TWI442178B - Curable composition, color filter using the same and manufacturing method therefor, and solid image pickup element - Google Patents

Description

Curable composition, color filter using the same, method for producing the same, and solid-state imaging element

The present invention relates to a curable composition suitable for use in the manufacture of color filters for liquid crystal display elements (LCDs), solid state photographic elements (such as CCDs and CMOS), and a color filter formed by the curable composition. Sheet, and its manufacturing method.

Color filters are important components for liquid crystal displays or solid-state imaging components.

Liquid crystal displays are replacing CRTs as television screens, personal computer screens, and other display devices because they are lightweight and have equal or better performance than CRTs that are widely used as display devices. In addition, in recent years, the trend of liquid crystal displays has changed from a relatively small screen of conventional monitor applications to a television application with large screen and high image quality.

As for color filters for liquid crystal displays (LCDs), the substrate size is increased by the manufacture of large television sets. For the hardenable composition of the application for the manufacture of the color filter using this large substrate, productivity improvement requires a low energy hardening force.

In addition, compared to monitor applications, it requires higher image quality, that is, contrast and color purity improvement for liquid crystal displays for TV applications.

For the curable composition for use in the manufacture of color filters, for the purpose of improving the comparison, it is required to use a coloring agent (organic pigment or the like) having a finer particle size (see, for example, Japanese Patent Application Laid-Open (JP-A) No. 2006-30541).

However, when the curable composition contains a pigment having a small particle size, if the pigment absorption property of the dispersant is improved for the purpose of improving the stability of the dispersion, since the pigment is crosslinked by the dispersant, it promotes pigment aggregation to make storage stability ( The developing power tends to decrease as the dispersion stability is lowered, or when a pattern is formed using the curable composition.

Further, in the case of using a finer pigment, the use of a finer pigment tends to increase the amount of the dispersant added for dispersing the pigment in the hardenable composition due to an increase in its surface area.

Further, if the acid value of the added resin is improved at the time of dispersion to secure the developing power, the pigment aggregation tends to be promoted due to the interaction between the acidic groups (e.g., hydrogen bonding).

If a developing force is to be obtained by adding a resin to the curable composition after dispersing the pigment, a large amount of the resin should be added.

Further, for the purpose of improving the color purity, a coloring agent (organic pigment) having a higher content ratio in the solid content is required in the curable composition for producing a color filter. However, when the coloring agent is contained in the curable composition at a high concentration, the content ratio of the photopolymerization initiator to the photopolymerizable monomer in the curable composition is lowered, and although the curable composition is required to be hardened by low energy, exposure is required. Part of the difficulty of obtaining hardening power is a problem.

On the other hand, for a hardenable composition for use in the manufacture of a color filter for solid-state imaging elements, a low energy hardening force is also required. Furthermore, for color filters for solid-state photographic elements, it promotes the development of thinner colored pattern films, thereby increasing the pigment concentration in the composition.

In addition, in the pigment-based color filter, the finer pigment is used to reduce the cause. The pigment is a tendency of color irregularities caused by relatively coarse particles, and the proportion of the pigment dispersant in the hardenable composition tends to increase. Similar to the curable composition for LCD manufacturing purposes, an increase in the proportion of the pigment dispersant in the curable composition tends to lower the storage stability (e.g., dispersion stability), and tends to decrease when the curable composition is used to form a pattern. The developing power is difficult to obtain a hardening force.

Further, in order to solve the problem of color irregularity in the colored pattern formed, there has been proposed a technique of using an organic solvent-soluble dye instead of a pigment as a coloring agent (see, for example, JP-A No. 2-127602). However, for dye-based color filters, the increase in dye concentration is accompanied by a problem of reduced storage stability, such as polymerization inhibition effects derived from dyes, and dye precipitation is remarkable.

As described above, the curable composition for use in the manufacture of color filters, whether in the case of a liquid crystal display device or a solid-state image pickup device, is a photopolymerization initiator and a photopolymerizable monomer. The content of the important component for hardening the hardenable composition is limited, and the concentration of the colorant is high, the hardening force cannot be obtained due to low sensitivity, the adhesion to the substrate is insufficient, and the development rate of the unexposed portion is lowered or residue is generated. It is extremely difficult to form a desired pattern, and in the case where the colorant is a dye, the stability of the dispersion and the deterioration of the developing power are degraded, and when the coloring agent is a dye, the storage stability is low (such as dye precipitation) and the like, causing various problems.

In order to solve these problems, it has been discussed to improve the sensitivity by providing a polymerizable property to a resin which is conventionally introduced to provide film forming properties, developing power and the like (see, for example, JP-A Nos. 2000-321763 and 2003-029018) Lee). Further, this technique is shown in the "Color Filter Latest Technique Trend" (published by Johokiko Co., Ltd.) columns 85 to 87, "Process Technique and Chemicals for Latest Color Filter" (published by CMC Publishing Co., Ltd.), 129th to 150 columns and so on. However, even in the case of using these resins, satisfactory exposure sensitivity has not been obtained. In addition, due to insufficient exposure sensitivity, insufficient hardening of the deep portion near the interface of the substrate causes a problem of poor adhesion of the substrate.

It is an object of the present invention to provide a hardenable composition which is hardened with extremely high sensitivity and which has better storage stability.

Further, another object of the present invention is to provide a color filter formed using the above-described hardenable composition, which has high sensitivity, few unexposed portions of development residue, excellent adhesion property to a hardened portion of a substrate, and high The color pattern of the resolution and the desired cross-sectional shape.

Further, it is still another object of the present invention to provide a method of manufacturing the above color filter with excellent productivity, and a solid-state photographic element having the above-described color filter manufactured by the manufacturing method.

In light of the detailed study on the above, the inventors have found that the above problems can be solved to complete the present invention.

The present invention has been accomplished in view of the above circumstances, and provides a hardenable composition, a color filter using the same, and a solid-state imaging element thereof.

The first aspect of the invention provides <1> A curable composition comprising a resin, an ethylene-containing A compound of an unsaturated double bond, and a photopolymerization initiator, wherein the resin is produced by polymerizing at least one monomer having a dipole moment of 2.0 or more as a copolymerization component.

The second aspect of the invention provides <2> A color filter having a colored pattern formed of a hardenable composition of a first aspect, further comprising a coloring agent or a sensitizer.

The third aspect of the invention provides <3> A method of producing a color filter, comprising: forming a coloring layer made of a curable composition by coating a first aspect of a curable composition (further containing a coloring agent) on a support; The colored layer is exposed through a photomask, and after the exposure, the colored layer is developed by developing the colored layer.

A fourth aspect of the invention provides <4> A solid-state photographic element comprising a color filter manufactured by a color filter manufacturing method according to a third aspect.

According to the present invention, even in the case of containing a coloring agent at a high concentration, it can provide a storage stability (e.g., dispersion stability), hardening by exposure with high sensitivity, and having a surface on the substrate of the hardened region. A highly adherent property, and a curable composition which can form a pattern having an unhardened portion of an uncured region and having excellent removal properties.

Further, according to the present invention, it is possible to provide a coloring pattern having excellent resolution and support adhesion properties, a color filter formed using the hardenable composition of the present invention, and a color filter for forming a color filter with high productivity. Manufacturing method.

Hereinafter, the curable composition of the present invention contains a resin, a compound containing an ethylenically unsaturated double bond, and a photopolymerization initiator, wherein the resin is polymerized by at least one monomer having a dipole moment of 2.0 or more. It is produced by copolymerizing components.

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

Further preferably, the curable composition of the present invention further comprises a color former.

The components contained in the curable composition of the present invention are continuously explained below.

<Resin (A)> The resin of the present invention is a resin produced by polymerizing at least one monomer having a dipole moment of 2.0 or more as a copolymerization component. Preferably, the resin of the present invention has an ethylenically unsaturated double bond in the side chain.

It is preferable that the above resin is a polymer having a group represented by the following formulas (1) to (3) in the side chain as the above-mentioned ethylenically unsaturated double bond.

In the formula, R ¹ to R ¹¹ each independently represent a hydrogen atom or a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom or -N-R ¹² , and Z represents an oxygen atom, a sulfur atom, -N-R ¹² or a phenyl group. R ¹² represents a hydrogen atom or a monovalent organic group.

In the above formula (1), R ¹ to R ³ each independently represent a monovalent organic group. As R ¹ , it may be a hydrogen atom or an alkyl group (which may have a substituent), an alkoxy group, an alkoxycarbonyl group or the like. Particularly, it is preferably a hydrogen atom, a methyl group, a methyl alkoxy group, and a methyl ester group. Further, R ² and R ³ each independently represent a hydrogen atom, a halogen atom, an amine group, a dialkyl group, a carboxyl group, an alkoxycarbonyl group, a thiol group, a nitro group, a cyano group, an alkyl group (which may have a substituent), and an aromatic group. a group (which may have a substituent), an alkoxy group (which may have a substituent), an aryloxy group (which may have a substituent), an alkylamino group (which may have a substituent), an arylamine group (which may have a substituent), An alkylsulfonyl group (which may have a substituent), an arylsulfonyl group (which may have a substituent), and the like. Particularly preferred are a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group (which may have a substituent), and an aryl group (which may have a substituent).

Here, as the substituent to be introduced, a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a methyl group, an ethyl group, a phenyl group or the like can be proposed.

X represents an oxygen atom, a sulfur atom or -N-R ¹² . Here, as for R ¹² , it may be mentioned that an alkyl group (which may have a substituent) or the like.

In the formula (1), as for the alkyl group, it may be a linear or cyclic alkyl group having 1 to 30 carbons. It is preferably an alkyl group having 1 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 10 carbon atoms.

In the formula (1), as the aryl group, it may be proposed to have 6 to 30 carbon atoms. It is preferably one having 6 to 20 carbon atoms, and particularly preferably having 6 to 10 carbon atoms.

In the above formula (2), R ⁴ to R ⁸ each independently represent a monovalent organic group. R ⁴ to R ⁸ may, for example, be a hydrogen atom, a halogen atom, an amine group, a dialkyl group, a carboxyl group, an alkoxycarbonyl group, a thiol group, a nitro group, a cyano group, an alkyl group (which may have a substituent), 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 alkylamino group (which may have a substituent), an arylamine group (which may have a substituent) An alkylsulfonyl group (which may have a substituent), an arylsulfonyl group (which may have a substituent), and the like. Particularly preferred are a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group (which may have a substituent), and an aryl group (which may have a substituent). As for the introduced substituent, it can be proposed to the formula (1). Y represents an oxygen atom, a sulfur atom or -N-R ¹² . As for R ¹² , it can be proposed to the formula (1). In the formula (2), as for the alkyl group and the aryl group, it can be proposed to the formula (1), and the same preferred examples can be applied.

In the above formula (3), R ⁹ to R ¹¹ each independently represent a monovalent organic group. As the organic group, it may specifically represent, for example, a hydrogen atom, a halogen atom, an amine group, a dialkyl group, a carboxyl group, an alkoxycarbonyl group, a thiol group, a nitro group, a cyano group, an alkyl group (which may have a substituent), and an aromatic group. a group (which may have a substituent), an alkoxy group (which may have a substituent), an aryloxy group (which may have a substituent), an alkylamino group (which may have a substituent), an arylamine group (which may have a substituent), An alkylsulfonyl group (which may have a substituent), an arylsulfonyl group (which may have a substituent), and the like. Particularly preferred are a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group (which may have a substituent), and an aryl group (which may have a substituent).

As for the introduced substituent, it can be proposed to the formula (1) in the same manner.

Z represents an oxygen atom, a sulfur atom, -N-R ¹² or a phenyl group. As for R ¹² , it can be proposed to the formula (1).

In the formula (3), as for the alkyl group and the aryl group, it can be proposed for the formula (1), and the same preferred examples can be applied.

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

A method for obtaining a desired polymer compound by synthesizing a polymer compound by copolymerizing one or more radical polymerizable compounds represented by the following formula (12) with a specified monomer described later, and taking out a base using a base Protons to separate Z.

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

In the 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, an alkyl group (which may have a substituent), or the like can be proposed. Particularly preferred are a hydrogen atom, a methyl group, a methyl alkoxy group, and a methyl ester group. A represents a divalent organic bond group. The divalent organic linking group as A is not particularly limited, and it may be proposed to have an alkyl group having a total of 1 to 30 atoms (for example, a methylene group, an exoethyl group, a cyclohexyl group) and have a total of 6 to An aryl group of 30 atoms (for example, a phenyl group, a trilene, a naphthyl group). It is particularly preferably an alkylene group having a total of 1 to 10 atoms and an extended aryl group having a total of 6 to 15 atoms.

In the formula (13), same as (1) the lines R ¹ to R ³ in the formula, and the same preferred examples can also be applied.

Synthesis method 2) A method for obtaining a desired polymer compound by synthesizing a dry polymer compound (including a polymer compound of a main chain) by copolymerizing one or more radical polymerizable compounds having a functional group and a specified monomer described later And a side chain functional group of the above stem polymer compound and a compound having a structure represented by the following formula (13).

As for the radically polymerizable compound represented by the formula (12), the following compounds can be cited as examples, but are not limited thereto.

The radically polymerizable compound represented by the formula (12) is easily obtained as a commercially available product or a synthesis method shown in the synthesis examples described later.

The group represented by the formula (1) can be obtained by polymerizing one or more of these radically polymerizable compounds and a specified monomer described later, if necessary, and other radical polymerizable compounds, by a general radical polymerization method for synthesizing a polymer compound. The desired amount of the base is dropped into the polymer solution under cooling or heating conditions for carrying out the reaction, if necessary and introduced by neutralization with an acid. For the manufacture of polymer compounds, it can be used by known suspension polymerization or dissolution. Liquid polymerization method, etc.

As the base, an inorganic compound or an organic compound can be used. As a preferred inorganic base, sodium hydroxide, lithium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate or the like can be mentioned. As the organic base, metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, organic amine compounds such as triethylamine, pyridine and diisopropylethylamine, and the like can be proposed.

In the synthesis method 2), as an example of a functional group of a radically polymerizable compound having a functional group for synthesis of a dry polymerizable compound, a hydroxyl group, a carboxyl group, a halogenated carboxylic acid group, a carboxylic anhydride group, an amine group, A halogenated alkyl group, an isocyanate group, an epoxy group or the like. As the radical polymerizable compound having such a functional group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, acrylic acid, and A can be proposed. Acrylic acid, acrylic acid chloride, methacrylic acid chloride, methacrylic anhydride, N,N-dimethyl-2-aminoethyl methacrylate, 2-chloroethyl methacrylate, 2-ethyl isocyanate methyl Acrylate, glycidyl acrylate, glycidyl methacrylate, and the like.

