JP5132160B2 - Curable composition, color filter, method for producing color filter, and graft polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition curing in an extremely high sensitivity, on applying it for a pattern formation on a hard substrate materia surface, showing a high close adhesion with the hard material surface in a cured region and excellent in its removable property in non-cured region, also a color filter formed by using the curable composition and a method for producing the color filter. <P>SOLUTION: (A) This curable composition contains a graft polymer having a branched polymer part containing at least &ge;2 structural units having a pendant ethylenically unsaturated double bond. The curable composition contains preferably (B) a photopolymerization initiator, (C) a coloring agent and (D) a sensitizer, etc. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention is applicable to image forming materials such as three-dimensional stereolithography, holography, color filters, photoresists, lithographic printing plate precursors, and color proofs, and photocurable materials such as inks, paints, adhesives, coating agents, and dental materials. The present invention relates to a curable composition that can be used, and a novel graft polymer used in the curable composition. Moreover, this invention relates to the color filter formed with the said curable composition, and its manufacturing method.

Graft polymers are becoming more important in recent years together with block polymers, and in forming composite materials and for controlling the surface structure of polymer materials, various film materials, adhesives and dispersions are also used. As an agent, it has been researched and developed over a very wide range. Graft polymer synthesis methods include the so-called Graft-from method (polymer initiator method in which monomers are grown from the initiation group on the trunk), and the Graft-onto method (on the linking group on the trunk). A method of coupling the end groups of the branched polymer).
On the other hand, a high molecular weight monomer (macromonomer) in which an ethylenic double bond is introduced at the end of a branching polymer is synthesized by Milkovich et al., And then a monomer copolymerizable with the macromonomer is polymerized to obtain (Graft-through method) has been developed and has been actively studied in recent years (US Pat. No. 3,842,059, US Pat. No. 3,862,101, US Pat. No. 3,928,255, JP-A-61-61). -89208, Macromonomer Chemistry and Industry (published by IPC Publishing). The feature of this method is that the molecular weight (length) and content of the branch polymer can be controlled over a wide range, and the method is extremely useful as a method for molecular design of various graft polymers by changing various copolymerization components. It is. The graft polymer obtained by this method is applied to, for example, a color filter, and a technique for improving the dispersibility of a pigment, adhesion to a substrate, physical properties of a coating film, and the like is known. (For example, refer to Patent Document 1.)

  On the other hand, compounds having an ethylenically unsaturated double bond can be cured in an extremely short time by irradiation with active energy rays such as ultraviolet rays, and are excellent in productivity. Therefore, three-dimensional stereolithography, holography, color filters and photoresists are available. It is widely used as image forming materials such as lithographic printing plate materials and color proofs, inks, paints, adhesives, coating agents, and dental materials. Examples of the compound having an ethylenically unsaturated double bond include polyethylene glycol diacrylate, trimethylol ethane triacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, diester Ethylene oxide and propylene oxide were added to polyfunctional alcohols such as pentaerythritol hexaacrylate, hexanediol acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane After acrylate, JP-A-5-170705, JP-A-11-193325, Urethane group-containing acrylates as described in JP-A Nos. 2000-239332 and 2005-104842, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates such as polyester acrylates, epoxy acrylates which are reaction products of epoxy resin and acrylic acid, and mixtures thereof. Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

In recent years, there has been an increasing demand for compounds having an ethylenically unsaturated double bond in the above-mentioned applications, and those that cure at lower energy, those that cure faster, and those that form finer images are required. It has been. Furthermore, in addition to high-sensitivity polymerizability, developability, dispersibility, film-forming properties, adhesiveness, plasticity, durability, rigidity, high refractive index, transparency, water repellency, hydrophilicity are tailored to the application. The compound which has the performance of these etc. is calculated | required.
For example, a resin having an ethylenically unsaturated double bond and a carboxy group in the side chain has been developed as a compound having high sensitivity and having both developability and film property (see, for example, Patent Document 2).

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

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

With respect to curable compositions for use in color filter production, a finer particle size is required for the colorant (organic pigment or the like) used for the purpose of improving contrast (see, for example, Patent Document 3).
However, since the surface area increases when the pigment is refined, the use of the refined pigment tends to increase the amount of dispersant added for dispersing the pigment in the curable composition. In addition, a curable composition for use in color filter production is required to have a higher colorant (organic pigment) content in the solid content in order to improve color purity. However, when the colorant is contained at a high concentration in the curable composition, the content of the photopolymerization initiator and the photopolymerizable monomer in the curable composition is decreased. While curability at low energy is desired, there is a problem that it is difficult to obtain curability at the exposed portion.

On the other hand, curing with low energy is also desired for curable compositions for use in the production of color filters for solid-state imaging devices. In addition, for color filters for solid-state imaging devices, the coloring pattern is becoming thinner, and accordingly, the pigment concentration in the composition is improved.
Furthermore, in a pigment-based color filter, the pigment dispersant content in the curable composition increases as the pigment is refined to reduce color unevenness due to the pigment being relatively coarse particles. There is a tendency that it is difficult to obtain curability.

  Further, in order to cope with problems such as color unevenness in the formed coloring pattern, a technique using an organic solvent-soluble dye instead of a pigment as a colorant has been proposed (for example, see Patent Document 4). However, in dye-based color filters, with the increase in dye concentration, problems such as a polymerization-inhibiting effect derived from dyes and a decrease in stability over time, such as precipitation of dyes, have become prominent.

  As described above, in the case of a curable composition for use in manufacturing a color filter, in either case for a liquid crystal display or a solid-state imaging device, photopolymerization is an essential component for curing the curable composition. The content of the colorant and the photopolymerizable monomer is limited, and the colorant concentration is high, so the sensitivity is low and sufficient curing cannot be obtained, and the adhesion to the substrate is insufficient. Has occurred.

In order to solve these problems, studies have been made on imparting polymerizability to a resin that has been introduced mainly for imparting film-formability, developability, and the like to improve sensitivity (for example, Patent Document 5, 6). In addition, the latest color filter technology trends (published by Information Organization), paragraphs 85 to 87, state-of-the-art color filter process technologies and chemicals (CMC Publishing), paragraphs 129 to 150, and the like can be cited. However, since these resins all have an ethylenically unsaturated double bond group in the very vicinity of the main chain, the mobility of the ethylenically unsaturated double bond is small and the polymerization reaction is saturated early. However, a satisfactory exposure sensitivity has not been obtained yet. Further, since the exposure sensitivity is insufficient, there is a problem that the curing is insufficient at a deep portion such as the vicinity of the substrate interface, and therefore the substrate adhesion is poor.
JP-A-7-170654 JP 2003-29018 A JP 2006-30541 A JP-A-2-127602 JP 2000-321863 A JP 2003-029018 A

The present invention has been made in view of the above problems, and is cured with extremely high sensitivity. When applied to pattern formation on the surface of a hard substrate, the cured region has high adhesion to the surface of the hard material, and the uncured region. Then, it aims at providing the curable composition excellent in the removability, and makes it the 1st subject to achieve this objective.
Another object of the present invention is to provide a color filter having excellent adhesion to a substrate and having a colored pattern having a desired cross-sectional shape, and a production method capable of producing the color filter with high productivity. This is the second problem.
In addition, it aims at providing the novel graft polymer suitable for the curable composition of this invention, and makes it the 3rd subject to achieve this objective.

Means for solving the above problems are as follows.
The curable composition of the present invention is derived from at least one monomer selected from (A) (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile, and styrene, and represented by the general formula (1A) described later. Including a repeating unit different from the repeating unit and a repeating unit represented by the general formula (1A) described later, and a repeating unit represented by the general formula (1A) described later in an amount of 50% by mass or more and 95% by mass. It contains a graft polymer which is a vinyl polymer contained below .
Moreover, it is preferable that the curable composition of this invention contains at least 1 of (B) photoinitiator, (C) coloring agent, and (D) sensitizer.

The color filter of this invention has the coloring pattern formed with the curable composition of this invention on the support body.
Moreover, the method for producing a color filter of the present invention comprises a colored layer forming step of forming a colored layer comprising the curable composition by applying the curable composition of the present invention on a support, and the colored layer comprising: It includes an exposure step of exposing through a mask and a development step of developing a colored layer after exposure to form a colored pattern.

The novel graft polymer of the present invention is derived from at least one monomer selected from (A) (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile, and styrene, and represented by the following general formula (1A). A vinyl containing a repeating unit different from the repeating unit and a repeating unit represented by the following general formula (1A), the repeating unit represented by the following general formula (1A) being 50% by mass or more and 95% by mass or less. It is a polymer.

[In the general formula (1A) , R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, —COOH, —CN, —CF ₃ , —CH ₂ OH, —CH ₂ COOH, —CH ₂ COOR. ^a, or an -COOR ^{b, X 1} represents a divalent organic group, Y is derived from a vinyl polymer containing a repeating unit represented by the general formula (2A) 5 or more 60 or less Represents a polymer chain . In the general formula (2A) , R ² and R ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, —COOH, —CN, —CH ₂ COOH, —CH ₂ COOR ^c , or —COOR ^d is represented, R ⁴ represents hydrogen, a methyl group, or an ethyl group, and X ² represents a divalent organic group. R ^{a to} R ^d each independently represents a hydrocarbon group having 1 to 6 carbon atoms. ]

Although the effect | action of the curable composition of this invention is not clear, it estimates as follows.
That is, the graft polymer contained in the curable composition of the present invention may be referred to as an ethylenically unsaturated double bond group (hereinafter simply referred to as “polymerizable group”) in the graft branch polymer portion having high mobility. ), The degree of decrease in mobility of the unreacted polymerizable group accompanying the progress of polymerization is small, and the polymerization reaction proceeds sufficiently. Moreover, since the exposure sensitivity is high, when the curable composition of the present invention is applied to pattern formation on the surface of a hard substrate, the polymerization proceeds to the deep part (to the vicinity of the hard substrate), and the surface of the hard material in the cured region Adhesion with is increased.
Moreover, since the graft polymer contained in the curable composition of the present invention has a graft structure having a branched polymer portion, the occupied volume is small instead of the molecular weight. Therefore, when the curable composition of the present invention is applied to pattern formation on the surface of a hard substrate, in an uncured region, solvation by the developer or the like and diffusion into the developer proceed quickly, and as a result , Excellent removability of the uncured region can be obtained. On the other hand, since sufficient sclerosis | hardenability is acquired in a hardening area | region, the influence of a developing solution etc. can be suppressed. Therefore, in pattern formation using the curable composition of the present invention, excellent curability in a cured region and excellent removability in an uncured region are compatible, and a good pattern having a desired cross-sectional shape is obtained. It is thought that it can be formed.

According to the present invention, when cured with extremely high sensitivity and applied to pattern formation on the surface of a hard substrate, the adhesiveness to the surface of the hard material is high in the cured region, and the curability is excellent in removability in the uncured region. A composition can be provided.
In addition, it is possible to provide a color filter having excellent adhesion to the substrate and having a colored pattern having a desired cross-sectional shape, and a manufacturing method capable of manufacturing the color filter with high productivity.
Furthermore, the present invention provides a novel graft polymer suitable for the curable composition of the present invention.

  Hereinafter, first, the graft polymer of the present invention (hereinafter, appropriately referred to as “specific graft polymer”) and the curable composition will be described in detail.

<Specific graft polymer>
The novel graft polymer (specific graft polymer) of the present invention is characterized by having a branched polymer portion containing at least two structural units pendant with ethylenically unsaturated double bonds.
Since the specific graft polymer has an ethylenically unsaturated double bond group in the highly branched graft branch polymer part, the degree of decrease in mobility of the unreacted ethylenically unsaturated double bond group as the polymerization proceeds In addition, by changing the structure of the pendant, the polarity difference between the trunk polymer part and the branch polymer part can be easily given in the synthesis, and it can be used as a dispersant. It is suitable for use in a curable composition, a dispersion in which fine particles such as organic or inorganic pigments and metals are dispersed in a solution, and a curable composition containing the same.

In the specific graft polymer, a polymer chain including at least two structural units pendant with an ethylenically unsaturated double bond is a “branch polymer portion”, and a polymer chain to which the branch polymer portion is bonded is referred to as a “trunk polymer portion”. "
The specific graft polymer only needs to have two or more ethylenically unsaturated double bonds pendant per branch polymer, and includes a structural unit in which the ethylenically unsaturated double bond is directly pendant to the trunk polymer. However, it does not have to be included.

  In the specific graft polymer, the main chain structure of the polymer constituting the branched polymer part and the trunk polymer part includes a single bond between carbon atoms, a double bond between carbon atoms, a triple bond between carbon atoms, an ester bond, and an ether bond. , A polymer chain containing an amide bond alone or in combination, among them, from the viewpoint of ease of synthesis, sensitivity, developability, storage stability, single bond between carbon atoms, ester bond, A polymer chain is preferred by combining an ether bond or an amide bond alone or in combination, and a polymer chain containing a single bond between carbon atoms is more preferred.

  The specific graft polymer preferably has an ethylenically unsaturated bond equivalent (unit: mol / g) per gram of the graft polymer of 0.00001 mol / g or more from the viewpoint of sensitivity and storage stability reduction. More preferably, it is 0001 mol / g or more and 0.01 mol / g or less, and most preferably 0.001 mol / g or more and 0.008 mol / g or less.

  The weight average molecular weight of the specific graft polymer of the present invention is preferably from 3,000 to 300,000, more preferably from 4,000 to 100,000, still more preferably from 5,000 to 50,000, most preferably from 6,000 to 25,000, from the viewpoints of sensitivity, developability, and storage stability. preferable.

