JP4855200B2 - Curable composition, color filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition curing in extremely high sensitivity and having good preservation stability, a color filter having less development residues in an un-exposed part, excellent in the close adhesion with a substrate of an exposing part, and equipped with a color pattern of a desired cross sectional shape and a method for producing the color filter, excellent in productivity. <P>SOLUTION: This curable composition contains a compound expressed by general formula (I) [wherein, R<SP>1</SP>is an n-valent organic group; R<SP>2</SP>is H or a 1-4C alkyl; R<SP>3</SP>, R<SP>5</SP>are each independently H or methyl; X is -O-, -NH-, -NR<SP>4</SP>- or -S-; R<SP>4</SP>is H or a monovalent organic group; and (n) is 1-12 integer] and a photopolymerization initiator. The curable composition is preferably contains further a coloring agent. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  INDUSTRIAL APPLICABILITY The present invention can be used for image forming materials such as three-dimensional stereolithography, holography, color filters, photoresists, lithographic printing plates, and color proofs, and photocurable materials such as inks, paints, adhesives, coating agents, and dental materials. The present invention relates to a curable composition, a color filter using the curable composition, and a manufacturing method thereof.

  Conventionally, a curable composition containing a polyfunctional acrylate compound can be cured in an extremely short time by irradiation with active energy rays such as ultraviolet rays, and has excellent productivity. Widely used as image forming materials such as resists, lithographic printing plate materials and color proofs, inks, paints, adhesives, coating agents, dental materials and the like.

Examples of such polyfunctional acrylate compounds include polyethylene glycol diacrylate, trimethylol ethane triacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and hexane. Diol acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, acrylated after adding ethylene oxide or propylene oxide to polyfunctional alcohols such as glycerin and trimethylolethane , Urethane group-containing acrylates (see, for example, Patent Documents 1 to 4), polyester Le acrylates (e.g., see Patent Document 5-7) acrylate multifunctional such as an epoxy acrylate which is a reaction product of an epoxy resin with acrylic acid and can be exemplified mixtures thereof.
Furthermore, what is introduce | transduced as a photocurable monomer and an oligomer is mentioned (for example, refer nonpatent literature 1).

  In recent years, the demand for a curable composition has been further increased in the above applications, and there is a demand for one that cures with lower energy, one that cures faster, and one that forms a finer image. Among these, curable compositions for color filters, inks, and paints contain a dye that absorbs active energy rays such as ultraviolet rays, so that the surface is cured, but the interior is not sufficiently cured.

In color filter applications for solid-state imaging devices (CCD, CMOS, etc.), it is desired to further refine the pattern, and since a film thickness of 1.2 μm or less is required, a large amount in the curable composition In this case, the ratio of the polyfunctional acrylate tends to decrease. Also, in color filter applications for liquid crystal displays (LCDs), the substrate size is expanding for large TV production, and low energy curing is desired to improve productivity when using large substrates. . Further, the proportion of the pigment dispersant in the composition increases and the proportion of the polyfunctional acrylate tends to decrease as the pigment is refined to improve the contrast. Due to these factors, both solid-state imaging devices and LCDs have low sensitivity, sufficient curing cannot be obtained, insufficient adhesion to the substrate, color loss at the exposed areas, and desired pattern formation. There were also problems such as being extremely difficult.
Japanese Patent Laid-Open No. 5-170705 Japanese Patent Laid-Open No. 11-193325 JP 2000-239332 A Japanese Patent Application Laid-Open No. 2005-104842 JP-A-48-64183 Japanese Patent Publication No.49-43191 Japanese Patent Publication No.52-30490 Journal of Japan Adhesion Association Vol. 20, no. 7, p. 300-308

  The present invention has been made in view of the above problems, and provides a curable composition that cures with extremely high sensitivity and good storage stability, and further, a colorant that absorbs active energy rays. A color filter having high sensitivity in the contained curing system, little development residue in the unexposed area, excellent adhesion to the substrate in the exposed area, and a colored pattern having a desired cross-sectional shape, and productivity of the color filter It aims at providing the manufacturing method which was excellent in, and makes it a subject to achieve these objectives.

  The present inventors have found that a curable composition containing a specific polyfunctional acrylate compound has good sensitivity, and also provides sufficient curability even in a curable system containing a colorant. Specific means for solving the above problems will be described below.

<1> A compound represented by the following general formula (I), a compound containing an ethylenically unsaturated double bond, and a photopolymerization initiator, containing a compound represented by the following general formula (I) The content is 0.01 to 90% by mass with respect to the total solid content of the composition, and the content ratio of the compound represented by the following general formula (I) to the compound containing the ethylenically unsaturated double bond is The total solid content of the compound which is 0.001 to 100 on a mass basis and the content of the photopolymerization initiator is a compound containing the ethylenically unsaturated double bond and the compound represented by the following general formula (I) a curable composition Ru 0.01 to 50% by mass with respect.

[In General Formula (I), R ¹ represents an n-valent organic group. R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁵ each independently represents a hydrogen atom or a methyl group. X represents —O—, —NH—, —NR ⁴ —, or —S—, and R ⁴ represents a hydrogen atom or a monovalent organic group. n represents an integer of 5 to 12. ]

<2> A curable composition containing a compound represented by the following general formula (II) and a photopolymerization initiator.

[In General Formula (II), R ¹ represents an n-valent organic group, and R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁵ each independently represents a hydrogen atom or a methyl group. n represents an integer of 5 to 12. ]

<3> The curable composition according to <1> or <2>, wherein the general formula (I) or (II) includes a compound in which n is an integer of 5 to 9.

<4> In the general formula (I) or (II), n is an integer of 5 to 12, and the n-valent R ¹ has a (meth) acrylate group as a substituent. <1> It is a curable composition as described in any one of-<3>.

<5> In the general formula (I) or (II), R ¹ is an aliphatic residue or aromatic that may have any one or more of a heteroatom, an aromatic ring, and a heterocyclic ring in the structure. It is a curable composition as described in any one of said <1>-<4> which is a group residue or a heterocyclic residue.

<6> Urethane reaction of the compound represented by the general formula (I) or (II) with a compound having at least one hydroxy group in the molecule and 1,1- (bisacryloyloxymethyl) ethyl isocyanate It is a curable composition as described in any one of <1>-<5> obtained by these.

<7> The photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, Triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivatives thereof, cyclopentadiene-benzene-iron complex and salt thereof, halomethyloxadiazole compound, 3-aryl substituted coumarin compound, It is a curable composition as described in any one of said <1>-<6> characterized by including the at least 1 type compound chosen from the group which consists of.

<8> The photopolymerization initiator is a trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone It is a curable composition as described in any one of said <1>-<6> characterized by including the at least 1 type compound chosen from the group which consists of a type | system | group compound.

<9> The curable composition according to any one of <1> to <8>, wherein the curable composition further contains a sensitizer.

<10> The curable composition according to any one of <1> to <9>, wherein the curable composition further contains a colorant.

<11> The curable composition according to any one of <1> to <10>, wherein the curable composition further contains an alkali-soluble resin.

<12> The curable composition according to <11>, wherein the alkali-soluble resin is a (meth) acrylic resin.

<13> The curable composition according to <10>, wherein the colorant is an organic or inorganic pigment.

<14> The curable composition according to <13>, wherein the colorant is a pigment having a primary particle size of 80 nm or less.

<15> The curable composition according to <10>, wherein the colorant is a dye.

<16> The colorant is triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo Curing property as described in any one of <10> or <13> to <15> above, which is a pigment selected from a dye, an anilinoazo, a pyrazolotriazole azo, a pyridone azo, and an anthrapyridone It is a composition.

<17> The above <10> or <13>, wherein the curable composition contains at least one compound represented by the following general formulas (III) to (V) as the colorant. It is a curable composition as described in any one of-<16>.

In [formula (III), A represents the direction aromatic heterocyclic diazo residue of Component A-NH ₂ aryl groups or 5- to 6-membered. B ¹ and ^{B 2} are each ^{independently, -CR 3 =, - CR 4} =, or a nitrogen atom, ^{B 1} and ^{B 2} do not simultaneously represent a nitrogen atom. R ⁵ and R ⁶ each independently represents a hydrogen atom or a substituent. G, R ³ and R ⁴ each independently represents a hydrogen atom or a substituent. R ³ and R ⁴ and / or R ⁵ and R ⁶ may be bonded to each other to form a 5-membered or 6-membered ring. ]

[In General Formula (IV), R ^a1 , R ^a3 and R ^a4 each independently represent a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, or an aryl group having 6 to 21 carbon atoms. Represents an aralkyl group having 7 to 21 carbon atoms. R ^a3 and R ^a4 may form a heterocyclic ring together with the nitrogen atom bonded ^thereto . R ^a2 represents an alkyl group having 1 to 10 carbon atoms, a methoxymethyl group, or a trifluoromethyl group. ].

[In General Formula (V), R ^b1 represents a hydrogen atom or a substituent, R ^{b2 to} R ^b5 each independently represents a hydrogen atom or a substituent, and R ^b6 and R ^b7 each independently represent an alkyl group or an alkenyl. A group or an aryl group, and Za and Zb each independently represent ^—N═ or —C (R ^b8 ) ^═ . R ^b8 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ^b2 and R ^b3 , R ^b3 and R ^b6 , R ^b4 and R ^b5 , R ^b5 and R ^b7 and / or R ^b6 and R ^b7 are bonded to each other, and each is independently a 5-, 6-, or 7-member The ring may be formed. ]

<18> The mass ratio of the colorant in the solid content of the curable composition is 20% by mass or more, according to any one of the above <10> or <13> to <17> It is a curable composition.

<19> The mass ratio of the colorant in the solid content of the curable composition is 30% by mass or more, according to any one of the above <10> or <13> to <17> It is a curable composition.

<20> A color filter having a colored pattern formed using the curable composition according to any one of the above items <1> to <19> on a support.

<21> The color filter according to <20>, wherein the color filter has a thickness of 2.0 μm or less.

<22> The color filter according to <20>, wherein the color filter has a thickness of 1.0 μm or less.

<23> The color filter according to <20>, wherein the color filter has a thickness of 0.7 μm or less.