The desired polymer compound can be obtained by polymerizing one or more of these radically polymerizable compounds with a specified monomer described later, if necessary and copolymerizing other dry polymer compounds for synthesizing a radically polymerizable compound, and having a reaction formula (13) ) is obtained as a compound based on the group.

Here, as an example of the compound having a group represented by the formula (13), a compound proposed as an example of the above radical polymerizable compound can be proposed.

In the present invention, the above compound having a group represented by the formula (2) may be borrowed At least one of the synthesis methods 3) and 4) is shown below.

Synthesis method 3) A radically polymerizable compound which polymerizes one or more ethylenically unsaturated groups having an unsaturated group represented by the formula (2) and having an addition polymerization property higher than that of an unsaturated group, a specified monomer described later, if necessary, and other freedoms A method of obtaining a polymer compound by polymerizing a compound. This method utilizes a compound having a plurality of ethylenically unsaturated groups having different addition polymerization properties in the molecule, such as allyl methacrylate.

Synthesis method 4) A method of copolymerizing one or more radically polymerizable compounds having a functional group with a specified monomer described later for synthesizing a polymer compound, and a reactive side chain functional group and a compound having a structure represented by the following formula (14), A method of introducing the basis represented by the formula (2) is introduced.

In the formula (14), R ⁴ to R ⁸ are the same as those in the formula (2), and the same preferred examples are also applied.

As the radically polymerizable compound having an unsaturated group represented by the formula (2) and an ethylenically unsaturated group having an addition polymerization property higher than that of the unsaturated group, it may be mentioned that allyl acrylate, allyl methacrylate, acrylic acid 2-allyloxyethyl ester, 2-allyloxyethyl methacrylate, propargyl acrylate, propargyl methacrylate, allyl acrylate, allyl methacrylate, diallyl acrylate , diallyl methacrylate, N-allyl acrylamide N-allylmethacrylamide or the like is exemplified.

Further, as an example of a polymer compound obtained by polymerizing one or more radically polymerizable compounds having a functional group, an example shown in the above synthesis method 2) can be proposed.

Examples of the compound having a structure represented by the formula (14) include allyl alcohol, allylamine, diallylamine, 2-allyloxyethanol, 2-chloro-1-butene, and allyl isocyanate.

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

Synthesis method 5) A radically polymerizable compound which copolymerizes one or more ethylenically unsaturated groups having an unsaturated group represented by the formula (3) and having an addition polymerization property higher than that of an unsaturated group, and a monomer specified later, if necessary A method of copolymerizing other radically polymerizable compounds to obtain a polymer compound.

Synthesis method 6) After synthesizing a polymerizable compound by copolymerizing one or more radically polymerizable compounds having a functional group and a specified monomer described later, reacting and introducing a compound having a structure represented by formula (15) and a side chain functional group method.

a radically polymerizable compound having an unsaturated group represented by the formula (3) and an ethylenically unsaturated group having an addition polymerization property higher than that of the unsaturated group, which may be Proposed vinyl acrylate, vinyl methacrylate, 2-phenylvinyl acrylate, 2-phenylvinyl methacrylate, 1-propenyl acrylate, 1-propenyl methacrylate, vinyl acrylamide, ethylene A methacrylamide or the like is exemplified.

As the polymer compound obtained by copolymerization, it can be obtained as an example of the above synthesis method 2).

In the formula (15), R ⁹ to R ¹¹ are the same as those in the formula (3), and the same preferred examples are also applied.

As the compound having a structure represented by the formula (15), it may be proposed as 2-hydroxyethyl monovinyl ether, 4-hydroxybutyl monovinyl ether, diethylene glycol monovinyl ether, 4-chloromethyl group. Styrene and the like are exemplified.

It is also preferred to use at least one of the following formulas (4) and (5) in the above synthesis method 1) instead of the synthesis method of the formula (12) used in the above synthesis method 1).

In the formula (4) or (5), R ⁵ , R ⁶ , R ⁷ represent hydrogen or a monovalent organic group, A ² represents an oxygen atom, a sulfur atom or -NR ⁸ -, and G ¹ represents an organic bonding group, and R ⁸ Represents hydrogen or a monovalent organic group, and n represents an integer from 1 to 10. R ¹ to R ³ are the same as in the formula (12), the A ¹ is the same as X in the formula (1), and the X ¹ is the same as Z in the formula (12).

R ⁹ to R ¹³ represent an oxygen or a monovalent organic group, at least one of which is a group represented by the following formula (6). R ¹⁴ to R ¹⁶ represent hydrogen or a monovalent organic group.

In the formula (4) or (5), the monovalent organic group is the same as the monovalent organic group in the formula (1), and the same preferred examples are also applied.

In the formula (6), G ² represents an organic bonding group, and m represents an integer of 1 to 10. R ¹ to R ³ , A ¹ and X ¹ are the same as those in the formula (4).

As a preferred designated example of the compound represented by the above formula (4) or (5), the following (i-1 to i-60) can be proposed.

When a compound having a group represented by the formula (1) (hereinafter also referred to as "polyvinyl group-based polymer compound") is synthesized by using the above formula (4) or (5), further depolymerization is carried out by the above-mentioned de-reaction reaction. Generally, a radically polymerizable compound and a compound having a double bond are also a specific embodiment of the present invention.

In the above synthesis methods 1) to 6), as described above, other general radical polymerizable compounds may be copolymerized if necessary. The general radical polymerizable compound copolymerized in the present invention may, for example, be selected from the group consisting of acrylates, methacrylates, N,N-disubstituted acrylamides, N,N-disubstituted methacrylamides, styrene, A radically polymerizable compound such as acrylonitrile or methacrylonitrile.

Specific examples include acrylates such as alkyl acrylates (the number of carbon atoms of the alkyl group is preferably from 1 to 20) (particularly, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, acrylic acid) Ethylhexyl ester, octyl acrylate, trioctyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, neopentyl Tetraol monoacrylate, propylene acrylate, benzyl acrylate, methoxybenzyl acrylate, furan acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (such as phenyl acrylate, etc.), methacrylate, such as An alkyl methacrylate (the number of carbon atoms of the alkyl group is preferably from 1 to 20) (particularly, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, A Amyl acrylate, cyclohexyl methacrylate, benzyl methacrylate, benzyl chloride methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, A Acrylic acid 2 ,2-dimethyl-3-hydroxypropane Esters, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furyl methacrylate, tetrahydrofurfuryl methacrylate, etc.), aryl methacrylate (such as phenyl methacrylate, toluene methacrylate, naphthyl methacrylate, etc.), styrene, such as styrene and alkyl styrene (such as methyl styrene, dimethyl styrene, trimethyl benzene) Ethylene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, mercapto styrene, benzyl styrene, chloromethyl styrene, three Fluoromethylstyrene, ethoxymethylstyrene, with ethoxymethylstyrene), alkoxystyrene (such as methoxystyrene, 4-methoxy-3-methylstyrene) With dimethoxystyrene), halogen styrene (such as chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene Fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, and 4-fluoro-3- Fluoro-methyl styrene), acrylonitrile, methacrylonitrile and the like.

As the carboxylic acid-containing radically polymerizable compound, for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, p-carboxystyrene or the like can be mentioned.

Further, as for the solvent used in the synthesis of the above polyvinyl group-based polymer compound, for example, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether may be mentioned. , ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl hydrazine, toluene, ethyl acetate, methyl lactate, ethyl lactate, 1-methyl-2- Pyrrolidone and the like.

These solvents may be used singly or as a mixture of two or more.

In the present invention, the resin as the copolymer is a resin produced by polymerizing at least one dipolar monomer having a dipole moment of 2.0 or more (hereinafter also referred to as "designated monomer") as a copolymerization component. The "designated monomer" is herein a monomer other than the alkali-soluble monomer described later.

As for the dipole moment described above, it is calculated using the following calculation method.

That is, the dipole moment is calculated by using CAChe 6.1 (manufactured by Fujitsu Corp.) by the calculation method AM1, and the optimum structure obtained by optimizing the structure of the above-mentioned designated monomer is calculated.

According to the specified monomer which is a copolymerization component of the resin of the present invention, although it does not limit the structure, the dipole moment calculated by the above calculation method is 2.0 or more. Particularly with respect to sensitivity and storage stability, the dipole moment value is preferably 2.5 or more, more preferably 2.5 or more and 15 or less, further preferably 3.0 or more and 10 or less. Preferably, it is 3.5 or more and 9.0 or less, and most preferably 3.5 or more and 8.0 or less.

Since the dipole moment of the above specified monomer is in the range of 2.5 or more and 15 or less, the convenience of resin synthesis, the sensitivity of the resin-containing hardenable composition, the developing property, and the storage stability are compared. good.

In the above examples, the specified monomer is particularly preferably one having at least one selected from the group consisting of an ether group, a cyano group, a phosphoric acid group, a lactone group, a urethane group, a carbonate group, and an acetal group.

The ether group contained in the specified monomer is preferably a linear, branched or cyclic ether group having 2 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic ether group having 2 to 15 carbon atoms. As an example of the ether group, it is possible to propose 2-methoxyethyl ether, 2-ethoxyethyl ether, MeOCH ₂ CH ₂ OCH ₂ CH ₂ -, MeO(CH ₂ CH ₂ O) ₂ CH ₂ CH ₂ - oxetan-2-yl, oxetan-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydro-2H-pyran-2-yl, octahydro-1H - Isochlomene-3-yl, oxylane-2-yl and the like.

The lactone group contained in the specified 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 for the example of the lactone group, the following structure can be proposed. In the following structure, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, wherein the alkyl group, the cycloalkyl group or the aryl group each independently has 1 to 20 carbon atoms.

The urethane group contained in the specified monomer is preferably a linear or cyclic urethane group having 1 to 30 carbon atoms, and is preferably a linear or cyclic amino group having 1 to 20 carbon atoms. Formate group.

As for the example of the urethane group, the following structure can be proposed, but is not limited thereto. In the following structure, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, wherein the alkyl group, the cycloalkyl group or the aryl group each independently has 1 to 20 carbon atoms.

The carbonic acid group contained in the specified monomer is preferably a linear or cyclic carbonic acid group having 1 to 30 carbon atoms, and is preferably a linear or cyclic carbonic acid group having 1 to 20 carbon atoms.

As for the example of the carbonate group, the following structure can be proposed, but is not limited thereto.

The acetal group contained in the specified monomer is preferably a linear or cyclic acetal group having 1 to 30 carbon atoms, and is preferably a linear or cyclic acetal group having 1 to 20 carbon atoms. As for the example of the acetal group, the following structure can be proposed, but is not limited thereto. In the following structure, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, wherein the alkyl group, the cycloalkyl group or the aryl group each independently has 1 to 20 carbon atoms.

The phosphate group contained in the specified monomer is preferably a linear or cyclic phosphate group having 1 to 30 carbon atoms, and is preferably a linear or cyclic phosphate group having 1 to 20 carbon atoms. As for the example of the phosphate group, the following structure can be proposed, but is not limited thereto.

As the specified examples of the above monomers, the following compounds can be preferably used, but are not limited thereto.

[Table 1]

The resin of the present invention is a resin produced by copolymerizing the above-mentioned specified monomer as a copolymerization component, and is preferably a component having a partial structure having an ethylenically unsaturated double bond which may be a resin side chain by copolymerization ( Hereinafter, it is also referred to as "a copolymer component which provides a resin double bond") and a resin produced by the above specified monomer.

The combination of the copolymerizable component of the resin of the present invention, that is, the combination of "designated monomer" and "copolymerized component providing a resin double bond" is preferably any of M-1, M-8, i-1, i. -7, i-8, i-10, i-16, and i-49 with any M-9A, M-11A, M-12A, M-13A, M-14A, M-15A, M-9MA, M Combination of -11MA, M-12MA, M-13MA, M-14MA, M-15MA, and M-16MA, more preferably any M-1, i-1, i-10, i-16, and i-49 Combination with any of M-11A, M-13A, M-14A, M-11MA, M-13MA, and M-14MA, and particularly preferred combination of example compound i-1 with the example compound M-14MA, example compound i -1 in combination with the example compound M-11MA, the combination of the example compound i-1 with the example compound M-13MA, the combination of the example compound M-1 with the example compound M-14MA, the example compound M-1 and the example compound M-11MA Combinations, and combinations of the example compound M-1 with the exemplified compound M-13MA.

The above combination is preferable in terms of easiness of resin synthesis, sensitivity to a resin-containing curable composition, developing power, and storage stability.

The configuration of the resin of the present invention as a copolymer may be a block copolymer, a random copolymer, a graft copolymer or the like. It is particularly preferred to be a block copolymer with respect to ease of resin synthesis.

The content of the copolymer component which provides the above resin double bond of the present invention is preferably 0.1 mol% to 95 mol%, more preferably 1 mol% to 85 mol%, and particularly preferably 5 mol% to 75 mol%.

The above "the content of the copolymerization component which provides a resin double bond" is specifically shown below.

In the above-mentioned synthesis method 1), it means "the content in the copolymer of the radically polymerizable compound represented by the formula (12)", and in the above synthesis methods 2), 4) and 6), it means " After copolymerizing a radically polymerizable compound having a functional group, the content of the functional group in any of the copolymers of the formula (13), (14) and (15) in the copolymer as a copolymerization component, and in the synthesis method In 3 or 5), it means "in a copolymer of a radically polymerizable compound having an unsaturated group represented by the formula (2) or (3) and an addition polymerization property higher than an ethylenically unsaturated group of an unsaturated group; content".

Since the content of the copolymerization component which provides the above double bond of the resin is in the above range, the sensitivity is improved and the adhesion property to the substrate is preferable, which is preferable.

In the resin of the present invention, the content of the above specified monomer as a copolymerization component is preferably from 1 mol% to 90 mol%, more preferably from 3 mol% to 70 mol%, and particularly preferably 5 mol%. Ear to 50% by mole.

Since the content of the above specified monomer is in the above range, the sensitivity is improved and the adhesion property to the substrate is preferred, which is preferable.

The molar ratio (composition ratio) of the "content of the above-mentioned specified monomer" in the resin and the "content of the copolymerized component of the resin double bond provided above" in the resin are preferably from 100:1 to 1:100, more preferably It is 50:1 to 1:50, and it is especially good for 10:1 to 1:10.