(Synthesis method)
The specific graft polymer of the present invention can be synthesized by the following method.
That is, example, it can be synthesized by a method to synthesize a precursor polymer having a grayed raft structure, introducing an ethylenically unsaturated double bond to the branch polymer portion of the precursor polymer.
As a synthesis method of the precursor polymer having a graft structure, (1) polymerization of a branch monomer from an initiating group on the trunk polymer (graft-from method), (2) a branch polymer to the trunk polymer (terminal functional or living) Polymer) bonding (coupling) (graft-onto method), (3) macromonomer method (copolymerization of macromonomer and trunk monomer as a branch) (graft-through method), and the like.

In the graft-from method of (1), for example, living radical polymerization, initiator method, chain transfer method, Ce (IV) salt method (cellulose, poval method), oxidation method, radiation irradiation method and the like are used. Examples of the living polymerization method include anionic polymerization, cationic polymerization, immortal polymerization, coordination polymerization, and group transfer polymerization. The initiator method is a method of starting radical polymerization or ionic polymerization from a functional group in the prepolymer.
In the graft-onto method of (2), introduction of a hydroxyl group, an amino group, a ketone group, a lactone group, an isocyanate group, a carboxyl group or the like as the terminal functional group of the terminal functional polymer can be mentioned.
As a method for synthesizing the macromonomer (3), an ion polymerization method, a radical (chain transfer) polymerization method, a living polymerization method such as an ATRP method, or the like is used.
Among the above-described precursor polymer synthesis methods, (3) the macromonomer method is preferred from the viewpoint of ease of synthesis, reproducibility, and the like.

Moreover, as a method of pendating an ethylenically unsaturated double bond to the precursor polymer obtained as described above, for example, the following methods (a) to (c) may be mentioned.
(A) A method of causing a compound having both a substituent capable of reacting with a nucleophilic group and an unsaturated double bond to act on a precursor polymer having a nucleophilic group in a branched polymer portion.
(B) A method of reacting a compound having both a nucleophilic group and an ethylenically unsaturated double bond with a precursor polymer having a substituent capable of reacting with the nucleophilic group in the branched polymer part.
(C) A structure that generates an ethylenically unsaturated double bond by the action of heat and / or light irradiation, acid, base, etc. is introduced in advance into the macromonomer, and the reaction between the macromonomer and another monomer A method of forming an ethylenically unsaturated double bond by forming a trunk polymer part to form a precursor polymer and then irradiating it with heat and / or light, or by acting an acid, a base or the like.

  In addition, as another example of the method for synthesizing the specific graft polymer of the present invention, (B) in a reaction of polymerizing a branch monomer from an initiating group on the trunk polymer (Graft-from method), a branch monomer is obtained by the polymerization reaction as a branch monomer. A method using a monomer having both a reactive group for forming a polymer chain and an ethylenically unsaturated bond that does not polymerize under the polymerization reaction conditions, or (C) a branched polymer is linked to a trunk polymer (Graft-onto method) ), A method using a branch polymer in which an ethylenically unsaturated bond is pendant is used as the branch polymer.

Specific graft polymer over the present invention preferably has a repeating unit represented by the following general formula (1A).

In the general formula (1A) , R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, —COOH, —CN, —CF ₃ , —CH ₂ OH, —CH ₂ COOH, —CH ₂ COOR ^a Or -COOR ^b .
Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ¹ , R ^a , or R ^b include a methyl group, an ethyl group, a propyl group, a butyl group, a propyl group, and a hexyl group. Group and ethyl group are preferable, and methyl group is more preferable.
R ¹ is preferably a hydrogen atom, a methyl group, —COOH, —CN, —CF ₃ , —CH ₂ OH, or —CH ₂ COOH, and more preferably a hydrogen atom or a methyl group.

The divalent organic group represented by X ¹ includes, in the chain, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a hydrocarbon ring structure having 3 to 10 carbon atoms, a heterocycle, an ether bond, A single atom or partial structure selected from the group consisting of an amino bond, a thioether bond, a urethane bond, a thiourethane bond, an ester bond, a sulfonate bond, a phosphate bond, an amide bond, a urea bond, and a thiourea bond. Or a hydrocarbon chain having 1 to 100 carbon atoms which may be contained in combination.
Among these, a partial structure selected from the group consisting of a hydrocarbon ring structure having 5 or 6 carbon atoms, an ether bond, a thioether bond, a urethane bond, a thiourethane bond, an ester bond, and an amide bond, A hydrocarbon chain having 1 to 50 carbon atoms which may be included in combination is preferable, and consists of a hydrocarbon ring structure having 6 carbon atoms, an ether bond, a thioether bond, a urethane bond, a thiourethane bond, an ester bond, and an amide bond. A C1-C40 hydrocarbon chain containing 2 or more types of partial structures selected from the group is more preferred.

The divalent organic group represented by X ¹ may further have a substituent. Preferred examples of the substituent that can be introduced include linear, branched or cyclic carbon atoms having 1 to 20 carbon atoms. Hydrogen group, C6-C20 aryl group, C1-C20 acyloxy group, C2-C20 alkoxycarbonyloxy group, C7-C20 aryloxycarbonyloxy group, C1-C20 Carbamoyloxy group, C1-20 carbonamido group, C1-20 sulfonamido group, C1-20 carbamoyl group, C0-20 sulfamoyl group, C1-20 alkoxy group An aryloxy group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an N-sulfamoylcarbamo having 1 to 20 carbon atoms Yl group, alkylsulfonyl group having 1 to 20 carbon atoms, arylsulfonyl group having 6 to 20 carbon atoms, alkoxycarbonylamino group having 2 to 20 carbon atoms, aryloxycarbonylamino group having 7 to 20 carbon atoms, 0 to carbon atoms 20 amino groups, 1-20 carbon imino groups, 3-20 carbon ammonio groups, carboxyl groups, sulfo groups, hydroxy groups, mercapto groups, 1-20 carbon alkylthio groups, 6-20 carbon atoms Arylthio group, ureido group having 1 to 20 carbon atoms, heterocyclic group having 2 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, sulfamoylamino group having 0 to 2 carbon atoms, silyl having 2 to 20 carbon atoms Group, isocyanate group, isocyanide group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), cyano group, nitro group and the like. Among them, a chain, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable from the viewpoint of availability of raw materials, and from the viewpoint of sensitivity and developability, a carboxyl group, a sulfo group, a hydroxy group, a mercapto group, A cyano group is preferred. Moreover, a methyl group, a hydroxy group, and a cyano group are the most preferable from the viewpoint of balance of availability of raw materials, sensitivity, and developability.

Y represents a polymer chain derived from a vinyl polymer containing 5 or more and 60 or less repeating units represented by the general formula (2A).
R ² and R ³ in the general formula (2A) are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, —COOH, —CN, —CF ₃ , —CH ₂ OH, —CH ₂ COOH. represents a _-CH 2 COOR ^c, or -COOR ^{d.
Wherein, R 2, R 3, R} c, or the hydrocarbon group having 1 to 6 carbon atoms represented by ^{R d,} wherein ^R 1, ^{R a,} or 1 to 6 carbon atoms represented by ^{R b} The same as the hydrocarbon group of
R ² and R ³ are each independently preferably a hydrogen atom, a methyl group, —COOH, —CN, —CF ₃ , —CH ₂ OH, or —CH ₂ COOH, more preferably a hydrogen atom or a methyl group. .
R ⁴ represents a hydrogen atom, a methyl group, or an ethyl group, and is preferably a hydrogen atom or a methyl group.

In addition, the divalent organic group represented by X ² includes an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a hydrocarbon ring structure having 3 to 10 carbon atoms, a hetero ring, an ether bond, A single atom or partial structure selected from the group consisting of an amino bond, a thioether bond, a urethane bond, a thiourethane bond, an ester bond, a sulfonate bond, a phosphate bond, an amide bond, a urea bond, and a thiourea bond. Or a hydrocarbon chain having 1 to 100 carbon atoms which may be contained in combination.
Among them, a partial structure selected from the group consisting of a hydrocarbon ring structure having 5 or 6 carbon atoms, an ether bond, a thioether bond, a urethane bond, a thiourethane bond, an ester bond, a urea bond, and an amide bond, Alternatively, a hydrocarbon chain having 1 to 50 carbon atoms which may contain a combination of a plurality thereof is preferable, and is selected from the group consisting of a hydrocarbon ring structure having 6 carbon atoms, an ether bond, a urethane bond, an ester bond, and an amide bond. A hydrocarbon chain having 1 to 30 carbon atoms having a partial structure alone or in combination of a plurality thereof is more preferable.
When the divalent organic group represented by X ² has a substituent, preferred examples thereof are the same as those in the case of X ¹ .

Specific graft polymer to synthesize a precursor polymer before having Kigu raft structure, it is preferable to be synthesized by a method of introducing an ethylenic unsaturated double bond to the branch polymer portion of the precursor polymer, in particular, precursors It is more preferable to synthesize by using the method (a) or (c) as a method of pendating an ethylenically unsaturated double bond to the polymer.
Hereinafter, various components used when synthesizing the specific graft polymer will be described.

First, the case where a specific graft polymer is synthesized by the method (a) will be described. In the method (a), a precursor polymer having a nucleophilic group is used in the branched polymer portion.
Here, as a monomer for forming the branched polymer portion, it is preferable to use a monomer having a nucleophilic group and / or a monomer obtained by protecting the nucleophilic group with an appropriate protecting group. The nucleophilic group as used herein is a functional group capable of performing a nucleophilic reaction, and is not particularly limited as long as it is a substituent having nucleophilicity. A group, a hydroxyl group, an amino group, and a mercapto group are preferable, and among them, a carboxy group or a hydroxyl group is preferable. Moreover, t-butyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like are preferably used as these protecting groups, and the deprotection reaction can be easily carried out under strongly acidic conditions.

  Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the like, and an acidic cellulose derivative having a carboxylic acid group in the side chain is also used. Can do. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful. Examples of the monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 3-hydroxypropyl. Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as methacrylate and 4-hydroxybutyl methacrylate, ethyleneoxy-modified products thereof, hydroxystyrene and the like are useful.

The branched polymer portion may be a copolymer of the monomer having the nucleophilic group and another monomer. The following (1) to (11) are preferably used as the monomer that can be copolymerized with a monomer having a nucleophilic group.
(1) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;
(2) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(3) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(4) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(5) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(6) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(7) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(8) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(9) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(10) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(11) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in JP-A Nos. 2002-309057 and 2002-311569.

  Furthermore, in order to introduce a nucleophilic group into the branched polymer part, it is also useful to polymerize a monomer having both an ester bond and an ethylenically unsaturated double bond, and then saponify to form a hydroxyl group. The monomer used in this method is preferably vinyl acetate.

In addition, as a method for synthesizing a precursor polymer having a nucleophilic group in the branched polymer portion, the (3) macromonomer method is preferably used.
As a method for synthesizing the macromonomer, first, a monomer having the nucleophilic group and / or a monomer in which the nucleophilic group is protected with an appropriate protecting group is polymerized alone, or another copolymer is used. After copolymerizing with a polymerization component to form a prepolymer, or after a monomer that generates a hydroxyl group by saponification alone or with another copolymerization component and saponifying to form a prepolymer, Macromonomerization is preferably performed by a known method.
In the (co) polymerization of the prepolymer, azo initiators such as azobiscyanovaleric acid and azobiscyanopentanol are preferably used, such as thioglycolic acid, mercaptoethanol, and 3-mercaptopropyltrimethoxysilane. More preferably, a chain transfer agent is allowed to coexist.
Moreover, when performing saponification, strong alkalis, such as sodium hydroxide, ammonia, amines, etc. are used preferably.

Among known macromonomer methods, the following methods are preferably used from the viewpoint of ease of synthesis and versatility.
When the prepolymer synthesized by the above method has a carboxy group at the terminal, it is preferable to act on a compound having both a glycidyl group and an ethylenically unsaturated bond. ) Acrylate is used. In addition, when the prepolymer has a hydroxy group or an amino group at the terminal, it is preferable to act an acid halide or isocyanate compound having an ethylenically unsaturated bond. As such a compound, (meth) acrylic acid Examples include chloride, isocyanate ethyl (meth) acrylate, 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate, and the like. Furthermore, when the prepolymer has a mercapto group at the terminal, it is preferable to perform Michael addition by allowing a compound having a plurality of ethylenically unsaturated bonds to act, and examples of such a compound include acryloyloxybutyl acrylate.
Moreover, you may use a commercial item as a macromonomer which has a nucleophilic group. Examples of such commercially available products include UM-9001, XM-9053, WM-9054, UC-3000, UC-3900, UC-3910, UC-3920, UF-5022 manufactured by Toagosei Co., Ltd. COOH group containing), AA-714, AX-714, AY-707, AY-714, UH-2000, UH-2032, UH-2041, UH-2170, UHE-2012 (above, containing -OH group), etc. Can be mentioned.

  The precursor (precursor polymer) of the specific graft polymer can be synthesized by copolymerizing the macromonomer synthesized by the above method with another monomer. As examples of other monomers used in this case, the monomers (1) to (11) are suitable.

As a method for introducing an ethylenically unsaturated bond into the branched polymer portion of the precursor polymer synthesized by the above method, the following method is used.
When the branched polymer portion of the precursor polymer has a carboxy group, a compound having both a glycidyl group and an ethylenically unsaturated bond is preferably allowed to act. As such a compound, glycidyl (meth) acrylate is used. Further, when the branched polymer portion of the precursor polymer has a hydroxy group or an amino group, it is preferable to act an acid halide or an isocyanate compound having an ethylenically unsaturated bond. ) Acrylic acid chloride, isocyanate ethyl (meth) acrylate and the like. Further, when the branched polymer portion of the precursor polymer has a mercapto group, it is preferable to perform Michael addition by causing a compound having a plurality of ethylenically unsaturated bonds to act, and as such a compound, acryloyloxybutyl acrylate is preferable. Used.