<24> A colored layer forming step of forming a colored curable composition layer by applying the curable composition according to any one of the above <1> to <19> on a support, and the colored curing A method for producing a color filter, comprising: an exposure step of pattern-exposing the photosensitive composition layer through a mask; and a development step of developing the colored curable composition layer after exposure to form a colored pattern. is there.
This manufacturing method may include a step of curing the pattern by heating and / or exposure as necessary, or may repeat these steps a plurality of times.
Further, a color filter having a coloring pattern composed of a plurality of colors may be formed by changing the dye.

  According to the present invention, it is possible to provide a curable composition that cures with extremely high sensitivity and also has good storage stability. Furthermore, according to the present invention, high sensitivity is exhibited even in a curing system containing a dye that absorbs active energy rays, the development residue in the unexposed area is small, the adhesion between the exposed area and the substrate is excellent, and the desired cross section is obtained. It is possible to provide a color filter having a colored pattern and a manufacturing method excellent in productivity of the color filter.

The curable composition of the present invention contains a compound represented by the general formula (I) (hereinafter sometimes referred to as “specific compound according to the present invention” or simply “specific compound”) and a photopolymerization initiator. In addition, other components such as a sensitizer, a colorant, a coating solvent, and an alkali-soluble resin can be contained as necessary.
Hereinafter, the compound represented by the general formula (I) may be referred to as “specific compound according to the present invention” or simply “specific compound”. Moreover, the curable composition containing a colorant may be referred to as a “colored curable composition”.
First, the specific compound according to the present invention will be described in detail.
<Compound represented by formula (I)>
The curable composition of this invention contains the compound represented by the following general formula (I).

In general formula (I), R ¹ represents an n-valent organic group, and R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁵ each independently represents a hydrogen atom or a methyl group. X represents —O—, —NH—, —NR ⁴ —, or —S—, and R ⁴ represents a hydrogen atom or a monovalent organic group. n represents an integer of 5 to 12. X is preferably -O-, and the general formula (I) is represented by the following general formula (II).

In general formula (II), R ¹ represents an n-valent organic group, and R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁵ each independently represents a hydrogen atom or a methyl group. n represents an integer of 5 to 12.
Examples of R ^{2 in} the general formulas (I) and (II) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group, preferably a hydrogen atom, a methyl group, and an ethyl group, and more A methyl group is preferred. R ³ and R ⁵ are preferably a hydrogen atom. Further, n represents preferably an integer of 5-9.

  The compound represented by the general formula (I) has, for example, a compound having at least one hydroxy group, primary amino group, secondary amino group, or thiol group in the molecule and two acrylates in the molecule. It can be obtained by urethanation reaction with monoisocyanate, urea reaction, or thiourethane reaction.

R ¹ in the general formulas (I) and (II) is an aliphatic residue or an aromatic residue of a compound having at least one hydroxy group, primary amino group, secondary amino group, or thiol group in the molecule. Or a heterocyclic residue, or an aliphatic residue having a heteroatom, an aromatic ring, or a heterocyclic ring in the molecule.

  The “aliphatic residue” is an aliphatic compound having at least one hydroxy group, primary amino group, secondary amino group, or thiol group in the molecule as a raw material when the specific compound according to the present invention is synthesized. Represents an aliphatic group obtained by removing the “hydroxy group, primary amino group, secondary amino group, or thiol group that reacts with an isocyanate compound during urethane bond formation reaction” from the structure of this raw material compound, It may be substituted or may have a substituent. (When it has two or more substituents, these substituents may be the same or different.)

  The “substituent” may be any group that can be substituted, such as an aliphatic group, aromatic group, heterocyclic group, halogen atom, hydroxy 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 sulfonamide group, aromatic sulfonamide group, heterocyclic sulfonamide group, acyl group, acyloxy group, acylamino group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, aliphatic oxy Carbonylamino group, aromatic oxycarbonylamino group, heterocyclic oxycarbonylamino group, aliphatic thiocarbonylamino group, aromatic Ocarbonylamino group, heterocyclic thiocarbonylamino group, aliphatic aminocarbonylamino group, aromatic aminocarbonylamino group, heterocyclic aminocarbonylamino group, carbamoyl group, carbamoyloxy group, carbamoylamino group, aliphatic sulfonyl group, aromatic 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 Group, heterocyclic oxycarbonyloxy group, sulfamoyloxy group, aliphatic sulfonyloxy group, aromatic sulfonyloxy group, anilino group, aliphatic azo group, aromatic azo group, heterocyclic azo group, aliphatic sulfinyl group, An aromatic sulfinyl group, It represents a heterocyclic sulfinyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, a heterocyclic sulfonyloxy group, a sulfamoyl group, a sulfo group, a phosphonyl group, a phosphonic acid group or phosphinoylamino group.

Among them, preferred substituents are 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 groups. , 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 aminocarbonylamino group, carbamoyl Group, aliphatic sulfonyl group, aromatic sulfonyl group, silyl group, aliphatic oxysilyl group, silyl group Alkoxy 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 and a phosphonyl group or a phosphonic group.

  More preferred substituents are aliphatic groups, aromatic groups, heterocyclic groups, halogen atoms, hydroxyl groups, thiol groups, (meth) acryloyl groups, carboxy groups, amino groups, aliphatic groups, particularly from the viewpoint of sensitivity and solubility. Aromatic amino group, aromatic 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 An aliphatic oxysilyl group, an aliphatic carbonyloxy group, an aliphatic oxycarbonyloxy group, an aliphatic sulfonyloxy group, a sulfo group, or a phosphone group.

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 may have the substituents mentioned in the explanation of the above “substituent”, and when it has two or more substituents, those substituents may be the same or different. It may be. 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 number 1-16, 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, adamantyl group, adamantylmethyl More preferably a group, 1- (1-adamantyl) ethyl group, 3,5-dimethyladamantyl group, quinuclidinyl group, cyclopentylethyl group, or bicyclooctyl group,

  Further, 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, a heptafluoropropyl group, Nonafluorobutyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, heptadecafluorooctyl group, tridecafluorooctyl group, nonadecafluorononyl group, heptadecafluorodecyl group, or perfluorodecyl group are preferable. Among these, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a tridecafluorohexyl group, and a pentadecafluoroheptyl group are more preferable, and further a trifluoromethyl group and a pentafluoroethyl group Heptafluoropropyl group, a nonafluorobutyl group or a tridecafluorohexyl group, is 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. An alkenyl group having 2 to 16 carbon atoms is more preferable, and an alkenyl group having 2 to 10 carbon atoms is 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, especially isocyanuric ring, epoxy Ring, tetrahydrofuran ring, tetrahydropyran ring, tetrahydrothiophene ring, pyrrolidine ring, piperidine ring, morpholine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, oxygen Tetrazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a lactone ring.

  The “aromatic residue” means that when an aromatic compound having at least one hydroxy group in the molecule is used as a raw material for synthesizing a specific compound, the structure of this raw material compound indicates “at the time of urethane bond formation reaction”. It represents an aromatic group excluding a “hydroxy group that reacts with an isocyanate compound” and may be unsubstituted or may have a substituent. (When it has two or more substituents, these substituents may be the same or different.)

  The above-mentioned “heterocyclic residue” means that, when a heterocyclic compound having at least one hydroxy group in the molecule is used as a raw material for the synthesis of a specific compound, “urethane bond formation” It represents a heterocyclic group excluding the “hydroxy ring group that reacts with an isocyanate compound during the reaction” and may be unsubstituted or may have a substituent. (When it has two or more substituents, these substituents may be the same or different.)

  The “aliphatic residue having a heteroatom, an aromatic ring, or a heterocycle in the molecule” means that it has at least one hydroxy group in the molecule as a raw material when synthesizing the specific compound according to the present invention, When an aliphatic compound having a heteroatom, aromatic ring, or heterocycle in the molecular structure is used, a residue obtained by removing the “hydroxy group that reacts with an isocyanate compound during urethane bond formation reaction” from the structure of this raw material compound It may be unsubstituted or may have a substituent. (When it has two or more substituents, these substituents may be the same or different). As a hetero atom, an oxygen atom, a sulfur atom, or a nitrogen atom is preferable, and an oxygen atom or a nitrogen atom is more preferable.

In the general formula (I), when X is —NR ⁴ —, R ⁴ is a hydrogen atom, or an ether bond, amino bond, thioether bond, or a hydrocarbon ring structure having 3 to 10 carbon atoms in the structure; It may have a partial structure selected from the group consisting of an aromatic ring, a heterocyclic ring, a urethane bond, a thiourethane bond, an ester bond, an amide bond, a urea bond, or a thiourea bond, and is saturated or unsaturated. The C1-C50 hydrocarbon residue which may be represented. The hydrocarbon residue may further have a substituent. If having a substituent, the substituent has the same meaning as the "substituent" described in R ¹ in the general formula (I) and (II), is the same and preferred examples thereof.

Among the compounds represented by the general formula (I), the “compound having at least one hydroxy group in the molecule” used as a starting material for the compound in which X is —O— is not particularly limited. For example, methanol, ethanol, propanol, butanol, pentanol, octanol, decyl alcohol, dodecanol, neopentyl alcohol, ethylene glycol, propanediol, neopentyl glycol, butanediol, hexanediol, octanediol, cyclopentanediol, cyclohexanediol, 4,4-isopropylidenedicyclohexanol, 1,3,5-cyclohexanetriol, cyclooctanediol, norbornanediol, decalindiol, inositol, 2- (hydroxymethyl) -1,3 Propanediol, threitol, glycerol, erythritol, adonitol, arabitol, xylitol, sorbitol, mannitol, iditol, dulcitol, ribose, xylose, galactose, glucose, sucrose, lactose, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,3 5-tris (2-hydroxyethyl) -cyanuric acid, hydroquinone, catechol, resorcinol, phloroglucinol, dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bisphenol A, 1,4-benzenedimethanol, dihydroxybenzophenone, flange Methanol, hydroxyindole, (hydroxymethyl) ethylene carbonate, dihydroxypyridine, Hydroxy pyridazine, cyanuric acid, dihydroxy pyrimidine,

2- (methylthio) ethanol, ethyl 2-hydroxyethyl sulfide, 3- (methylthio) -1-propanol, 4- (methylthio) -1-butanol, 3- (methylthio) -1-hexanol, 2,2′-thio Diethanol, 2-hydroxyethyl disulfide, 3,6-dithia-1,8-octanediol, 3,3′-thiodipropanol, 3-methylthio-1,2-propanediol, 3-ethylthio-1,2-propane Diol, D-glucose diethyl mercaptal, 1-thio-β-D-glucose, sodium salt dihydrate, trans-1,2-dithian-4,5-diol, 1,5-dithiacyclooctane-3-ol 1,4-dithiaspiro (4.5) decan-8-ol, 1,4-dithian-2,5-diol Triethanolamine, 2-amino-2-methyl-1,3-propanediol, bis-homotris, N, N, N ′, N′-tetrakis (2-hydroxypropyl) -ethylenediamine, 1,3-bis [tris (Hydroxymethyl) -methylamino] propane, (R)-(+)-3-pyrrolidinol, 1- [2- (2-hydroxyethoxy) ethyl] -piperazine, 4- (2-hydroxyethyl) morpholine, or publication Examples include various diols described in JP-A-2005-326556, which may be unsubstituted or may have a substituent. When it has two or more substituents, they may be the same or different.