Since the ratio of the composition of the above-mentioned designated monomer and the above-mentioned copolymerized component which provides the double bond of the resin is in the above range, the sensitivity is improved and the adhesion property to the substrate is preferable, which is preferable.

The resin of the present invention may be a resin produced by polymerizing an alkali-soluble group-containing monomer as a copolymerization component. The "alkali-soluble group" here means a functional group which is dissociated by the developing solution used when forming a pattern to improve the solubility of the developing solution (basic aqueous solution). The alkali-soluble group is preferably a functional group having a pKa of 11 or less in water at 25 °C. As the functional group, for example, a carboxyl group, a thiol group, a decylamino group, a phosphoric acid group, a phenol type hydroxyl group or the like can be proposed. It is particularly preferably a carboxyl group.

The content of the above alkali-soluble group-containing monomer as a copolymerization component is preferably from 1 mol% to 90 mol%, more preferably from 3 mol% to 70 mol%, and particularly preferably from 5 mol% to 50%. Moer%.

Since the content of the above-mentioned alkali-soluble group-containing monomer as a copolymerization component is in the above range, the sensitivity is improved and the adhesion property to the substrate is preferable, which is preferable.

The weight average molecular weight (polystyrene equivalent value in GPC measurement) is preferably from 500 to 100,000, further preferably from 1,000 to 50,000, particularly preferably from 1,000 to 30,000. The molecular weight distribution (ratio of the weight average molecular weight to the number average molecular weight) of the resin is preferably 3.0 or less, and more preferably 2.0 or less.

Designated examples of the resin of the present invention and its weight average molecular weight are set forth below, but the present invention is not limited thereto.

The total content (% by mole) of the copolymerizable component of the specified monomer and the double bond of the above resin is preferably from 2 mol% to 98 mol%, more preferably from 5 mol% to 90 mol, in accordance with the resin of the present invention. Ear %, and particularly preferably from 10 mol% to 80 mol%.

Since the above total content is in the above range, the sensitivity is improved and the adhesion property to the substrate is better, which is preferable.

The content of the above resin is preferably from 0.1% by mass to 75% by mass, more preferably from 1% by mass to 50% by mass, and particularly preferably from 2% by mass to 40% by mass, based on the total solid content of the curable composition of the present invention. According to this range, better sensitivity and pattern formation properties can be obtained.

<Photopolymerization initiator> The curable composition of the present invention contains a photopolymerization initiator (B) for improving sensitivity and pattern forming properties.

The photopolymerization initiator of the present invention is a compound which is photodegradable and which is used for initiating and promoting the polymerization of the polymerizable component of the present invention, and preferably has an absorption in a region of a wavelength of from 300 to 500 nm. Further, the photopolymerization initiator may be used singly or in combination of two or more.

As the photopolymerization initiator, for example, an organic halide compound, an oxadiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide compound, an azo compound, a xanthan compound, or a stack can be proposed. A nitrogen compound, a metal aromatic compound, a hexaaryldiimidazole compound, an organic boronic acid compound, a disulfonate compound, an oxime ester compound, a phosphonium salt compound, a mercaptophosphine (oxide) compound, an alkylamine compound, or the like.

Each compound is described in detail below.

As for the organic halide compound, it can be proposed by Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Application Publication (JP-B) No. 46-4605 , JP-A Nos. 48-36281, 55-32070, 60-239736, 61-169835, 61-169837, 62-58241, 62-212401, 63-70243, 63-298339, MP Hutt" Journal of Heterocyclic Chemistry" 1 (No. 3), (1970) and the like. In particular, trihalomethyl substituted oxazole compounds and s-three can be proposed. Compound.

As for s-three a compound, more preferably wherein at least one of the mono-, di- or tri-halogen-substituted methyl-bonded s-three Ring s-three Derivatives, more particularly, can be proposed, for example, 2,4,6-paran (monochloromethyl)-s-three , 2,4,6-gin (dichloromethyl)-s-three , 2,4,6-para (trichloromethyl)-s-three 2-methyl-4,6-anthracene (trichloromethyl)-s-three 2-n-propyl-4,6-fluorene (trichloromethyl)-s-three , 2-(α,α,β-trichloroethyl)-4,6-indole (trichloromethyl)-s-three 2-phenyl-4,6-fluorene (trichloromethyl)-s-three , 2-(p-methoxyphenyl)-4,6-fluorene (trichloromethyl)-s-three , 2-(3,4-epoxyphenyl)-4,6-fluorene (trichloromethyl)-s-three , 2-(p-chlorophenyl)-4,6-fluorene (trichloromethyl)-s-three ,2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-fluorene (trichloromethyl)-s-three 2-styryl-4,6-fluorene (trichloromethyl)-s-three , 2-(p-methoxystyryl)-4,6-fluorene (trichloromethyl)-s-three , 2-(p-isopropoxystyryl)-4,6-fluorene (trichloromethyl)-s-three , 2-(p-tolyl)-4,6-indole (trichloromethyl)-s-three , 2-(4-naphthyloxynaphthyl)-4,6-fluorene (trichloromethyl)-s-three 2-phenylthio-4,6-indole (trichloromethyl)-s-three 2-Benzylthio-4,6-indole (trichloromethyl)-s-three , 2,4,6-parade (dibromomethyl)-s-three , 2,4,6-parade (tribromomethyl)-s-three 2-methyl-4,6-anthracene (tribromomethyl)-s-three 2-methoxy-4,6-indole (tribromomethyl)-s-three Wait.

As the oxadiazole compound, it is possible to propose 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(cyanostyryl)-1 , 3,4-oxadiazole, 2-trichloromethyl-5-(naphthalen-1-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-styrene Styryl-1,3,4-oxadiazole and the like.

As for the carbonyl compound, it may be proposed as a diphenyl ketone derivative such as diphenyl ketone, benzyl ketone, 2-methyl diphenyl ketone, 3-methyl diphenyl ketone or 4-methyl diphenyl ketone. , 2-chlorodiphenyl ketone, 4-bromodiphenyl ketone, and 2-carboxydiphenyl ketone, acetophenone derivatives, such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyphenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(p-isopropyl Phenyl phenyl ketone, 1-hydroxy-1-(p-dodecylphenyl) ketone, 2-methyl-(4'-(methylthio)phenyl)-2-morpholine-1-propanone, 1,1,1-trichloromethyl-(p-butylphenyl)one, and 2-benzyl-2-dimethylamino-4-morpholinone, sulfur Derivatives such as sulfur 2-ethylsulfide 2-isopropylsulfur 2-chlorosulfur 2,4-dimethylsulfur 2,4-diethyl sulphide And 2,4-diisopropyl sulfide a benzoate derivative such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

As the ketal compound, a benzyl methyl ketal, a benzyl-β-methoxyethyl ethyl ketal or the like can be mentioned.

As the benzoin compound, it may be mentioned that benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-besylbenzoate, and the like.

As the acridine compound, it may be mentioned that 9-phenyl acridine, 1,7-fluorene (9-acridinyl) heptane or the like.

As the organic peroxide compound, for example, trimethylcyclohexane peroxide, acetylacetone peroxide, 1,1-anthracene (t-butylperoxy)-3,3,5- Trimethylcyclohexane, 1,1-anthracene (t-butylperoxy)cyclohexane, 2,2-anthracene (t-butylperoxy)butane, tert-butyl hydroperoxide, Cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethyl hydroperoxide Butyl, tributyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, peroxide 2 , 5-oxoyl, oxidized amber thiol, benzammonium peroxide, 2,4-dichlorobenzhydryl peroxide, diisopropyl peroxydicarbonate, peroxy Di-2-ethylhexyl dicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-peroxydicarbonate) 3-methoxybutyl ester), tert-butyl peroxyacetate, tert-butyl peroxytrimethylacetate, tert-butyl peroxy neodecanoate , tert-butyl peroxyoctanoate, tert-butyl peroxy laurate, tercyl carbonate, 3,3',4,4'-tetra (t-butylperoxycarbonyl) Diphenyl ketone, 3,3',4,4'-tetrakis(trihexylperoxycarbonyl)diphenyl ketone, 3,3',4,4'-tetra(p-isopropyl cumyl) Peroxycarbonyl)diphenyl ketone, carbonyl bis(t-butylperoxydihydrodicaprate), carbonyldi(t-hexylperoxydihydrodicaprate) and the like.

As the azo compound, for example, an azo compound or the like described in JP-A No. 8-108621 can be proposed.

As for the kaempferol compound, it can be proposed, for example, 3-methyl-5-amino group ((s-three) -2-yl)amino)-3-phenylcumene, 3-chloro-5-diethylamino ((s-three) -2-yl)amino)-3-phenylcumene, 3-butyl-5-diethylamino ((s-three) -2-yl)amino)-3-phenylcumene and the like.

As for the azide compound, the organic azide compound described in U.S. Patent Nos. 2,848,328, 2,852,379 and 2,940,853, 2,6-fluorene (azidobenzylidene)-4-ethylcyclohexanone (BAC-E) can be proposed. Wait.

As the metal aromatic hydrazine compound, various titanocene compounds described in JP-A Nos. 59-152396, 61-151197, 63-41484, 2-249, 2-4705, and 5-83588 can be proposed, such as two. Cyclopentadienyl-Ti-fluorenylphenyl, dicyclopentadienyl-Ti-贰-2,6-difluorophenyl-1-yl, dicyclopentadienyl-Ti-贰-2,4- Difluorophenyl-1-yl, dicyclopentadienyl-Ti-indole-2,4,6-trifluorophenyl-1-yl, dicyclopentadienyl-Ti-贰-2,3,5, 6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-贰-2,3,4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti- Indole-2,6-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-indole-2,4,6-trifluorophenyl-1-yl, dimethylcyclopentadienyl- Ti-贰-2,3,5,6-tetrafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-贰-2,3,4,5,6-pentafluorophenyl-1-yl An iron-aromatic hydrocarbon complex or the like described in JP-A Nos. 1-104453 and 1-152109.

As for the hexaaryldiimidazole compound, various compounds such as those described in JP-B-6-29285, U.S. Patent Nos. 3,479,185, 4,311,783, 4,622,286, etc., especially 2,2'-fluorene (o-chlorobenzene) can be proposed. -4,4',5,5'-tetraphenyldiimidazole, 2,2'-indole (o-bromophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2, 2'-贰(o-, p-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-fluorene (o-chlorophenyl)-4,4',5 , 5'-tetrakis (m-methoxyphenyl) diimidazole, 2,2'-fluorene (o-, o-'-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-贰(o-nitrophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-fluorene (o-methylphenyl)-4,4',5 , 5'- Tetraphenyldiimidazole, 2,2'-fluorene (o-trifluoromethylphenyl)-4,4',5,5'-tetraphenyldiimidazole, and the like.

As for the organic boronic acid compound, for example, JP-A Nos. 62-143044, 62-150242, 9-188685, 9-188686, 9-188710, 2000-131837, and 2002-107916, and Japanese Patent No. 2,764,769, JP-A No. 2002-116539, et al., and organic borate esters described by Kunz, Martin, "Rad Tech '98. Proceeding April 19-22, 1998, Chicago", JP-A No. 6-157623, 6 -Organic borofluorene complex or organooxo-inclusion complex as described in JP-A No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The organoboron ruthenium complex disclosed in Japanese Patent No. 9-188710, the organoboron transition metal coordination of JP-A Nos. 6-348011, 7-128785, 7-140589, 7-306527, and 7-292014 Things etc. are specified examples.

As the disulfonic acid compound, a compound described in the specification of JP-A No. 61-166544, JP-A No. 2002-328465, and the like can be proposed.

As the oxime ester compound, it can be proposed by JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and JP-A No. 2000-66385. The compound, the compound described in JP-A No. 2000-80068, and the Japanese Patent Application Publication No. 2004-534797.

As the onium salt compound, it can be proposed, for example, by S.I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), and T. S. Bal et al. The diazonium salt disclosed in Polymer, 21, 423 (1980), the specification of U.S. Patent No. 4,069,055, and the ammonium salt disclosed in JP-A No. 4-365049, the bismuth salt disclosed in U.S. Patent Nos. 4,069,055 and 4,069,056, European Patent No. Anthraquinone salts and the like described in U.S. Patent Nos. 339,049 and 410,201, and JP-A Nos. 2-150848 and 2-296514.

The onium salt which is preferably used in the present invention is a diarylsulfonium salt. From the viewpoint of stability, it is preferably substituted with 2 or more electron-donating groups such as an alkyl group, an alkoxy group and an aryloxy group.

As for the onium salt which is preferably used in the present invention, it is possible to provide European Patent Nos. 370,693, 390,214, 233,567, 297,443, and 297,442, and U.S. Patent Nos. 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, and 2,833,827, and The onium salts disclosed in German Patent Nos. 2,904,626, 3,604,580 and 3,604,581. From the standpoint of sensitivity, it is preferably substituted by an electron withdrawing group. Preferably, the electron withdrawing group has a Hammett value greater than zero. As the electron withdrawing group, a halogen atom, a carboxylic acid or the like can be proposed.

Further, as for other preferred onium salts, one may have an absorption of an onium salt of 300 nm or more, and one of the substituents of the triarylsulfonium salt has a broad gelatin and an anthracene structure. Further, as for other preferred onium salts, an onium salt having an absorption of 300 nm or more may be proposed, and a triarylsulfonium salt having an allyloxy group or an arylthio group may be used as a substituent.

Further, as for the onium salt compound, it can be proposed by J. V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. V. Crivello et al. Selenium salts described by J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), and Tech by CWen et al., Proc. Conf. Rad. Curing ASIA, p 478 Tokyo, Oct (1988) Said strontium salt and the like.

As the mercaptophosphine (oxide) compound, it can be proposed as IRUGACURE 819, DAROCURE 4265, DAROCURE TPO, and the like manufactured by Ciba Speciality Chemicals Corp.

As the alkylamino group-based compound, for example, a compound having a dialkylaminophenyl group, or JP-A No. 9-281698, paragraph [0047], JP-A Nos. 6-19240 and 6-19249 The patent discloses an alkylamine compound. In particular, as for the compound having a dialkylaminophenyl group, it may be a compound such as ethyl p-dimethylaminobenzoate, and a dialkylaminophenylcarboxaldehyde such as p-diethylaminobenzoate. Carboxaldehyde and 9- Further, as the alkylamine compound, triethanolamine, diethanolamine, triethylamine or the like can be mentioned.