Next, the case where the specific graft polymer is synthesized by the method (c) will be described. In the method (c), a macromonomer having a structure that generates an ethylenically unsaturated double bond by the action of heat and / or light irradiation, an acid, a base, or the like is used. As a method for generating an ethylenically unsaturated double bond, it is preferable to irradiate heat and / or light, or an acid or a base to act, and a method using an elimination reaction with a base is more preferable.
As the macromonomer used in the method (c), a monomer having a structure generating an ethylenically unsaturated double bond by the action of heat and / or light irradiation, acid, base, etc. is polymerized alone, or other It is preferable to synthesize a prepolymer by copolymerizing with the above-mentioned copolymerization monomer, and then to convert it into a macromonomer by a known method. Among them, a known method is a method in which a monomer having a structure that generates an ethylenically unsaturated double bond by elimination reaction with a base is polymerized alone or copolymerized with another copolymerizable monomer to synthesize a prepolymer. It is preferable to form a macromonomer.

  Here, as a monomer having a structure that generates an ethylenically unsaturated double bond by elimination reaction, “a structure in which an acid is added to an ethylenically unsaturated bond part of a (meth) acryloyl group or a styryl group” Monomers having the same structure are preferably used, and among them, monomers having partial structures of the following general formulas (3) to (6) are preferable.

The general formula (3), and in the general formula ^(4), R a to R ^d each independently represent a hydrogen atom, or a monovalent substituent.
The “monovalent substituent” may be any group that can be substituted on the benzene ring in the general formula (3) and the general formula (4), and examples thereof include an aliphatic group, an aromatic group, and a heterocyclic group. , Halogen atom, hydroxyl group, thiol group, cyano group, nitro group, (meth) acrylate group, carboxy group, amino group, aliphatic amino group, aromatic amino group, heterocyclic amino group, aliphatic oxy group, aromatic Oxy group, heterocyclic oxy group, aliphatic thio group, aromatic thio group, heterocyclic thio group, aliphatic sulfonamido group, aromatic sulfonamido group, heterocyclic sulfonamido group, acyl group, acyloxy group, acylamino group, Aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, aliphatic oxycarbonylamino group, aromatic oxycarbonylamino group, heterocyclic oxy Rubonylamino group, aliphatic thiocarbonylamino group, aromatic thiocarbonylamino group, heterocyclic thiocarbonylamino group, aliphatic aminocarbonylamino group, aromatic aminocarbonylamino group, heterocyclic aminocarbonylamino group, carbamoyl group, carbamoyl Oxy group, carbamoylamino group, aliphatic sulfonyl group, aromatic sulfonyl group, heterocyclic sulfonyl group, aliphatic oxyamino group, aromatic oxyamino group, heterocyclic oxyamino group, silyl group, aliphatic oxysilyl group, silyloxy group , Aliphatic oxycarbonyloxy group, aromatic oxycarbonyloxy group, heterocyclic oxycarbonyloxy group, sulfamoyloxy group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, anilino group, aliphatic azo group, aromatic Azo group, Hete Ring azo group, aliphatic sulfinyl group, aromatic sulfinyl group, heterocyclic sulfinyl group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, heterocyclic sulfonyloxy group, sulfamoyl group, sulfo group, phosphonyl group, phosphonic acid group, Or a phosphinoylamino group is mentioned.

  Among them, preferable monovalent substituents include aliphatic groups, aromatic groups, heterocyclic groups, halogen atoms, hydroxyl groups, thiol groups, cyano groups, nitro groups, (meth) acryloyl groups, carboxy groups, amino groups, Aliphatic amino group, aromatic amino group, heterocyclic amino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonamido group, aromatic sulfonamido Group, acyl group, aliphatic oxycarbonyl group, aliphatic oxycarbonylamino group, aromatic oxycarbonylamino group, aliphatic thiocarbonylamino group, aromatic thiocarbonylamino group, aliphatic aminocarbonylamino group, aromatic aminocarbonyl Amino group, carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, silyl group, aliphatic oxysilyl group Silyloxy group, an aliphatic carbonyloxy group, an aromatic carbonyl group, a heterocyclic carbonyloxy group, an aliphatic oxycarbonyl group, an aliphatic sulfonyloxy group, a sulfamoyl group, a sulfo group, a phosphonyl group, and a phosphonic group.

  In particular, from the viewpoint of sensitivity and solubility, aliphatic groups, aromatic groups, heterocyclic groups, halogen atoms, hydroxyl groups, thiol groups, (meth) acryloyl groups, carboxy groups, amino groups, aliphatic amino groups, aromatics Amino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic thio group, aliphatic sulfonamido group, aliphatic oxycarbonyl group, aliphatic oxycarbonylamino group, silyl group, aliphatic oxysilyl group, An aliphatic carbonyloxy group, an aliphatic oxycarbonyloxy group, an aliphatic sulfonyloxy group, a sulfo group, or a phosphone group is preferred.

  The “aliphatic group” means an alkyl group, an alkenyl group, or an alkynyl group. The aliphatic group may have a branch and may form a ring. Moreover, it may be unsubstituted or may have a substituent. When the aliphatic group has a substituent, it can have the various substituents mentioned in the description of the “monovalent substituent” above, and when it has two or more substituents, the substituents are the same. Or different. When the aliphatic group is an alkyl group, it may be linear, branched, or may form a ring, and preferably has 1 to 21 carbon atoms, It is more preferable that it is C1-C16, and it is especially preferable that it is C1-C12.

  Examples of the alkyl group having 1 to 21 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n -Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n -Nonadecyl group, n-eicosanyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, Neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group,

2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl Group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, branched pentadecyl group, branched hexadecyl group, branched heptadecyl group, branched octadecyl group, linear or Branched nonadecyl group, linear or branched eicosanyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl Group, cyclododecyl group, Rubornyl group, bornyl group, cis-miltanyl group, isopinocanphenyl group, noradamantyl group, adamantyl group, adamantylmethyl group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentyl Preferred examples include an ethyl group and a bicyclooctyl group.

  Among the above, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl Branched nonyl group, branched decyl group, branched undecyl group, branched dodecyl group, branched tridecyl group, branched tetradecyl group, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group , Cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, cis-miltanyl group, isopinocamphenyl group, noradamantyl group, adamantylmethyl, adamantylmethyl More preferably a group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentylethyl group, or bicyclooctyl group,

  Furthermore, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, i -Propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, linear or branched Heptyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, branched decyl group, cyclopropyl group, cyclopropylmethyl , Cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group, bornyl group, noradamantyl group, adamantylmethyl, adamantylmethyl A group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, cyclopentylethyl group, or bicyclooctyl group is particularly preferred.

  Among the alkyl groups exemplified above, an alkyl group substituted with fluorine is also particularly suitable. Examples of the fluorine-substituted alkyl group include a trifluoromethyl group, a trifluoroethyl group, a pentafluoroethyl group, and a heptafluoropropyl group. Nonafluorobutyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, tridecafluorooctyl group, nonadecafluorononyl group, heptadecafluorodecyl group, or perfluorodecyl group is preferable. Among them, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, tridecafluorohexyl group, pentadecafluoroheptyl group are more preferable, and further trifluoromethyl group, pentafluoroethyl group Heptafluoropropyl group, a nonafluorobutyl group, or tridecafluorohexyl group are particularly preferred.

  When the aliphatic group is an alkenyl group, it may be unsubstituted or may have a substituent, and an alkenyl group having 2 to 21 carbon atoms is preferable. A C2-C16 alkenyl group is more preferable, and a C2-C10 alkenyl group is still more preferable. Examples of the alkenyl group having 2 to 21 carbon atoms include a vinyl group, isopropenyl group, 2-propenyl group, 2-methyl-propenyl group, 1-methyl-1-propenyl group, 1-butenyl group and 3-butenyl group. 1-methyl-1-butenyl group, 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 2,6-dimethyl-5-heptenyl group, 9-decenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl-2-cyclohexenyl group, 1,4-dihydro-2 -Methylphenyl group, octenyl group, citronellyl group, oleyl group, geranyl group, farnesyl group, 2- (1-cyclohexenyl) ethyl group and the like are preferable. It is.

  Among the above, vinyl group, isopropenyl group, 2-propenyl group, 2-methyl-propenyl group, 1-methyl-1-propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group 1,1-dimethyl-3-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-heptenyl group, 1-cyclopentenyl group, 2-cyclo Pentenylmethyl group, cyclohexenyl group, 1-methyl-2-cyclohexenyl group and 1,4-dihydro-2-methylphenyl group are more preferable, and vinyl group, isopropenyl group, 2-propenyl group, 2-methyl group are more preferable. -Propenyl group, 1-methyl-1-propenyl group, 1-butenyl group, 3-butenyl group, 1-methyl-1-butenyl group, 1,1-dimethyl-3- Tenenyl group, 1-pentenyl group, 2-pentenyl group, 1-ethyl-1-pentenyl group, 1-hexenyl group, 1-cyclopentenyl group, 2-cyclopentenylmethyl group, cyclohexenyl group, 1-methyl-2- A cyclohexenyl group and a 1,4-dihydro-2-methylphenyl group are particularly preferable.

The “aromatic group” means an aryl group. The aryl group may be unsubstituted or may have a substituent, and preferably has 6 to 21 carbon atoms. Especially, a C6-C15 aryl group is preferable and a C6-C10 aryl group is more preferable.
Preferred examples of the aryl group having 6 to 21 carbon atoms include a phenyl group, a naphthyl group, a biphenylenyl group, an acenaphthenyl group, a fluorenyl group, an anthracenyl group, an anthraquinonyl group, and a pyrenyl group. Group, naphthyl group, biphenylenyl group, acenaphthenyl group, fluorenyl group or anthracenyl group is more preferable, and further, phenyl group, naphthyl group, biphenylenyl group or fluorenyl group is particularly preferable.
The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

  The “heterocycle” has a heteroatom (for example, a nitrogen atom, a sulfur atom, an oxygen atom) in the ring, and may be a saturated ring or an unsaturated ring. Or a condensed ring, which may be unsubstituted or may have a substituent. It is preferable that carbon number of a heterocyclic ring is 1-32, and 2-16 are more preferable. For example, isocyanuric ring, epoxy ring, oxetane ring, furan ring, tetrahydrofuran ring, pyran ring, tetrahydropyran ring, dioxane ring, trioxane ring, tetrahydrothiophene ring, thiophene ring, dithiane ring, trithiane ring, pyrrolidine ring, piperidine ring, piperazine Ring, triazine ring, triazacyclononane ring, morpholine ring, thiomorpholine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, oxazole ring, isoxazole ring, thiazole ring, thiadiazole ring, indole ring, carbazole Ring, benzofuran ring, pyridine ring, quinoline ring, pyrimidine ring, pyridazine ring, pyrazine ring, phenanthroline ring, quinazoline ring, acridine ring, uracil ring, lactone ring, etc.

  Among them, isocyanuric ring, epoxy ring, furan ring, tetrahydrofuran ring, pyran ring, tetrahydropyran ring, tetrahydrothiophene ring, thiophene ring, pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, pyrrole ring, pyrazole ring, Imidazole ring, triazole ring, oxazole ring, thiazole ring, thiadiazole ring, indole ring, carbazole ring, benzofuran ring, pyridine ring, quinoline ring, pyrimidine ring, pyridazine ring, pyrazine ring, uracil ring, lactone ring, particularly isocyanuric ring , Epoxy ring, tetrahydrofuran ring, tetrahydropyran ring, tetrahydrothiophene ring, pyrrolidine ring, piperidine ring, morpholine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, Kisazoru ring, a thiazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a lactone ring.

Moreover, Z < ¹ > in General formula (3) and General formula (5), and Z < ² > in General formula (4) and General formula (6) represent an anionic leaving group.
In the said General formula (5) and General formula (6), R < ¹ > -R < ³ > represents a monovalent organic group each independently. Preferable examples are the same as R ^{1 to} R ³ in the following general formula (7) and general formula (8).

  In the present invention, examples of the most preferable monomer among the monomers having a structure that generates an ethylenically unsaturated double bond by elimination reaction include the following general formula (7), general formula (8), or general formula: The radically polymerizable compound represented by (9) is mentioned.