Among the compounds represented by the general formula (I), the “compound having at least one primary amino group in the molecule” used as a raw material for the compound in which X is —NH— is not particularly limited. For example, n-alkylamine having 1 to 32 carbon atoms, 1,3-dimethylbutylamine, methylamine, methylamine hydrochloric acid, methylamine- ^13C hydrochloric acid, methylhydrazine, ethylamine, ethylamine hydrochloric acid, propylamine, propylamine hydrochloric acid, Butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, 1-tetradecylamine, pentadecylamine, 1-hexadecylmian, octadecylamine, isopropylamine, sec-buchi Amine, (S)-(+)-sec-butylamine, (R)-(−)-sec-butylamine, isobutylamine, tert-butylamine, tert-butylhydrazine hydrochloride, 1-methylbutylamine, 1-ethylpropylamine, (S)-(−)-2-methylbutylamine, 2-methylbutylamine, isoamylamine, 1,2-dimethylpropylamine, tert-amylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-amino Heptane, 3-aminoheptane, 1-methylheptylamine, 2-ethylhexylamine, 1,5-dimethylhexylamine, tert-octylamine,

Ethylenediamine, ethylenediaminedihydrochloric acid, 1,3-diaminopropane, 1,3-diaminopropanedihydrochloric acid, 1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino-2-methylpropane, DYTEK EP diamine 1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, hexamethylenediamine, DYTEK A amine, 1,7-diaminoheptane, 1,8-diaminooctane, C, C, C-trimethyl -1,6-hexanediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, N, N-dimethylmethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine N- (2-aminoethyl) -1,3-propanediamine, , 3′-diamino-N-methyldipropylamine, N- (3-aminopropyl) -1,3-propanediamine, spermidine, 4- (aminomethyl) -1,8-octanediamine, tris (2-amino Ethyl) amine, (aminomethyl) cyclopropane, cyclobutylamine, cyclopentylamine, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, cyclohexylamine, 4,4′-methylenebis (cyclohexyl-amine) 4,4′-methylenebis (2-methylcyclohexylamine), 1,2-diaminocyclohexane, trans-1,4-diaminocyclohexane, cyclohexanemethylamine, 1,3-cyclohexanebis (methylamine), cyclooctylamine, EXO-2-aminonorbornane 1-adamantanamine, 2,2 '-(ethylenedioxy) -bis (ethylamine), 4,7,10-trioxa-1,13-tridecanediamine, tetrahydrofurfurylamine,

Ethanolamine, 3-amino-1-propanol, 4-amino-1-butanol, 1,4-bis (3-aminopropyl) piperazine, 4- (2-aminoethyl) morpholine, aniline, 3-aminothiophenol, 4,4'-ethylenedianiline, 3,3'-methylenedianiline, 4,4'-methylenedianiline, 4,4'-oxydianiline, 4-aminophenol, 4,4'-thiodianiline, o- Tolidine, 5,5 ′-(hexafluoroisopropylidene) -di-o-toluidine, 3,5-bis (trifluoromethyl) -aniline, 4,4′-methylenebis (2,6-diethylaniline), 4, 4′-diaminooctafluorobiphenyl, 1,3-phenylenediamine, 1,4-phenylenediamine, pararosaniline base, 2, -Diaminonaphthalene, binaphthyl-2,2'-diamine, meso-1,2-bis (4-methoxyphenyl) -ethylenediamine, 2- [2- (aminomethyl) phenylthio] benzyl alcohol, m-xylylenediamine, p -Xylylenediamine etc. are mentioned, These may be unsubstituted or may have a substituent. When it has two or more substituents, they may be the same or different.

Among the compounds represented by the general formula (I), the “compound having at least one secondary amino group in the molecule” used as a raw material for the compound in which X is —NR ⁴ — is not particularly limited. For example, dimethylamine, 1,1-dimethylhydrazine, N-ethylmethylamine, diethylamine, N-methylpropylamine, N-methylisopropylamine, N-ethylisopropylamine, dipropylamine, diisopropylamine, N- Methylbutylamine, N-ethylbutylamine, N-methyl-tert-butylamine, N-tert-butylisopropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, tert-amyl-tert-butylamine, dipentylamine, N-methyl Hexylamine, di Hexylamine, tert- amyl -tert- octylamine, di-octylamine, bis (2-ethylhexyl) amine, didecylamine, N- methyl octadecylamine,

N-methylethylenediamine, N-ethylethylenediamine, N-propylethylenediamine, N-isopropylethylenediamine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-diisopropylethylenediamine, N, N, N ′ -Trimethylethylenediamine, N, N-dimethyl-N'-ethylethylenediamine, N, N-diethyl-N'-methylethylenediamine, N, N, N'-triethylethylenediamine, N, N, N ', N'-tetramethyl Ethylenediamine, N-methyl-1,3-propanediamine, N-propyl-1,3-propanediamine, N-isopropyl-1,3-propanediamine, N, N′-diethyl-1,3-propanediamine, N , N′-Diisopropyl-1,3- Lopandiamine, N, N, N′-trimethyl-1,3-propanediamine, N, N′-dimethyl-1,6-hexanediamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-isopropylcyclohexylamine, N-tert-butylcyclohexylamine, dicyclohexylamine, (1S, 2S) -N, N′-bis (3,3-dimethylbutyl) -1,2-cyclohexanediamine, diallylamine, N-allylcyclopentylamine, allylcyclohexylamine Bis (2-methoxyethyl) amine, diphenylamine, N-phenylbenzylamine, 1,2-dianilinoethane, etc., which may be unsubstituted or may have a substituent. When it has two or more substituents, they may be the same or different.

  Among the compounds represented by the general formula (I), the “compound having at least one thiol group in the molecule” used as a raw material of the compound in which X is —S— is not particularly limited. For example, methanethiol, ethanethiol, 1-propanethiol, 1-butanethiol, 1-pentanethiol, 1-hexanethiol, heptyl mercaptan, 1-octanethiol, nonyl mercaptan, 1-decanethiol, 1-dodecanethiol, hexa Decyl mercaptan, octadecyl mercaptan, 2-methyl-1-propanethiol, 2-methyl-1-butanethiol, 3-methyl-1-butanethiol, 2-propanethiol, 1-methyl-1-propanethiol, 2-methyl 2-propanethiol, 2-methyl-2-butanethio , Allyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexane Dithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2,2,2-trifluoroethanethiol, 3-chloro-1-propanethiol, 2-mercaptoethanol, 1-mercapto-2-propanol, 3 -Mercapto-1-propanol, 3-mercapto-2-butanol, 3-mercapto-1,2-propanediol, 2,3-dimercapto-1-propanol, dithiothreitol, dithioerythritol, 1,4-dithio-L -Threitol, 2-mercap Ethyl ether, 2-mercaptoethyl sulfide, furfuryl mercaptan, thiophenol, thiocresol, ethylthiophenol, benzyl mercaptan, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, Bicyclo [2,2,1] hepta-exo-cis-2,3-dithiol,

1,1-bis (mercaptomethyl) cyclohexane, diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), Ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis ( 3-mercaptopropionate),

1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 1,2-bis (2-mercaptoethyl) benzene, 1,3-bis (2-mercaptoethyl) benzene, 1,4-bis (2-mercaptoethyl) benzene, 1,2- Bis (2-mercaptoethyleneoxy) benzene, 1,3-bis (2-mercaptoethyleneoxy) benzene, 1,4-bis (2-mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1, 2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene,

1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (2-mercapto Ethyl) benzene, 1,2,4-tris (2-mercaptoethyl) benzene, 1,3,5-tris (2-mercaptoethyl) benzene, 1,2,3-tris (2-mercaptoethyleneoxy) benzene, 1,2,4-tris (2-mercaptoethyleneoxy) benzene, 1,3,5-tris (2-mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3 5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1, , 3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyl) benzene, 1,2,3 5-tetrakis (2-mercaptoethyl) benzene, 1,2,4,5-tetrakis (2-mercaptoethyl) benzene, 1,2,3,4-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2, 3,5-tetrakis (2-mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (2-mercaptoethyleneoxy) benzene, 2,2′-dimercaptobiphenyl, 4,4′-thiobis-benzenethiol 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4 Toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene -1,3-dithiol, 9,10-anthracene dimethanethiol,

2-bis (2-mercaptoethylthio) benzene, 1,3-bis (2-mercaptoethylthio) benzene, 1,4-bis (2-mercaptoethylthio) benzene, 1,2-bis (2-mercaptoethyl) Thiomethyl) benzene, 1,3-bis (2-mercaptoethylthiomethyl) benzene, 1,4-bis (2-mercaptoethylthiomethyl) benzene, 1,2,3-tris (2-mercaptoethylthio) benzene 1,2,4-tris (2-mercaptoethylthio) benzene, 1,3,5-tris (2-mercaptoethylthio) benzene, 1,2,3,4-tetrakis (2-mercaptoethylthio) benzene 1,2,3,5-tetrakis (2-mercaptoethylthio) benzene, 1,2,4,5-tetrakis (2-mercaptoethylthio) benzene Zen, bis (2-mercaptoethyl) sulfide, bis (2-mercaptoethylthio) methane, 1,2-bis (2-mercaptoethylthio) ethane, 1,3-bis (2-mercaptoethylthio) propane, , 2,3-tris (2-mercaptoethylthio) propane, tetrakis (2-mercaptoethylthiomethyl) methane, 1,2-bis (2-mercaptoethylthio) propanethiol, 2,5-dimercapto-1,4 -Dithiane, bis (2-mercaptoethyl) disulfide, 3,4-thiophenedithiol, 1,2-bis (2-mercaptoethyl) thio-3-mercaptopropane, bis- (2-mercaptoethylthio-3-mercaptopropane) ) Sulfides and the like. These may be unsubstituted or may have a substituent. When it has two or more substituents, they may be the same or different.