<Photopolymerization Initiator (B)> The photopolymerization inhibitor (B) used in the present invention is preferably one selected from three from the viewpoint of exposure sensitivity. a main compound, an alkylamino compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a mercaptophosphine main compound, a phosphine oxide-based compound, a metal aromatic quinone compound,肟 main compound, diimidazole-based compound, ruthenium-based compound, benzothiazole-based compound, diphenyl ketone compound as main compound, acetophenone-based compound and its derivative, cyclopentadiene-benzene-iron A complex compound and a salt thereof, a halomethyl oxadiazole compound, and a compound substituted with a 3-aryl-substituted oxacin compound.

It is better for three Main compound, alkylamine based compound, α-amino ketone compound, decyl phosphine-based compound, phosphine oxide-based compound, ruthenium-based compound, diimidazole-based compound, ruthenium-based compound, diphenyl ketone The main compound or acetophenone is the main compound. Further preferably, at least one selected from the group consisting of three A main compound, an alkylamino compound, a ruthenium-based compound, and a compound mainly composed of diimidazole.

The content of the photopolymerization initiator (B) is preferably from 0.1% by mass to 50% by mass, more preferably from 0.5% by mass to 30% by mass, and particularly preferably from 1% by mass to the total solid content of the curable composition of the present invention. 20% by mass. According to this range, better sensitivity and pattern formation properties can be obtained.

<Compound (C) containing ethylenically unsaturated double bond> In addition to the above resin, the curable composition of the present invention may contain a compound containing an ethylenically unsaturated double bond (hereinafter may be simply referred to as "ethylene-containing unsaturated double bond compound").

In addition to the above resins, the ethylene-containing unsaturated double bond compound used in the present invention may be selected from an addition polymerization compound having at least one ethylenically unsaturated double bond having at least one, preferably two or more terminal ethylenically unsaturated bonds. . This group of compounds is well known in the art and therefore can be used in the present invention without any limitation. It has chemical specific examples of, for example, monomers, prepolymers (having oligomers of dimers or trimers), mixtures thereof, and copolymers thereof. As examples of the monomer and its copolymer, it is possible to propose an unsaturated carboxylic acid (such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), an ester thereof, and a guanamine thereof. . It is preferred to use an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an unsaturated carboxylic acid and an aliphatic group. An amine of a valence amine compound. Further, it is also preferred to use an addition reaction product of an unsaturated carboxylic acid ester or decylamine having a nucleophilic substituent such as a hydroxyl group, an amine group and a mercapto group, and a monofunctional or polyfunctional isocyanate or epoxy group. Or a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid or the like. Further preferred is an addition reaction of an unsaturated carboxylic acid ester or decylamine having an electrophilic substituent such as an isocyanato group and an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol. The product, in addition to the substitution reaction product of an unsaturated carboxylic acid ester or decylamine having a de-substituted substituent such as a halogen group and a tosyloxy group, with a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, as for other examples, a compound group in which the above unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, styrene, vinyl ether or the like can also be used.

A specified example of a monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, which is an acrylate such as ethylene glycol diacrylate, triethylene glycol diacrylate, or 1,3-butylene glycol Acrylate, butanediol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene methoxypropyl) ether, three Hydroxymethylethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, neopentyl alcohol diacrylate, neopentyl alcohol triacrylate Ester, neopentyl alcohol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate Ester, tris(methacryloxyethyl) cyanide, polyester acrylate oligomer, and trisuccinate with EO modified triacrylate.

It has methacrylates such as butanediol dimethacrylate, three Ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate , 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, neopentyl alcohol dimethacrylate, neopentyl alcohol trimethacrylate, neopentyl alcohol tetramethyl Acrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, hydrazine [p-(3-methyl) Propenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, and hydrazine [p-(methacryloxyethoxy)phenyl]dimethylmethane.

It has an itaconate such as ethylene glycol diconconate, propylene glycol diconconate, 1,3-butanediol diconcanate, 1,4-butanediol diconcanate, Butanediol diconconate, pentaerythritol diconconate, and sorbitol tetraconcanate. It has a crotonate such as ethylene glycol dicrotonate, butanediol dicrotonate and pentaerythritol dicrotonate. It has isocrotonate such as ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol dicrotonate. It has a maleic acid ester such as ethylene glycol dimaleate, triethylene glycol dimaleate, neopentyl alcohol dimaleate, and sorbitol tetras Butenediates.

As an example of the other ester, it is also preferred to use an aliphatic alcohol-based ester as described in JP-B No. 51-47334 and JP-A No. 57-196231, JP-A No. 59-5240, JP. An ester having an aromatic skeleton as described in JP-A No. 59-5241 and JP-A No. 2-226149, and an amine group-containing ester described in JP-A No. 1-156613. Further, the above ester monomers may also be used as a mixture.

Further, as a specific example of a monomer of an aliphatic polyhydroxyamine compound and a decylamine of an unsaturated carboxylic acid, it is methylene fluorenyl decylamine, methylene hydrazine methacrylamide, 1,6-extension hydrazine. Acrylamide, 1,6-extended decyl methacrylamide, diethylenediamine propylene amide, xylene propylene amide, and xylene methacrylamide. Other examples of preferred guanamine-based monomers include monomers having a cyclohexene structure as described in JP-B No. 54-21726.

Further, a urethane-based addition polymerization compound is preferably used, which is produced by an addition reaction of an isocyanate and a hydroxyl group. As a specific example thereof, there may be mentioned, for example, a vinyl urethane compound containing two or more polymerizable vinyl groups in a molecule, which is a vinyl group having a hydroxyl group in a compound represented by the following formula (A). The polyisocyanate compound having two or more isocyanate groups in the molecule described in JP-B No. 48-41708 or the like is added.

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

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

Further preferred are urethane acrylates described in JP-A No. 51-37193, JP-B No. 2-32293, and JP-B No. 2-16765, and JP-B No. 58- A urethane compound having an ethylene oxide-based skeleton as described in JP-A No. 49,860, JP-B No. 56-17654, JP-B No. 62-39417, and JP-B No. 62-39418. Further, an addition polymerization compound having an amine structure or a sulfide structure in a molecule described in JP-A No. 63-277653, JP-A No. 63-260909, and JP-A No. 1-105238 can be used. A photopolymerizable composition having a very excellent photospeed.

Other examples include polyfunctional acrylates and methacrylates such as polyester acrylates, and JP-A No. 48-64183, JP-B No. 49-43191 The epoxy acrylate obtained by the reaction of an epoxy resin with a (meth) acrylate as described in each of JP-B No. 52-30490. Further examples include the specified unsaturated compounds described in JP-B No. 46-43946, JP-B No. 1-40337, and JP-B No. 1-40336, and JP-A No. 2-25493 The vinylphosphonic acid is the main compound. In some cases, it is preferred to use the perfluoroalkyl-containing structure described in JP-A No. 61-22048. Further, a compound which is a photocurable monomer and an oligomer can be used as disclosed in Journal of Adhesion Society of Japan, Vol. 20, No. 7, pp. 300-308 (1984).

The structure (individually or in combination), the amount of addition, and the like of these addition polymerization compounds can be set as desired depending on the performance of the curable composition. For example, it may be selected from the following points.

Regarding the sensitivity, it is preferably a structure having a large amount of unsaturated groups per molecule. In many cases, it is preferably one or more functional groups. Further, in order to improve the strength of the image portion (i.e., the cured film), it is preferably one or more functional groups. In addition, a method of adjusting sensitivity and strength by using a different amount of functional groups and different polymerizable groups (such as acrylate, methacrylate, styrene-based compound, and vinyl ether as a main compound) is also effective. From the viewpoint of hardening sensitivity, it is preferred to use a compound having two or more (meth) acrylate structures, more preferably a compound having three or more (meth) acrylate structures. It is also preferred to use a compound containing four or more (meth) acrylate structures. Further, from the viewpoint of the hardening sensitivity and the developing power of the unexposed portion, it is preferably an EO-modified substance. In addition to the hardening sensitivity and the intensity of the exposed portion From the viewpoint, it is preferably a urethane-containing bond.

Further, regarding the compatibility and dispersion properties of other components (such as a resin, a photopolymerization initiator, and a pigment) in the curable composition, the selection and usage of the addition polymerization compound are important factors. For example, the use of low purity compounds or a combination of two or more may improve compatibility. Further, in order to improve the adhesion properties of the substrate, etc., it is possible to select a specific structure.

From the above point of view, it may be proposed to be a biphenol A diacrylate, an EO modified biphenol A diacrylate material, trimethylolpropane triacrylate, trimethylolpropane tris(propylene oxypropyl) ether, Trimethylolethane triacrylate, tetraethylene glycol diacrylate, neopentyl alcohol diacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, dipentaerythritol tetraacrylate , dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, iso-cyanuric acid A preferred example is propylene methoxyethyl ester), EO modified neopentyl alcohol tetraacrylate material, EO modified dipentaerythritol hexaacrylate material and the like. Further, as for the commercially available product, it is preferably a urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo-Kokusaku Pulp Corp.), DPHA-40H (manufactured 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.).

More preferably, it is modified by EO, bisphenol A diacrylate, neopentyl alcohol triacrylate, neopentyl alcohol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, different three Cyanuric acid Ethyl ester), neopentyltetraol tetraacrylate modified by EO, and neopentyltetraol hexaacrylate modified by EO. As for the commercially available product, it is more preferably DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (Kyoeisha Chemical) Co., Ltd. manufacture).

In the present invention, the compound containing an ethylenically unsaturated double bond other than the resin (C); the content of the above resin (A) in the solid content of the curable composition of the present invention is preferably from 1% by mass to 90% by mass, more preferably 5% by mass to 80% by mass, and further preferably 10% by mass to 70% by mass.

In particular, in the case where the curable composition of the present invention is used to form a colored pattern of a color filter, the content of the compound containing an ethylenically unsaturated double bond other than the resin (C) is preferably 5 in the above range. From 5% to 50% by mass, more preferably from 7% by mass to 40% by mass, and further preferably from 10% by mass to 35% by mass.

Further, the content ratio (mass ratio) of the compound containing the ethylenically unsaturated double bond other than the above-mentioned resins (A) and (C) and the resin (A) from the viewpoints of the sensitivity and the elimination force (developing power) of the unexposed portion ( A)/(C) is preferably from 0.001 to 100, more preferably from 0.005 to 50, and further preferably from 0.01 to 10.

<Colorant (D)> It is preferred that the curable composition of the present invention contains a coloring agent (D).

The coloring agent contained in the curable composition of the present invention is not particularly limited, and various conventional dyes and pigments may be used alone or as a mixture of two or more. The colorant is preferably a pigment from the viewpoint of durability (heat resistance and light resistance).

As the pigment contained in the curable composition of the present invention, various conventional inorganic pigments or organic pigments can be used, and it is preferred to have a high transmittance.

As the inorganic pigment, a metal compound such as a metal oxide, a metal complex salt or the like can be proposed. In particular, metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals can be proposed.

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

In the present invention, it is particularly preferable to use a compound having a basic N atom in the structural formula of the pigment. A pigment having a basic N atom exhibits excellent dispersing properties in the composition of the present invention. Although the reason is not fully understood, its inference The photopolymerization component has an influence on the good affinity of the pigment.

As the pigment which is preferably used in the present invention, it can be proposed as follows. However, the invention is not limited thereto: CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; CI Pigment Orange 36, 71; CI Pigment Red 122, 150 , 171, 175, 177, 209, 224, 242, 254, 255, 264; CI Pigment Violet 19, 23, 32; CI Pigment Blue 15; 1, 15:3, 15:6, 16, 22, 60, 66 ; CI Pigment Black 1.

These organic pigments may be used singly or in combination to enhance color purity. An example of a combination is shown below. For example, a ruthenium-based main pigment, a ruthenium-based pigment or a diketopyrrolopyrrole as a main pigment may be used as a red pigment alone, or at least one of them may be a diazo-based yellow pigment, an iso-porphyrin as a main yellow pigment, or a quinone. The ketone is a yellow pigment or a mixture of ruthenium as the main red pigment. For example, ruthenium-based pigments include C.I. Pigment Red 177, ruthenium-based pigments include C.I. Pigment Red 155 and C.I. Pigment Red 224, and diketopyrrolopyrrole-based pigments include C.I. Pigment Red 254. From the viewpoint of color reproducibility, it is preferably a mixture of C.I. Pigment Yellow 139. The mass ratio between the red pigment and the yellow pigment is preferably from 100:5 to 100:50. In the case where the ratio is 100:4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and in some cases, the color purity cannot be enhanced. In addition, when the ratio is 100:51 or more, the dominant wavelength is toward a short wavelength, and in some cases, the NTSC target The deviation of the hue becomes larger. In particular, this mass ratio is optimally in the range of 100:10 to 100:30. In the case of combining red pigments, this ratio can be adjusted in accordance with the chromaticity.

In addition, as for the green pigment, the halogenated phthalocyanine-based pigment may be used alone, or the diazonium-based yellow pigment, the quinacridone-based yellow pigment, the azomethine-based yellow pigment, or the isoporphyrin may be used. A mixture of primary yellow pigments. As examples thereof, it is preferably a mixture of, for example, CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, or CI Pigment Yellow 185. . The mass ratio of the green pigment to the yellow pigment is preferably from 100:5 to 100:150. The above mass ratio is particularly preferably in the range of 100:30 to 100:120.

As for the blue pigment, it can be used alone as the main pigment, or its dioxin A mixture of predominantly purple pigments. It is preferably, for example, a mixture of CI Pigment Blue 15:6 and CI Pigment Violet 23. The mass ratio of the blue pigment to the yellow pigment is preferably from 100:0 to 100:30, more preferably 100:10 or less.

Further, as for the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide, or a mixture thereof is used alone. It is preferably a combination of carbon and titanium carbon. The mass ratio of carbon to titanium is preferably in the range of from 100:0 to 100:60.

In the case of using it for a color filter, the average particle diameter of the pigment is preferably 100 nm or less from the viewpoint of color irregularity and contrast, and more preferably 5 from the viewpoint of dispersion stability. Nano or smaller. The average particle diameter of the pigment is more preferably from 5 to 75 nm, further preferably from 5 to 55 nm, and particularly preferably from 5 to 35 nm.

The average particle diameter of the pigment can be determined by a known method such as an electron microscope.

The pigment is particularly preferably a pigment selected from the group consisting of hydrazine series, azo methine series, benzylidene series, cyanine series, diketopyrrolopyrrole series, and indigo series.

Further, in the case where the composition of the present invention is used for a color filter, it is preferred to use a dye which is uniformly dissolved in the composition from the viewpoint of color irregularity and contrast.

