JP2016090797A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition with high definition and excellent light blocking properties favorable for black matrix formation by achieving both high sensitivity and chemical resistance.SOLUTION: A curable composition contains: an ethylenically unsaturated compound (A), which is a reaction product obtained by an esterification reaction of a polybasic acid anhydride with an epoxy addition compound having a structure where an unsaturated monobasic acid is added to an epoxy compound having a phenylindane skeleton represented by the general formula (I) in the figure; and an oxime ester based polymerization initiator (B) having a specific structure.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition containing an ethylenically unsaturated compound having a specific structure and an oxime ester radical polymerization initiator having a cycloalkylalkyl group.

  The curable composition usually contains a compound having an ethylenically unsaturated bond (hereinafter referred to as an ethylenically unsaturated compound) and a polymerization initiator. Since this curable composition can be rapidly polymerized and cured by irradiation with ultraviolet rays or electron beams, it is useful in various applications. Such a curable composition is required to have chemical resistance to obtain a high-definition pattern, and transparency to be used for clear applications such as a display. When using a black pigment, the curable composition is required to have high sensitivity to ultraviolet rays and electron beams.

  In a black matrix using a black pigment, it is required to increase light shielding for the purpose of improving contrast and to form a high-definition pattern with a low exposure amount. In order to increase the light shielding property, it has been proposed to increase the concentration of the black pigment in the composition. However, when black pigments are blended at a high concentration, the light for curing does not easily reach the bottom, which may lead to poor curing due to a decrease in sensitivity of the curable composition. And may lead to a decrease in definition. There is a trade-off between light shielding properties and curability, and it is difficult to achieve both. Therefore, a black matrix having high sensitivity and high definition while having excellent light shielding properties is desired.

  The following Patent Documents 1, 2, and 3 disclose oxime ester radical polymerization initiators having a cycloalkylalkyl group, and the following Patent Document 4 contains an oxime ester radical polymerization initiator having a cycloalkylalkyl group. It has been disclosed that a colored alkali development type curable resin composition characterized by having both high sensitivity and high definition while maintaining high light shielding properties. However, a sufficiently high-definition black matrix is not obtained while maintaining the light shielding property.

Special table 2012-519191 gazette Special table 2012-526185 gazette Special table 2013-543875 gazette JP 2013-190459 A

  Accordingly, an object of the present invention is to provide a curable composition having high sensitivity to ultraviolet rays and electron beams and good chemical resistance. Another object of the present invention is to provide a curable composition having a high light-shielding property and capable of forming a highly sensitive and fine pattern when a black pigment is used as a colorant.

（式中、Ｍは下記式（イ）又は（ロ）で表される基を表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜１０のアルコキシ基、又はハロゲン原子を表し、ｐは０〜１０の数である。ｐが１以上の場合においてＭは下記式（イ）、（ロ）単独であっても混在してもよい。）

（式中、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環基、又はハロゲン原子を表し、上記アルキル基及びアリールアルキル基中のアルキレン部分は、不飽和結合、−Ｏ−又は−Ｓ−で中断されてもよく、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１７、Ｒ^１８、Ｒ^１９及びＲ^２０は、隣接するＲ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１７、Ｒ^１８、Ｒ^１９及びＲ^２０同士で環を形成してもよい。） Ethylene which is a reaction product obtained by esterification reaction of an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the following general formula (I) and a polybasic acid anhydride The present inventors have found that a curable composition containing a polymerizable unsaturated compound (A) and a polymerization initiator (B) represented by the following general formula (II) can solve the above problems, and has reached the present invention.

(In the formula, M represents a group represented by the following formula (I) or (B), and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and p is a number from 0 to 10. In the case where p is 1 or more, M is the following: (Formulas (a) and (b) may be used alone or in combination.)

(Wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Represents a C2-C20 heterocyclic group or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are adjacent to each other R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^20. May form a ring.)

（式中、Ｒ^２５は、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３及びＲ^３４は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ^３５、ＯＲ^３６、ＳＲ^３７、ＮＲ^３８Ｒ^３９、ＣＯＲ^４０、ＳＯＲ^４１、ＳＯ_２Ｒ^４２又はＣＯＮＲ^４３Ｒ^４４を表し、
Ｘ^１は、酸素原子、硫黄原子、セレン原子、ＣＲ^４５Ｒ^４６、ＣＯ、ＮＲ^４７又はＰＲ^４８を表し、
Ｘ²は、単結合又はＣＯを表し、
Ｒ^３５、Ｒ^３６、Ｒ^３７、Ｒ^３８、Ｒ^３９、Ｒ^４０、Ｒ^４１、Ｒ^４２、Ｒ^４３、Ｒ^４４、Ｒ^４５、Ｒ^４６、Ｒ^４７及びＲ^４８は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、又は炭素原子数２〜２０の複素環基を表し、
該アルキル基又はアリールアルキル基中のアルキレン基中の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基又は複素環基で置換されていてもよく、該アルキル基又はアリールアルキル基中のアルキレンは−Ｏ−で中断されていてもよく、
Ｒ^２９とＲ^３０は、互いに結合して環を形成していてもよく、
ｎは、１〜５の整数、ｍは、１〜６の整数を表す。）

