TWI781112B - Curable composition, cured product, and manufacturing method of cured product - Google Patents

Abstract

The present invention relates to a curable composition comprising: wet silica particles (A) with an average particle diameter of 50 nm or less, a polymerizable compound (B), a polymerization initiator (C) and a colorant (D ). Preferably, the content of the metal in the above-mentioned wet-type silica particles (A) is 1000 ppm or less. Moreover, it is preferable that the above-mentioned wet-type silica particles (A) are colloid-dispersed silica particles.

Description

Curable composition, hardened product and method for producing hardened product

The present invention relates to a curable composition containing silicon dioxide particles and a coloring agent.

A curable composition containing a polymerizable compound and a polymerization initiator (may contain a colorant if necessary) can be polymerized and hardened by irradiation with active energy rays such as ultraviolet rays or by heating, so it is used in various applications such as display materials useful in.

In recent years, black photoresists for color filters used in IPS/FFS (In-Plane Switching/Fringe Field Switching) mode liquid crystal displays require high light-shielding properties and high resistance (high Insulation), high precision, but there is the following problem, that is, there is no color filter with high resistance and high precision at a higher level.

In Patent Documents 1, 2, 3 and 4, compositions capable of producing high-resistance cured products are disclosed. Patent Document 1 discloses a photosensitive composition that contains a photocurable resin, acrylic resin particles, and a light-shielding pigment, and can obtain a cured product with high resistance. Patent Document 2 discloses a coloring composition that can obtain a high-resistance cured product by using a silica-coated coloring agent. Patent Document 3 discloses a coloring composition that can obtain a high-resistance hardened product by using silicon dioxide enclosed in carbon black. Patent Document 4 discloses a photosensitive resin composition for black photoresist that can obtain a cured product with high resistance by containing granular silica synthesized by a gas phase reaction, a black organic pigment, and a photocurable resin.

[Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2010-256589

Patent Document 2: Japanese Patent Laid-Open No. 2001-115043

Patent Document 3: Japanese Patent Laid-Open No. 2008-150428

Patent Document 4: Japanese Patent Laid-Open No. 2008-304583

However, the cured product obtained from the photosensitive composition described in Patent Document 1 has a problem of low light-shielding properties. The cured product obtained from the colored photosensitive material described in Patent Document 2 has the following problems: since the surface of the colorant is coated with silica, it presents a whitish color, and it is difficult to obtain a cured product with high jet blackness. In the cured product obtained from the coloring composition described in Patent Document 3, sufficient electrical resistance was not obtained. The photocurable resin described in Patent Document 4 has a problem of storage stability, and further has a problem of smoothness of the obtained cured product.

Therefore, an object of the present invention is to provide a curable composition capable of producing a cured product of a grade capable of producing high-resistance and high-definition patterns. Also, in the case of a curable composition using a black pigment as a colorant, a highly light-shielding cured product can be produced.

The present invention achieves the above objects by providing the following [1] to [8].

[1] A curable composition comprising: wet silica particles (A) with an average particle diameter of 50 nm or less [hereinafter also referred to as silica particles (A)], a polymerizable compound (B), A polymerization initiator (C) and a coloring agent (D).

[2] The curable composition according to the above [1], wherein the content of the metal in the silica particles (A) is 1000 ppm or less.

[3] The curable composition according to the above [1] or [2], wherein the polymerizable compound (B) is a compound represented by the following general formula (I), An unsaturated compound having a structure in which a compound represented by the following general formula (I) is esterified with an unsaturated monobasic acid, or an unsaturated compound having a structure in which the following general formula ( I) The epoxy compound represented by esterification with unsaturated monobasic acid is formed by esterification of unsaturated compound with polybasic acid anhydride.