The dye which is a coloring agent contained in the curable composition of the present invention is not particularly limited, and a dye for a color filter can be used. For example, JP-A Nos. 64-90403, 64-91102, 1-94301, and 6-11614, Japanese Patent Registration No. 2,592,207, U.S. Patent Nos. 4,808,501, 5,667,920 and 5,059,500, JP-A No. 5-333207, 6-35183, 6-51115, 6-194828, 8-211599, 4-249549, 10-123316, 11-302283, 7-286107, 2001-4823, 8-15522, 8-29771, 8- Pigments disclosed in 146215, 11-343437, 8-62416, 2002-14220, 2002-14221, 2002-14222, 2002-14223, 8-302224, 8-73758, 8-179120, and 8-151531.

As for the chemical structure, a pyrazolyl azo series, an anilino azo series, a triphenylmethane series, a hydrazine series, an anthrapyridone series, a benzylidene series, an oxonol series, and a pyrazole can be used. Triazole series, pyridone azo series, cyanine series, phenol thiophene Series, pyrrolylpyrazole azo methine series, Series, indigo series, benzopyran series, and bismuth series of dyes.

Further, after the pattern exposure of the curable composition and the hardening of the exposed portion, It forms a pattern by removing the unexposed portion by water or alkali development, for example, when forming a color pattern of a photoresist or a color filter, by completely removing the viewpoint of the binder and the dye at the unirradiated portion of the light generated by the development, In some cases, acid dyes and/or derivatives thereof may be suitably used.

Further, direct dyes, basic dyes, mordant dyes, acid dyes, azo dyes, disperse dyes, oil-soluble dyes, food dyes and/or derivatives thereof can also be used usefully.

The acid dye is not particularly limited as long as it has an acidic group such as a sulfonic acid and a carboxylic acid, but it may be selected in consideration of necessary properties such as a solubility property to an organic solvent or a developing solution, a salt forming property with a basic compound, The degree of light absorption, interaction with other components in the composition, overall light resistance and heat resistance.

The following are examples of acid dyes, however the invention is not limited thereto. Examples include: acid violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70 , 74, 80, 83, 86, 87, 90, 92, 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259 , 267, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; acid chrome purple K; acid magenta; acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104 , 105, 106, 109; limes 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173 Acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 394, 401, 412, 417, 418, 422, 426; sour purple 6B, 7, 9, 17, 19; sour 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, 2 30, 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 purple 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; mordant 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.

Preferred among the above acid dyes are acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324:1; lime orange 8, 51, 56, 74, 63; acid red 1, 4, 8, 34, 37, 42, 52, 57, 80, 97, 114, 143, 145, 151, 183, 217, 249; acid purple 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; acid green 25 dye, and these dyes derivative.

In addition to the above dyes, it is preferably an azo series, The acid dyes of the series and the indigo series are also preferably used as acid dyes such as CI Solvent Blue 44, 38; CI Solvent Orange 45; Rose Red B and Rose Red 110, and derivatives of these dyes.

Wherein the coloring agent (D) is preferably one selected from the group consisting of triallyl methane series, hydrazine series, azo methine series, benzylidene series, oxaphthalocyanine series, cyanine series, phenol thiophene series Series, pyrrolylpyrazole azo methine series, Series, indigo series, benzopyran series, anthraquinone series, pyrazolyl azo series, anilino azo series, pyrazolyl triazole azo series, pyridone azo series, coloration with anthraquinone series Agent.

In the case of forming the colored pattern of the color filter, the content of the colorant in the curable composition of the present invention is preferably from 30% by mass to 85% by mass, more preferably from 40% by mass to 80% by mass, and most preferably A range of 50% by mass to 75% by mass.

<Binder Polymer (E)> For the purpose of improving the coating film and the like, the present invention may contain the binder polymer (E) which does not degrade the effects of the present invention.

It is preferred to use a linear organic polymer as the binder polymer. As for the "linear organic polymer", it is possible to use a conventional person as the case may be. For water-developable or weakly alkaline water development, it is preferred to select a linear organic polymer which is soluble or swellable in water or weakly alkaline water. The linear organic polymer is selected in accordance with not only a film forming agent but also a water, weak alkaline water or organic solvent developer. For example, water development can be carried out using a water-soluble organic polymer. As for the linear organic polymer, it may be a radical polymerization product having a carboxylic acid group in a side chain, such as a resin obtained by polymerizing or copolymerizing a monomer having a carboxyl group, which will be polymerized or copolymerized by the same element. A resin obtained by hydrolysis, semi-esterification or semi-deuteration of an acid anhydride unit produced by an acid anhydride monomer, borrowed An epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride, for example, JP-A No. 59-44615, JP-B Nos. 54-34327, 58-12577, and 54-25957, JP -A is described in the patents Nos. 54-92723, 59-53836 and 59-71048. As the monomer having a carboxylic acid group, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene or the like can be mentioned. As the monomer having an acid anhydride, maleic anhydride or the like can be proposed.

Further, there are similarly acidic cellulose derivatives having a carboxylic acid group in a side chain. Further, it is also possible to use a cyclic acid anhydride added to a polymer having a hydroxyl group.

In the case where the above binder polymer is used as the alkali-soluble copolymer, as the compound to be copolymerized, a monomer other than the above may be used. Examples of the other monomer include the following compounds (1) to (12): (1) an acrylate having an aliphatic hydroxyl group and a methacrylate such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylic acid 3- Hydroxypropyl ester, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate.

(2) alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, acrylic acid Benzyl ester, 2-chloroethyl acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, acryl allyl Ester, 2-allyloxyethyl acrylate, and propargyl acrylate.

(3) alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, methacrylic acid Hexyl ester, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, methacrylic acid 3,4- Epoxycyclohexylmethyl ester, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate And propargyl methacrylate.

(4) acrylamide or methacrylamide, such as acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl Acrylamide, vinyl methacrylamide, N,N-diallyl acrylamide, N,N-diallyl methacrylamide, allyl acrylamide, and allyl Acrylamide.

(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 benzene Vinyl ether.

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

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

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

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

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

(11) an unsaturated quinoid imine such as maleimide, N-propylene decyl acrylamide, N-ethyl methacryl decylamine, N-propyl methacryl decylamine, and N-(p-chlorobenzoyl)methacrylamide.

(12) A hetero atom-bonded α-position of methacrylic acid as a main monomer, such as a compound described in JP-A Nos. 2002-309057 and 2002-311569.

In these examples, a (meth)acrylic resin having an allyl group or a vinyl ester group and a carboxyl group in a side chain, a base having a double bond in a side chain as described in JP-A No. 2000-187322 and No. 2002-62698 The solvent-soluble resin and the alkali-soluble resin having a guanamine group in the side chain as described in JP-A No. 2001-242612 are preferred because of an excellent balance of film strength, sensitivity, and developing power.

In addition, JP-B No. 7-12004, JP-B No. 7-120041, JP-B No. 7-120042, JP-B No. 8-12424, JP-A No. 63-287944, JP-A No. The urethane-based binder polymer having an acid group described in JP-A No. 1-271741, JP-A No. 1-271741, and Japanese Patent Application No. 10-116232, and JP-A No. 2002 The urethane-based binder polymer having an acid group and a double bond in the side chain described in the '107 patent is excellent in strength, and thus is advantageous for low exposure suitability.

The acetal modified polyvinyl alcohol-based adhesive polymer having an acid group as described in the European Patent No. 993, 966, the European Patent No. PCT No. and Suitable for.

Further, as for the water-soluble linear organic polymer, polyvinylpyrrolidone and polyethylene oxide can be used. Further, in order to enhance the strength of the cured film, an alcohol-soluble nylon and a polyether of 2,2-indole (4-hydroxyphenyl)propane and epichlorohydrin may also be used.

The weight average molecular weight of the binder polymer (E) is preferably 3,000 or more, and more preferably in the range of 5,000 to 300,000. The number average molecular weight is preferably 1,000 or more, and further preferably in the range of 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and further preferably in the range of 1.1 to 10.

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

The binder polymer (E) can be synthesized by a conventional method. As the solvent to be used in the synthesis, it may, for example, be tetrahydrofuran, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, acetic acid 2-methoxy B. Ester, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N-dimethyl Ethyl amide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl hydrazine, water, and the like. These solvents may be used singly or in combination of two or more.

As the radical polymerization initiator for synthesizing the binder polymer used in the present invention, a known compound such as an azo-based initiator and a peroxide initiator can be proposed.

Balance of stability and development power of pigment dispersion over time In view of the fact that when the curable composition of the present invention is used to form a colored pattern of a color filter, the content of the binder polymer (E) is preferably 5% by mass relative to the total solid content of the curable composition of the present invention. 60% by mass, more preferably 7% by mass to 50% by mass, and most preferably 10% by mass to 40% by mass.

If necessary, the curable composition of the present invention may further contain the following components as detailed.

<(F) Dispersant> In the case where the curable composition of the present invention contains a pigment as the colorant (D), it is preferred to add (F) a dispersant from the viewpoint of improving the dispersion property of the pigment.

As the dispersant (pigment dispersant) used in the present invention, a polymer dispersant can be proposed [e.g., polyamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyglycolic acid) Ester, modified polyester, modified poly(meth)acrylate, (meth)acrylate-based copolymer, and naphthalenesulfonic acid-formaldehyde condensation product], and polyoxyalkyleneethyl phosphate, poly Oxygen extended ethyl alkylamine, alkanolamine, pigment derivative, and the like.

The polymeric dispersants can be further classified into linear polymers, terminal modified polymers, grafted polymers, and block polymers by structure.

The polymeric dispersant adsorbs on the surface of the pigment to prevent reaggregation. Therefore, a terminal modified polymer having a fixed surface of a pigment, a graft type polymer, and a block type polymer can be proposed as preferred structures. On the other hand, the pigment derivative provides an effect of promoting adsorption of the polymer dispersant by improving the surface of the pigment.

Designated examples of the pigment dispersant used in the present invention include BYK "Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylate), 110 (copolymer containing acid group), 130 (polyamine), 161, 162, 163, 164 manufactured by Chemie Corp. , 165, 166, 170 (high molecular weight copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)"; "EFKA 4047, 4050, 4010, 4165 (polyurethane) manufactured by EFKA Corp. Ester-based), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylic acid), 6220 (aliphatic polyester) , 6745 (indigo derivative), 6750 (azo pigment derivative), Ajinomoto Fan Techno Co., "AJISPER PB-821, PB-822" manufactured by Corp., manufactured by Kyoeisha Chemical Co., Ltd. FROREN TG-710 (urethane oligomer), "POLYFLOW No. 50E, No. 300 (acrylic-based copolymer)", "DISPERON KS-860, 873SN, 874, manufactured by Kusumoto Kasei Corp." #2150(aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725", "DEMOL RN, N (Naphthalenesulfonic acid formaldehyde) manufactured by Kao Corp. Condensation product), MS, C, SN-B (Aromatic condensation product of aromatic sulfonic acid formaldehyde), "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMARGEN 920, 930, 935, 985 (polyoxyethyl phenyl ether)", " ACETAMINE 86 (stearylamine acetate), "SOLSPACE 5000 (indigo derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 manufactured by RUBERESOL Corp. "polymer of functional group portion", 24000, 28000, 32000, 38500 (graft type polymer)", "NIKKOL T106 (polymerized by NIKKO CHEMICAL Corp.) Oxygen-extended ethyl sorbitan monooleate), MYS-IEX (polyoxy-extension ethyl monostearate), and the like.

These dispersants may be used singly or in combination of two or more. It is particularly preferred in the present invention to use a pigment derivative in combination with a polymeric dispersant.

The content of the dispersant in the present invention is preferably from 1% by mass to 100% by mass, more preferably from 3% by mass to 100% by mass, and further preferably from 5% by mass to 80% by mass, based on the pigment.

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

In the case where a pigment and a dispersing agent are used in the present invention, the sum of the content of the pigment and the dispersing agent is preferably from 35% by mass to 90% by mass based on the total solid content of the hardening composition, from the viewpoint of hardening sensitivity and color density. It is more preferably from 45% by mass to 85% by mass, and further preferably from 50% by mass to 80% by mass.

<(G) sensitizer> In order to improve the radical generating efficiency of the polymerization initiator and to obtain a long sensitizing wavelength, it is preferred that the curable composition of the present invention contains a (G) sensitizer. As the sensitizer used in the present invention, it is preferred that the photopolymerization initiator can be sensitized by an electron transfer mechanism or an energy transfer mechanism.

As for the sensitizer used in the present invention, it can be proposed to belong to the following combinations And have an absorption wavelength in the wavelength range of 300 nm to 450 nm.

As a preferred sensitizer, it can be proposed to belong to this compound and have an absorption wavelength in the wavelength range of 330 nm to 450 nm.

It may, for example, be a polynuclear aromatic group (such as phenanthrene, anthracene, anthracene, anthracene, triphenylene, and 9,10-dialkoxyfluorene), (such as fluorescent yellow, blush, red algae, rose red B, and bengal red), sulfur (isopropyl sulphide Diethyl sulphide Chlorosulfur ), Huaqing (such as thiocarbocyanine and carbocyanine), Pinhuaqing (such as Pinocyanin, Cyclone Cyanine), indigo, thiophene (such as thiazide, methyl blue and toluidine blue), acridine (such as acridine orange, chloroflavin and acridine flavin), hydrazine (such as hydrazine), isosuccinium (squalium) (such as Isobutane oxime), acridine orange, oxacillin (eg 7-diethylamino-4-methylinvalidin), keto-encain, thiophene ,coffee , styrylbenzene, azo compound, diphenylmethane, triphenylmethane, distyrylbenzene, carbazole, porphyrin, spiro compound, quinacridine, anthracene, styryl, pyrylium a compound, a pyrazole compound, a pyrazolyl triazole compound, a benzothiazole compound, a barbituric acid derivative, a thiobarbituric acid derivative, an acetophenone, a diphenyl ketone, a 9-oxosulfur An aromatic ketone compound (such as mazakirone), a heterocyclic compound (such as N-aryloxazolidinedione), and the like. Further, the compounds described in the patents of European Patent No. 568,993, U.S. Patent Nos. 4,508,811 and 5,227,227, JP-A Nos. 2001-125255 and 11-271969 can be cited.

As an example of a further preferred sensitizer, the following compounds represented by the formulae (i) to (iv) can be proposed.