(In the formula, R ²⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Or a heterocyclic group having 2 to 20 carbon atoms,
R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R ³⁵ , OR ³⁶ , SR ³⁷ , NR ³⁸ R ³⁹ , COR ⁴⁰ , SOR ⁴¹ , SO ₂ R ⁴² or CONR ⁴³ R ⁴⁴ ,
X ¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁴⁵ R ⁴⁶ , CO, NR ⁴⁷ or PR ⁴⁸ ,
X ² represents a single bond or CO,
R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are each independently the number of carbon atoms. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,
The hydrogen atom in the alkylene group in the alkyl group or arylalkyl group may be substituted with a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group or heterocyclic group, and in the alkyl group or arylalkyl group The alkylene of may be interrupted by -O-
R ²⁹ and R ³⁰ may be bonded to each other to form a ring,
n represents an integer of 1 to 5, and m represents an integer of 1 to 6. )

  The present invention also provides a black matrix and a color filter produced by adding a black pigment as a colorant to the curable composition.

  According to the present invention, a curable composition having both high sensitivity and chemical resistance can be provided. Moreover, when carbon black which is a black pigment is used for the said curable composition, it is excellent in the light-shielding property suitable for black matrix formation, and can provide a highly precise curable composition.

It is a schematic diagram which shows the cross-sectional shape of the width direction of the pattern formed from the curable composition. (A) is a figure which shows the cross-sectional shape of the pattern which has not produced the undercut, (b) is a figure which shows the cross-sectional shape of the pattern which produced the undercut.

  Hereinafter, the curable composition of this invention is demonstrated based on preferable embodiment.

  The curable composition of the present invention contains an ethylenically unsaturated compound (A) and a polymerization initiator (B) represented by the above general formula (II). Hereinafter, each component will be described in order.

<Ethylenic unsaturated compound (A)>
The ethylenically unsaturated compound (A) used in the curable composition of the present invention includes an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (I), It is a reaction product obtained by an esterification reaction with a polybasic acid anhydride.

In the general formula (I), the alkyl group having 1 to 20 carbon atoms represented by R ^{1 to} R ⁸ includes methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso -Butyl, amyl, iso-amyl, tert-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl , Isotridecyl, myristyl, palmityl, stearyl, trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoro Oropuropiru, trifluoropropyl, perfluorobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like,
Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ^{1 to} R ⁸ include methyloxy, ethyloxy, iso-propyloxy, propyloxy, butyloxy, pentyloxy, iso-pentyloxy, hexyloxy, heptyloxy, Octyloxy, 2-ethylhexyloxy and the like,
Examples of the halogen atom represented by R ^{1 to} R ⁸ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

M in the general formula (I) is a substituent selected from the group represented by the above formulas (I) and (B), and is an alkyl group having 1 to 20 carbon atoms represented by R ^{9 to} R ^24. Examples of the alkoxy group having 1 to 10 carbon atoms include those exemplified for R ^{1 to} R ⁸ above.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ^{9 to} R ²⁴ include phenyl, naphthyl, anthracen-1-yl, phenanthren-1-yl, o-tolyl, m-tolyl, p-tolyl, 4 -Vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2 -Ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4 -Di-t-butylphenyl, 2,5-di-t-butylphenyl, 2,6-di-t-butylphenyl 2,4-di-t-pentylphenyl, 2,5-di-t-amylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-tri Chlorophenyl, 4-trifluorophenyl, perfluorophenyl, etc.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ^{9 to} R ²⁴ include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, 4-chlorophenylmethyl and the like. ,
Examples of the heterocyclic group represented by R ^{9 to} R ²⁴ include pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, furyl, furanyl, benzofuranyl , Thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, urolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidone-1 -Yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl and the like.