In the said General formula (7) and General formula (8), R < ¹ > -R < ³ > represents a hydrogen atom or a monovalent substituent each independently. Examples of R ¹ include a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom, a methyl group, a methylalkoxy group, and a methyl ester group are preferable. R ² and R ³ may each independently have a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or a substituent. Alkyl group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituted An arylamino group that may have a group, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like, among them, 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 are preferable.
Here, examples of the substituent that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

In the general formula (7), R ⁴ represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, —COOH, —CN, —CF ₃ , —CH ₂ OH, —CH ₂ COOH, —CH ₂ COOR ′. Or —COOR ″. Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ′ or R ″ include a methyl group, an ethyl group, a propyl group, a butyl group, a propyl group, and a hexyl group. Of these, a methyl group and an ethyl group are preferred. R ′ or R ″ is preferably a hydrogen atom, a methyl group, —COOH, —CN, —CF ₃ , —CH ₂ OH, or —CH ₂ COOH, and more preferably a hydrogen atom or a methyl group.
Q represents an oxygen atom, —NH—, or —NR ⁰¹ — (wherein R ⁰¹ represents an alkyl group which may have a substituent).
A represents a divalent linking group. Although not particularly limited, preferably, in the structure, an oxygen atom, a nitrogen atom, a sulfur atom, a hydrocarbon ring structure having 3 to 20 carbon atoms, a heterocycle, an ester bond, a sulfonate bond, a phosphate bond, a urethane It is preferably an alkyl group having 2 to 60 carbon atoms or an aryl group which may have an atom or a partial structure selected from the group consisting of a bond, a thiourethane bond, an amide bond, a urea bond, and a thiourea bond. In the structure, oxygen atom, nitrogen atom, sulfur atom, hydrocarbon ring structure having 3 to 20 carbon atoms, ester bond, urethane bond, thiourethane bond, amide bond, urea bond, and thiourea bond A linear or branched alkyl group having 1 to 40 carbon atoms which may have an atom or a partial structure selected is more preferable. Linear or branched carbon number 1 which may have an atom or a partial structure selected from the group consisting of an atom, a hydrocarbon ring structure having 3 to 12 carbon atoms, an ester bond, a urethane bond, and an amide bond More preferred is an alkyl group of ˜40.

The divalent linking group represented by A may further have a substituent when it can be introduced. Examples of the substituent that can be introduced include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, chain, branched or cyclic alkenyl groups having 2 to 20 carbon atoms, and alkynyl groups having 2 to 20 carbon atoms. Group, aryl group having 6 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms, alkoxycarbonyloxy group having 2 to 20 carbon atoms, aryloxycarbonyloxy group having 7 to 20 carbon atoms, carbamoyl having 1 to 20 carbon atoms An oxy group, a carbonamido group having 1 to 20 carbon atoms, a sulfonamide group having 1 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryloxy group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an N-acylsulfur having 1 to 20 carbon atoms Amoyl group, N-sulfamoylcarbamoyl group having 1 to 20 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms, arylsulfonyl group having 6 to 20 carbon atoms, alkoxycarbonylamino group having 2 to 20 carbon atoms, carbon number 7-20 aryloxycarbonylamino group, C0-20 amino group, C1-20 imino group, C3-20 ammonio group, hydroxy group, mercapto group, C1-20 alkyl A sulfinyl group, an arylsulfinyl group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, a ureido group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, C1-C20 acyl group, C2-C2 sulfamoylamino group, C2-C20 silyl group, isocyanate group, isocyanide A halogen atom (e.g., fluorine atom, chlorine atom, bromine atom), a cyano group, a nitro group, an onium group, and a group having an ethylenically unsaturated double bond. Among these, a chain, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable from the viewpoint of availability of raw materials, and a hydroxy group, a mercapto group, and an ethylenically unsaturated bond from the viewpoint of sensitivity and developability. The group having is preferable. Further, a hydroxy group is most preferable from the viewpoint of balance between sensitivity and developability.
Furthermore, X represents an oxygen atom, a sulfur atom, or —NR ⁰² —, where R ⁰² includes an alkyl group that may have a substituent.
In addition, Z ¹ represents an anionic leaving group.

In the general formula (8), R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent organic group.
Here, the monovalent organic group represented by R ^5, and R ^6, include such hydrocarbon group having 1 to 6 carbon atoms, among them, a methyl group, an ethyl group, a phenyl group is preferable.
In the general formula (8), ^{R 7} has the same meaning as ^{R 4} in the general formula (7), and preferred examples are also the same.
A ¹ represents —G—X—, wherein G represents a divalent organic group linked to G ^1, and X represents an oxygen atom, a sulfur atom, or —NR ⁰³ — (where , R ⁰³ represents a hydrogen atom or an alkyl group which may have a substituent, and the substituent which may be introduced here is the same as the example described in the description of the “monovalent substituent” above. The same applies to the preferred examples).
Further, A ² represents an oxygen atom, a sulfur atom, or —NR ⁰⁴ — (where R ⁰⁴ represents a hydrogen atom, a hydrogen atom, or an alkyl group which may have a substituent, and is introduced here. The substituent which may be used is the same as the example shown in the description of the “monovalent substituent”, and the preferred examples are also the same).
In addition, G ¹ represents an n + 1 valent linking group. Although not particularly limited, preferably, in the structure, an oxygen atom, a nitrogen atom, a sulfur atom, a hydrocarbon ring structure having 3 to 20 carbon atoms, a heterocycle, an ester bond, a sulfonate bond, a phosphate bond, a urethane It is preferably an alkyl or aryl group having 2 to 60 carbon atoms, which may have an atom or a partial structure selected from the group consisting of a bond, a thiourethane bond, an amide bond, a urea bond, and a thiourea bond, In the structure, selected from the group consisting of oxygen atom, nitrogen atom, sulfur atom, hydrocarbon ring structure having 3 to 20 carbon atoms, ester bond, urethane bond, thiourethane bond, amide bond, urea bond, and thiourea bond Is more preferably a linear or branched alkyl group having 1 to 40 carbon atoms, which may have an atom or a partial structure, in which oxygen atom, nitrogen A linear or branched carbon number 1 which may have an atom or a partial structure selected from the group consisting of a C 3-12 hydrocarbon ring structure, an ester bond, a urethane bond, and an amide bond More preferred is an alkyl group of ˜40.

The n + 1 valent linking group represented by G ¹ may further have a substituent when it can be introduced. Examples of the substituent that can be introduced include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, chain, branched or cyclic alkenyl groups having 2 to 20 carbon atoms, and alkynyl groups having 2 to 20 carbon atoms. Group, aryl group having 6 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms, alkoxycarbonyloxy group having 2 to 20 carbon atoms, aryloxycarbonyloxy group having 7 to 20 carbon atoms, carbamoyl having 1 to 20 carbon atoms An oxy group, a carbonamido group having 1 to 20 carbon atoms, a sulfonamide group having 1 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryloxy group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an N-acylsulfur having 1 to 20 carbon atoms Amoyl group, N-sulfamoylcarbamoyl group having 1 to 20 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms, arylsulfonyl group having 6 to 20 carbon atoms, alkoxycarbonylamino group having 2 to 20 carbon atoms, carbon number 7-20 aryloxycarbonylamino group, C0-20 amino group, C1-20 imino group, C3-20 ammonio group, hydroxy group, mercapto group, C1-20 alkyl A sulfinyl group, an arylsulfinyl group having 6 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms, a ureido group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, C1-C20 acyl group, C2-C2 sulfamoylamino group, C2-C20 silyl group, isocyanate group, isocyanide A halogen atom (e.g., fluorine atom, chlorine atom, bromine atom), a cyano group, a nitro group, an onium group, and a group having an ethylenically unsaturated double bond. Among these, a chain, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable from the viewpoint of availability of raw materials, and a hydroxy group, a mercapto group, and an ethylenically unsaturated bond from the viewpoint of sensitivity and developability. The group having is preferable. Further, a hydroxy group is most preferable from the viewpoint of balance between sensitivity and developability. n represents an integer of 1 to 10.
Z ² represents an anionic leaving group.

In the general formula (9), R ^{8 to} R ¹² each independently represent a hydrogen atom or a monovalent substituent, and at least one is a group represented by the following general formula (10). .
Here, examples of the monovalent substituent represented by R ^{8 to} R ¹² include the substituents described in the description of the “monovalent substituent”, and preferred examples thereof are also the same. ^{13 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent organic group. Here, as a monovalent organic group represented by R < ¹³ > -R < ¹⁵ >, a C1-C6 hydrocarbon group etc. are mentioned, Especially, a methyl group, an ethyl group, and a phenyl group are preferable.

In the general formula (10), G ² represents an m + 1 valent linking group, and examples thereof include the examples of the linking group described in G ¹ in the general formula (8), and preferred examples are the same as G ^1. It is. m represents an integer of 1 to 10.
Further, ^R 1 ~R 3, ^{Z 2} in the general formula (10), and ^{A 1, R} 1 ~R 3, ^{Z 2,} and ^{A 1} synonymous in the general formula (8).

  Specific examples (M-1) to (M-12) of the radical polymerizable compound represented by the general formula (7) are shown below, but the present invention is not limited thereto.

  Specific examples [i-1 to i-60] of the radically polymerizable compound represented by the general formula (8) and the radically polymerizable compound represented by the general formula (9) are shown, but the present invention is limited thereto. Is not to be done.

  Preferred examples of the monomer copolymerizable with a monomer having a structure that generates an ethylenically unsaturated double bond by elimination reaction as described above include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, Examples include fumaric acid and 4-carboxylstyrene, and acidic cellulose derivatives having a carboxylic acid group in the side chain can also be used. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful. Also, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, etc. Of these, acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group, ethyleneoxy-modified products thereof, hydroxystyrene and the like are useful. Furthermore, the monomers (1) to (11) are preferably used.

After a monomer having a structure that generates an ethylenically unsaturated double bond by the elimination reaction is polymerized alone or after copolymerization with the copolymerizable monomer to form a prepolymer, a known method is used. It is preferable to use a macromonomer.
In the (co) polymerization of the prepolymer, azo initiators such as azobiscyanovaleric acid and azobiscyanopentanol are preferably used, such as thioglycolic acid, mercaptoethanol, and 3-mercaptopropyltrimethoxysilane. More preferably, a chain transfer agent is allowed to coexist.
Among known macromonomer methods, the following methods are preferably used from the viewpoint of ease of synthesis and versatility.
When the prepolymer synthesized by the above method has a carboxy group at the terminal, it is preferable to act on a compound having both a glycidyl group and an ethylenically unsaturated bond. ) Acrylate is used. In addition, when the prepolymer has a hydroxy group or an amino group at the terminal, it is preferable to act an acid halide or isocyanate compound having an ethylenically unsaturated bond. As such a compound, (meth) acrylic acid is used. Examples include chloride and isocyanate ethyl (meth) acrylate. Furthermore, when the prepolymer has a mercapto group at the terminal, it is preferable to perform Michael addition by allowing a compound having a plurality of ethylenically unsaturated bonds to act, and examples of such a compound include acryloyloxybutyl acrylate.

  A precursor (precursor polymer) of a specific graft polymer can be synthesized by forming a trunk polymer portion by reaction (copolymerization) of the macromonomer synthesized by the above method with another monomer. As examples of other monomers used in this case, the monomers (1) to (11) are suitable.

  As a method of performing an elimination reaction on the precursor polymer synthesized by the above method to generate an ethylenically unsaturated double bond, a desired amount of base is cooled or heated in the precursor polymer solution. A method is preferred in which the reaction is carried out by dropping and reacting under conditions, and if necessary, neutralization with an acid. As the base, either an inorganic compound or an organic compound may be used. Preferred inorganic bases include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like, and organic bases include sodium methoxide, sodium ethoxide, potassium t-butoxide. And metal amine alkoxide, triethylamine, pyridine, diisopropylethylamine, and organic amine compounds such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU).

The case where the specific graft polymer is synthesized by the method (b) will be described. In the method (b), a precursor polymer having a substituent capable of reacting with a nucleophilic group in the branched polymer portion is used. This precursor polymer is obtained by the methods (a) and (c). It is synthesized using a macromonomer method similar to that used. In this case, as a substituent capable of reacting with a nucleophilic group, a glycidyl group, an isocyanate group, and the like are preferable, and a glycidyl group is more preferably used. As a raw material macromonomer used for this macromonomer method, for example, Toagosei Co., Ltd. UG-4000, UG-4010, UG-4030, UG-4040, UG-4070, WM-9080, XM-9081 (or more Commercially available products such as glycidyl group-containing) may be used.

(Identification method)
The structure of the specific graft polymer of the present invention can be identified by the following method.
When the specific graft polymer of the present invention is synthesized by the synthesis method of (a) described above, first, at the time of synthesis of the macromonomer, quantification of residual monomer (HPLC method, etc.), molecular weight measurement (gel permeation chromatograph (GPC) ) Method))) If necessary, the content of the nucleophilic group is quantified by acid value measurement (alkaline solution titration method). Here, by confirming that the value obtained by dividing the molecular weight by the nucleophilic group is 2 or more, it is determined whether or not a substituent containing a plurality of nucleophilic groups is pendant in the macromonomer. To do.

  Then, after synthesizing a precursor polymer by copolymerizing this macromonomer and another copolymerization monomer, for the synthesis product, similarly, quantification of residual monomer by HPLC method or the like, molecular weight measurement by GPC method or the like, The acid value is measured by an alkali solution titration method or the like to confirm that the macromonomer has been consumed, the molecular weight has increased, and the acid value has decreased. This determines that the macromonomer has been introduced into the precursor polymer.

In the reaction of introducing an ethylenically unsaturated double bond into the precursor polymer, a compound having both a substituent that reacts with a nucleophilic group in the precursor polymer and an ethylenically unsaturated double bond has been consumed. Is confirmed by disappearance of the residual monomer peak by HPLC method or the like. Furthermore, it is confirmed that the molecular weight has been increased by the GPC method and the acid value has been reduced.
In addition, when the ethylenically unsaturated double bond site in the specific graft polymer is a (meth) acrylic group, the amount of the ethylenically unsaturated double bond in the specific graft polymer should be determined by the following hydrolysis method. Can do. That is, a specific graft polymer is dissolved in an appropriate solvent, a strong alkali solution such as sodium hydroxide or potassium hydroxide is added and stirred for 2 hours or more, and the (meth) acrylic acid produced by hydrolysis is determined by HPLC. It is a method to do.