In the formula (i), A ¹ is a sulfur atom or NR ⁵⁰ , R ⁵⁰ is an alkyl group or an aryl group, and L ² is a non-metal atomic group which binds a neighboring A ¹ and an adjacent carbon atom to form a basic nucleus of a pigment. And R ⁵¹ and R ^{52 are} each independently a hydrogen atom or a monovalent non-metal atom group, which may be coupled to each other to form an acid core of the pigment. W is an oxygen atom or a sulfur atom. As the above alkyl group of R ⁵⁰ , it may be an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and most preferably an alkane having 1 to 10 carbon atoms. base. As the aryl group of the above R ⁵⁰ , it may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and most preferably an aromatic group having 6 to 10 carbon atoms. base.

In the formula (ii), Ar ¹ and Ar ^{2 are} each independently an aryl group which is bonded via a -L ³ - bond. Here, L ³ is -O- or -S-. Further, the W system is the same as that shown in the formula (i). As the aryl group of the above A ¹ , it may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and most preferably an aromatic group having 6 to 10 carbon atoms. base. As the aryl group of the above A ² , it may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and most preferably an aromatic group having 6 to 10 carbon atoms. base.

In the formula (iii), A ² is a sulfur atom or NR ⁵⁹ , and L ⁴ is a non-metal atomic group which binds a neighboring A ² and a carbon atom to form a basic nucleus of a dye, and R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ^56. R ⁵⁷ and R ^{58 are} each independently a monovalent non-metal atomic group, and R ⁵⁹ is an alkyl group or an aryl group. As the alkyl group of R ⁵⁹ , it may be an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and most preferably an alkyl group having 1 to 10 carbon atoms. . As the aryl group of R ⁵⁹ , it may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and most preferably an aryl group having 6 to 10 carbon atoms. .

In the formula (iv), A ³ and A ^{4 are} each independently -S-, -NR ⁶² - or -NR ⁶³ -. R ⁶² and R ^{63 are} each independently a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and L ⁵ and L ^{6 are} each independently a dye formed by bonding adjacent A ³ with A ⁴ and an adjacent carbon atom. The non-metal atomic group of the basic core, R ⁶⁰ and R ^{61 are} each independently a monovalent non-metal atomic group, or they may be coupled to each other to form an alicyclic or aromatic ring. As the alkyl group of R ⁶² and R ⁶³ , it may be an alkyl group having 1 to 30 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and most preferably having 1 to 10 carbon atoms. Alkyl group. As the aryl group of R ⁶² and R ⁶³ , it may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and most preferably having 6 to 10 carbon atoms. The aryl group. As the substituent in the case of substitution, it is preferably an alkyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkoxy group, an alkoxycarbonyl group, a decyl group, a hydroxyl group, and an amine group. The number of carbon atoms of these substituents is preferably from 1 to 30, more preferably from 1 to 20, and most preferably from 1 to 10.

Further, as a preferred sensitizer to be contained in the curable composition of the present invention, in addition to the above, at least one compound selected from the following formulas (IV) to (VI) may be mentioned. They may be used singly or in combination of two or more.

In the 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 from 0 to 5, and n' is an integer from 0 to 5, where n is not 0 different from n'. In the case where n is 2 or more, R ¹ may be the same or different in the presence of a plurality of. In the case where n' is 2 or more, R ^{2 in the} presence of a plurality may be the same or different. As the above monovalent substituent, it is preferably an alkyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), an alkoxy group, an alkoxycarbonyl group, a decyl group, a hydroxyl group, and an amine group. The number of carbon atoms of these substituents is preferably from 1 to 30, more preferably from 1 to 20, and most preferably from 1 to 10.

In the case of obtaining a coloring agent, the compound represented by the formula (IV) is preferably a compound represented by the following formula (IV-1) from the viewpoints of coloring properties and sensitivity.

In the formula (IV-1), R ¹ and R ^{2 are} each independently a monovalent substituent. n is an integer from 0 to 5, and n' is an integer from 1 to 5. In the case where n is 2 or more, R ¹ may be the same or different in the presence of a plurality of. In the case where n' is 2 or more, R ^{2 in the} presence of a plurality may be the same or different.

In the formula (IV-1), the sum represented by the R ¹ and R ² system and the monovalent substituent in the formula (IV) represented by the sum R ¹ and R ² identical monovalent substituent, and the preferred range is also the same applications.

As for the compound represented by the formula (IV) or (V), it is preferred that the molar absorption coefficient ε at a wavelength of 365 nm is 500 mol ^-1 . L. The centimeters ^-1 or larger, more preferably the ε at 365 nm wavelength is 3,000 m ^-1 . L. The centimeters are ^-1 or larger, and the optimum is 20,000 m ^-1 at 365 nm wavelength. L. Centimeters ^-1 or greater. Since the Mohr absorption coefficient ε at each wavelength is in the above range, the sensitivity improvement effect is high, which is preferable from the viewpoint of light absorption efficiency.

Here, the molar absorption coefficient ε can be measured by using a sample of a dye solution adjusted to a concentration of 0.01 g/liter in a 1-methoxy-2-propanol solution, and the sample is measured at a penetration spectrum of 365 nm. The absorbance was calculated from the UV-visible absorption spectrum of the sample. As for the measuring device, a UV-Vis-MR Spectrophotometer Cary 5G spectrophotometer manufactured by Varian Corp. was used.

Preferred examples of the compound represented by the formula (IV) or (V) are shown below, but the invention is not limited thereto.

Here, the formula can be represented by a simple structural formula in which a solid line or the like which does not describe an element or a substituent represents a hydrocarbon group. Further, in the following designated examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, n-Bu represents an n-butyl group, and Ph represents a phenyl group.

In the formula (VI), A is an aromatic ring or a 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, a sulfur atom or -N (R ^{3 )} )-. R ¹ , R ² and R ^{3 are} each independently a hydrogen atom or a monovalent non-metal atom group. A, R ¹ , R ² , and R ³ may be coupled to each other to form an alicyclic or aromatic ring.

In the formula (VI), in the case where R ¹ , R ² and R ³ are a monovalent non-metal atom, it is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkene. A substituted or unsubstituted aromatic heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

As the above alkyl group, it is preferably a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 15 carbon atoms. It may, for example, be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-octyl, n-dodecyl, cyclopentyl, benzyl, bicyclo[2 , 2,1]-heptan-2-yl and the like.

As the above aryl group, it 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. It may, for example, be a phenyl group, a naphthyl group or the like

As the above alkenyl group, it is preferably a linear form having 1 to 30 carbon atoms. Or a branched or cyclic alkenyl group, more preferably having from 1 to 20 carbon atoms, and particularly preferably having from 1 to 15 carbon atoms. It may, for example, be a vinyl group, an allyl group, a cyclohexenyl group, a geranyl group or the like.

The above aromatic heterocyclic residue is preferably a substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed cyclic aromatic heterocyclic residue of 5 to 7 members. More preferably, the aromatic heterocyclic residue has a ring substituent atom selected from the group consisting of a carbon atom, a nitrogen atom and a sulfur atom, and at least one of the hetero atoms is a nitrogen atom, an oxygen atom and a sulfur atom. Further preferred are 5 or 6 membered aromatic heterocyclic residues having 3 to 30 carbon atoms. It may, for example, be 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl, imidazol-2-yl and the like.

As the above alkoxy group, it is preferably a linear, branched or cyclic alkoxy group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. By. It may, for example, be a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a third butoxy group or the like.

As the above alkylthio group, it is preferably a linear, branched or cyclic alkylthio group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. By. It may, for example, be a methylthio group, an ethylthio group, a n-decylthio group or the like.

The above monovalent non-metal atomic group may be substituted as described above. As the substituent, an alkyl group, an alkenyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkoxy group, an alkoxycarbonyl group, a decyl group, a hydroxyl group, an alkylthio group, an arylthio group or the like can be proposed. In the case where these substituents have carbon, the total number of carbons is preferably from 1 to 30, further preferably from 1 to 20, and most preferably from 1 to 10.

From the viewpoint of improving the decomposition efficiency of the photopolymerization initiator, in the compound represented by the formula (VI), Y is preferably an oxygen atom or -N(R ³ )-, and most preferably -N(R ³ )-. R ^{3 is} each independently a hydrogen atom or a monovalent non-metal atom group.

The specified examples (VI1) to (VI124) of the preferred compounds represented by the formula (VI) are shown below, but the invention is not limited thereto. Further, the isomer caused by the double bond of the bonded acidic core and the basic nucleus is not clear, and the present invention is not limited to any isomer.

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

For example, a sensitizer (hereinafter referred to as "sensitizing dye") and an addition polymerization compound structure (such as an acrylonitrile group and a methacryl fluorenyl group) are bonded by a covalent bond, an ionic bond, a hydrogen bond or the like. High exposure film strength can be achieved and unnecessary precipitation of the sensitizing dye from the film after exposure can be limited.

Further, a sensitizing dye and a partial structure having a radical generating ability in the above photopolymerization initiator (such as a reductive decomposition moiety such as a halogenated alkyl group, a phosphonium salt, a peroxide, a diimidazole, and an oxidative separation moiety such as a boronic acid group, The bonding of the amine, trimethyldecylmethyl, carboxymethyl, carbonyl, and imine) significantly improves the photographic properties, particularly at low concentrations in the state of the system.

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

The concentration of the coloring agent in the curable composition is extremely high, so that the light transmittance of the colored pattern (photosensitive layer) is extremely low, especially in the photosensitive layer formed without adding the sensitizing dye at 365 nm. In the case where the light ratio is 10% or less, the effect of improving the photosensitive property can be remarkably exhibited by adding the compound represented by the above formulas (IV) to (VI). Particularly, the compound represented by the formula (VI) is the most preferable among the above formulae (IV) to (VI). In particular, the best is (VI56) To the compound of (VI122).

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

The content of the sensitizer in the curable composition of the present invention is preferably from 0.1% by mass to 20% by mass, and more preferably from the viewpoint of the light absorption efficiency of the deep portion and the initial decomposition efficiency, with respect to the total solid content of the curable composition. It is from 0.5% by mass to 15% by mass. The above range is preferred because the light absorption efficiency of the deep portion of the hardenable composition is increased, and the initial decomposition efficiency is advantageous.

<(H)Cosensitizer> The curable composition of the present invention may contain a co-sensitizer. In the present invention, the co-sensitizer further has an effect of improving the sensitivity of the sensitizing dye or the photopolymerization initiator to light-like radiation, or limiting the polymerization of the polymerizable compound by oxygen.

Examples of such co-sensitizers include amines, such as "Journal of Polymer Society" by MRSander et al., Vol. 10, p. 3, 173 (1972), JP-B No. 44-20189, JP-A No. 51- Compounds of 82102, 52-134692, 59-138205, 60-84305, 62-18537, 64-33104, Research Disclosure No. 33825. Specifically, it may be mentioned as triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-nonyldimethylaniline, p-methylthiodimethylaniline or the like.

Other examples of the co-sensitizer include a mercaptan and a sulfide, such as a thiol compound described in JP-A No. 53-702, JP-B No. 55-500806, and JP-A No. 5-142772, and The disulfide compound described in JP-A No. 56-75643, in particular 2-mercaptobenzothiazole, 2-mercaptobenzopyrene Oxazole, 2-mercaptobenzimidazole, 2-mercapto-4(3H)-quinazoline, and β-mercaptophthalene.

Further, other examples of the co-sensitizer include an amino acid compound (for example, N-phenylglycine, etc.), an organometallic compound (for example, tributyltin acetate, etc.) described in JP-B No. 48-42965, JP. -B a hydrogen compound as described in Patent No. 55-34414, and a sulfur compound (for example, trithiazine or the like) described in JP-A No. 6-308727.

The content of the total sensitizer relative to the total solid content of the hardenable composition is preferably in the range of 0.1% by mass to 30% by mass, more preferably 0.5%, from the viewpoint of improving the curing speed according to the polymerization growth rate and the chain-to-chain transfer balance. It is in the range of % to 25% by mass, and even more preferably in the range of 1.0% by mass to 20% by mass.

<(I) Polymerization inhibitor> It is desirable in the present invention to add a small amount of a polymerization inhibitor to suppress unnecessary thermal polymerization of a compound having a polymerizable ethylenically unsaturated double bond during the manufacture or storage of the curable composition.

As the thermal polymerization inhibitor used in the present invention, it may be proposed to hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, tert-butylcatechol, benzoquinone, 4, 4 '-Thionine (3-methyl-6-tert-butylphenol), 2,2'-methylene hydrazine (4-methyl-6-tert-butylphenol), N-nitrosophenyl Hydroxylamine sulfonium salts and the like.

The amount of the thermal polymerization inhibitor added is preferably from about 0.01% by mass to about 5% by mass based on the total mass of the entire composition. If necessary, in order to prevent polymerization inhibition by oxygen, it may be added with a high-carbon fatty acid derivative such as rosin and decanoic acid. And unevenly distributed on the surface of the photosensitive layer during the drying process after coating. The high carbon fatty acid derivative is preferably added in an amount of from about 0.5% by mass to about 10% by mass based on the total of the composition.

<Other additives> Further, in the present invention, known additives such as an inorganic filler which improves the physical properties of the cured coating film, a plasticizer, a sensitizer for improving the ink absorbing property of the surface of the photosensitive layer, and a modified substrate for improving the adhesion property of the substrate may be added. Substrate adhesion agent.

As the plasticizer, for example, dioctyl phthalate, di-dodecyl phthalate, triethylene glycol dicaprylate, dimethylene phthalate, tricresol phosphate, dioctyl adipate may be proposed. Ester, dibutyl sebacate, triethylene glyceryl, and the like. In the case where a coupling agent is used, it may be added to the total mass of the compound having a ethylenically unsaturated double bond and the coupling agent of 10% by mass or less. In the case where the curable composition of the present invention is applied to a surface of a hard material such as a substrate, an additive for improving the adhesion to the surface of the hard material (hereinafter referred to as "substrate adhesion agent") may be added.

As the substrate adhesive, a known material can be used. It is particularly preferred to use a decane-based coupling agent, a titanate-based coupling agent, or an aluminum-based coupling agent.