The unsaturated monobasic acid is an acid having an unsaturated bond in the structure and having one hydrogen atom per molecule that can be ionized to form a hydrogen ion.
Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, And dicyclopentadiene malate.
The polybasic acid anhydride represents an acid anhydride of a polybasic acid having an unsaturated bond in the structure and having a plurality of hydrogen atoms per molecule that can be ionized to form hydrogen ions.
Examples of the polybasic acid anhydride include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2′-3. , 3′-benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, nadic acid anhydride, methyl nadic acid anhydride, Trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-anhydride Maleic acid adduct, dodecenyl anhydride Acid, anhydride methylhymic Mick acid.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.
That is, in the epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the hydroxyl group of the epoxy adduct is 1 It is preferable that the polybasic acid anhydride structure of the polybasic acid anhydride has a ratio of 0.1 to 1.0.
Reaction Example 1, which is one of the reaction examples of the epoxy compound, the unsaturated monobasic acid, and the polybasic acid anhydride, is shown below, but the present invention is not limited to the following Reaction Example 1.

As the ethylenically unsaturated compound (A), the epoxy compound represented by the general formula (I), be used as R ¹ to R ⁸ is a hydrogen atom, an effect of easy availability and the present invention It is preferable from the viewpoint of further enhancement. From the same viewpoint, M is a group represented by (A) and R ^{9 to} R ¹⁶ are hydrogen atoms, or M is a group represented by (B), and R ^{17 to} R It is also preferred to use one in which ²⁴ is a hydrogen atom.
Further, those using 5 or less carbon atoms are preferable as the unsaturated basic acid, and those using acrylic acid, methacrylic acid or the like are particularly preferable. As the polybasic acid anhydride, those having a benzene ring or a saturated alicyclic ring are preferred, and those using biphenyltetracarboxylic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, biphthalic anhydride, etc. are particularly preferred.

In the curable composition of the present invention, the content of the ethylenically unsaturated compound (A) is not particularly limited, but a total of 100 masses of the ethylenically unsaturated compound (A) and the polymerization initiator (B). The amount is preferably 60 to 99.9 parts by mass, more preferably 70 to 95 parts by mass with respect to parts. If the content of the ethylenically unsaturated compound (A) is less than 60 parts by mass, a high-definition pattern may not be obtained. If it is greater than 99.9 parts by mass, a sufficient cured film may not be obtained. There is.
For example, when forming a cured film having a thickness of 1 to 3 μm, the content of the ethylenically unsaturated compound (A) is 100 parts by mass in total of the ethylenically unsaturated compound (A) and the polymerization initiator (B). On the other hand, it is preferably 60 to 99.9 parts by mass, and more preferably 70 to 95 parts by mass.

<Polymerization initiator (B)>
As a polymerization initiator (B) used for the curable composition of this invention, the compound represented by the said general formula (II) is preferable from the point of a sensitivity and heat resistance.

In the substituent represented by R ²⁵ and R ^{35 to} R ⁴⁸ in the general formula (II), an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a 7 to 20 carbon atom Examples of the arylalkyl group and the heterocyclic group having 2 to 20 carbon atoms include those exemplified above for R ^{9 to} R ²⁴ .

  Examples of the oxime ester radical polymerization initiator having a commercially available cycloalkylalkyl group include TR-PBG-304, TR-PBG-305, TR-PBG-309 (manufactured by TRONLY), and the like.

As the polymerization initiator (B), in the compound represented by the general formula (II), R ²⁵ is a methyl group or a phenyl group; R ³² is a hydrogen atom, 2-methylbenzoyl or a nitro group R ²⁹ and R ³⁰ are hydrogen atoms or bonded to each other to form a ring; R ²⁶ , R ²⁷ , R ²⁸ , R ³¹ , R ³³ , R ³⁴ are hydrogen atoms; X ² is a single atom; Those which are a bond or CO; those where n is an integer of 1 or 2; those where m is an integer of 3 are preferable from the viewpoint of further enhancing the effects of the present invention and availability.

In the curable composition of the present invention, the content of the polymerization initiator (B) is not particularly limited, but a total of 100 parts by mass of the ethylenically unsaturated compound (A) and the polymerization initiator (B). The amount is preferably 0.1 to 40 parts by mass, and more preferably 1.0 to 20 parts by mass. When the content of the polymerization initiator is smaller than 0.1 parts by mass, curing by exposure may be insufficient, and when it is larger than 40 parts by mass, the polymerization initiator may be precipitated in the curable composition. is there.
For example, when forming a cured film having a thickness of 1 to 3 μm, the content of the polymerization initiator (B) is 100 parts by mass in total of the ethylenically unsaturated compound (A) and the polymerization initiator (B). The amount is preferably 0.1 to 40 parts by mass, and more preferably 1.0 to 20 parts by mass.