As the monoisocyanate compound having two acrylates, specifically, 1,1- (bisacryloyloxymethyl) ethyl isocyanate is used.

Specific examples of the following polyfunctional acrylate compound (I-1) ~ (I -62), the polyfunctional acrylate compound represented by the general formula (I), of which specific examples (I-6), ( I-7), (I-10), (I-12), (I-13), (I-22), (I-24), (I-26), (I-28), (I- 30), (I-49), and (I-50). The present invention is not limited by these.

  Next, a method for preparing the compound represented by the general formula (I) will be described.

  Among the compounds represented by the general formula (I), in order to obtain a compound in which X is —O—, in particular, in the molecule relative to the hydroxy group of the compound having at least one hydroxy group in the molecule. It is prepared so that the molar ratio of the isocyanate group of the monoisocyanate having two acrylates is 0.7 to 1.5, preferably 0.8 to 1.3, more preferably 0.9 to 1.2, most Preferably, it is adjusted to 0.95 to 1.1. If it is less than 0.7, the proportion of products having unreacted hydroxy groups increases, and purification may be difficult. On the other hand, when the ratio is larger than 1.5, an undesirable side reaction may proceed even after the completion of the reaction to cause gelation.

  Further, among the compounds represented by the general formula (I), in particular, in order to obtain a compound in which X is —NH—, the primary amino group of a compound having at least one primary amino group in the molecule is used. The molar ratio of the isocyanate group of the monoisocyanate having two acrylates in the molecule is adjusted to 0.7 to 1.5, preferably 0.8 to 1.3, more preferably 0.9 to 1. .2, most preferably 0.95 to 1.1. If it is less than 0.7, the ratio of the product having unreacted primary amino groups increases, which may make purification difficult. On the other hand, when the ratio is larger than 1.5, an undesirable side reaction may proceed even after the completion of the reaction to cause gelation.

Similarly, among the compounds represented by the general formula (I), in order to obtain a compound in which X is —NR ⁴ — in particular, a secondary amino group of a compound having at least one secondary amino group in the molecule is used. The molar ratio of the isocyanate group of the monoisocyanate having two acrylates in the molecule to the group is adjusted to 0.7 to 1.5, preferably 0.8 to 1.3, more preferably 0. .9 to 1.2, most preferably 0.95 to 1.1. If it is less than 0.7, the ratio of the product having unreacted secondary amino groups increases, and purification may be difficult. On the other hand, when the ratio is larger than 1.5, an undesirable side reaction may proceed even after the completion of the reaction to cause gelation.

  Furthermore, among the compounds represented by the general formula (I), in order to obtain a compound in which X is -S-, in particular, the molecule is compared with the thiol group of the compound having at least one thiol group in the molecule. It is prepared so that the molar ratio of the isocyanate group of the monoisocyanate having two acrylates therein is 0.7 to 1.5, preferably 0.8 to 1.3, more preferably 0.9 to 1.2. Most preferably 0.95 to 1.1. If it is less than 0.7, the proportion of products having unreacted thiol groups increases, and purification may become difficult. On the other hand, when the ratio is larger than 1.5, an undesirable side reaction may proceed even after the completion of the reaction to cause gelation.

The catalyst used in the urethanization reaction, amidation reaction, or thiourethanation reaction is not particularly limited, but preferably bismuth tris (2-ethylhexanoate), dibutyltin dilaurate, dibutyltin acetate, dibutyltin. Organic tin (meth) acrylates such as dichloride, tin octylate, organic zinc (meth) acrylates such as zinc octylate and zinc naphthenate, tertiary amines such as triethylenediamine and triethylamine, or 1,8-diazabicyclo [5, (Meth) acrylate having an amidine skeleton such as 4,0] undecene-7 is used and added in an amount of 0.0001 to 10 parts by mass with respect to 100 parts by mass of thiol or isocyanate.

  In the above reaction, a temperature range of −50 ° C. to 100 ° C. is usually applied. Below -50 ° C, the progress of the reaction is extremely slow. Above 100 ° C, by-products are increased and the yield is lowered. Dilute with solvent if necessary. Solvents used can be used except alcohols, carboxylic acids, amines and the like that react with isocyanates. From the viewpoint of reaction rate and solubility, acetonitrile, N, N-dimethylformamide (DMF), N, A polar solvent such as N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), or N-methyl-2-pyrrolidone (NMP), a chlorinated solvent such as chloroform, or an aromatic solvent such as toluene or xylene is preferably used. . A dehydrated solvent is preferably used to prevent the reaction between residual water and isocyanate.

  In order to prevent an undesirable side reaction (acrylate polymerization reaction) during the urethanization reaction, it is preferable to add a polymerization inhibitor. As the polymerization inhibitor to be used, quinones such as hydroquinone and benzoquinone, phenols such as p-methoxyphenol, N-nitrosophenylhydroxylamine salts and the like are used.

The curable composition of this invention can use the compound represented by the said general formula (I) individually or in combination of 2 or more types.
Content of the said specific compound in the curable composition of this invention is 0.01-90 mass% with respect to the total solid of this composition from the point of a sensitivity and developability, 0.1-70 % By mass is more preferable, and 0.5 to 50% by mass is particularly preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The content of the compound containing an ethylenically unsaturated double bond other than the specific compound is preferably 1% by mass to 90% by mass in the solid content of the curable composition of the present invention, and 5% by mass to 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 containing an ethylenically unsaturated double bond other than the specific compound is 5% by mass to 50% in the above range. The mass is preferably 7% by mass, more preferably 7% by mass to 40% by mass, and still more preferably 10% by mass to 35% by mass.

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

<Photopolymerization initiator>
The curable composition of the present invention contains a photopolymerization initiator in addition to the specific compound. The photopolymerization initiator that can be used in the curable composition of the present invention is a compound that can cause a radical-generating chemical reaction to light such as UV, Deep UV, visible light, infrared light, and electron beam. The radical (initiating species) generated by this compound acts on the binder described later coexisting in the curable composition layer made of the curable composition to be insolubilized by reactions such as crosslinking, polymerization, decomposition of acidic groups, etc. Or by causing a reaction such as polymerization of a polymerizable monomer or oligomer described later coexisting in the curable composition layer or crosslinking of a crosslinking agent to proceed and proceed with the alkali developer. Used for insolubilization.
Examples of radiation-sensitive compounds that can cause chemical reactions such as acid generation and base generation by radiation include photoacid generators and photobase generators in addition to the photopolymerization initiators. In order to cause and accelerate the polymerization reaction of the polyfunctional acrylate compound, it is preferable to use a photopolymerization initiator.

  The photopolymerization initiator is not particularly limited as long as it can polymerize the polyfunctional acrylate compound of the present invention and the polymerizable monomer, depending on the starting species generated from the initiator, but the characteristics, initiation efficiency, absorption wavelength, availability It is preferable to be selected from the viewpoint of cost and the like. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyl oxadiazole compound, a halomethyl-s-triazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acyl. Phosphine compounds, phosphine oxide compounds, metallocene compounds, 3-aryl-substituted coumarin compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes And salts thereof, or oxime compounds.

  Examples of active halogen compounds such as halomethyloxadiazole include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl-5, and the like. -Styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, and 2-trichloromethyl-5- (p-methoxystyryl) ) -1,3,4-oxadiazole and the like.

  As photopolymerization initiators of halomethyl-s-triazine compounds, vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho-) described in JP-A-53-133428 are disclosed. 1-yl) -4,6-bis-halomethyl-s-triazine compounds and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compounds.

Other specific examples include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl) -1,3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1 -P-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4, 6-bis-trichloromethyl-s-triazine, 2,4-trichloromethyl (piphenyl) -6-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloro Methyl -s- triazine,
2- (4-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl- s-triazine, 2- [4- (2-methoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphtho 1-yl] -4,6-bis-trichloromethyl-s-triazine,

  2- [4- (2-Butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6- Bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2) -Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7 -Dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimension Xyl-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, N -Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (PN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6-di (trichloro Methyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN , N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonyl) Til) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro -PN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) amino Phenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) ) -S-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-p- N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine,

  4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di ( Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s- Triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl) ) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Til) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-) Ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s- Triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-tri 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine and the like can be mentioned.

  Other commercially available products that can be used as photopolymerization initiators include TAZ series, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, and TAZ manufactured by Midori Chemical. -123, PANCHIM T series, T-OMS, T-BMP, T-R, TB, Ciba Geigy Irgacure series, Irgacure 369, Irgacure 784, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261, Darocur Series, Darocur 11734, 4′-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2- Oh Tandione, 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, 2,2-dimethoxy-2-phenylacetophenone, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o -Fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer 2-mer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercapto Phenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, etc. are also useful.

Other known photopolymerization initiators other than the photopolymerization initiator can be used in combination with the curable composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triallylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound disclosed in Japanese Patent Publication No. 51-48516 / Triha And lomethyl-s-triazine compounds.

Content in the curable composition of a photoinitiator is 0.01-50 mass% with respect to the total solid of the polyfunctional acrylate compound of this invention, and the said polymerizable monomer , and 1-40 mass%. Is more preferable, and 1 to 30% by mass is particularly preferable. When the content is less than 0.01% by mass, the polymerization is difficult to proceed. When the content exceeds 50% by mass, the polymerization rate increases, but the molecular weight may decrease and the film strength may be weakened.

<Sensitizer>
In the curable composition of the present invention, a sensitizer or a light stabilizer may be used in combination with the use of the photopolymerization initiator for the purpose of improving radical generation efficiency and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, those that sensitize the above-mentioned photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism are preferable.
Specific examples of sensitizers and light stabilizers include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, and 2-bromo-9-. Anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, Xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzalacetone, p- (dimethylamino) ) Phenylstyryl ketone, p- (dimethylamino) phenyl p-methylstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone and the like, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400 and the like.