Examples of the decane coupling agent include γ-(2-aminoethyl)aminopropyltrimethoxydecane, γ-(2-aminoethyl)aminopropyldimethoxydecane, β-(3, 4-epoxycyclohexyl)ethyltrimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-methylpropoxypropyltrimethoxy矽, γ-methacryloxypropyltriethoxydecane, γ-propyleneoxypropyltrimethoxydecane, γ-acryloxypropyltriethoxydecane, γ- Isocyanatopropyltrimethoxydecane, γ-isocyanatopropyltriethoxydecane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxy Base decane. Hydrochloride, γ-glycidylpropyltrimethoxydecane, γ-glycidylpropyltriethoxydecane, aminodecane, γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyl Triethoxy decane, methyltrimethoxy decane, methyl triethoxy decane, vinyl triethoxy decane, γ-chloropropyl trimethoxy decane, hexamethylene diazoxide, γ-aniline Propyl trimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (β-methoxyethoxy) decane, octadecyl dimethyl chloride [3- (trimethoxydecyl)propyl]ammonium, γ-chloropropylmethyldimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, methyltrichlorodecane, dimethyldichlorodecane , trimethylchlorodecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, decallyltrimethoxydecane, tetraethoxydecane, anthracene (trimethoxydecyl) Hexane, phenyltrimethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3-aminopropyltriethoxydecane, N-(3-methylpropenyloxy-2 -hydroxypropyl 3-aminopropyltriethoxydecane, (methacryloxymethyl)methyldiethoxydecane, and (acryloxymethyl)methyldimethoxydecane.

It is particularly preferably γ-methacryloxypropyltrimethoxydecane, γ-methylpropoxypropyltriethoxydecane, γ-acryloxypropyltrimethoxydecane, γ-propyleneoxyl Propyltriethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, and phenyltrimethoxydecane, and most preferably γ-methylpropenyloxypropane Trimethoxy decane.

Examples of titanate-based coupling agents include isopropyl triisostearate titanium Acid ester, isopropyltridecylbenzenesulfonate titanate, isopropyl ginseng (dioctyl pyrophosphate) titanate, tetraisopropylphosphonium (dioctylphosphite) titanate , tetraoctyl fluorene (di-tridecyl phosphite) titanate, tetrakis(2,2-diallyloxymethyl) ruthenium (di-tridecyl) phosphate titanate, ruthenium (dioctyl pyrophosphate) oxyacetate titanate, bismuth (dioctyl pyrophosphate) extended ethyl titanate, isopropyl trioctadecyl titanate, isopropyl dimethyl propylene Stearic acid based titanate, isopropyl isostearyl decyl bis propylene titanate, triisopropyl tris(dioctyl phosphate) titanate, isopropyl triisopropyl phenyl phenyl titanium Acid ester, isopropyl tris(N-nonylaminoethyl.aminoethyl) titanate, dicumylphenyl oxyacetate titanate, and diisostearate Acid ester.

Examples of the aluminum-based coupling agent include aluminum diisopropylacetate.

In the case where the curable composition is exposed, the content of the substrate adhesive is preferably from 0.1% by mass to 30% by mass based on the total solid content of the curable composition of the present invention, from the viewpoint of preventing the residue from remaining on the unexposed portion. It is preferably from 0.5% by mass to 20% by mass, and particularly preferably from 1% by mass to 10% by mass.

According to the above configuration, the curable composition of the present invention can be hardened with high sensitivity and better storage stability. Further, the curable composition of the present invention exhibits high adhesion properties to the surface of a material to be used such as a hard material such as a substrate. Therefore, the curable composition of the present invention can be preferably used in the field of image forming materials, such as three-dimensional light decoration, hologram and color filter, or ink, paint, adhesive, coating agent, etc.

[Color filter and method of manufacturing the same]

The color filter of the present invention and a method of manufacturing the same are explained below.

The color filter of the present invention is characterized in that it has a colored pattern using the curable composition of the present invention on a support.

The color filter of the present invention will be described in detail below with reference to its manufacturing method (method for producing the color filter of the present invention).

The method for producing a color filter of the present invention comprises the step of forming a colored layer of a colored layer of a curable composition by applying the curable composition of the present invention to a support member, and exposing the colored layer to a mask. An exposure step, and a development step of forming a colored pattern by developing the colored layer after exposure.

The steps of the manufacturing method of the present invention are explained below.

<Colored layer forming step> In the colored layer forming step, the curable composition is formed by applying the curable composition of the present invention to the support member.

Examples of the support which can be used in this step include soda glass, Pyrex (registered trademark) glass, quartz glass, and a photoelectric conversion element substrate for a liquid crystal display element, for a photographic element (for example, a ruthenium substrate and a complementary metal oxide thin film semiconductor) (CMOS)) Glass with a transparent sensing film. In some cases, it forms a black strip separating the pixels on these substrates.

If necessary, an undercoat layer may be provided on these supports to improve adhesion to the upper layer, prevent diffusion of substances, and flatten the surface of the substrate.

As for the method of coating the curable composition of the present invention on the support member, various coating methods such as slit coating, inkjet coating, spin coating, cast coating, roll coating, and screen coating can be used. cover.

From the viewpoint of film uniformity of the coating film and ease of drying of the coating solution, the thickness of the film of the curable composition just after coating is preferably from 0.1 to 10 μm, more preferably from 0.2 to 5 μm, and further It is preferably in the range of 0.2 to 3 microns.

The coloring layer (curable composition layer) coated on the substrate may be dried (pre-baked) in a hot plate, oven or the like at 50 to 140 ° C for 10 to 300 seconds.

The thickness of the coating film after drying (hereinafter also referred to as "dry film thickness") as a curable composition of a color filter for LCD is preferably 0.1 μm or the viewpoint of the compatibility of the thin LCD and the color density. It is larger and smaller than 2.0 μm, more preferably 0.2 μm or more and less than 1.8 μm, and particularly preferably 0.3 μm or more and less than 1.75 μm.

Further, from the viewpoint of ensuring the color density and reducing the difference in the light-collecting ratio between the end portion of the region and the center, for the color filter for IS, the thickness is preferably 0.05 μm or more and less than 1.0 μm. More preferably, it is 0.1 μm or more and 0.8 μm or less, and particularly preferably 0.2 μm or more and 0.7 μm or less.

<Exposure step> In the exposure step, the coloring layer (curable composition layer) formed in the above-described colored layer forming step is exposed through a photomask having a predetermined mask pattern.

According to the exposure of this step, the pattern exposure of the coating film can be performed by exposing through a predetermined mask pattern, and only hardening the portion of the coating film irradiated with light. As for the radiation used in the exposure, it is preferable to use ultraviolet rays such as g-line and i-line. The irradiation amount is preferably 5 to 1,500 mJ/cm 2 , more preferably 10 to 1,000 mJ/cm 2 and most preferably 10 to 500 mJ/cm 2 .

In the case where the color filter of the present invention is used for a liquid crystal display device, the above range is preferably 5 to 200 mJ/cm 2 , more preferably 10 to 150 mJ/cm 2 , and most preferably 10 to 100 mJ/cm 2 . In the case where the color filter of the present invention is used for a solid-state photographic element, the above range is preferably 30 to 1,500 mJ/cm 2 , more preferably 50 to 1,000 mJ/cm 2 , and most preferably 80 to 10,000. 500 mJ/cm 2 .

<Development step> Then, by performing an alkali developing process (developing step), only the light non-irradiated portion is dissolved in an alkaline aqueous solution to retain the above exposure to photocure. It can be carried out by developing a developing coating solution to form a patterned coating film having various colors (3 or 4 colors). As for the developing solution, it is preferably an organic alkaline developing solution which does not impair the risk of the basic circuit. The development temperature is usually from 20 ° C to 30 ° C, and the development time is from 20 to 90 seconds.

Examples of the alkaline agent as the developing solution include organic base compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and , 8-diazabicyclo-[5,4,0]-7-undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, and potassium hydrogencarbonate. It can be preferably used to obtain an alkaline aqueous solution by diluting these alkaline agents in pure water to have a concentration of from 0.001% by mass to 10% by mass, preferably from 0.01% by mass to 1% by mass. In the case of using a developing solution made of this alkaline aqueous solution, it is usually washed with pure water after development (rushing wash).

It is then dried after washing to remove excess developing solution.

If necessary, the manufacturing method of the present invention may include a hardening step of forming a colored pattern by heating (post-baking) and/or exposure hardening after performing the colored layer forming step, the exposing step, and the developing step.

The post-baking is a heat treatment in which hardening is completed after development, and it is usually subjected to a heat hardening treatment at 100 ° C to 240 ° C. When the substrate is a glass substrate or a tantalum substrate, it is preferably from 200 ° C to 240 ° C in the above temperature range.

Thereafter, the baking treatment can be carried out continuously or in a batch manner using a heating means such as a heating plate, a convection oven (hot air circulation dryer), and a high-frequency heating machine, so that the developed coating film is under the above conditions.

The color filter having the desired color tone can be prepared by repeating the above-described coloring layer forming step, exposure step, and development step (and, if necessary, hardening step) in accordance with the desired amount of color tone.

The use of the curable composition of the present invention has been described primarily with respect to the application of pixels to color filters; however, it is also apparently applicable to black matrices provided between pixels of color filters. The black matrix can be formed in the same manner as the above method of exposing the pattern by exposure, alkali development, and then post-baking to promote film hardening to produce pixels, except for the coloring agent to which a black pigment (such as carbon black or titanium black) is added. A curable composition of the present invention.

Since the color filter of the present invention is produced using the curable composition of the present invention having excellent exposure sensitivity, the hardened composition of the exposed portion has excellent substrate adhesion properties and development resistance, and the colored pattern formed has a support member substrate High adhesion properties, in addition to providing the desired cross-sectional shape Has a high resolution.

Further, the solid-state photographic element of the present invention comprises the color filter of the present invention produced by the above-described method for producing the color filter of the present invention.

Therefore, in particular, the color filter of the present invention can be preferably used for a solid-state imaging device such as a liquid crystal display device and a CCD, and particularly, it can be preferably used for a high-resolution CCD element or CMOS having more than 1,000,000 pixels. . The color filter of the present invention can be used as a color filter disposed between a light receiving portion including each pixel of a CCD element and a microlens for light focusing.

Instance

The invention is explained in further detail below with reference to examples, but the invention is not limited thereto.

[Synthesis Example 1]

<Synthesis of Compound (i-1)> 58.6 g of 2-hydroxyethyl acrylate was placed in a 500 ml three-necked flask and 250 ml of acetone was added thereto and stirred. After adding 39.2 g of pyridine and 0.1 g of p-methoxyphenol, it was cooled in an ice bath with ice water. When the temperature of the liquid mixture was 5 ° C or lower, 114.9 g of 2-bromoisobutyric acid bromide was added dropwise to the dropping funnel over 3 hours. After the completion of the dropping operation, the ice bath was removed and further stirred for 3 hours. After the reaction mixture was poured into 750 ml of water, it was stirred for 1 hour. The aqueous mixture solution was extracted 3 times with 500 ml of ethyl acetate using a separatory funnel. The organic layer was successively washed with 500 ml of 1 M hydrochloric acid, 500 ml of a saturated solution of sodium hydrogencarbonate, and 500 ml of a saturated brine. After the organic layer was added to 100 g of magnesium sulfate for dehydration drying, it was filtered. Vacuum exclusion The solvent gave 120.3 g of a residue.

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

(1) Synthesis of Resin (I) 86 g of 1-methyl-2-pyrrolidone placed in a 1,000 ml three-necked flask was heated to 90 ° C under a nitrogen stream. 55 g of compound (i-1), 47 g of the example compound M-14MA, 13 g of methacrylic acid, 8.2 g of 2,2'-arsenazo (2-methylpropionate) (V-601, Wako Pure) Produced by Chemical Industries, Ltd., and 86 g of 1-methyl-2-pyrrolidone were added dropwise over 2 hours. After the completion of the dropping operation, it was stirred for another 2 hours. After the reaction solution was cooled to room temperature, it was poured into 7 liters of water to precipitate a polymer compound. The precipitated polymer was filtered, washed with water and dried to give 110 g of a polymer compound.

The weight average molecular weight of the obtained polymer compound was measured by gel permeation chromatography (GPC) using polystyrene as a reference material, and it was 13,100. Further, by measuring the acid value by titration, it was found to be 1.25 meq/g (calculated value was 1.30 meq/g), thus confirming that the polymerization system was normally carried out.

110 g of the obtained polymer compound, 0.1 g of p-methoxyphenol, and 470 g of 1-methyl-2-pyrrolidone were placed in a 1,000 ml three-necked flask to be cooled in an ice bath with ice water. After the temperature of the liquid mixture was 5 ° C or lower, 100 g of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) was added dropwise over 1 hour using a dropping funnel. After the completion of the dropping operation, the ice bath was removed and stirred for another 8 hours. After adding concentrated hydrochloric acid to the reaction solution to obtain pH 7, it is poured into 7 liters of water to precipitate a polymer compound. Resin (I). The precipitated polymer compound was filtered, washed with water and dried to give 95 g of a polymer.

According to the ¹ H NMR measurement of the obtained polymer compound, it was confirmed that 100% of the side chain group derived from the compound (i-1) was converted into an ethyl methacrylate group. In addition, by gel permeation chromatography (GPC) with polystyrene as a reference material, the weight average molecular weight measurement was 12,100. In addition, the acid value measured by titration was 1.45 meq/g (calculated as 1.51 meq/g).

[Example 1] [A1. Preparation of hardenable composition]

An example of preparing a pigment-containing hardenable composition for forming a color filter for use in a liquid crystal display device will be explained below.

A1-1. Preparation of Pigment Dispersion Solution Preparation of Pigment Dispersion Liquid A mixture of 40 parts by mass of CI Pigment Green 36 and CI Pigment Yellow 219 as a pigment was mixed and dispersed in a ball mill (average particle size was 61 奈50 parts by mass (about 22.6 parts by mass in terms of solid content) BYK2001 (Disperbyk: manufactured by Bic Chemie (BYK) Corp., solid content concentration: 45.1% by mass) as a dispersing agent, and 5 parts by mass of the above invention A pigment dispersion (P1) was prepared by a resin (I), and a liquid mixture of 110 parts by mass of ethyl 3-ethoxypropionate as a solvent over 15 hours.

The average particle diameter of the pigment was measured by a dynamic light scattering method, which was 32 nm, using a Microtrac Nanotrac UPA=EX 150 (manufactured by Nikkiso Co., Ltd.) for the pigment dispersion (P1) without further diluting P1.

A1-2. Preparation of hardenable composition (coating solution) The curable composition solution was prepared by using the above-described pigment dispersion solution P1 to be stirred and mixed in a dispersion procedure to have the following composition ratio.

[A2. Manufacture of color filters]

A2-1. Formation of a hardenable composition layer The sclerosing composition containing the above pigment was applied as a photoresist solution to a 550 mm × 650 mm glass substrate under the following conditions, allowed to stand for 10 minutes, and vacuum drying and prebaking were provided (100). The curing film coating film (curable composition layer) was formed at ° C for 80 seconds.