<Colorant (C)>
As a coloring agent (C) used for the curable composition of this invention, an inorganic color material or an organic color material can be used, These can be used individually or in mixture of 2 or more types.
Examples of the inorganic color material or organic color material include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, and quinacridones. Compound, anthanthrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid, azo dye, metal complex compound of cyanine dye, lake pigment, furnace Carbon black obtained by the method, channel method or thermal method, or carbon black such as acetylene black, ketjen black or lamp black, Carbon black prepared or coated with an epoxy resin, carbon black previously dispersed with a resin in a solvent, 20 to 200 mg / g of resin adsorbed, and carbon black treated with an acidic or alkaline surface Carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a carbon black having a total oxygen amount calculated from CO and CO ₂ in a volatile content at 950 ° C. of 9 mg or more per 100 m ^{2 of} surface area, Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black, and other black pigments, chromium oxide green, miloli blue, Coba Ruto green, cobalt blue, manganese-based, ferrocyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridiane, emerald green, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), Organic or inorganic pigments such as cadmium red, synthetic iron black, and amber can be used.

  As the inorganic color material or organic color material, commercially available pigments can also be used. For example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 3, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, and the like.

  As the inorganic color material or organic color material, known dyes can be used. Known dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, Examples thereof include phthalocyanine dyes and cyanine dyes.

  When using the curable composition of this invention as a black matrix, a black pigment is used as a coloring agent (C). As the black pigment, carbon black or titanium black is preferably used.

In the curable composition of the present invention, the content of the colorant (C) is preferably 0 to 200 mass with respect to a total of 100 mass parts of the ethylenically unsaturated compound (A) and the polymerization initiator (B). Parts, more preferably 0 to 150 parts by mass. When the amount exceeds 200 parts by mass, the colorant tends to aggregate and storage stability may deteriorate.
For example, when forming a cured film having a thickness of 1 to 3 μm, the content of the colorant (C) is 100 parts by mass in total of the ethylenically unsaturated compound (A) and the polymerization initiator (B). Preferably it is 0-200 mass parts, More preferably, it is 0-150 mass parts.

<Coupling agent (D)>
In the curable composition of the present invention, a coupling agent (D) can be further used. Examples of the coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, etc. (Meth) acrylic acid ester functional alkoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- ( Epoxy-functional alkoxysilanes such as 3,4-epoxycyclohexyl) propyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-amino Aminofunctional alkoxysilanes such as propyltrimethoxysilane, mercaptofunctional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate functional alkoxysilanes such as 3-isocyanatopropyltriethoxysilane, 3-ureidopro Ureido functional alkoxysilanes such as rutrialkoxysilane, isocyanurate functional alkoxysilanes such as tris- (trimethoxysilylpropyl) isocyanurate, titanium alkoxides such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium dioctyloxy Titanium chelates such as bis (octylene glycolate) and titanium diisopropoxy bis (ethyl acetoacetate), zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate, zirconium tributoxy monostearate, etc. Zirconium acylates and isocyanate silanes such as methyl triisocyanate silane can be used. Methyl silane as Kokishishiran, epoxy functional alkoxy γ- glycidoxypropyltrimethoxysilane as the silane, methyl triisocyanate silane as an isocyanate silane, since high adhesiveness even after exposure to high temperature and high humidity preferable.

  Although the usage-amount of the said coupling agent (D) is not specifically limited, Preferably, it is 0-20 mass parts with respect to a total of 100 mass parts of an ethylenically unsaturated compound (A) and a polymerization initiator (B). It is a range. For example, when forming a cured film having a thickness of 1 to 3 μm, the content of the coupling agent (D) is 100 parts by mass in total of the ethylenically unsaturated compound (A) and the polymerization initiator (B). 0 to 20 parts by mass.

  In the curable composition of the present invention, a polymerizable compound having an ethylenically unsaturated bond can be further used. The polymerizable compound having an ethylenically unsaturated bond is not particularly limited, and those conventionally used in curable compositions can be used. For example, ethylene, propylene, butylene, isobutylene, vinyl chloride can be used. , Unsaturated aliphatic hydrocarbons such as vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, Isocrotonic acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω- A carboxypolycaprolactone mono (meth) acrylate, etc. having a carboxy group and a hydroxyl group at both ends Mer mono (meth) acrylates; having hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or one carboxyl group and two or more (meth) acryloyl groups Unsaturated monobasic acids such as polyfunctional (meth) acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, the following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (t-butyl) (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenylmaleimide, N -Unsaturated imides such as cyclohexylmaleimide; Indenes such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromolecules having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc .; vinyl chloride, vinylidene chloride, divinyls Cuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and vinyl isocyanate compounds of polyisocyanate compounds, hydroxyl groups Examples thereof include vinyl monomers containing vinyl monomers and polyepoxy compounds.