(In the formula, M represents a direct bond, a hydrocarbon group with 1 to 20 carbon atoms, -O-, -S-, -SO ₂ -, -SS-, -SO-, -CO-, -OCO-, selected from the following For the substituents in the group represented by the above formula (a), (b), (c) or (d), the hydrogen atom in the group represented by M may be replaced by a halogen atom, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ (hereinafter also referred to as R ¹ to R ⁸ ) each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms or a halogen atom, and R ¹ The methylene group in the group represented by ~R ⁸ may also be substituted with -O- under the condition that it is not adjacent to oxygen, n is a number from 0 to 10, and when n is other than 0, there is A plurality of R ¹ to R ⁸ and M may be the same or different).

(In the formula, R ⁹ represents a hydrocarbon group with 1 to 20 carbon atoms, 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 , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ (hereinafter also referred to as R ¹⁰ to R ³⁸ ) each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, a group with 2 to 20 carbon atoms containing a heterocyclic ring, or a halogen atom, and R ¹⁰ to The methylene group in the group represented by R ³⁸ may be substituted with -O- or -S- under the condition that it is not adjacent to oxygen, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ²² and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ³⁰ and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ , R ³⁸ and R ³¹ , R ³¹ and R ³² , When R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ and R ³⁶ and R ³⁷ are bonded to form a ring, the * in the formula means that the group represented by the equation has the * part and the adjacent basis for bonding).

[4] The curable composition according to any one of the above [1] to [3], wherein the above-mentioned polymerization initiator (C) is a compound having a group represented by the following general formula (II).

(wherein, R ⁴¹ and R ⁴² independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms or a group with 2 to 20 carbon atoms containing a heterocyclic ring, R ⁴¹ and The hydrogen atom in the hydrocarbon group with 1 to 20 carbon atoms represented by R ⁴² or the group with 2 to 20 carbon atoms containing a heterocyclic ring is substituted by halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, In the case of methacryl group, acryl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or a group with 2 to 20 carbon atoms containing a heterocyclic ring, R ⁴¹ and R ⁴² represent The methylene group in the base is also substituted by -O-, -CO-, -COO-, -OCO-, -NR ⁴³ -, -NR ⁴³ CO-, -S-, -CS-, -SO ₂ In the case of -, -SCO-, -COS-, -OCS- or CSO-, R ⁴³ represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, m represents 0 or 1, and * in the formula means The base indicated is bonded with the adjacent base by the * moiety).

[5] The curable composition according to any one of the above [1] to [4], wherein the colorant (D) is a black pigment.

[6] A method for producing a cured product, comprising the steps of: using the curable composition according to any one of [1] to [5] above and curing the curable composition.

[7] A cured product of the curable composition described in any one of [1] to [5] above.

[8] A color filter comprising the cured product described in [7] above.

1( a ), ( b ) are schematic diagrams showing an angle θ corresponding to an inclination angle between a pattern formed on a substrate and the substrate.

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

The curable composition of the present invention contains wet silica particles (A) having an average particle diameter of 50 nm or less, a polymerizable compound (B), a polymerization initiator (C) and a colorant (D). Hereinafter, each component will be demonstrated sequentially.

<Silica particles (A)>

The silica particles (A) used in the curable composition of the present invention contain an average particle diameter of Wet silicon dioxide particles below 50nm. The so-called wet silica is amorphous silica synthesized in liquid. The silica particles (A) used in the curable composition of the present invention are, for example, a precipitation method or a gel method in which sodium silicate is neutralized with an inorganic acid, or a sol-gel method in which an alkoxysilane is hydrolyzed. obtained by law.

In the present invention, colloid-dispersed silica particles are particularly preferred among wet-type silica in terms of good dispersibility to polymerizable compounds or solvents, and from the same viewpoint, preferred are Surface treated silica.

The content of metals as impurities in the silica particles (A) used in the curable composition of the present invention is not particularly limited, but the content of metals is preferably less. The concentration of the metal in the silica particles (A) can be determined with high sensitivity by ICP-MS (Inductively coupled plasma-Mass spectrometry) after being dispersed in an appropriate dispersion medium To measure.

Moreover, iron, sodium, titanium, aluminum, potassium, calcium, zirconium, and magnesium are mentioned as a metal unpreferable if contained in a silica particle (A). The metal content in the silica particles (A) is preferably at most 1000 ppm, more preferably at most 100 ppm, still more preferably at most 1 ppm.