In addition, when the specific graft polymer of the present invention is synthesized by the synthesis method (c), first, the amount of residual monomer (such as HPLC method) at the time of macromonomer synthesis, molecular weight measurement (gel permeation chromatograph (GPC) method) Etc.)) Acid value measurement (alkaline solution titration method) is performed as necessary. Here, the value obtained by dividing the molecular weight by “the amount of introduction of a substituent that gives an ethylenically unsaturated double bond by treatment with a base (hereinafter referred to as an ethylenically unsaturated double bond precursor site)” is 2. By confirming the above, it is determined whether or not a plurality of ethylenically unsaturated double bond precursor sites are pendant in the macromonomer.
Moreover, the amount of ethylenically unsaturated double bond precursor sites introduced into the macromonomer can also be measured by the hydrolysis method.

Thereafter, macromonomer and other copolymerization monomer are copolymerized to synthesize a precursor polymer. Similarly, residual monomer quantification by HPLC, molecular weight measurement by GPC, etc., acid value measurement by alkali titration method, etc. are carried out. Confirm that the macromonomer has been consumed, the molecular weight has increased, and the acid value has decreased. This determines that the macromonomer has been introduced into the precursor polymer.
And after making a base act on a precursor polymer and implementing elimination | elimination reaction, it confirms that the ethylenically unsaturated double bond produced | generated by the said hydrolysis method.

  The specific graft polymer of the present invention is preferably synthesized by the synthesis method (a) or (c) from the viewpoint of versatility, ease of synthesis, sensitivity, and stability over time. Most preferably, it is synthesized by (c). Among the synthesis methods (a) and (c), preferred synthesis methods are shown below.

(Synthesis using synthesis method (a))
First, a nucleophilic group or a monomer obtained by protecting the nucleophilic group with an appropriate protecting group is polymerized alone or copolymerized with another monomer, and then an ethylenically unsaturated bond is introduced at the terminal to form a macromonomer. To do. Next, the macromonomer is polymerized alone or copolymerized with other monomers to form a trunk polymer portion. When the nucleophilic group is protected, it is subjected to a deprotection reaction after being converted into a macromonomer or after forming a trunk polymer part. Finally, a compound having both a substituent capable of reacting with the nucleophilic group and an unsaturated double bond is allowed to act.

Preferred examples of compounds, structures and methods used in each step of this synthesis method are summarized below.
That is, the nucleophilic group is preferably a carboxy group or a hydroxyl group, and most preferably a carboxy group. Further, it is preferable to copolymerize a nucleophilic group or a monomer obtained by protecting the nucleophilic group with an appropriate protecting group and another monomer.
As the monomer used when forming the branched polymer portion, a (meth) acrylic, styrene, or vinyl monomer is preferable, a (meth) acrylic or styrene monomer is more preferable, and a (meth) acrylic monomer is used. Most preferred.

Furthermore, as the ethylenically unsaturated bond group to be introduced at the terminal when making the macromonomer, (meth) acrylic, styrene, and vinyl are preferable, (meth) acrylic, or styrene are more preferable, The (meth) acrylic type is most preferred. When the macromonomer is used to form the trunk polymer portion, it is preferably copolymerized with other monomers, and the copolymer monomer is preferably a (meth) acrylic, styrene, or vinyl monomer, and (meth) acrylic Or styrene monomers are more preferred, and (meth) acrylic monomers are most preferred.
The compound having both a substituent capable of reacting with the nucleophilic group and an unsaturated double bond has “a substituent capable of reacting with the nucleophilic group” as a glycidyl group, an alicyclic group Epoxy groups and isocyanate groups are preferred, and the “unsaturated double bond” is preferably (meth) acrylic, styrene or vinyl, more preferably (meth) acrylic or styrene, most preferably (meth) acrylic. preferable.

(Synthesis using synthesis method (c))
First, a monomer having a structure that generates an ethylenically unsaturated double bond by the action of heat or light irradiation, acid, base, etc. is polymerized alone, or copolymerized with other copolymerization monomers to form a prepolymer. After the synthesis, an ethylenically unsaturated bond is introduced at the terminal to form a macromonomer. Next, the macromonomer is polymerized alone or copolymerized with other monomers to form a trunk polymer portion. Finally, an ethylenically unsaturated double bond is generated by the action of heat or light irradiation, acid, base or the like.

Preferred examples of compounds, structures and methods used in each step of this synthesis method are summarized below.
That is, as a method for generating an ethylenically unsaturated double bond, a method using an elimination reaction with a base is preferable.
As a monomer having a structure that generates an ethylenically unsaturated double bond by elimination reaction, the same structure as “a structure in which an acid is added to an ethylenically unsaturated bond part of a (meth) acryloyl group or styryl group” is used. The radically polymerizable compound represented by the general formula (12), the general formula (4), or the general formula (5) is more preferably used, and the general formula (12) or The radically polymerizable compound represented by the formula (4) is most preferably used.

Moreover, when synthesizing a prepolymer of a macromonomer, it is preferable to copolymerize a monomer having a structure that generates an ethylenically unsaturated double bond by an elimination reaction with another monomer. The monomer used in this case is preferably a (meth) acrylic, styrene, or vinyl monomer, more preferably a (meth) acrylic or styrene monomer, and most preferably a (meth) acrylic monomer. Furthermore, as the ethylenically unsaturated bond group to be introduced at the end of the macromonomerization, (meth) acrylic, styrene and vinyl are preferable, (meth) acrylic and styrene are more preferable, ) Acrylic is most preferred.
When the macromonomer is used to form the trunk polymer part, it is preferably copolymerized with other monomers, and the copolymer monomer is preferably a (meth) acrylic, styrene, or vinyl monomer, (meth) Acrylic or styrene monomers are more preferred, and (meth) acrylic monomers are most preferred.

  As a method for generating an ethylenically unsaturated double bond by elimination reaction, a desired amount of base is dropped into the precursor polymer solution under a cooling or heating condition, and the reaction is carried out. A method of carrying out neutralization treatment with is preferred.

  Specific examples (I) to (IX) of the specific graft polymer of the present invention are shown below, but the present invention is not limited thereto.

<Curable composition>
The curable composition of the present invention must contain (A) the graft polymer (specific graft polymer) of the present invention, and (B) a photopolymerization initiator, (C) a colorant, and (D) an increase. It is preferable to contain a sensitizer and the like.
The curable composition of the present invention is cured with extremely high sensitivity, and when applied to pattern formation on the surface of a hard substrate, the adhesiveness to the surface of the hard material is high in the cured region, and the removability in the uncured region. Excellent. From this, the curable composition of the present invention is an image forming material such as three-dimensional stereolithography, holography, color filter, photoresist, lithographic printing plate and color proof, ink, paint, adhesive, coating agent, dental It can be preferably used in the field of materials and the like. In particular, in color filter applications for solid-state imaging devices or LCDs, it is possible to form a colored pattern having a desired cross-sectional shape with excellent adhesion to the substrate.
Hereinafter, each component contained in the curable composition of this invention is demonstrated one by one.

[(A) Graft polymer having a branched polymer part containing at least two structural units pendant with ethylenically unsaturated double bonds (specific graft polymer)]
The graft polymer of the present invention may be used alone or in combination of two or more.
As content of the graft polymer of this invention, 0.01 mass%-99.5 mass% are preferable with respect to the total solid contained in the curable composition of this invention, and 1 mass%-90 mass%. Is more preferable, 2% by mass to 80% by mass is further preferable, and 3% by mass to 60% by mass is most preferable.
In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the (A) specific graft polymer is 0.01 with respect to the total solid content contained in the curable composition. % By mass to 90% by mass is preferable, 2% by mass to 60% by mass is more preferable, and 5% by mass to 40% by mass is still more preferable.

[(B) Photopolymerization initiator]
The curable composition of the present invention preferably contains (B) a photopolymerization initiator.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and initiates and accelerates polymerization of the component (A) and the component (E) described later, and has absorption in the wavelength region of 300 to 500 nm. It is preferable that Moreover, a photoinitiator may be used individually by 1 type and can also use 2 or more types together.

Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryes. Examples thereof include a rubiimidazole compound, an organic boric acid compound, a disulfonic acid compound, an oxime compound, an onium salt compound, an acylphosphine (oxide) compound, and an alkylamino compound.
Hereinafter, each of these compounds will be described in detail.

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

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts, organoboron sulfonium complexes or organoboron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 Described in JP-A-6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527 Specific examples include organoboron transition metal coordination complexes and the like disclosed in JP-A-7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2002-328465.

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

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

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

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

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

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

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

  As the photopolymerization initiator (B) used in the present invention, from the viewpoint of exposure sensitivity, a triazine compound, an alkylamino compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, Phosphine oxide compounds, metallocene compounds, oxime compounds, biimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halo A compound selected from the group consisting of a methyloxadiazole compound and a 3-aryl-substituted coumarin compound is preferred.

  More preferably, they are triazine compounds, alkylamino compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, biimidazole compounds, onium compounds, benzophenone compounds, acetophenone compounds. More preferably, at least one compound selected from the group consisting of triazine compounds, alkylamino compounds, oxime compounds, and biimidazole compounds.

(B) The content of the photopolymerization initiator is preferably 0.1% by mass to 50% by mass, more preferably 0.5% by mass to the total solid content of the curable composition of the present invention. 30% by mass, particularly preferably 1% by mass to 20% by mass.
In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the (B) photopolymerization initiator is 0. 5 mass%-50 mass% are preferable, 1 mass%-30 mass% are more preferable, 2 mass%-20 mass% are still more preferable.

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

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

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

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

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

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

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

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

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

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

  In addition, as a pigment used when the curable composition of the present invention is used for forming a black matrix of a color filter, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used. A combination is preferred. The mass ratio of carbon to titanium carbon is preferably in the range of 100: 0 to 100: 60.

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

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

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

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

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

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

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

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

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

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

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

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

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

  The content of the colorant (C) in the curable composition of the present invention is 30% by mass with respect to the total solid content contained in the curable composition, including the case where it is used for forming a color pattern of the color filter. It is preferably ˜95% by mass, more preferably 40% by mass to 85% by mass, and most preferably 50% by mass to 75% by mass.

[(D) Sensitizer]
The curable composition of the present invention may contain (D) a sensitizer for the purpose of (B) improving the radical generation efficiency by the photopolymerization initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, a sensitizer that sensitizes the above-described (B) photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.

Examples of the sensitizer that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred sensitizers include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.
Further, European Patent No. 568,993, US Patent No. 4,508,811, No. 5,227,227, Japanese Patent Application Laid-Open No. 2001-125255, Japanese Patent Application Laid-Open No. 11-271969, etc. And the like.

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

In general formula (i), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² forms a basic nucleus of the dye together with adjacent A ¹ and a carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus of the dye. Good. W represents an oxygen atom or a sulfur atom.

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

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

In general formula (iv), A ³ and A ⁴ each independently represent —S— or —NR ⁶² —, R ⁶² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and L ⁵ , L ⁶ each independently represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ , A ⁴ and adjacent carbon atoms, and R ⁶⁰ and R ⁶¹ each independently represents a monovalent group. It can be a non-metallic atomic group or can be bonded to each other to form an aliphatic or aromatic ring.

  Moreover, as a preferable sensitizer which can be contained in the curable composition of this invention, at least 1 type selected from the compound represented by the following general formula (v)-general formula (vii) other than the above thing is mentioned. It is done.

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

  The compound represented by the general formula (v) is preferably a compound represented by the following general formula (v-1) from the viewpoints of sensitivity and colorability when a pigment is contained.

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

In formula (v-1), the monovalent substituent represented by ^{R 1} and ^{R 2} is a monovalent substituent as defined for the general formula (v) represented by ^{R 1} and ^{R 2} The preferable range is also the same.

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

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

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

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

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

Preferred specific examples (1) to (124) of the compound represented by the general formula (vii) are shown below, but the present invention is not limited thereto.
Further, it is not clear about an isomer by a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

With respect to the sensitizing dye in the present invention, various chemical modifications for improving the properties of the curable composition can be further performed.
For example, sensitizing dye and addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) are bonded by a method such as covalent bond, ionic bond, hydrogen bond, etc. Unnecessary precipitation suppression of the sensitizing dye from the later film can be performed.
In addition, partial structures having radical generating ability in the sensitizing dye and the above-described photopolymerization initiator (for example, reductive decomposable sites such as alkyl halide, onium, peroxide, biimidazole, borate, amine, trimethylsilylmethyl) , An oxidatively cleavable site such as carboxymethyl, carbonyl, imine, etc.), the photosensitivity can be remarkably enhanced particularly in a state where the concentration of the starting system is low.

  When the compound represented by the above general formulas (v) to (vii) has a very high pigment concentration in the curable composition and the light transmittance of the formed colored pattern is extremely low, for example, More specifically, when the curable composition of the present invention is used for forming a coloring pattern of a color filter, the light transmittance of 365 nm of the photosensitive layer when formed without adding a sensitizing dye is 10%. By adding in the following cases, the effect is remarkably exhibited. In particular, among the above general formulas (v) to (vii), the compound represented by the general formula (vii) is most preferable, and specifically, the compounds of (56) to (122) are most preferable.

A sensitizer may be used individually by 1 type and may use 2 or more types together.
The content of the (D) sensitizer in the curable composition of the present invention is curable from the viewpoint of light absorption efficiency to the deep part and starting decomposition efficiency, including the case where it is used for forming a color filter color pattern. It is preferable that it is 0.1 mass%-20 mass% with respect to the total solid of a composition, and 0.5 mass%-15 mass% are more preferable.