  In addition, as the polymerizable compound having an ethylenically unsaturated bond, an acrylic ester copolymer, a phenol and / or cresol novolac epoxy resin, or a polyphenylmethane type epoxy resin having a polyfunctional epoxy group may be used. it can.

  In the curable composition of the present invention, the content of the polymerizable compound having an ethylenically unsaturated bond other than the ethylenically unsaturated compound (A) is 5 with respect to 100 parts by mass of the ethylenically unsaturated compound (A). It is preferable that it is -50 mass parts, and it is more preferable that it is 10-40 mass parts.

Among the polymerizable compounds having an ethylenically unsaturated bond, when a compound having an acid value is used, alkali developability can be imparted to the curable composition of the present invention. When using the compound which has the said acid value, it is preferable to make the usage-amount become 50-99 mass% of the whole polymeric compound which has the said ethylenically unsaturated bond.
The compound having an acid value can be used after adjusting the acid value by further reacting with a monofunctional or polyfunctional epoxy compound. The alkali developability of the curable resin can be improved by adjusting the acid value of the compound having the acid value. The compound having an acid value (that is, a polymerizable compound having an ethylenically unsaturated bond imparting alkali developability) preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and is monofunctional or polyfunctional. The amount of the functional epoxy compound used is preferably selected so as to satisfy the acid value.

  Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl. Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the above-mentioned compound no. A2, No. A3 etc. are mentioned.

As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a colored curable resin composition with better characteristics can be obtained.
As the bisphenol type epoxy compound, an epoxy compound represented by the general formula (I) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) can be used such as methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds can also be used.

  In addition, the curable composition of the present invention may contain a compound that does not have an ethylenically unsaturated bond and imparts alkali developability. As such a compound, an alkaline aqueous solution is obtained by having an acid value. Although it is not particularly limited as long as it is a compound soluble in water, a typical example is an alkali-soluble novolak resin (hereinafter simply referred to as “novolak resin”). The novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like are used. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-xy Nord, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methyl resorcinol and bisphenol A are preferred. These phenols are used alone or in combination of two or more.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p N-butylbenzaldehyde and the like are used, and among these compounds, formal Dehydr, acetaldehyde and benzaldehyde are preferred. These aldehydes may be used alone or in combination of two or more. Aldehydes are preferably used in a proportion of 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of phenol.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid. The amount of these acid catalysts used is preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol per mol of phenols. In the condensation reaction, water is usually used as a reaction medium. However, if the phenols used in the condensation reaction do not dissolve in an aqueous solution of aldehydes and become heterogeneous from the beginning of the reaction, the reaction medium is hydrophilic. A solvent can also be used. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of the reaction medium used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. Although the reaction temperature of a condensation reaction can be suitably adjusted according to the reactivity of a reaction raw material, it is 10-200 degreeC normally, Preferably it is 70-150 degreeC. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally raised to 130 to 230 ° C., and the volatile component is distilled off under reduced pressure. Next, the melted novolac resin is collected on a steel belt or the like.
After completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane or n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.

  Examples other than the novolak resin include polyhydroxystyrene or a derivative thereof, styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, and the like.

  A solvent can be further added to the curable composition of the present invention. As the solvent, the above components (ethylenically unsaturated compound (A), polymerization initiator (B), colorant (C), coupling agent (D), etc.) are usually dissolved or dispersed as necessary. Solvents such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc .; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1, Ether solvents such as 2-diethoxyethane and dipropylene glycol dimethyl ether; esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol Solvent: ethylene glycol Cellosolve solvents such as methyl ether, ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate , Ether ester solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX systems such as benzene, toluene and xylene Solvent: Aliphatic hydrocarbon solvent such as hexane, heptane, octane, cyclohexane; Terpene hydrocarbon oil such as turpentine oil, D-limonene, pinene; Minera Paraffin solvents such as Spirit, Swazol # 310 (manufactured by Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (manufactured by Exxon Chemical); Halogenated aliphatics such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane Hydrocarbon solvents; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, etc. can be mentioned, and these solvents can be used as one or a mixture of two or more of them, among them, ketones, ether ester solvents, etc., especially propylene glycol- 1-monomethyl ether-2- Acetate (PGMEA), cyclohexanone, and the like are preferable because the coloring composition has good compatibility between the resist and the polymerization initiator.