Moreover, the sensitizer which belongs to the compounds enumerated below and has an absorption wavelength in a 300 nm-450 nm wavelength range is also mentioned.
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 thereof include ketone compounds, heterocyclic compounds such as N-aryloxazolidinones, European Patent No. 568,993, and US Patent No. 4,50. , 811 Pat, 5,227,227 Pat, JP 2001-125255, JP-like compounds described in JP-A-11-271969 Patent Publication.

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

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

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

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

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

  Moreover, as a preferable sensitizing dye which can be contained in the curable composition of the present invention, in addition to the above (e) sensitizing dye, at least selected from compounds represented by the following general formulas (VI) to (VIII) One kind is mentioned. These may be used individually by 1 type, and may use 2 or more types together.

In general formula (VI) or general formula (VII), 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 (VI) is preferably a compound represented by the following general formula (VI-1) from the viewpoint of sensitivity and colorability in the case of containing a pigment.

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

The compound represented by the general formula (VI) or the general formula (VII) preferably has a molar extinction coefficient ε at a wavelength of 365 nm of 500 mol ⁻¹ · L · cm ⁻¹ or more, and 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 the transmission spectrum of a sample at 365 nm using a dye solution prepared at 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 (VI) or general formula (VII) is illustrated below, the sensitizer used for the curable composition of 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 (VIII), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom, a sulfur atom, or —N (R ³ ) —, Y represents an oxygen atom, A sulfur atom or -N (R < ³ >)-is represented. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ¹ , R ² , and R ³ are each bonded to each other to form an aliphatic group Or you may form an aromatic ring.

In the general formula (VIII), 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, It is preferably a substituted or unsubstituted aromatic 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 (VIII), 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 (VIII-1) to (VIII-124) of the compound represented by the general formula (VIII) are shown below, but the sensitizer used in the curable composition of the invention is limited to these. is not. Further, it is not clear about an isomer by a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

The compound represented by the general formula (VI) according to the present invention can be further subjected to various chemical modifications for improving the properties of the curable composition.
For example, the sensitizing dye and an addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) are bonded by a method such as covalent bond, ionic bond, hydrogen bond, etc. Unnecessary precipitation suppression of the sensitizing dye from the film after exposure can be performed.
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.

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

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

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

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

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

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

  The content of these co-sensitizers is 0.1% by mass to 30% by mass with respect to the mass of the total solid content of the curable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The range is preferable, the range of 0.5% by mass to 25% by mass is more preferable, and the range of 1.0% by mass to 20% by mass is still more preferable.

  In addition to the above sensitizers and co-sensitizers, it is preferable to add a thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol. , T-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. Is useful.

<Colorant>
When the curable composition of the present invention contains a colorant, the colorant may be a dye or a pigment, but it is a triallylmethane, anthraquinone, azomethine, benzylidene, oxonol. A dye selected from the group, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo, anilinoazo, pyrazolotriazole azo, pyridone azo, anthrapyridone It is preferable that it is a compound represented by the following general formulas (III) to (V).

In formula (III), A represents the direction aromatic heterocyclic diazo residue of Component A-NH ₂ aryl groups or 5- to 6-membered. B ¹ and ^{B 2} are each ^{independently, -CR 3 =, - CR 4} =, or a nitrogen atom, ^{B 1} and ^{B 2} do not simultaneously represent a nitrogen atom. R ⁵ and R ⁶ each independently represents a hydrogen atom or a substituent. G, R ³ and R ⁴ each independently represents a hydrogen atom or a substituent. R ³ and R ⁴ and / or R ⁵ and R ⁶ may be bonded to each other to form a 5-membered or 6-membered ring.

In general formula (IV), R ^a1 , R ^a3 and R ^a4 each independently represent a hydrogen atom, an alkyl group having 1 to 21 carbon atoms, an alkenyl group having 2 to 21 carbon atoms, an aryl group having 6 to 21 carbon atoms, An aralkyl group having 7 to 21 carbon atoms is represented. R ^a3 and R ^a4 may form a heterocyclic ring together with the nitrogen atom bonded ^thereto . R ^a2 represents an alkyl group having 1 to 10 carbon atoms, a methoxymethyl group, or a trifluoromethyl group.

In general formula (V), R ^b1 represents a hydrogen atom or a substituent, R ^{b2 to} R ^b5 each independently represents a hydrogen atom or a substituent, and R ^b6 and R ^b7 each independently represent an alkyl group or an alkenyl group. Or an aryl group, Za and Zb each independently represent ^—N═ or —C (R ^b8 ) ^═ . R ^b8 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ^b2 and R ^b3 , R ^b3 and R ^b6 , R ^b4 and R ^b5 , R ^b5 and R ^b7 and / or R ^b6 and R ^b7 are bonded to each other, and each is independently a 5-, 6-, or 7-member The ring may be formed.

  Examples of the colorant represented by the general formula (III) include JP-A 2005-99677, JP-A 2005-250224, JP-A 2006-39301, JP-A 2006-58701, JP-A 2006-91190, JP-A 2006-243040, and Examples of the colorant (pigment and dye) described in JP-A-2006-243173 include the colorant (pigment and dye) described in JP-A-2006-124634. Examples of the colorant represented by the general formula (V) include colorants (pigments and dyes) described in JP-A-2006-58700 and JP-A-2006-72135, which are used in the curable composition of the present invention. The colorant is not limited to these.

-Dye-
When the curable composition of the present invention contains a dye as a colorant, a known dye 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 Colorants disclosed in JP-A-6-194828 can be used.

The chemical structure includes the above-mentioned triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo , Anilinoazo, pyrazolotriazole azo, pyridone azo, anthrapyridone, triphenylmethane, anthraquinone, phthalocyanine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene , Phthalocyanine, benzopyran, and indigo are more preferable, and pyrazole azo, anilinoazo, pyrazolotriazole azo, phthalocyanine, pyridone are particularly preferable. Zone system, a dye of the anthrapyridone system. As the dye classification, acid dyes, direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof may be usefully used. I can do it. These dyes may be used alone or in combination of two or more.

-Pigment-
When the curable composition of the present invention contains a pigment, various conventionally known inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment that is as fine as possible. Moreover, when handling property is also considered, 0.01 micrometer-0.1 micrometer are preferable and, as for the average particle diameter of the said pigment, 0.01 micrometer-0.05 micrometer are more preferable.
Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, or Examples thereof include metal oxides such as antimony and further complex oxides of the above metals.

As the organic pigment, for example, the following pigments can be used. However, the present invention is not limited to these.
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;
Examples thereof include carbon black.

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

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

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

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

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

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

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

Further, pigments described in JP-A Nos. 2003-315998 and 2005-331610 can be used. These pigments may be used alone or in combination of two or more. Moreover, you may use together with dye.

  When used for a color filter, the primary particle diameter of the pigment is 80 nm or less from the viewpoint of color unevenness and contrast, and 5 nm or more from the viewpoint of dispersion stability. Moreover, Preferably it is 5-75 nm, More preferably, it is 5-55 nm, Most preferably, it is 5-35 nm.

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

  The chemical structure includes the above-mentioned triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo Type, anilinoazo type, pyrazolotriazole azo type, pyridone azo type and anthrapyridone type are preferable, and a pigment selected from anthraquinone type, azomethine type, benzylidene type, cyanine type, diketopyrrolopyrrole type and phthalocyanine type is more preferable. .

  When the curable composition of the present invention is used for forming a coloring pattern of a color filter, the content of the pigment is such that the mass ratio in the solid content of the curable composition is 20% by mass or more and 85% by mass or less. It is preferably 30% by mass or more and 80% by mass or less, and particularly preferably 50% by mass or less and 75% by mass or less.

<Dispersant>
When the curable composition of the present invention contains a pigment, a conventionally known pigment dispersant or surfactant can be added for the purpose of improving the dispersibility of the pigment.
Dispersants (pigment dispersants) that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified polymers. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

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

  As these dispersants, many kinds of compounds are used. For example, a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Geneca), organosiloxane polymer KP341 (Shin-Etsu) Chemical Industries, Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho), and other cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether Nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic surfactants such as W004, W005, and W017 (manufactured by Yusho); EFKA-46 , EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disp Polymer dispersants such as Sease Aid 8, Disperse Aid 15 and Disperse Aid 9100 (manufactured by Sannopco); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) And Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.).

  Further, “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, manufactured by BYK Chemie, Inc. 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (both blocks) manufactured by EFKA. Polymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ", Ajinomoto Made by Fan Techno "Ajisper PB821, PB822", "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., Ltd., "Polyflow No. 50E, No. 300 (acrylic copolymer)", "Disparon KS-860, 873SN" manufactured by Enomoto Kasei Co., Ltd. , 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 "," Demol RN, N (naphthalenesulfonic acid formalin) manufactured by Kao Corporation Polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) ”,“ homogenol L-18 (polymer polycarboxylic acid) ”,“ Emulgen 920, 930, 935, 985 (polyoxy) Ethylene nonyl phenyl ether) "," acetamine 86 (stearylamine acetate) ", 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft-type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan) manufactured by Nikko Chemicals Monooleate), MYS-IEX (polyoxyethylene monostearate) "and the like.

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

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

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

<Binder>
The curable composition of the present invention can contain a binder for the purpose of improving film properties. In addition, the curable composition of the present invention does not necessarily contain a crosslinking agent, but if desired, it preferably contains at least one binder.
The binder that can be used in the present invention is not particularly limited as long as it is an alkali-soluble polymer compound, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, etc., and methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer. There are polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain are particularly useful. In addition to this, an acid anhydride added to a polymer having a hydroxyl group, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. Is also useful.

  Further, as the binder, a copolymer obtained by copolymerizing a monomer having a hydrophilic group may be used. Examples of this include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (Meth) acrylamide, N-methylol acrylamide, secondary and tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholino (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (Meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, etc. And the like.

  In addition, examples of the monomer having a hydrophilic group that can be used for forming the binder include tetrahydrofurfuryl group, phosphoric acid, phosphoric acid ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, morpholinoethyl group, etc. Also useful are monomers containing.

The binder may have a polymerizable group in the side chain from the viewpoint of improving the crosslinking efficiency, such as a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Useful.
Examples of the polymer having these polymerizable groups include commercially available products such as KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.).
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.