[(E) Compound having ethylenically unsaturated double bond]
It is preferable that the curable composition of this invention contains the compound which has ethylenically unsaturated double bond other than the said (A) specific graft polymer.

  The compound having an ethylenically unsaturated double bond that can be used in the present invention is (A) an addition polymerizable compound having at least one ethylenically unsaturated double bond other than the specific graft polymer. , Selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

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

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

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

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

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

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

^{_{CH 2 = C (R 10)}} COOCH 2 CH (R 11) OH formula (a)
(However, R ¹⁰ and R ¹¹ each represent H or CH _3. )

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

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

  About these addition polymerizable compounds, the details of usage methods such as the structure, single use or combined use, addition amount and the like can be arbitrarily set according to the performance design of the curable composition. For example, it is selected from the following viewpoints.

From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). It is also effective to adjust both sensitivity and intensity by using both of these. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of a curing sensitivity and the developability of an uncured area. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.
In addition, the selection and use method of the addition polymerization compound is an important factor for the compatibility and dispersibility with other components (for example, resin, photopolymerization initiator, pigment) in the curable composition, For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion with a substrate or the like.

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

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

(E) It is preferable that content of the compound which has an ethylenically unsaturated double bond is 1 mass%-90 mass% with respect to the total solid of the curable composition of this invention. More preferably, it is 80 mass%, and it is still more preferable that it is 10 mass%-70 mass%.
In particular, when the curable composition of the present invention is used for forming a colored pattern of a color filter, the content of the compound (E) having an ethylenically unsaturated double bond is the total solid content of the curable composition of the present invention. Is preferably 5% by mass to 50% by mass, more preferably 7% by mass to 40% by mass, and still more preferably 10% by mass to 35% by mass.

  When the (A) specific graft polymer and the compound (E) having an ethylenically unsaturated double bond other than the (A) specific graft polymer are used in combination, the content ratio (mass ratio) is: From the viewpoint of sensitivity and storage stability, (A) / (E) is preferably 0.001 to 100, more preferably 0.01 to 10, and still more preferably 0.1 to 1.

[(F) Binder polymer]
The curable composition of the present invention may contain a binder polymer (F) other than the (A) specific graft polymer for the purpose of improving film properties.
It is preferable to use a linear organic polymer as the binder polymer. As such a “linear organic polymer”, a known one can be arbitrarily used. For example, when the curable composition of the present invention is applied to an application in which a pattern is formed by removing an unexposed portion by water or alkali development after pattern exposure and curing of an exposed portion, preferably water development or weakness is used. In order to enable alkaline water development, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected. The linear organic polymer is selected and used not only as a film forming agent but also according to the type of water, weak alkaline water, or organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP 59-44615, JP-B 54-34327, JP-B 58-12577, JP-B 54-. No. 25957, JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048. In other words, a resin having a carboxyl group alone or copolymerized, a resin having an acid anhydride alone or copolymerized, and a hydrolyzed, half-esterified or half-amidated acid anhydride unit, epoxy Examples thereof include epoxy acrylate obtained by modifying a resin with an unsaturated monocarboxylic acid and an acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, an acidic cellulose derivative having a carboxylic acid group in the side chain can also be used. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  As described above, when the radical polymer having a carboxylic acid group in the side chain is a copolymer, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

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

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

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

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

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

(F) The binder polymer can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used in synthesizing the binder polymer that can be used in the present invention include known compounds such as an azo initiator and a peroxide initiator.

  (F) When the curable composition of the present invention is used for forming a color filter color pattern, the content of the binder polymer is that of the present invention from the viewpoint of the balance between the pigment dispersion stability over time and the developability. The total solid content of the curable composition is preferably 1% by mass to 60% by mass, more preferably 5% by mass to 50% by mass, and more preferably 10% by mass to 40% by mass. Most preferred.

  When the (A) specific graft polymer and the (F) binder polymer other than the (A) specific graft polymer are used in combination, the content ratio (mass ratio) is from the viewpoint of sensitivity and storage stability. , (A) / (F) is preferably 0.001 to 1000, more preferably 0.01 to 100, and still more preferably 0.1 to 10.

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

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

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

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

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

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

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

  In the present invention, when a pigment and a dispersant are used, the total content of the pigment and the dispersant is 35% by mass with respect to the total solid content constituting the curable composition from the viewpoint of curing sensitivity and color density. It is preferable that it is -90 mass%, It is more preferable that it is 45 mass%-85 mass%, It is still more preferable that it is 50 mass%-80 mass%.

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

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

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

  (H) Content of co-sensitizer is 0.1 mass%-30 mass with respect to the mass of the total solid of a curable composition from a viewpoint of the improvement of the cure rate by the balance of a polymerization growth rate and chain transfer. % Range is preferable, a range of 0.5 mass% to 25 mass% is more preferable, and a range of 1.0 mass% to 20 mass% is still more preferable.

[(I) Polymerization inhibitor]
In the present invention, during the production or storage of the curable composition, unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond in the molecule, such as component (A) or component (E), is prevented. Therefore, it is desirable to add a small amount of a thermal polymerization inhibitor as a polymerization inhibitor (I).
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

(I) As for the addition amount of a polymerization inhibitor, about 0.01 mass%-about 5 mass% are preferable with respect to the mass of a curable composition.
Further, if necessary, a higher fatty acid derivative such as behenic acid or behenamide is added to prevent polymerization inhibition by oxygen, and the curable composition of the present invention is unevenly distributed on the surface until it is dried. You may let them. The addition amount of the higher fatty acid derivative is preferably about 0.5% by mass to about 10% by mass with respect to the mass of the curable composition.

[(J) solvent]
In preparing the curable composition of the present invention, a solvent can generally be used. The solvent used is not particularly limited as long as it satisfies the solubility of each component of the composition and the applicability of the curable composition, but is preferably selected in consideration of safety.
Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3-oxypropionic acid Alkyl esters of 3-oxypropionic acid such as ethyl; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropyl Ethyl pionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons such as toluene and xylene are preferred.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate (PGMEA) and the like are more preferable.

[Other ingredients]
Furthermore, the curable composition of the present invention includes a filler, a plasticizer, a polymer compound other than those described above, a surfactant, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor for improving the physical properties of the cured film. Etc. can be blended.
More specifically, fillers such as glass and alumina; plastics such as dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin Agents: Polymer compounds such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, nonionic, cationic and anionic surfactants; 2,2-thiobis (4-methyl-6) -T-butylphenol), 2,6-di-t-butylphenol and other antioxidants: 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. ultraviolet Absorbents; and aggregation inhibitor such as sodium polyacrylate and the like.

Further, when the curable composition of the present invention is applied to the surface of a hard material such as a substrate, an additive for improving the adhesion to the surface of the hard material (hereinafter referred to as “substrate adhesion agent”). May be added.
As the substrate adhesion agent, known materials can be used, and it is particularly preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.
Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.

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

  Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

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

In addition, when the curable composition of the present invention is applied to a use in which a pattern is formed by removing an unexposed portion with water or alkali development after pattern exposure and curing of an exposed portion, the alkali solubility is promoted and developed. In order to further improve the property, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less can be added to the curable composition.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

When the curable composition of the present invention contains a pigment as the colorant (C), the curable composition contains (A) a specific graft polymer, (C) a pigment, (G) a dispersant as a component, and the like. It is preferably prepared through a mixing and dispersing step of mixing and mixing using various mixers and dispersers. That is, it is preferable to prepare the curable composition of the present invention by preparing a pigment dispersion by performing a mixing and dispersing step in advance and mixing the pigment dispersion and the remaining components.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

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

The method for producing a color filter of the present invention comprises a colored layer forming step of forming a colored layer comprising the curable composition by applying the curable composition of the present invention on a support, and using the colored layer as a mask. And a developing step of developing the colored layer after exposure to form a colored pattern.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

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

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these glasses, imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
In addition, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the colored layer, prevent diffusion of substances, or flatten the surface.

As a coating method of the curable composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.
The film thickness immediately after application of the curable composition is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, from the viewpoint of film thickness uniformity of the coating film and ease of drying of the coating solvent. 0.2-3 micrometers is still more preferable.

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

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

[Exposure process]
In the exposure step, the colored layer (curable composition layer) formed in the colored layer forming step is exposed through a mask having a predetermined mask pattern.
As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is preferably 5~1500mJ / cm ^2, more preferably 10~1000mJ / cm ^2, and most preferably 10 to 500 mJ / cm ^2.
If the color filter of the present invention is a liquid crystal display device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter of the present invention is for a solid-state imaging device, more preferably 30~1500mJ / cm ² is preferably 50~1000mJ / cm ² within the above range, and most preferably 80~500mJ / cm ^2.

<Development process>
Next, by performing an alkali development process (development process), the unexposed part in the exposure process is eluted in the developer, and only the photocured part remains.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and the like, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like. The concentration of these alkali agents is 0.001% by mass to 10%. An alkaline aqueous solution diluted with pure water so as to have a mass%, preferably 0.01 mass% to 1 mass%, is preferably used as the developer. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
Next, excess developer is washed away and dried.

  In addition, in the manufacturing method of this invention, after performing the colored layer formation process, exposure process, and image development process which were mentioned above, the formed colored pattern is hardened by heating (post-baking) and / or exposure as needed. A curing step may be included.

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

  By repeating the colored layer forming step, the exposing step, and the developing step (and the curing step if necessary) as described above for the desired number of hues (3 colors or 4 colors), a color filter having a desired hue is produced. The

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

Since the color filter of the present invention uses the curable composition of the present invention, the formed colored pattern exhibits high adhesion to the support, and the uncured region is easily removed by the developer. Therefore, it has good adhesion to the support and a high-resolution colored pattern having a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels.
The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

[Synthesis Example 1: (A) Synthesis of Specific Graft Polymer (I)]
(A) A specific synthesis method (steps 1 to 3) of the specific graft polymer (I) will be described using a reaction scheme shown below.

(Step 1: Synthesis of Compound (Ia))
A 1 L three-necked flask was charged with 54.2 g of 1-methyl-2-pyrrolidinone, purged with nitrogen, heated to 80 ° C., 30 g (300 mmol) of methyl methacrylate, 2- (2-bromo-2-methylpropanoyloxy) ) Ethyl methacrylate 83.7 g (300 mmol), mercaptoethanol 2.34 g (30 mmol), and dimethyl 2,2′-azobis (2-methylpropionate) (trade name: V-601) 691 mg (3 mmol) 1- A solution of 54.2 g of methyl-2-pyrrolidinone was added dropwise over 2 hours. After dropping, the mixture was stirred at 80 ° C. for 2.5 hours.
About this reaction liquid, it confirmed that the peak of methyl methacrylate which is a raw material and 2- (2-bromo-2-methylpropanoyloxy) ethyl methacrylate disappeared by HPLC method, and left to cool to room temperature.
Then, reprecipitation refinement | purification was carried out by dripping the reaction liquid in 1.9L of water. The precipitate was collected by filtration and dried to obtain compound (Ia).
The number average molecular weight (Mn) of the obtained compound (Ia) was found to be 2340 and the weight average molecular weight (Mw) to be 3980 by polystyrene conversion GPC measurement. Moreover, the amount of 2- (2-bromo-2-methylpropanoyloxy) ethyl methacrylate introduced was examined by the following hydrolysis method, and it was confirmed that it was introduced quantitatively.

(Hydrolysis method)
0.1 g (solid) of the obtained compound (Ia) was precisely weighed into a 50 mL volumetric flask, 25 mL of 1-methoxy-2-propanol was added using a whole pipette and dissolved by ultrasonic waves, and 2N After adding NaOH solution to make 50 mL in total, this solution was stirred at 25 ° C. for 2 hours. In HPLC, it was calculated that 0.022 g of methacrylic acid was generated by extrapolation from the peak area derived from methacrylic acid.

(Step 2: Synthesis of Macromonomer (Ib))
50 g of compound (Ia) is dissolved in 100 g of tetrahydrofuran, and 200 mg (0.317 mmol) of bismuth tris (2-ethylhexanoate) (trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.)) is added. A homogeneous solution was obtained. The mixture was heated to 60 ° C., and 20 g (0.129 mol) of 2-isocyanatoethyl methacrylate (trade name: Karenz MOI (manufactured by Showa Denko KK)) was added dropwise. After completion of dropping, the mixture was stirred at 60 ° C. for 6 hours.
As a result of performing NMR measurement on this reaction solution, it was confirmed that the urethanation reaction progressed quantitatively because the chemical shift derived from the proton of carbon bonded to the -NCO group of 2-isocyanatoethyl methacrylate was changed. confirmed.
Thereafter, 5 g of methanol was added to the reaction solution and allowed to cool to room temperature. The reaction solution was purified by reprecipitation by dropping it into a mixed solution of 290 mL of water and 1.1 L of methanol. The precipitate was collected by filtration and dried to obtain macromonomer (Ib).
It was found that the number average molecular weight (Mn) of the macromonomer (Ib) obtained by GPC measurement in terms of polystyrene was 2400, and the weight average molecular weight (Mw) was 4080.