  In the curable composition of the present invention, the amount of the solvent used is preferably such that the concentration of the composition other than the solvent is 5 to 30% by mass, and if it is less than 5% by mass, it is difficult to increase the film thickness. It is not preferable because it cannot sufficiently absorb light of a desired wavelength, and when it exceeds 30% by mass, the storage stability of the composition due to precipitation of the composition is decreased, and the viscosity is improved, so that handling is decreased. Absent.

  A dispersant can be further used in the curable composition of the present invention. As the dispersant, any dispersant can be used as long as it can disperse and stabilize the colorant (C). Commercially available dispersants such as BYK series manufactured by BYK Chemie can be used, and polyester having a basic functional group. , A polymer dispersant made of polyether or polyurethane, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / g Are preferably used.

  The curable composition of the present invention may further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable. In the curable composition of the present invention, the content of the inorganic compound is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the solid content of the curable composition. Yes, one or more of these inorganic compounds can be used.

By containing an inorganic compound in the curable composition of the present invention, it can be used as a curable paste composition. The curable paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.
These inorganic compounds are also suitably used as, for example, fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

  In addition, the curable composition of the present invention includes, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; a filler; Conventional additives such as a foaming agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect accelerator, a cross-linking agent, and a thickener can be added.

In the curable composition of the present invention, a conventionally known radical polymerization initiator can be used in combination with the polymerization initiator (B). Conventionally known radical polymerization initiators include photopolymerization initiators and thermal polymerization initiators.
Examples of the photopolymerization initiator include benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2- Morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2- Hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloro Methane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2-methyl-4,6-bis (Trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, 2,2-bis (2-Chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1-2′-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine, camphorquinone, N-1414, N -1717, N-1919, NCI-831, NCI-930 (manufactured by ADEKA), IRGACURE 369, IRGACURE 907, IRGACURE XE 01, IRGACURE OXE 02 (BASF), and the like,
As the thermal polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (methylisobutyrate), 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1 ′ -Azo initiators such as azobis (1-acetoxy-1-phenylethane); benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, di (4-t-butylcyclohexyl) per Examples thereof include peroxide initiators such as oxydicarbonate, and persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

  The curable composition of the present invention may further contain a chain transfer agent, a sensitizer, a surfactant, melamine, and the like.

  As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compound, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, Karenz PE1, NR1 manufactured by Showa Denko KK and the like.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

  In the curable composition of the present invention, ethylenic unsaturated compound (A), polymerization initiator (B), colorant (C), coupling agent (D), and ethylenically unsaturated compound (A) are excluded. The content of optional components other than the unsaturated compound and the solvent is appropriately selected depending on the purpose of use and is not particularly limited, but is preferably 20 parts by mass or less in total with respect to 100 parts by mass of the solid content of the curable composition. And

  The curable composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal, paper, plastic. It can be applied on a supporting substrate such as. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  In addition, as the light source of the active light used when the curable composition of the present invention is cured, a light source that emits light having a wavelength of 300 to 450 nm can be used. For example, ultrahigh pressure mercury, mercury vapor arc, carbon An arc, a xenon arc, or the like can be used.

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

  The curable composition of the present invention (or a cured product thereof) is a color in a curable paint or varnish, an adhesive, a printed board, or a color display liquid crystal display panel such as a color television, a PC monitor, a portable information terminal, or a digital camera. Filter, color filter of CCD image sensor, touch panel, electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, gel coat, photoresist for electronics, electroplating resist, etching resist, liquid and dry Both films, solder resists, insulating films, resists for making color filters for various display applications, or for forming structures in the manufacturing process of plasma display panels, electroluminescent display devices, and LCDs, electrical and electronic Composition for encapsulating parts, solder resist, Gas recording materials, micromechanical parts, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for producing 3D objects by stereolithography, holography Recording materials, image recording materials, fine electronic circuits, bleaching materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and visible laser direct It can be used for various applications such as a photoresist material for an image system, a photoresist material used for forming a dielectric layer in the sequential lamination of a printed circuit board, or a protective film, and the application is not particularly limited.

  The curable composition of the present invention is used for the purpose of forming a black matrix when a black pigment is used, and the black matrix is particularly useful for a color filter for a display device for an image display device such as a liquid crystal display panel. is there.