  Among the various binders, the binder in the present invention is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. As the acrylic resin, a copolymer composed of a monomer selected from benzyl (meth) acrylate, (meth) acryl, hydroxyethyl (meth) acrylate, (meth) acrylamide and the like is preferable, and a commercially available product that can be suitably used. Examples of the product include KS-resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P-series, and the like.

Moreover, alkali-soluble phenol resin is mentioned as another example of the binder used for this invention. The alkali-soluble phenol resin can be suitably used when the colored curable composition of the present invention is a positive composition.
More specifically, examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolak resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols used for synthesizing the novolak resin include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, or benzaldehyde.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.

Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol, or a mixture thereof and formalin.
The novolak resin may be one having a molecular weight distribution adjusted by means of fractionation or the like, or a low molecular weight component having a phenolic hydroxyl group such as bisphenol C or bisphenol A may be mixed with the novolak resin.

As the binder, a polymer having a mass average molecular weight of 1000 to 2 × 10 ⁵ , which is a polystyrene conversion value measured by GPC (Gel Permeation Chromatography) method, is preferable, and a polymer having 2000 to 1 × 10 ⁵ is more preferable. A polymer of ˜5 × 10 ⁴ is particularly preferred.
The amount of the binder used in the colored curable composition of the present invention is preferably 0 to 90% by mass, more preferably 0 to 60% by mass, based on the total solid content in the composition. 0-30 mass% is especially preferable.

<Crosslinking agent>
In the present invention, by using a polyfunctional acrylate compound represented by the general formula (I), the curing reaction of the film can be advanced to a higher degree than before, and a film having good curability can be obtained. By additionally using a crosslinking agent in the composition, it is possible to obtain a more highly cured film.

  The cross-linking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a cross-linking reaction. A melamine compound, a guanamine compound, a glycoluril compound, or a urea compound substituted with at least one selected substituent, (c) at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group Examples include substituted phenol compounds, naphthol compounds, and hydroxyanthracene compounds. A polyfunctional epoxy resin is particularly preferable.

[(A) Epoxy resin]
The epoxy resin (a) used for the crosslinking agent may be any epoxy resin having an epoxy group and crosslinkability. Examples of these compounds include bisphenol A-glycidyl ether, Divalent glycidyl such as ethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate, N, N-diglycidyl aniline Group-containing low molecular weight compounds, as well as trivalent glycidyl group-containing low molecular weight compounds represented by trimethylolpropane triglycidyl ether, trimethylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc. Similarly, tetravalent glycidyl group-containing low molecular weight compounds typified by pentaerythritol tetraglycidyl ether, tetramethylol bisphenol-A-tetraglycidyl ether, dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, etc. Typical examples include polyglycidyl group-containing low molecular weight compounds, polyglycidyl (meth) acrylate, and 1,2-epoxy-4- (2-oxiranyl) cyclohexane adducts of 2,2-bis (hydroxymethyl) -1-butanol. Examples thereof include glycidyl group-containing polymer compounds.

[(B) Melamine compound, guanamine compound, glycoluril compound, or urea compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group (crosslinking agent (b)) ]
The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) component is 2 to 6 in the case of melamine compounds, and 2 in the case of glycoluril compounds, guanamine compounds, and urea compounds. 4, preferably 5 to 6 in the case of a melamine compound, and 3 to 4 in the case of a glycoluril compound, a guanamine compound and a urea compound.

  Hereinafter, the melamine compound, guanamine compound, glycoluril compound, and urea compound of (b) are collectively referred to as a compound (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) according to (b). Sometimes.

  The methylol group-containing compound according to (b) can be obtained by heating the alkoxymethyl group-containing compound according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound according to (b) can be obtained by mixing and stirring a methylol group-containing compound with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound in (b) having the above substituent are given.
Examples of melamine compounds include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol melamine And a compound in which 1 to 5 of the methylol groups are acyloxymethylated or a mixture thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol guanamine. Or a compound obtained by acyloxymethylating 1 to 3 methylol groups, or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, and 1 of the methylol groups of tetramethylolglycoluril. A compound in which ˜3 are acyloxymethylated or a mixture thereof is exemplified.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea. These may be used alone or in combination.
The compounds according to (b) may be used alone or in combination.

[(C) Phenol compound, naphthol compound or hydroxyanthracene compound substituted with at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group (crosslinking agent (c))]
Crosslinking agent (c): a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an acyloxymethyl group, and an alkoxymethyl group is the crosslinking agent (b). In the same manner as described above, the thermal cross-linking suppresses intermixing with the overcoated photoresist and further increases the film strength.
Hereinafter, these compounds may be collectively referred to as the compound according to (c) (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound).

  The number of methylol groups, acyloxymethyl groups, and alkoxymethyl groups contained in the crosslinking agent (c) is at least two per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2-position and 4-position of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3rd or 5th position of the phenolic compound serving as the skeleton may be unsubstituted or may have a substituent. Also in the naphthol compound serving as the skeleton, other than the ortho position of the OH group may be unsubstituted or may have a substituent.

  As the methylol group-containing compound according to the crosslinking agent (c), a compound in which the ortho-position or para-position (2-position or 4-position) of the phenolic OH group is a hydrogen atom is used as a raw material. It can be obtained by reacting with formalin in the presence of a basic catalyst such as potassium, ammonia or tetraalkylammonium hydroxide. The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeleton compound in the crosslinking agent (c) component include phenol compounds in which the ortho or para position of the phenolic OH group is unsubstituted, naphthol compounds, hydroxyanthracene compounds, for example, phenol, cresol isomers, 2,3- Bisphenols such as xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenol-A, 4,4′-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry Co., Ltd.) ), Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) component include, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3-cresol , Tri (methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, dimethylolcresol such as 2,6-dimethylol-4-cresol, and tetramethylolbisphenol -A, tetramethoxymethyl bisphenol-A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol-A, tetramethylol-4,4'-bishydroxybiphenyl, tetramethoxymethyl-4,4 ' -Bishydroxy Biphenyl, hexamethylol of Tris P-PA, hexamethoxymethyl of Tris P-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated hexamethylol of Tris P-PA, there is bishydroxymethyl naphthalene diol.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

Among these compounds, trimethylol phenol, bishydroxymethyl-p-cresol, tetramethylol bisphenol A, hexamethylol body of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or their methylol group is alkoxy. It is a phenol compound substituted with both a methyl group and a methylol group and an alkoxymethyl group.
These compounds related to (c) may be used alone or in combination.

  In the colored curable composition of the present invention, it is not always necessary to contain a cross-linking agent. 1-70 mass% is preferable with respect to solid content of a composition, 5-50 mass% is more preferable, and 7-30 mass% is especially preferable.

<Polymerizable monomer>
By using the polyfunctional acrylate compound represented by the above general formula (I), the curable composition of the present invention allows the film curing reaction to proceed to a higher degree than before, and the film has good curability. However, it is possible to obtain a more highly cured film by supplementarily using another polysynthetic monomer in the composition.
Hereinafter, polymerizable monomers other than the polyfunctional acrylate compound represented by the general formula (I) will be described.

  The polymerizable monomer other than the polyfunctional acrylate compound represented by the general formula (I) has at least one addition-polymerizable ethylene group and has an ethylenic unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. A compound having a group is preferable, and examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) ) Acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane (Meth) acrylate after addition of ethylene oxide or propylene oxide, urethane as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193 Acrylates, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, reaction products of epoxy resin and (meth) acrylic acid D And polyfunctional acrylates or methacrylates of alkoxy acrylates such as and the like, and mixtures thereof.

  Furthermore, the Japan Adhesion Association Vol. 20, no. 7, pages 300 to 308 are introduced as photocurable monomers and oligomers.

  The content of the polymerizable monomer in the colored curable composition is preferably 0.1 to 90% by mass, more preferably 1.0 to 80% by mass, and 2.0 to 70% by mass with respect to the solid content. Particularly preferred.

<Solvent>
In preparing the curable composition of the present invention, a solvent can generally be contained. 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-oxy Ethyl lopionate, 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 Acetates, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; aromatic hydrocarbons such as toluene and xylene are preferred.

  Among the above, 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 methyl ether acetate and the like are more preferable.

<Other various additives>
In the colored curable composition of the present invention, various additives other than the above components as necessary, for example, fillers, polymer compounds other than those described above, surfactants, adhesion promoters, antioxidants, UV absorbers Further, an aggregation preventing agent or the like can be blended.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 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. And an anti-aggregation agent such as sodium polyacrylate.

  Further, when the alkali solubility of the non-irradiated part (non-image part) is promoted and the developability of the curable composition of the present invention is further improved, the composition is provided with an organic carboxylic acid, preferably a molecular weight. Addition of 1000 or less low molecular weight organic carboxylic acid can be performed. Specifically, 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, glutar Aliphatic dicarboxylic acids such as 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 carbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa 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, the curable composition includes a polyfunctional acrylate compound represented by the general formula (I), a pigment, a radiation-sensitive compound, and an alkali used as necessary. It is preferable to prepare it through a mixing and dispersing step in which a soluble resin and other additives are mixed with a solvent and mixed and dispersed using various mixers and dispersers. The mixing and dispersing step preferably includes kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

  As a preferred method for producing the composition of the present invention, the colorant is kneaded with the resin component so that the viscosity after the kneading and dispersing treatment is 10,000 mPa · s or higher, desirably 100,000 mPa · s or higher. Dispersion treatment, and then adding a solvent, fine dispersion treatment so that the viscosity after the fine dispersion treatment is 1,000 mPa · s or less, preferably 100 mPa · s or less, and further a high boiling point solvent, etc. The method of adding and stirring and mixing is preferable.

  The machines used in the kneading and dispersing treatment are two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single and twin screw extruders, etc., which disperse while giving a strong shearing force. . Next, a solvent is added and finely dispersed with beads made of glass or zirconia having a particle diameter of 0.1 to 1 mm, mainly using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. To process. It is also possible to omit the kneading and dispersing process. In that case, beads are dispersed with a pigment, a dispersant or a surface treatment agent, and the acrylic copolymer and solvent in the present invention. For details on kneading and dispersing, see T.W. C. It is also described in Paton, “Paint Flow and Pigment Dispersion” (published by John Wiley and Sons, 1964), and this method may be used.