(Step 3: (A) Synthesis of specific graft polymer (I))
A solution of 1.65 g (19 mmol) of methacrylic acid and 8.8 g of macromonomer (Ib) in 17.4 g of 1-methyl-2-pyrrolidinone is heated to 80 ° C., and dimethyl 2,2′-azobis (2- A solution of 25 mg (0.11 mmol) of 1-methyl-2-pyrrolidinone (methyl propionate) (trade name: V-601) was added dropwise over 15 minutes. After dropping, the mixture was stirred at 80 ° C. for 3 hours. 50 mg (0.22 mmol) of dimethyl 2,2′-azobis (2-methylpropionate) (trade name: V-601) was added, and the mixture was stirred at 80 ° C. for 2 hours. The reaction solution was heated to 90 ° C., and further stirred for 30 minutes.
About this reaction liquid, it confirmed that the peak derived from the methacrylic acid which is a raw material had disappeared by HPLC method, and it stood to cool to room temperature.
Then, the high molecular compound was deposited by dripping the reaction liquid in 300 mL of water. The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 10.3 g of a polymer compound.
When the obtained polymer compound was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, the number average molecular weight (Mn) was 6820, and the weight average molecular weight (Mw) was 11,200. . Further, the acid value of this polymer compound was determined by titration. As a result, it was 102.5 mgKOH / g (calculated value 103.0 mgKOH / g), and it was confirmed that the polymerization was normally performed.

  10.3 g of the polymer compound obtained as described above is placed in a 100 ml three-necked flask, 0.01 g of p-methoxyphenol is added, and 50 g of 1-methyl-2-pyrrolidone is added and dissolved, and ice water is added. Cooled in an ice bath. After the temperature of the mixed solution became 5 ° C. or lower, 5 g of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) was further added dropwise using a dropping funnel over 10 minutes. After completion of the dropwise addition, the ice bath was removed and the mixture was further stirred for 8 hours. The obtained reaction liquid was adjusted to pH 7 by adding concentrated hydrochloric acid, and then poured into 300 mL of water to precipitate a polymer compound (specific graft polymer (I)). The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 8.62 g of the target specific graft polymer (I).

When ¹ H-NMR of the obtained polymer compound was measured, it was confirmed that 100% of the side chain groups derived from the 2-bromo-2-methylpropanoyloxy group were converted to methacryloyl groups. Furthermore, when the acid value of this polymer compound was determined by titration, it was 123.0 mgKOH / g (calculated value 123.3 mgKOH / g). The number average molecular weight (Mn) of the specific graft polymer (I) obtained by GPC measurement in terms of polystyrene was 5800, and the weight average molecular weight (Mw) was 8900. Further, the content of methacryloyl group in the side chain was examined by the following hydrolysis method, and it was confirmed that an average of 10 units was introduced per one branched polymer.

(Hydrolysis method)
0.1 g (solid) of the resulting polymer compound is precisely weighed into a 50 mL volumetric flask, 25 mL of 1-methoxy-2-propanol is added using a whole pipette and dissolved by ultrasound, and 2N NaOH solution is added. After the total volume was 50 mL, the solution was stirred at 25 ° C. for 2 hours. It was calculated that 0.021 g of methacrylic acid was generated by extrapolation from the peak area derived from methacrylic acid generated in HPLC. Thereby, the amount of ethylenically unsaturated bonds introduced into the obtained polymer compound was calculated to be 0.0024 mol / g.

[Synthesis Example 2: Synthesis of specific graft polymer (II)]
A specific synthesis method (steps 1 to 4) of the specific graft polymer (II) will be described using a reaction scheme shown below.

(Step 1: Synthesis of Compound (II-a))
In a 1 L three-necked flask, 210 g of 1-methyl-2-pyrrolidinone was substituted with nitrogen, heated to 80 ° C., then 25 g (250 mmol) of methyl methacrylate, 151 g (1.75 mol) of methacrylic acid, 3.9 g of mercaptoethanol ( 50 mmol), and a solution of 230 mg (1 mmol) of dimethyl 2,2′-azobis (2-methylpropionate) (trade name: V-601) in 210 g of 1-methyl-2-pyrrolidinone was added dropwise over 2 hours. After dropping, the mixture was stirred at 80 ° C. for 4.5 hours.
About this reaction liquid, it confirmed that the peak of the methyl methacrylate and methacrylic acid which are raw materials had disappeared by HPLC method, and left to cool to room temperature.
Then, reprecipitation refinement | purification was carried out by dripping the reaction liquid in 5 L of water. The precipitate was collected by filtration and dried to obtain 179 g of compound (II-a).
It was found that the number average molecular weight (Mn) of the compound (II-a) obtained by GPC measurement in terms of polystyrene was 2800, and the weight average molecular weight (Mw) was 4320. Further, the acid value of this polymer compound was determined by titration. As a result, it was 102.5 mgKOH / g (calculated value 103.0 mgKOH / g), and it was confirmed that the polymerization was normally performed. Further, the acid value of this polymer compound was determined by titration. As a result, it was 546 mgKOH / g (calculated value 546.2 mgKOH / g), and it was confirmed that the polymerization was normally performed.

(Step 2: Synthesis of macromonomer (II-b))
179 g of compound (II-a) was dissolved in 550 g of 1-methyl-2-pyrrolidinone, and bismuth tris (2-ethylhexanoate) (trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.)) 600 mg (0. 951 mmol) was added to make a homogeneous solution. The mixture was heated to 60 ° C., and 7.8 g (50 mmol) of 2-isocyanatoethyl methacrylate (trade name: Karenz MOI (manufactured by Showa Denko KK)) was added dropwise. After completion of dropping, the mixture was stirred at 60 ° C. for 6 hours.
As a result of measuring NMR for the reaction solution, it was confirmed that the urethanization reaction proceeded quantitatively from the change in the chemical shift derived from the proton of carbon bonded to the -NCO group of 2-isocyanatoethyl methacrylate. did.
Thereafter, 5 g of methanol was added to the reaction solution and allowed to cool to room temperature. The reaction solution was purified by reprecipitation by dropping it into a mixed solution of 290 mL of water and 1.1 L of methanol. The precipitate was collected by filtration and dried to obtain 187 g of macromonomer (II-b). It was found that the number average molecular weight (Mn) of the macromonomer (II-b) obtained by GPC measurement in terms of polystyrene was 2420, and the weight average molecular weight (Mw) was 4450.

(Step 3: Synthesis of graft polymer precursor (II-c))
A solution of 15 g (85 mmol) of benzyl methacrylate, 15 g (144 mmol) of styrene and 40 g of macromonomer (II-b) in 105 g of 1-methyl-2-pyrrolidinone was heated to 80 ° C., and dimethyl 2,2′-azobis (2 -Methylpropionate) (trade name: V-601) 552 mg (24 mmol) of 1-methyl-2-pyrrolidinone 10 g solution was added dropwise over 15 minutes. After dropping, the mixture was stirred at 80 ° C. for 3 hours. 552 mg (24 mmol) of dimethyl 2,2′-azobis (2-methylpropionate) (trade name: V-601) was added and stirred at 80 ° C. for 2 hours. The reaction solution was heated to 90 ° C., and further stirred for 30 minutes.
About the reaction liquid, it confirmed that the peak derived from benzyl methacrylate which is a raw material and styrene disappeared by HPLC method, and it stood to cool to room temperature.
Then, the high molecular compound was deposited by dripping the reaction liquid in 5 L of water. The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 70 g of a polymer compound.

  When the obtained polymer compound was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance, the number average molecular weight (Mn) was 21300, and the weight average molecular weight (Mw) was 37100. The acid value of this polymer compound was determined by titration to be 297 mgKOH / g (calculated value 297.9 mgKOH / g), confirming that polymerization was normally performed.

(Step 4: Synthesis of specific graft polymer (II))
70 g of the polymer compound obtained as described above was placed in a 500 mL three-necked flask, and 200 g of 1-methyl-2-pyrrolidone was added and dissolved. Further, 30 g (212 mmol) of glycidyl methacrylate and 0.2 g of p-methoxyphenol were added, and the mixture was heated to 85 ° C., and 1.7 g (0.7 mmol) of tetrabutylammonium bromide was further added. After the addition, the mixture was stirred at 85 ° C for 5 hours.
About the reaction liquid, it confirmed that the peak derived from the raw material glycidyl methacrylate disappeared by HPLC method, and it stood to cool to room temperature. The obtained reaction solution was diluted with 100 g of 1-methyl-2-pyrrolidone and then poured into 5 L of water to precipitate a polymer compound (specific graft polymer (II)). The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 98 g of the intended specific graft polymer (II). It was found that the number average molecular weight (Mn) of the graft polymer (II) obtained by GPC measurement in terms of polystyrene was 29500, and the weight average molecular weight (Mw) was 53100. Further, when the acid value of this polymer compound was determined by titration, it was 88.9 mgKOH / g (calculated value 89.3 mgKOH / g), and it was confirmed that the addition reaction of glycidyl methacrylate was normally performed. . Further, the content of methacryloyl group in the side chain was examined by the following hydrolysis method, and it was confirmed that an average of 20 units was introduced per one branched polymer.

(Hydrolysis method)
0.1 g (solid) of the resulting polymer compound is precisely weighed into a 50 mL volumetric flask, 25 mL of 1-methoxy-2-propanol is added using a whole pipette and dissolved by ultrasound, and 2N NaOH solution is added. After the total volume was 50 mL, the solution was stirred at 25 ° C. for 2 hours. It was calculated that 0.018 g of methacrylic acid was generated by extrapolation from the peak area derived from methacrylic acid generated in HPLC. Thereby, it was calculated that the ethylenically unsaturated bond introduction amount of the obtained polymer compound was 0.0021 mol / g.

[Synthesis Example 3: Synthesis of Comparative Polymer (X)]
In a 1000 ml three-necked flask, 120 g of propylene glycol monomethyl ether was added and heated to 90 ° C. under a nitrogen stream. To this was added dropwise 120 g of propylene glycol monomethyl ether solution of 74 g of benzyl methacrylate, 84 g of methacrylic acid, and 9.7 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) over 2 hours. After completion of dropping, the mixture was further stirred for 2 hours. Thereafter, the reaction solution was cooled to room temperature, and then poured into 8 L of water (liter; the same applies hereinafter) to precipitate a polymer compound. The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 150 g of a polymer compound.
As a result of measuring the mass average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 12,000. Further, when the acid value of this polymer compound was determined by titration, it was 202 mgKOH / g (calculated value 204 mgKOH / g), and it was confirmed that the polymerization was normally performed.

Thereafter, 40 g of the obtained polymer compound was added to a 1000 ml three-necked flask, 110 mg of p-methoxyphenol was added thereto, and 60 g of propylene glycol monomethyl ether was further added and dissolved. To this was further added 820 mg of tetrabutylammonium bromide, and after heating to 80 ° C., 10 g of glycidyl methacrylate was added and stirred for 6 hours. And it was confirmed by gas chromatography that the peak derived from glycidyl methacrylate disappeared. This reaction solution was poured into 7 L of water to precipitate a polymer compound (comparative polymer (X)). The precipitated polymer compound was collected by filtration, washed with water and dried to obtain 54 g of a comparative polymer (X).
The obtained polymer compound (Comparative Polymer (X)) was measured to have a mass average molecular weight of 17800 by gel permeation chromatography (GPC) using polystyrene as a standard substance. Furthermore, when the acid value of this polymer compound was determined by titration, it was 120 mgKOH / g.
The structure of the comparative polymer (X) is shown below.

Further, specific examples (III) to (IX) of the specific graft polymer (A) having the above structure were synthesized using the same method as in Synthesis Example 1 or Synthesis Example 2.
The physical properties of the obtained (A) specific graft polymers (I) to (IX) and the comparative polymer (X) are shown in Table 1 below.

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

[A1. Preparation of curable composition]
A1-1. Preparation of pigment dispersion C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 30/70 (mass ratio) mixture 40 parts by mass (primary grain size 32 nm), BYK2001 (Disperbyk: manufactured by BYK) (solid content concentration 45.1% by mass) 50 parts by mass (as a dispersant) (22.6 parts by mass in terms of solid content), (A) 5 parts by mass of the specific graft polymer (I), and 110 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed and dispersed by a bead mill for 15 hours. Thus, a pigment dispersion P1 was prepared.
For the pigment dispersion P1, the average particle diameter of the pigment was measured by a dynamic light scattering method (measured without further dilution of P1 using Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 61 nm. It was.

A1-2. Preparation of curable composition (coating liquid) Various components were stirred and mixed using the pigment dispersion liquid P1 subjected to the dispersion treatment so as to have the following composition ratio, thereby preparing a curable composition (coating liquid).
-(C) Colorant (Pigment dispersion P1) 600 parts by mass-(B) Photopolymerization initiator (2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- 1,2'-biimidazole) 30 parts by mass (E) Ethylene unsaturated double bond compound (pentaerythritol tetraacrylate) 50 parts by mass (F) Binder polymer (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate) Copolymer, molar ratio: 80/10/10, Mw: 10000) 5 parts by mass. (J) Solvent (PGMEA) 900 parts by mass. Substrate adhesion agent (3-methacryloxypropyltrimethoxysilane) 1 part by mass. D) 15 parts by mass of sensitizer (compound α below) 15 parts by mass of (H) co-sensitizer (2-mercaptobenzimidazole)

[A2. (Production of color filter)
A2-1. Formation of Colored Layer (Curable Composition Layer) A curable composition (coating solution) containing the above pigment as a resist solution was slit-coated on a 550 mm × 650 mm glass substrate under the following conditions, and then left as it was for 10 minutes. It was made to wait, vacuum drying and prebaking (100 degreeC80 second) were performed, and the colored layer (curable composition layer) was formed.

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

A2-2. Exposure and development Thereafter, the colored layer (curable composition layer) is exposed in a pattern using a test mask with a line width of 20 μm using a 2.5 kW ultra-high pressure mercury lamp, and then the entire surface of the layer is organic The sample was covered with a 10% aqueous solution of a system developer (trade name: CD, manufactured by FUJIFILM Electronics Materials Co., Ltd.) and allowed to stand for 60 seconds.