The black matrix includes (1) a step of forming a coating film of the curable composition of the present invention on a substrate, (2) a step of irradiating the coating film with active light through a mask having a predetermined pattern shape, (3) It is preferably formed by a step of developing the cured film with a developer (particularly an alkali developer), and (4) a step of heating the film after development. The colored composition of the present invention is also useful as an ink jet composition without a development process.
Manufacture of color filters for use in liquid crystal display panels, etc. is made by repeating the above steps (1) to (4) using the present invention or other colored compositions and combining patterns of two or more colors. Can do.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

[Production Example 1] Ethylenically unsaturated compound No. 1 Preparation of 1 184 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 58 g of acrylic acid, 0.26 g of 2,6-di-tert-butyl-p-cresol, tetra-n -0.11 g of butylammonium bromide and 105 g of PGMEA were charged and stirred at 120 ° C for 16 hours. The reaction solution was cooled to room temperature, 160 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and after stirring at 120 ° C. for 4 hours, at 100 ° C. for 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours, and at 40 ° C. for 11 hours, PGMEA 128 g was added to obtain a PGMEA solution As ethylenically unsaturated compound No. 1 (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mgKOH / g) was obtained.

[Production Example 2] Ethylenically unsaturated compound No. 1 Preparation of 2 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane 43 g, acrylic acid 11 g, 2,6-di-tert-butyl-p-cresol 0.05 g, tetrabutylammonium acetate 0.11 g and PGMEA 23 g were charged and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 35 g of PGMEA and 9.4 g of biphenyltetracarboxylic dianhydride were added and stirred at 120 ° C. for 8 hours. Further, 6.0 g of tetrahydrophthalic anhydride was added and stirred at 120 ° C. for 4 hours, 100 ° C. for 3 hours, 80 ° C. for 4 hours, 60 ° C. for 6 hours, and 40 ° C. for 11 hours, and then PGMEA 27 g was added to prepare a PGMEA solution As ethylenically unsaturated compound No. 2 was obtained (Mw = 4000, Mn = 2100, acid value (solid content) 86 mgKOH / g).

[Comparative Production Example 1] Comparative ethylenically unsaturated compound No. 1 Production of 1 9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p-cresol 0.273 g, tetrabutylammonium chloride 0.585 g And PGMEA 65.9 g, and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour and 120 ° C. for 14 hours. After cooling to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride, and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 90.0 g of 9,9-bis (4-glycidyloxyphenyl) fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol and 1.50 g of PGMEA were added, and 90 minutes at 90 ° C. After stirring at 120 ° C. for 4 hours, 122.2 g of PGMEA was added, and the comparative ethylenically unsaturated compound No. 1 as the target product as a PGMEA solution was added. 1 (Mw = 4190, Mn = 2170, acid value (solid content) 52 mg · KOH / g)

[Examples 1 to 5 and Comparative Examples 1 to 3] Preparation of curable compositions
Each component was mixed according to the mixing | blending of [Table 1], and the curable composition (Examples 1-5 and Comparative Examples 1-3) was obtained. In addition, a number represents a mass part.

[Evaluation Examples 1 to 5 and Comparative Evaluation Examples 1 to 3]
The following evaluation was performed in the curable compositions of Examples 1 to 5 and Comparative Examples 1 to 3.

