrometer. The image photographed with the microscope MX-50 (Olympus Corp. product) was analyzed about the luminance distribution of this apply | coated glass plate.

-Evaluation standard-

A: Pixels within ± 5% of deviation from average account for over 99% of the total number of pixels

B: Pixels with deviations from the mean within ± 5% account for more than 95% and less than 99% of the total number of pixels

C: Pixels with deviations from the mean within ± 5% account for less than 95% of the total number of pixels

Comparative Example 3

Except not using resin (I) in the curable composition manufactured in Example 12, the color filter in which the coloring pattern was formed was obtained by the same method as Example 12, and the same evaluation as Example 12 was performed. The results are shown in Table 3.

Examples 13 to 22 and Comparative Example 4

A color filter was produced in the same manner as in Example 12 except that the resin shown in Table 3 was used in place of the resin (I) in the curable composition prepared in Example 12, and the same evaluation as in Example 12 was performed. The results are shown in Table 3.

From the results in Table 3, it can be seen that the curable composition (pigment system) of the example containing the resin of the present invention used for color filter formation for solid state imaging devices is excellent in storage stability in a solution state. In addition, when a colored pattern is formed on a support member using this curable composition, compared with the comparative example which does not use resin in this invention, exposure sensitivity is high, developability is excellent, and substrate adhesiveness, pattern cross-sectional shape, It can be seen that a color filter having excellent color unevenness is obtained.

From these results, it can be seen that the curable composition of the embodiment realizes excellent pattern formation in both the case of producing color filters for solid-state image pickup devices and the case of producing color filters for liquid crystal display devices.

Example 23

Hereinafter, the Example which manufactures the curable composition containing the coloring agent (dye) for formation of the color filter for solid-state image sensor use is demonstrated.

[C1. Preparation of Resist Solution and Preparation of Silicon Substrate with Base Coating Layer]

[B1. In Example 12]. Preparation of Resist Solution] and [B2. Manufacture of Silicon Substrate with Base Coating Layer] A silicon substrate with base coating layer was produced in the same manner as the above.

[C2. Preparation of Curable Composition (Coating Liquid)]

The compound of the following composition was mixed and melt | dissolved, and the coloring photosensitive resin composition was produced.

80 parts by mass of cyclohexanone (solvent)

(D) Valifast Yellow 1101 (dye) 6.0 parts by mass

(D) Acid Red 57 (dye) 6.0 parts by mass

2.5 parts by mass of (C) dipentaerythritol hexaacrylate

(B) 2.0 mass parts of oxime system photoinitiators

(CGI-124, product of Ciba Specialty Chemicals Corp.)

1.5 parts by mass of resin (I) in the present invention

[C3. Preparation and Evaluation of Color Filter by Curable Composition]

B5. Production and Evaluation of Color Filter by Curable Composition] The color filters were produced and evaluated in the same manner as the above. The results are shown in Table 4.

[Comparative Example 5]

In the curable composition prepared in Example 23, except that the resin (I) was changed to pentaerythritol triacrylate, a color filter in which a coloring pattern was formed was produced in the same manner as in Example 23, and the same evaluation as in Example 23 was performed. The results are shown in Table 4.

Examples 24-33, Comparative Example 6

In the curable composition prepared in Example 23, except that the resin shown in Table 4 was used instead of the resin (I), a color filter was produced in the same manner as in Example 23, and the same evaluation as in Example 23 was performed. The results are shown in Table 4.

The results of Table 4 show that the curable composition (dye system) of the Example containing the resin of the form of the present invention used for the formation of the color filter for use in the solid state imaging device has excellent storage stability in the solution state.

Moreover, from the result of the Example which formed the coloring pattern on the support member using this curable composition, compared with the comparative example, the color filter which is high in exposure sensitivity, excellent in developability, and excellent in board | substrate adhesiveness and pattern cross-sectional shape is obtained. It can be seen that.

From these results, it can be seen that the curable composition of the embodiment realizes excellent pattern formation similarly to the case of manufacturing the color filter for the liquid crystal display device even when the color filter for the solid state imaging device is manufactured.

Embodiment of this invention is shown below.

A curable composition comprising a <1> resin, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, wherein the resin is prepared by polymerizing a monomer having a dipole moment of at least 2.0 as a copolymerization component.

<2> The curable composition as described in <1>, wherein the monomer is a monomer having a dipole moment of 2.5 or more.

<3> The curable composition as described in <1>, wherein the resin is obtained by polymerizing a monomer having a dipole moment of 2.5 or more as a copolymerization component, and having an ethylenically unsaturated double bond in the side chain.

<4> The curable composition according to any one of <1> to <3>, wherein the monomer having a dipole moment of 2.0 or more is an ether group, cyano group, ester phosphate group, lactone group, urethane group, ester carbonate group, and acetal group. Curable composition, characterized in that it has at least one selected from the group consisting of.

<5> The curable composition according to any one of <1> to <4>, further containing a coloring agent.

<6> Curable composition in any one of <1>-<5> characterized by further containing a sensitizer.

<7> Color filter which has a coloring pattern formed from curable composition of <5> or <6>.

<8> Process of forming the colored layer which consists of curable composition by apply | coating curable composition of <5> or <6>, the process of exposing the said colored layer through a mask, and developing a coloring layer after exposure, and forming a colored pattern. Process for producing a color filter comprising the step of.

<9> A solid-state image sensor comprising the color filter manufactured by the color filter manufacturing method of <8>.

Claims (9)

A curable composition comprising a resin, a compound having an ethylenically unsaturated double bond, and a photopolymerization initiator, wherein the resin is prepared by polymerizing a monomer having at least a dipole moment of 2.0 or more as a copolymerization component. The curable composition of claim 1, wherein the monomer has a dipole moment of 2.5 or more. The curable composition according to claim 1, wherein the resin is obtained by polymerizing a monomer having an ethylenically unsaturated double bond in the side chain and having at least a dipole moment of 2.5 or more as a copolymerization component. The monomer of claim 1, wherein the monomer having a dipole moment of 2.0 or more has at least one group selected from the group consisting of an ether group, a cyano group, an ester phosphate group, a lactone group, a urethane group, an ester carbonate group, and an acetal group. Curable composition. The curable composition according to claim 1, further comprising a colorant. The curable composition according to claim 1, further comprising a sensitizer. It has a coloring pattern formed from the curable composition of Claim 5, The color filter characterized by the above-mentioned. The process of forming the colored layer which consists of curable composition by apply | coating the curable composition of Claim 5 on a support body, the process of exposing the said colored layer through a mask, and the process of forming a coloring pattern by developing the said post-exposure colored layer is carried out. Method for producing a color filter comprising the. A solid state image pickup device comprising the color filter manufactured by the method for producing a color filter according to claim 8.