  The curable composition of the present invention is used for forming colored pixels such as color filters used in liquid crystal display elements (LCD) and solid-state imaging elements (for example, CCD, CMOS, etc.) by containing a colorant, and printing. It can be suitably used as a production application for inks, inkjet inks, paints, and the like.

[Color filter and manufacturing method thereof]
The color filter of the present invention is characterized by using the specific compound of the present invention. In addition, such a color filter comprises at least one kind of the colored curable composition of the present invention as a support. It is produced by a manufacturing method comprising: a colored layer forming step of forming a colored layer by coating on the surface; and a developing step of pattern-exposing the colored layer through a mask and developing to form a colored pattern be able to.

Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the colored curable composition of the present invention is used. The color filter of the present invention is radiation sensitive by applying the colored curable composition of the present invention on a support by a coating method such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like. A colored curable composition layer (colored layer) is formed (colored layer forming step), exposed through a predetermined mask pattern, and developed with a developer to form a colored pattern (resist pattern). (Development process). Then, the hardening process which hardens the formed pattern by heating and / or exposure as needed can be implemented. The obtained colored pattern constitutes a pixel in the color filter.

  The thickness of the colored curable composition layer formed from the colored curable composition is appropriately selected according to the purpose, and the smaller the thickness, the better, as long as the desired color density is secured. It is preferably 0 μm or less, more preferably 1.0 μm or less, and particularly preferably 0.7 μm or less.

In order to use as a color filter for LCD (Liquid Crystal Display Element), the thickness of the colored curable composition layer can cope with LCD thinning and is preferably from 0.1 μm to less than 2.0 μm from the viewpoint of securing color density. 0.2 μm to 1.8 μm is more preferable, and 0.3 μm to 1.75 μm is particularly preferable.
Further, in order to use as a color filter for IS (Image Sensor), the light in the oblique direction does not reach the light receiving unit from the viewpoint of securing the color density, and the light collection rate is not improved between the end and the center of the device. From the viewpoint of reducing inconveniences such as significant difference, 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.

  As light or radiation used in this development process or curing process, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

  In the production of a color filter having pixels of a plurality of hues, a color filter configured in a desired number of hues is created by repeating the development process (and the curing process if necessary) according to the desired number of colors. be able to.

As a developer used in the method for producing a color filter of the present invention, as long as it has a composition that dissolves the uncured portion of the colored curable composition of the present invention and does not dissolve the radiation irradiated portion (cured portion), Any thing can be used. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
Examples of the organic solvent that can be used for development include the above-mentioned solvents used in preparing the composition of the present invention.

  Examples of alkaline aqueous solutions that can be used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium. Concentration of an alkaline compound such as hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. %, An alkaline aqueous solution dissolved to a concentration of% is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

As a support used in the color filter of the present invention, for example, soda glass, Pyrex (registered trademark) glass, quartz glass used in a liquid crystal display element or the like, and those having a transparent conductive film attached thereto, an imaging element, or the like. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate and a complementary metal oxide semiconductor (CMOS). These supports may be formed with black stripes that separate pixels.
In addition, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface of the support.

  The color filter of the present invention can be used for a solid-state image pickup device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS device having more than 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 of Polyfunctional Acrylate Compound Represented by General Formula (I) of the Present Invention]
Below, the specific synthesis | combining method of the said exemplary compound (I-1) is shown. Other polyfunctional acrylates according to the present invention can be synthesized by the same scheme. In addition, the synthesis method of polyfunctional acrylate is not limited to the following method.

[Synthesis Example 1]: Synthesis of Exemplified Compound (I-1) After adding 20 ml of acetonitrile to 1.5 g (0.0136 mol) of hydroquinone and dissolving it, bismuth tris (2-ethylhexanoate) (trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) 60 mg (0.095 mmol) was added to make a uniform solution. The mixture was heated to 60 ° C., and a solution of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (trade name: Karenz BEI (manufactured by Showa Denko KK)) 6.72 g (0.028 mol) in acetonitrile was added dropwise. After completion of dropping, the mixture was stirred at 55 to 65 ° C. for 8 hours. After completion of the reaction, the reaction solution was cooled to room temperature, 30 ml of ethyl acetate was added, 50 ml of n-hexane was added, and the precipitated colorless crystals were collected by filtration. An operation of adding 30 ml to the colorless crystals and then adding 50 ml of n-hexane and filtering the precipitated colorless crystals was further repeated twice to obtain 1.2 g of compound (I-1) (0.0216 mol (yield: 48%)). Hydroquinone manufactured by Wako Pure Chemical Industries, Ltd. was used.

When the structure of the compound (I-1) obtained above was confirmed by NMR, ¹ H-NMR (400 MHz, solvent: deuterated chloroform, standard substance: tetramethylsilane) δ 7.10 (4H, s), 6.48 ppm (4H, dd), 6.17 ppm (2H, d), 6.13 ppm (2H, d), 5.91 ppm (4H, dd), 5.45 ppm (2H, brs), 4.44 ppm (4H) , D), 4.37 ppm (4H, d), 1.50 ppm (6H, s).

[Synthesis Example 2]: Synthesis of Exemplary Compound (I-3) After adding 30 ml of acetonitrile to 2.61 g (0.010 mol) of 1,3,5-tris (2-hydroxyethyl) -cyanuric acid and dissolving it. Bismuth tris (2-ethylhexanoate) (trade name: Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.)) 130 mg (0.20 mmol) was added to obtain a homogeneous solution. The mixture was heated to 60 ° C., and a solution of 7.51 g (0.032 mol) of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (trade name: Karenz BEI (manufactured by Showa Denko KK)) in 10 ml of acetonitrile was added dropwise. After completion of dropping, the mixture was stirred at 55 to 65 ° C. for 6 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/1) to give 7.83 g (0. 008 mol (yield: 80%)). 1,3,5-tris (2-hydroxyethyl) -cyanuric acid manufactured by Aldrich was used.

When the structure of the compound (I-3) obtained above was confirmed by NMR, ¹ H-NMR (400 MHz, solvent: deuterated chloroform, standard substance: tetramethylsilane) δ 6.42 ppm (6H, dd), 6.14 ppm (3H, d), 6.12 ppm (3H, d), 5.87 ppm (6H, dd), 5.43 ppm (3H, brs), 4.36 ppm (6H, d), 4.29 ppm (6H) , T), 4.28 ppm (6H, d), 4.16 ppm (6H, t), 1.40 ppm (9H, s).

[Synthesis Example 3]: Synthesis of Exemplified Compound (I-5) After dissolving 30 ml of acetonitrile in 2.5 g (0.0184 mol) of pentaerythritol, bismuth tris (2-ethylhexanoate) (trade name) : Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.)) 125 mg (0.19 mmol) was added to obtain a homogeneous solution. The mixture was heated to 60 ° C., and a solution of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (trade name: Karenz BEI (manufactured by Showa Denko)) 18.2 g (0.077 mol) in acetonitrile 10 ml was added dropwise. After completion of dropping, the mixture was stirred at 55 to 65 ° C. for 6 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and then purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/1) to obtain 15.8 g (0. 0) of the compound (I-5). 0144 mol (yield: 78%)) was obtained. Pentaerythritol was manufactured by Aldrich.

The structure of the compound (I-5) obtained above was confirmed by NMR. As a result, 1H-NMR (400 MHz, solvent: deuterated chloroform, standard substance: tetramethylsilane) δ 6.44 ppm (8H, dd), 6 .17 ppm (4H, d), 6.13 ppm (4H, d), 5.89 ppm (8H, dd), 5.22 ppm (4H, brs), 4.37 ppm (8H, d), 4.30 ppm (8H, d) 4.16 ppm (8H, s) and 1.42 ppm (12H, s).

[Synthesis Example 4]: Synthesis of Exemplified Compound (I-6) After dissolving 15 ml of acetonitrile in 1.0 g (0.0039 mol) of dipentaerythritol, bismuth tris (2-ethylhexanoate) (product) Name: 60 mg (0.094 mmol) of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) was added to make a uniform solution. The solution was heated to 60 ° C., and a solution of 1,1- (bisacryloyloxymethyl) ethyl isocyanate (trade name: Karenz BEI (manufactured by Showa Denko KK)) 5.38 g (0.0248 mol) in 5 ml of acetonitrile was added dropwise. After completion of dropping, the mixture was stirred at 55 to 65 ° C. for 6 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/1) to give 4.0 g (0. 0) of the compound (I-6). 0023 mol (yield: 59%)) was obtained. Dipentaerythritol was manufactured by Aldrich.

About the compound (I-6) obtained from the above, when the structure was confirmed by NMR, ¹ H-NMR (400 MHz, solvent: deuterated chloroform, standard substance: tetramethylsilane) δ 6.42 ppm (12H, dd), 6.16 ppm (6H, d), 6.12 ppm (6H, d), 5.87 ppm (12H, dd), 5.47 ppm (6H, brs), 4.38 ppm (12H, d), 4.32 ppm (12H) D) 4.03 ppm (12H, s), 3.31 ppm (4H, s), 1.42 ppm (18H, s).

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

A1-1. Preparation of pigment dispersion C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 150 100/60 (mass ratio) mixture 40 parts by mass (primary particle size 32 nm), and as a dispersant BYK2001 (Disperbyk: manufactured by BYK) (solid content concentration 45.1% by mass) 50 parts by mass ( A pigment dispersion (P1) was prepared by mixing and dispersing a mixed solution consisting of about 22.6 parts by mass in terms of solid content) and 110 parts by mass of ethyl 3-ethoxypropionate as a solvent using a bead mill for 15 hours.