[Evaluation method]
(OD value)
The curable composition was spin-coated on a glass substrate (10 cm × 10 cm), and heated at 100 ° C. for 100 seconds to form a 1.0 μm coating film on the surface of the glass substrate. Thereafter, using a proximity exposure machine manufactured by Microtech Co., Ltd., after exposure at an exposure amount of 40 mJ / cm ² , baking treatment was performed at 230 ° C. for 30 minutes to obtain a cured film. The OD value of the obtained cured film was measured using a Macbeth transmission densitometer, and the OD value per unit film thickness (/ μm) was calculated by dividing the OD value by the film thickness after post-baking. Generally, the higher the OD value, the better the light shielding property. The results are shown in Table 1.
(Pattern linearity)
The curable composition was spin-coated on a glass substrate (10 cm × 10 cm), and heated at 100 ° C. for 100 seconds to form a 1.0 μm coating film on the surface of the glass substrate. Then, using a proximity exposure machine manufactured by Microtech Co., Ltd., the film was exposed at an exposure amount of 40 mJ / cm ² (Gap 100 μm) through a negative mask on which a pattern with a line width of 6 μm was formed. The exposed film was developed with a 0.04 mass% KOH aqueous solution at 23 ° C. for 40 seconds and then baked at 230 ° C. for 30 minutes to obtain a pattern. The obtained 6 μm pattern was observed with an optical microscope, and the pattern linearity was evaluated. The pattern linearity was evaluated as “good” when the pattern did not have chipping or swelling, and “bad” when there was chipping or swelling. In general, it is known that chemical resistance is required for good pattern linearity. If the pattern linearity is good, high definition can be achieved. The results are shown in Table 1.
(Taper angle)
First, the curable composition was spin-coated on a glass substrate (10 cm × 10 cm) and heated at 100 ° C. for 100 seconds to form a 1.0 μm coating film on the surface of the glass substrate. Then, using a proximity exposure machine manufactured by Microtech Co., Ltd., the film was exposed at an exposure amount of 40 mJ / cm ² (Gap 100 μm) through a negative mask on which a pattern with a line width of 6 μm was formed. The exposed film is developed with a 0.04 mass% KOH aqueous solution at 23 ° C. for 40 seconds, then baked at 230 ° C. for 30 minutes, and a bonding angle (taper angle) between the pattern and the substrate with a scanning electron microscope. ) Was measured. This taper angle corresponds to the angle θ in (a) and (b) of FIG. 1 shown below. The measured taper angle is shown in the table. If the taper angle is an acute angle as shown in FIG. 1A, it means that there is no undercut in the pattern. If the taper angle is an obtuse angle as shown in FIG. 1B, the pattern is undercut. Means that exists. When an undercut is present in the pattern, the contrast of a display device using a black matrix produced from this curable composition as a color filter is lowered, resulting in poor image quality. The results are shown in Table 1.
(Minimum contact line width)
First, the photosensitive resin composition was spin-coated on a glass substrate (10 cm × 10 cm), and heated at 100 ° C. for 100 seconds, thereby forming a 1.0 μm coating film on the surface of the glass substrate. Thereafter, an exposure dose of 40 mJ / cm ² (Gap 100 μm) was passed through a negative type mask on which a plurality of types of patterns differing by 1 μm in a range of 1 to 20 μm were formed using a proximity exposure machine manufactured by Microtech. ). The exposed film was developed with 0.04 mass% KOH aqueous solution at 23 ° C. for 40 seconds and then baked at 230 ° C. for 30 minutes. Observed with an optical microscope, the line width of the photomask pattern having the smallest line width in which the peeling from the substrate was not observed among the above patterns having different line widths was defined as the minimum adhesion line width. The results are shown in Table 1.

From the above result, the curable composition of this invention has shown the favorable result in pattern linearity, a taper angle, and the minimum contact | adherence line | wire width compared with the existing curable composition. Therefore, it is particularly useful in a black matrix having high sensitivity and high definition and a color filter having excellent display quality.

Claims (7)

Ethylene which is a reaction product obtained by esterification reaction of an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the following general formula (I) and a polybasic acid anhydride A curable composition containing a polymerizable unsaturated compound (A) and a polymerization initiator (B) represented by the following general formula (II).

(In the formula, M represents a group represented by the following formula (I) or (B), and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and p is a number from 0 to 10. In the case where p is 1 or more, M is the following: (Formulas (a) and (b) may be used alone or in combination.)

(Wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Represents a C2-C20 heterocyclic group or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are adjacent to each other R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ^20. May form a ring.)

(In the formula, R ²⁵ represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. Or a heterocyclic group having 2 to 20 carbon atoms,
R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ are each independently a hydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R ³⁵ , OR ³⁶ , SR ³⁷ , NR ³⁸ R ³⁹ , COR ⁴⁰ , SOR ⁴¹ , SO ₂ R ⁴² or CONR ⁴³ R ⁴⁴ ,
X ¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁴⁵ R ⁴⁶ , CO, NR ⁴⁷ or PR ⁴⁸ ,
X ² represents a single bond or CO,
R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are each independently the number of carbon atoms. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms,
The hydrogen atom in the alkylene group in the alkyl group or arylalkyl group may be substituted with a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group or heterocyclic group, and in the alkyl group or arylalkyl group The alkylene of may be interrupted by -O-
R ²⁹ and R ³⁰ may be bonded to each other to form a ring,
n represents an integer of 1 to 5, and m represents an integer of 1 to 6. )   Furthermore, the curable composition of Claim 1 containing a coloring agent (C).   The curable composition according to claim 2, wherein the colorant (C) is a black pigment.   Furthermore, the curable composition as described in any one of Claims 1, 2, and 3 containing a coupling agent (D).   Hardened | cured material of the curable composition as described in any one of Claims 1, 2, 3, and 4.   The black matrix manufactured using the curable composition as described in any one of Claim 3 and 4. A color filter comprising the black matrix according to claim 6.

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