(sewing conditions)

A2-2. Exposure, development The test composition film of the curable composition was then exposed in a pattern using a test mask of 20 micrometers line width using a 2.5 watt ultrahigh pressure mercury lamp. After the exposure, the entire surface of the coating film was coated with a 10% aqueous solution of an organic developing solution (trade name: CD, manufactured by Fuji Film Electronics Material Corp.), and it was allowed to stand for another 60 seconds.

A2-3. Heat treatment The developing solution was washed by spraying pure water (e.g., spray) after standing, so that the coating film to which the exposure (photocuring) procedure and the developing procedure were applied was heated in an oven at 220 ° C for 1 hour (post-baking). Thus, a color filter having a coating film (colored layer) of a curable composition formed on a glass substrate was obtained.

[A3. Performance Evaluation]

The storage stability of the coating solution prepared by the above-prepared hardenable composition was evaluated as follows, and the hardening composition was hard formed on the glass substrate. Exposure sensitivity of the coating film (colored layer) of the composition, substrate adhesion property, development property, and cross-sectional shape of the pattern. The results are shown in Table 1.

A3-1. Storage stability of hardenable composition After the hardening composition (coating solution) prepared as described above was stored at room temperature for 1 month, the viscosity of the solution was measured to be evaluated in accordance with the following criteria.

-Measurement criteria - A: Viscosity has not risen B: viscosity increases by 5% or more to less than 10% C: viscosity increased by 10% or more

A3-2. Exposure sensitivity of the coating film (colored layer) of the curable composition The curable composition coating film was exposed at various varying exposure amounts of 10 to 100 mJ/cm 2 to evaluate the exposure dose of the pattern line width after baking to obtain 20 μm as the exposure sensitivity. The smaller the exposure sensitivity value, the higher the sensitivity.

A3-3. Developing force, pattern cross-section shape, substrate adhesion properties The development properties, the cross-sectional shape of the pattern, and the adhesion property of the substrate were evaluated by observing the surface of the substrate after the post-baking and the cross-sectional shape thereof by optical microscopy and SEM. The details of the assessment method and the evaluation criteria are as follows.

<developing force> The residue in the region (unexposed portion) where no light was irradiated in the exposure step was observed to evaluate the developing power.

-Evaluation Criteria- A: Confirm that there is no residue in the unexposed part B: It is confirmed that the unexposed part of the residue is not causing problems in actual use. Micro level C: Confirmed that there is obvious residue in the unexposed part

<pattern cross section shape> The cross-sectional shape of the formed pattern was observed. The shape of the cross-section of the pattern is preferably a forward-inclined cone, and the second best is a rectangle. The inverted tip is not good.

<Substrate adhesion properties> The adhesion properties of the substrate were evaluated in accordance with the observation of whether or not the pattern was missing. The evaluation criteria are as follows.

-Evaluation Criteria- A: No pattern is observed at all. B: Almost no pattern was observed, but a partial lack was observed. C: A lack of pattern was clearly 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 hardenable composition prepared in Example 1, and was used for the same evaluation as in Example 1. The results are shown in Table 2.

[Examples 2 to 10]

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

[Example 11, Comparative Example 2] A color filter was prepared in the same manner as in Example 1 except that the following resins (II) and (III) synthesized in the same manner as the resin (I) were used instead of the hardenability prepared in Example 1. The resin (I) in the composition was used for the same evaluation as in Example 1. The dipole moment of the monomer a used for the resin (II) was calculated to be 2.48. In addition, the dipole of n-butyl acrylate for resin (III) The moment is calculated to be 1.58. The results are shown in Table 2.

As is apparent from the results of Table 2, the hardenable composition containing the example of the resin of the present invention has excellent storage stability in a solution state. Further, it has been found that, with respect to the comparative example in which the resin of the present invention is not used, the use of the curable composition to form a colored pattern on the support member provides high exposure sensitivity and excellent developing power, and excellent substrate adhesion properties and patterns. A color filter with a cross-sectional shape.

[Example 12]

An example of preparing a curable composition containing a colorant (pigment) for forming a color filter for solid-state photographic element application is explained below.

[B1. Preparation of Photoresist Solution]

A photoresist solution was prepared by mixing and dissolving the components of the following compositions.

<Composition of photoresist solution>

[B2. Manufacture of base substrate with base coating]

A heat treatment was applied to the 6-inch wafer in a 200 ° C oven for 30 minutes. Then, the photoresist solution was coated on the germanium wafer to obtain a dry film thickness of 1.5 μm, and further heated and dried in a 220 ° C oven for 1 hour to form a base coat layer, thereby obtaining a base coating-coated twin crystal. Round substrate.

[B3. Preparation of Pigment Dispersion]

Mixing and dispersing 40 parts by mass of a 30/70 (mass ratio) mixture of CI Pigment Yellow 36 and CI Pigment Yellow 150 as a pigment in a ball mill (average particle diameter of 65 nm), 50 parts by mass (about 22.6 in terms of solid content) Qual.) BYK2001 (Disperbyk: manufactured by BYK Chemie (BYK) Corp., solid content concentration: 45.1% by mass), 10 parts by mass of the resin (I) of the present invention, and 110 parts by mass of propylene glycol-A as a solvent A pigment dispersion (P2) was prepared by a liquid mixture of ether over 15 hours.

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

[B4. Preparation of hardenable composition (coating solution)]

The curable composition solution was prepared by stirring and mixing in the dispersion procedure using the above pigment dispersion liquid P2 to have the following composition ratio.

[B5. Fabrication of color filters from hardenable compositions and evaluation]

<pattern formation and sensitivity evaluation> The curable composition prepared as described above was coated on the undercoat layer of the base-coated ruthenium wafer obtained in the above method B2 to form a color layer (coating film). Then, a dry film thickness of a coating film of 0.7 μm was obtained by heat treatment (prebaking) using a hot plate at 100 ° C for 120 seconds.

Then, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), it was passed through an island-type pattern mask having a 2 micrometer square pattern to a wavelength of 365 nm at 50 to 1,200 mJ/cm 2 . Exposure exposure.

Then, the tantalum wafer substrate on which the irradiated coating film was formed was placed on a horizontal rotating table of a rotary spray developing machine (DW-30 type, manufactured by Chemitronics Corp.) using CD-2000 (manufactured by Fuji Film Electronics Material Corp.). A paddle development was performed at 23 ° C for 60 seconds to form a colored pattern on the germanium wafer substrate.

The silicon wafer forming the colored pattern is fixed on the horizontal rotating table by a vacuum clamping system, and when the silicon wafer substrate is rotated by a rotating frequency of 50 rpm by the rotating device, the spraying nozzle from above the rotating center (such as spraying) Pure water is supplied for the rinsing process and then spray dried.

The size of the colored pattern was then measured using a length measurement SEM "S-9260A" (manufactured by Hitachi High Technologies Corp.). An exposure amount which produces a pattern line width of 2 μm 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 force> The residue in the region (unexposed portion) where no light was irradiated in the exposure step was observed to evaluate the developing power.

-Evaluation Criteria- A: Confirm that there is no residue in the unexposed part B: It is confirmed that the unexposed part of the residue is not slightly affected by the actual use. C: Confirmed that there is obvious residue in the unexposed part

<pattern formation properties> The cross-sectional shape of the formed pattern was observed. The shape of the cross-section of the pattern is preferably a forward-inclined cone, and the second best is a rectangle. The inverted tip is not good.

<Substrate adhesion properties> The adhesion properties of the substrate were evaluated in accordance with the observation of whether or not the pattern was missing. The evaluation criteria are as follows.

-Evaluation Criteria- A: No pattern is observed at all. B: Almost no pattern was observed, but a partial lack was observed. C: A lack of pattern was clearly observed.

<Storage stability of hardenable composition> The curable composition (coating solution) prepared in the above step B4 After storage for 1 month at room temperature, the viscosity of the solution was measured to evaluate according to the following criteria.

-Measurement criteria - A: Viscosity has not risen B: viscosity increases by 5% or more to less than 10% C: viscosity increased by 10% or more

<color irregularity> Color irregularities were evaluated by analyzing the luminance distribution by finding the ratio of pixels within ± 5% of the average of the total number of pixels. The evaluation criteria are as follows.

The method of measuring the luminance distribution is explained below. First, a curable composition is applied to a base coat layer of a glass plate having a base coat layer obtained by the same method as the above step B2 to form a color layer (coating film). Then, a dry film thickness of a coating film of 0.7 μm was obtained by heat treatment (prebaking) using a hot plate at 100 ° C for 120 seconds. The luminance distribution of the coated glass plate of the photograph taken with a microscope MX-50 (manufactured by Olympus Corp.) was analyzed.

-Measurement criteria - A: Deviations from the average of ± 5% of the pixels accounted for 99% or more of the total number of pixels B: pixels out of the mean ± 5% account for 95% or more of the total number of pixels and less than 99% C: pixels out of the mean ± 5% account for less than 95% of the total number of pixels

[Comparative Example 3]

A color filter forming a colored pattern was produced in the same manner as in Example 12 except that the resin (I) was not used in the hardenable composition prepared in Example 12. And used for the same evaluation as in Example 12. The results are shown in Table 3.

[Examples 13 to 22, 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 instead of the resin (I) in the hardenable composition prepared in Example 12, and used for The same evaluation of Example 12. The results are shown in Table 3.

As is clear from the results of Table 3, the curable composition (pigment-based) containing the example of the resin of the present invention (for forming a color filter for solid-state image sensor application) has excellent storage stability in a solution state. Further, it is clear that compared with the comparative example in which the resin of the present invention is not used, when the colored composition is formed on the support member using the curable composition, it has high exposure sensitivity and excellent developing power, and also has Excellent color filter for substrate adhesion, cross-sectional shape and color irregularity.

From these results, it is clear that the hard curable composition of the examples is obtained in the production of color filters for solid-state imaging device applications and in the production of color filters for liquid crystal display device applications. Forming properties.

[Example 23]

An example of preparing a curable composition containing a colorant (dye) for forming a color filter for solid-state photographic element application is explained below.

[C1. Preparation of Photoresist Solution and Fabrication of Substrate with Substrate Coating]

A base substrate having a base coat layer was produced in the same manner as in [Example 12] Preparation of Photoresist Solution of Example 12 and [B2. Fabrication of Substrates with Base Coating].

[C2. Preparation of hardenable composition (coating solution)]

A color photosensitive resin composition was prepared by mixing and dissolving the compound of the following composition.

[C3. Manufacture of color filters from hardenable compositions and evaluation]

The color filter was fabricated and evaluated in the same manner as described above [B5. Color filter produced from the curable composition and evaluated]. The results are shown in Table 4.

[Comparative Example 5]

A color filter forming a colored pattern was produced in the same manner as in Example 23 except that the resin (I) of the curable composition produced in Example 23 was changed to neopentyl alcohol triacrylate, and was used as in Example 23. The same assessment. The results are shown in Table 4.

[Examples 24 to 33, Comparative Example 6]

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

As is apparent from the results of Table 4, the sclerosing composition (dye-based) containing a resin of one aspect of the present invention (for forming a color filter for solid-state photographic element application) has excellent storage in a solution state. Stability.

Further, as a result of an example in which a colored pattern was formed on the support member using the curable composition, it was found that, in comparison with the comparative example, when the colored composition was formed on the support using the curable composition, it was obtained in the example. A color filter with high exposure sensitivity and excellent developing power, and excellent substrate adhesion properties and cross-sectional shape of the pattern.

Further, from these results, it is known that the hardening composition of the example is used in the case of manufacturing a color filter for solid-state imaging device applications, as in the case of manufacturing a color filter for a liquid crystal display device, and realizing an excellent pattern. form.

Some specific embodiments of the invention are shown below.

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

<2> A hardenable composition according to <1>, wherein the above monomer is a monomer having a dipole moment of at least 2.5 or more.

<3> The curable composition of <1>, wherein the above resin has an ethylenically unsaturated double bond in a side chain by polymerizing at least one monomer having a dipole moment of 2.5 or more as a copolymerization component. Got it.

<4> The hardenable composition according to any one of <1> to <3> wherein the monomer having a dipole moment of 2.0 or more has at least one selected from the group consisting of an ether group, a cyano group, and a phosphoric acid. An ester group, a lactone group, a urethane group, a carbonate group, and an acetal group.

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

<6> The curable composition according to any one of <1> to <5> which further contains a sensitizer.

<7> A color filter having a colored pattern formed of a curable composition of <5> or <6>.

<8> A method of producing a color filter, comprising: forming a coloring layer made of a curable composition by coating a curable composition of <5> or <6>, and exposing the colored layer to a mask, And after the exposure, the colored layer is formed by developing the colored layer.

<9> A solid-state photographic element comprising a color filter manufactured by the color filter manufacturing method of <8>.

Claims (11)

A curable composition comprising a resin, a compound containing an ethylenically unsaturated double bond, and a photopolymerization initiator, wherein the resin is polymerized by polymerizing at least one monomer having a dipole moment of 2.0 or more Manufactured by polymerizing a component; wherein the monomer having a dipole moment of 2.0 or more has at least one group selected from the group consisting of a phosphate group, a lactone group, a urethane group, and a carbonate group. group. A sclerosing composition according to claim 1, wherein the dipole moment is 2.0 or greater. The sclerosing composition of claim 1, wherein the resin has an ethylenically unsaturated double bond in a side chain, and is obtained by polymerizing at least one monomer having a dipole moment of 2.0 or more as a copolymerization component. . The sclerosing composition of claim 1, wherein the resin has an ethylenically unsaturated bond in a side chain and has a group represented by the following general formula (1) as the ethylenically unsaturated bond, Wherein R ¹ to R ³ each independently represent a monovalent organic group. The sclerosing composition of claim 1, wherein the photopolymerization initiator is an oxime-based compound. The sclerosing composition of claim 1, wherein the at least one base is a lactone group. The sclerosing composition of claim 1, wherein the coloring agent is further included. The sclerosing composition of claim 1, wherein the sensitizer is further contained. A color filter having a colored pattern formed by the curable composition of claim 7 of the patent application. A method for producing a color filter, comprising: forming a coloring layer made of a curable composition by coating a curable composition of claim 7 on a support; and exposing the colored layer to a mask And forming a colored pattern by developing the colored layer after exposure. A solid-state photographic element comprising a color filter manufactured by the color filter manufacturing method of claim 10 of the patent application.