A2-3. Heat treatment After standing still, pure water was sprayed in a shower to wash away the developer, and the exposed and developed layer was heated in a 220 ° C. oven for 1 hour (post-baking). Thereby, a color filter formed by forming a colored pattern on the glass substrate was obtained.

[A3. (Performance evaluation)
Storage stability of the coating solution comprising the curable composition prepared above, exposure sensitivity of the colored layer (curable composition layer) coated on the glass substrate using the curable composition, unexposed part The developability, the substrate adhesion of the formed colored pattern, and the cross-sectional shape of the pattern were evaluated as follows. The results are shown in Table 2.

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

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

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

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

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

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

[Examples 2 to 9]
A color filter was prepared in the same manner as in Example 1 except that (A) the specific graft polymer (I) was changed to the specific graft polymer shown in Table 2 below in the curable composition prepared in Example 1. Then, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

[Comparative Example 1]
In the curable composition prepared in Example 1, a color filter was prepared in the same manner as in Example 1 except that (A) the graft polymer (I), which is a specific graft polymer, was not used. Similar evaluations were made. The results are shown in Table 2.

[Comparative Example 2]
In the curable composition prepared in Example 1, a color filter was prepared in the same manner as in Example 1 except that (A) the specific graft polymer (I) was changed to the comparative polymer (X) having the above structure. The same evaluation as in Example 1 was performed. The results are shown in Table 2.

From the results in Table 2, it can be seen that the curable compositions of Examples 1 to 9 containing (A) specific graft polymers (I) to (IX) are excellent in storage stability in the solution state. . Further, when a colored pattern is formed on a support (substrate) using this curable composition, it is compared with Comparative Example 2 using a comparative polymer (X) different from (A) the specific graft polymer. Thus, it can be seen that a color filter having high exposure sensitivity, excellent developability, and excellent substrate adhesion and pattern cross-sectional shape is obtained.
Note that (A) the curable composition of Comparative Example 1 in which the specific graft polymer was not used had insufficient curable properties and substrate adhesion at the exposed portion even when irradiated with an exposure amount of 100 mJ / cm ² , and the development process. As a result, all the colored layers were eluted in the developer.

[Example 10]
Hereinafter, an example of preparing a curable composition containing a colorant (pigment) for forming a color filter for use in a solid-state imaging device will be described.

[B1. Preparation of resist solution
Components of the following composition were mixed and dissolved to prepare a resist solution.
<Composition of resist solution>
-(J) Solvent (PGMEA) 19.20 parts by mass-(J) Solvent (ethyl lactate) 36.67 parts by mass-(F) Binder polymer (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate) 40% PGMEA solution of coalescence (molar ratio = 60/22/18)
30.51 parts by mass (E) Compound having ethylenically unsaturated double bond (dipentaerythritol hexaacrylate) 12.20 parts by mass (I) Polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass Fluorosurfactant (F-475, manufactured by Dainippon Ink & Chemicals, Inc.) 0.83 parts by mass (B) Photopolymerization initiator (trihalomethyltriazine photopolymerization initiator: TAZ-107, Midori Chemical Co., Ltd.) 0.586 parts by mass

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

[B3. Preparation of pigment dispersion
As a pigment, C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 30/70 (mass ratio) mixture 40 parts by mass (primary particle size 32 nm), as a dispersing agent BYK2001 (Disperbyk: BYK Corporation (BYK), solid content concentration 45.1% by mass) 50 parts by mass ( (22.6 parts by mass in terms of solid content), (A) 5 parts by mass of the specific graft polymer (I), and 110 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed and dispersed by a bead mill for 15 hours. Thus, a pigment dispersion P2 was prepared.
With respect to the pigment dispersion P2, the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 200 nm.

[B4. Preparation of curable composition (coating liquid)]
Various components were stirred and mixed using the pigment-dispersed liquid P2 subjected to the dispersion treatment to obtain the following composition ratio to prepare a curable composition (coating liquid).
(C) Colorant (Pigment dispersion P2) 600 parts by mass (B) Photopolymerization initiator (oxime photopolymerization initiator: CGI-124, manufactured by Ciba Specialty Chemicals) 30 parts by mass (E ) Compound having an ethylenically unsaturated double bond (TO-1382 (manufactured by Toagosei Co., Ltd.)) 25 parts by mass (E) Compound having an ethylenically unsaturated double bond (dipentaerythritol hexaacrylate) 30 parts by mass -(J) Solvent (PGMEA) 900 parts by mass-Substrate adhesion agent (3-methacryloxypropyltrimethoxysilane) 1 part by mass

[B5. Preparation and evaluation of color filter with curable composition]
<Evaluation of pattern formation and sensitivity>
The curable composition prepared as described above was prepared using the B2. The colored layer (curable composition layer) was formed on the undercoat layer of the silicon wafer with the undercoat layer obtained in (1). And the heat processing (prebaking) were performed for 120 second using a 100 degreeC hotplate so that the dry film thickness of this layer might be set to 0.7 micrometer.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at various exposure doses of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the colored layer is formed is placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics Material). Paddle development was carried out at 23 ° C. for 60 seconds to form a colored pattern on the silicon wafer substrate.

A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the center of rotation to the shower nozzle to perform a rinsing treatment, and then spray-dried.
Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure dose at which the pattern line width was 2 μm was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity. The measurement results are shown in Table 3 below.

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

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

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

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

<Color unevenness>
The color unevenness was evaluated by analyzing the luminance distribution by the following method and based on the ratio of the pixels whose deviation from the average is within ± 5% to the total number of pixels. The evaluation criteria are as follows.
A method for measuring the luminance distribution will be described. First, the curable composition is mixed with the B2. It applied on the undercoat layer of the glass plate with an undercoat layer obtained by the same method, and the colored layer (curable composition layer) was formed. Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm. The luminance distribution of this coated glass plate was analyzed using an image taken with a microscope MX-50 (Olympus).
-Evaluation criteria-
○: Pixels whose deviation from the average is within ± 5% is 99% or more of the total number of pixels Δ: Pixels whose deviation from the average is within ± 5% is 95% or more and less than 99% of the total number of pixels × : Pixels whose deviation from the average is within ± 5% is less than 95% of the total number of pixels

[Examples 11 to 18]
In the curable composition prepared in Example 10, a color filter was prepared in the same manner as in Example 10 except that (A) the specific graft polymer (I) was changed to the specific graft polymer shown in Table 3 below. Then, the same evaluation as in Example 10 was performed. The results are shown in Table 3.

[Comparative Example 3]
In the curable composition prepared in Example 10, a color filter in which a colored pattern was formed was obtained in the same manner as in Example 10 except that (A) the specific graft polymer (I) was not used. The same evaluation was performed. The results are shown in Table 3.

[Comparative Example 4]
In the curable composition prepared in Example 10, a color filter was prepared in the same manner as in Example 10 except that (A) the specific graft polymer (I) was changed to the comparative polymer (X) having the above structure. The same evaluation as in Example 10 was performed. The results are shown in Table 3.

From the results of Table 3, the curable compositions of Examples 10 to 18 containing (A) specific graft polymers (I) to (IX) used for forming a color filter for use in a solid-state imaging device were in the solution state. It can be seen that the storage stability is excellent. Further, when a colored pattern is formed on a support (substrate) using this curable composition, it is different from (A) Comparative Example 3 in which no specific graft polymer is used and (A) a specific graft polymer. Compared with Comparative Example 4 using the comparative polymer (X), the exposure sensitivity is high, the developability is excellent, and a color filter excellent in both substrate adhesion and pattern cross-sectional shape is obtained. I understand.
From these results, the curable compositions of Examples 10 to 18 are excellent in pattern formation even when producing a color filter for use in a solid-state imaging device, as in the case of producing a color filter for use in a liquid crystal display device. It was found that sex was realized.

[Example 19]
Hereinafter, an example of preparing a curable composition containing (dye) for forming a color filter for use in a solid-state imaging device will be described.

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

[C2. Preparation of curable composition (coating liquid)]
The compound of the following composition was mixed and melt | dissolved and the colored photosensitive resin composition was prepared.
-(J) Solvent (cyclohexanone) 80 parts by mass-(C) Colorant (Valifast Yellow 1101 (dye)) 6.0 parts by mass-(C) Colorant (Acid Red 57 (dye)) 6.0 parts by mass (E) Compound having ethylenically unsaturated double bond (dipentaerythritol hexaacrylate) 4.0 parts by mass (B) Photopolymerization initiator (oxime photopolymerization initiator: CGI-124, Ciba Specialty Chemicals) 2.0 parts by mass) (A) Specific graft polymer (I) 1.5% by mass

[C3. Preparation and evaluation of color filter with curable composition]
[B5. Production and evaluation of a color filter were carried out in the same manner as in [Production and evaluation of color filter by colored photosensitive resin composition]. The results are shown in Table 4.

[Examples 20 to 27]
A color filter was prepared in the same manner as in Example 19 except that (A) the specific graft polymer (I) was changed to the specific graft polymer described in Table 4 below in the curable composition prepared in Example 19. Then, the same evaluation as in Example 19 was performed. The results are shown in Table 4.

[Comparative Example 5]
In the curable composition prepared in Example 19, a color filter in which a colored pattern was formed was obtained in the same manner as in Example 19 except that (A) the specific graft polymer (I) was not used. The same evaluation was performed. The results are shown in Table 4.

[Comparative Example 6]
A color filter was prepared in the same manner as in Example 19 except that (A) the specific graft polymer (I) was changed to the comparative polymer (X) having the above structure in the curable composition prepared in Example 19. The same evaluation as in Example 19 was performed. The results are shown in Table 4.

From the results shown in Table 4, the curable compositions (dye systems) of Examples 19 to 27 containing (A) specific graft polymers (I) to (IX) used for forming a color filter for solid-state imaging devices were used. It can be seen that it is excellent in storage stability in the solution state. Further, when a colored pattern is formed on a support (substrate) using this curable composition, it is compared with Comparative Example 6 using a comparative polymer (X) different from (A) the specific graft polymer. Thus, it can be seen that a color filter having high exposure sensitivity, excellent developability, and excellent substrate adhesion and pattern cross-sectional shape is obtained.
Note that (A) the curable composition of Comparative Example 5 in which the specific graft polymer was not used had insufficient exposure part curability and substrate adhesion even when irradiated with an exposure amount of 1200 mJ / cm ^2. As a result, all the colored layers were eluted in the developer.
From these results, the curable compositions of Examples 19 to 27 are excellent in pattern formation even when producing a color filter for use in a solid-state imaging device, as in the case of producing a color filter for use in a liquid crystal display device. It was found that sex was realized.

Claims (8)

(A) a repeating unit derived from at least one monomer selected from (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile, and styrene, and different from the repeating unit represented by the following general formula (1A) A graft polymer that is a vinyl polymer containing a repeating unit represented by the following general formula (1A) and a repeating unit represented by the following general formula (1A): 50% by mass to 95% by mass hardening composition you.

[In the general formula (1A), R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, —COOH, —CN, —CF ₃ , —CH ₂ OH, —CH ₂ COOH, —CH ₂ COOR. ^a or -COOR ^b , X ¹ represents a divalent organic group, and Y is derived from a vinyl polymer containing 5 or more and 60 or less repeating units represented by the general formula (2A). Represents a polymer chain. In the general formula (2A), R ² and R ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, —COOH, —CN, —CH ₂ COOH, —CH ₂ COOR ^c , or —COOR ^d is represented, R ⁴ represents a hydrogen atom, a methyl group, or an ethyl group, and X ² represents a divalent organic group. R ^{a to} R ^d each independently represents a hydrocarbon group having 1 to 6 carbon atoms. ] The polymer chain represented by Y in the general formula (1A) is further derived from at least one monomer selected from (meth) acrylic acid, (meth) acrylic acid ester, and styrene, and the general formula (2A) The curable composition of Claim 1 containing the repeating unit different from the repeating unit represented by this. Furthermore, (B) The curable composition according to 請 Motomeko 1 or claim 2 you photopolymerization initiator. Further, (C) The curable composition according to any one of 請 Motomeko 1 to claim 3 you a colorant. Further, the curable composition according to any one of 請 Motomeko 1 to claim 4 you containing (D) a sensitizer. On a support, Luca color filter having a colored pattern formed by the curable composition according to any one of claims 1 to 5. A colored layer forming step of forming a colored layer comprising the curable composition by applying the curable composition according to any one of claims 1 to 5 on a support, and the colored layer exposure step and the developing step and the including color production method of filter for developing the colored layer after exposure to form a colored pattern to be exposed through a mask. A repeating unit derived from at least one monomer selected from (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile, and styrene, and different from the repeating unit represented by the following general formula (1A); The graft polymer which is a vinyl polymer containing 50 mass% or more and 95 mass% or less of repeating units represented by the following general formula (1A) including the repeating unit represented by Formula (1A) .

[In the general formula (1A), R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, —COOH, —CN, —CF ₃ , —CH ₂ OH, —CH ₂ COOH, —CH ₂ COOR. ^a or -COOR ^b , X ¹ represents a divalent organic group, and Y is derived from a vinyl polymer containing 5 or more and 60 or less repeating units represented by the general formula (2A). Represents a polymer chain. In the general formula (2A), R ² and R ³ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, —COOH, —CN, —CH ₂ COOH, —CH ₂ COOR ^c , or —COOR ^d is represented, R ⁴ represents a hydrogen atom, a methyl group, or an ethyl group, and X ² represents a divalent organic group. R ^{a to} R ^d each independently represents a hydrocarbon group having 1 to 6 carbon atoms. ]