A1-2. Preparation of curable composition (coating liquid) A curable composition solution was prepared by stirring and mixing the pigment dispersion liquid P1 subjected to the dispersion treatment so as to have the following composition ratio.
-Preparation of liquid composition Pigment dispersion (P1) 600 parts by mass-2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole [light Polymerization initiator] 30 parts by mass / dipentaerythritol hexaacrylate 50 parts by mass [ethylenically unsaturated bond-containing compound]
-Exemplified compound (I-6) 10 parts by mass-Alkali-soluble resin 10 parts by mass (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10,000)
-Solvent: 900 parts by mass of PGME-1 part by mass of 3-methacryloxypropyltrimethoxysilane-12 parts by mass of sensitizer (the following compound sensitizer α)-Co-sensitizer: 12 parts by mass of 2-mercaptobenzimidazole

[A2. (Production of color filter)
A2-1. Formation of the curable composition layer The curable composition containing the pigment as a resist solution was slit-coated on a 550 mm × 650 mm glass substrate under the following conditions, and then allowed to stand for 10 minutes, followed by vacuum drying and pre-baking ( prebake) (100 ° C., 80 seconds) to form a curable composition coating film (curable composition layer).
[Slit application conditions]
Gap of the opening at the tip of the coating head: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 1.7 μm
Application temperature: 23 ° C

A2-2. Exposure and development Thereafter, the colored curable composition coating film is exposed in a pattern using a test photomask having a line width of 20 μm using a 2.5 kw ultra-high pressure mercury lamp. After the exposure, the entire surface of the coating film is organic The sample was covered with a 10% aqueous solution of a system developer (trade name: CD, manufactured by Fuji Film Arch 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 coating film subjected to the photocuring treatment and development treatment was heated in an oven at 220 ° C. for 1 hour (post-baking). As a result, a colored curable composition film (color filter) was formed on the glass substrate.

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

A3-1. Storage stability of coating solution After storing the coating solution at room temperature for 1 month, the viscosity of the solution was measured and evaluated according to the following criteria.
<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 the colored curable composition layer,
Exposure was performed by changing the exposure dose to various exposure doses of 10 to 100 mJ / cm ² , and the exposure dose at which the pattern line width after post-baking was 20 μm was evaluated as exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

A3-3. Developability, pattern cross-sectional shape, substrate adhesion The substrate surface and cross-sectional shape after post-baking were confirmed by an ordinary method by optical microscope and SEM photograph observation.
In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability.
<Developability>
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.

The cross-sectional shape of the formed pattern was observed. The pattern cross-sectional shape is most preferably a forward taper, and a rectangular shape is next preferred. Reverse taper is not preferred.
As an evaluation of substrate adhesion, it was observed whether or not a pattern defect occurred. These evaluation items were evaluated based on the following criteria <Board adhesion>
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

( Reference Example 2 to Reference Example 4, Example 5, Reference Example 6 to Reference Example 7, Example 8, Reference Example 9, Example 10, Reference Example 11 to Reference Example 15)
In the curable composition of Example 1, a colored pattern was obtained in the same manner as in Example 1 except that the exemplified compound (I-6) was replaced with the exemplified compound shown in Table 1 below. The same evaluation was performed. The results are shown in Table 1.

(Comparative Examples 1 and 2)
In the curable composition of Example 1, everything was carried out in the same manner as in Example 1 except that the exemplified compound (I-6) was changed to the compounds shown in Table 1, and a colored pattern was obtained. Was evaluated. The results are shown in Table 1.

  From the result of Table 1, the colored curable composition of the Example using the polyfunctional acrylate compound according to the present invention has a storage stability in a solution state compared to the comparative example using the other polyfunctional acrylate compound. In addition, when this colored curable composition is used, it can be seen that the exposure sensitivity, developability, substrate adhesion, and pattern cross-sectional shape are excellent.

(Example 16)
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.
<Resist solution composition>
Propylene glycol monomethyl ether acetate 19.20 parts by mass (PGMEA: solvent)
-Ethyl lactate 36.67 parts by mass-Binder polymer 30.51 parts by mass [40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18)]
Dipentaerythritol hexaacrylate 12.20 parts by mass [(C) ethylenically unsaturated bond-containing compound]
-Polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass-Fluorosurfactant 0.83 parts by mass (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
・ Trihalomethyltriazine-based photopolymerization initiator 0.586 parts by mass (TAZ-107, manufactured by Midori Chemical Co., Ltd.) [(B) Photopolymerization initiator]

[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 as to have a dry film thickness of 2 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer, thereby obtaining a silicon wafer substrate with an undercoat layer. It was.

[B3. Preparation of pigment dispersion
As a pigment, C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass (primary particle size: 32 nm) of 70/30 (mass ratio) of CI Pigment Yellow 139, 50 parts by mass of BYK2001 (Disperbyk: BYK Corporation (solid content concentration: 45.1% by mass)) as a dispersant A pigment dispersion (P1) was prepared by mixing and dispersing a mixture of about 22.6 parts by mass in terms of solid content) and 110 parts by mass of propylene glycol monomethyl ether as a solvent using a bead mill for 15 hours.

[B4. Preparation of curable composition (coating liquid)]
A curable composition solution was prepared by stirring and mixing the pigment dispersion P1 subjected to the dispersion treatment so as to have the following composition ratio.
-Preparation of liquid composition Pigment dispersion (P1) 600 parts by mass-Oxime-based photopolymerization initiator [photopolymerization initiator] 30 parts by mass (CGI-124, manufactured by Ciba Specialty Chemicals)
・ TO-1382 (manufactured by Toagosei Co., Ltd.) [ethylenically unsaturated bond-containing compound] 61 parts by mass ・ Exemplary compound (I-6) 8 parts by mass ・ Solvent: PGMEA 900 parts by mass ・ 3-methacryloxypropyltrimethoxysilane 1 Parts by mass

[B5. Preparation and evaluation of color filter using colored photosensitive resin composition]
-Pattern formation and sensitivity evaluation-
B4 prepared above. A curable composition (coating liquid) was added to the B2. The coated film (colored curable composition layer) was formed on the undercoat layer of the silicon wafer substrate with the undercoat layer obtained in (1). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at various exposure doses of 50 to 1600 mJ / cm ² through an Island pattern mask having a pattern of 1.2 μm square at a wavelength of 365 nm. .
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

  The silicon wafer substrate on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying. Thereafter, the size of the colored pattern was measured using a length measuring SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure dose at which the pattern line width was 1.2 μm was evaluated as the exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity. The results of measurement evaluation are shown in Table 2 below.

In the exposure step, the presence or absence of residue in the area not irradiated with light (unexposed portion) was observed to evaluate developability.
<Developability>
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.

The cross-sectional shape of the formed pattern was observed. The pattern cross-sectional shape is preferably rectangular, and reverse taper is not preferable.
As an evaluation of substrate adhesion, it was observed whether or not a pattern defect occurred. These evaluation items were evaluated based on the following criteria <Board adhesion>
○: 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.

Further, the liquid aging stability (storage stability) was evaluated according to the following criteria by measuring the viscosity of the liquid after storing the coating liquid at room temperature for 1 month.
<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.

( Reference Example 17 to Reference Example 18, Example 19, Reference Example 20 to Reference Example 22)
In the curable composition of Example 16, all except that Exemplified Compound (I-6) was changed to the Exemplified Compound shown in Table 2 below, the same procedure as in Example 16 was performed to obtain a colored pattern. Evaluation similar to 16 was performed. The results are shown in Table 2.

[Comparative Example 3]
In the curable composition of Example 16, except that Exemplified Compound (I-6) was replaced with the compound shown in Table 2 below, the same procedure as in Example 16 was performed to obtain a colored pattern. The same evaluation was performed. The results are summarized in Table 2.

(Example 23)
Hereinafter, an example of preparing a curable composition containing a colorant (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], [B2. A silicon substrate with an undercoat layer was prepared in the same manner as in [Preparation of silicon substrate with undercoat layer].

[C2. Preparation of curable composition (coating liquid)]
A compound having the following composition was mixed and dissolved to prepare a colored curable composition.
・ 80 parts by mass of cyclohexanone [solvent] ・ 6.0 parts by mass of the following compound A [dye] ・ 6.0 parts by mass of Acid Red 57 [dye] 4.0 parts by mass of dipentaerythritol hexaacrylate [containing ethylenically unsaturated bond] Compound〕
Exemplified compound (I-6) 2.0 parts by mass Oxime-based photopolymerization initiator [photopolymerization initiator] 2.0 parts by mass (CGI-124, manufactured by Ciba Specialty Chemicals)

[C3. Preparation and evaluation of color filter with colored curable composition]
[B5. Preparation and evaluation of color filters were carried out in the same manner as in [Preparation and evaluation of color filters with colored curable composition]. The results are shown in Table 2 above.

( Reference Examples 24-30)
In the curable composition of Example 23, except that Exemplified Compound (I-6) was replaced with the Exemplified Compound shown in Table 2 above, the same procedure was carried out as in Example 23 to obtain a colored pattern. Evaluation similar to 23 was performed. The results are shown in Table 2 above.

[Comparative Example 4]
In the curable composition of Example 23, except that Exemplified Compound (I-6) was changed to the compounds shown in Table 2 above, the same procedure as in Example 23 was performed to obtain a colored pattern. The same evaluation was performed. The results are shown in Table 2 above.

  From the results of Table 2 above, the colored curable compositions of the examples using the polyfunctional acrylate compounds according to the present invention are stable in storage in the solution state compared to the comparative examples using other polyfunctional acrylate compounds. It can be seen that when this colored curable composition is used, the exposure sensitivity, developability, substrate adhesion, and pattern cross-sectional shape are excellent.

Claims (4)

A compound represented by the following general formula (I), a compound containing an ethylenically unsaturated double bond, and a photopolymerization initiator, the content of the compound represented by the following general formula (I) is The content ratio of the compound represented by the following general formula (I) to the compound containing 0.01 to 90% by mass with respect to the total solid content of the composition and containing the ethylenically unsaturated double bond is based on mass. 0.001 to 100, and the content of the photopolymerization initiator is based on the total solid content of the compound containing the ethylenically unsaturated double bond and the compound represented by the following general formula (I) 0.01 to 50% by mass Te Ru curable composition.

[In General Formula (I), R ¹ represents an n-valent organic group. R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁵ each independently represents a hydrogen atom or a methyl group. X represents —O—, —NH—, —NR ⁴ —, or —S—, and R ⁴ represents a hydrogen atom or a monovalent organic group. n represents an integer of 5 to 12. ]
  Furthermore, a coloring agent is contained, The curable composition of Claim 1 characterized by the above-mentioned.   A color filter having a colored pattern using the curable composition according to claim 2.   A colored layer forming step of forming a colored curable composition layer by applying the curable composition according to claim 2 on a support, and an exposure step of exposing the colored curable composition layer through a mask. And a developing step of developing the colored curable composition layer after exposure to form a colored pattern.