The silica particles (A) used in the curable composition of the present invention have an average particle diameter of 50 nm or less, so that a stable curable composition without impairing the dispersibility of the colorant and a self-curable composition can be obtained. The average particle diameter is preferably 30 nm or less, more preferably 20 nm or less, in terms of high fineness of the cured product. The lower limit of the average particle diameter of the silica particles (A) is not particularly limited, and may be 10 nm or more. The average particle diameter of the silica particles can be measured using a laser diffraction particle size distribution measuring device, and as the laser diffraction particle size distribution measuring device, a Microtrac particle size distribution meter manufactured by Nikkiso Co., Ltd. is exemplified.

The so-called surface-treated silica refers to one of the silanol groups on the surface of silica particles. Part or all of the chemical reaction can be exemplified by adding organic silicon compounds such as silicon dioxide particles and alkoxysilane compounds, solvents, and if necessary, hydrolyzing the above organic silicon compounds as catalysts. Acid or alkali and heating the silicon dioxide particles obtained.

As the above-mentioned silica particles (A), commercially available products can be preferably used, for example: PL-1-IPA, PL-1-TOL, PL-2L-PGME, PL-2L-MEK (above, Fuso chemical industry); YA010C-LDI, YA050C-LHI, YA010C-SP3 (manufactured by Admatechs); organic silicon sol MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST -UP, EG-ST, NPC-ST-30, PGM-ST, DMAC-ST, MEK-ST-40, MEK-ST-UP, MIBK-ST, MIBK-ST-L, CHO-ST-M, EAC -ST, PMA-ST, TOL-ST, MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Y, PGM-AC-4130Y, MIBK-AC-4130Y, MIBK-AC -2140Y, MIBK-SD-L, MEK-EC-2130Y, MEK-EC-6150P, MEK-EC-7150P, EP-F2130Y, EP-F6140P, EP-F7150P (manufactured by Nissan Chemical Industries, Ltd. above), etc.

In the curable composition of the present invention, the content of the above-mentioned silica particles (A) is not particularly limited, but it is preferably 0.1-70 parts by mass, more preferably 0.5 parts by mass relative to 100 parts by mass of the above-mentioned colorant (D). ~50 parts by mass, more preferably 5~20 parts by mass. When the content of the silica particles (A) is within the above range, a curable composition with excellent dispersibility of the silica particles and the colorant and a cured product with high resistance and high fineness can be obtained, so it is preferable. .

For example, when forming a cured product with a thickness of 1 to 3 μm, the content of the above-mentioned silica particles (A) is not particularly limited, but it is preferably 0.1 to 70 parts by mass relative to 100 parts by mass of the above-mentioned colorant (D). More preferably, it is 0.5-50 mass parts, More preferably, it is 5-20 mass parts.

<Polymerizable compound (B)>

The polymerizable compound (B) used in the curable composition of the present invention is a compound having polymerizable properties such as radical polymerization, cationic polymerization, and anionic polymerization. In terms of good reactivity and a wide variety of polymerizable compounds, Radical polymerizable compounds and cation polymerizable compounds can be preferably used.

唑啉、乙烯基咔唑、乙烯基吡咯啶酮、乙烯基吡啶、含羥基之乙烯基單體、聚異氰酸酯化合物之乙烯基胺基甲酸酯化合物、含羥基之乙烯基單體及多聚環氧化合物等乙烯基環氧化合物。 The radically polymerizable compound is not particularly limited, and conventionally known radically polymerizable compounds can be used, for example, ethylene, propylene, butene, isobutylene, vinyl chloride, vinylidene chloride, and vinylidene fluoride and tetrafluoroethylene and other unsaturated aliphatic hydrocarbons; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, bicycloheptenedicarboxylic acid, crotonic acid, methacrylic acid , vinyl acetic acid, allyl acetic acid, cinnamic acid, hexadienoic acid, mesaconic acid, mono[2-(meth)acryloxyethyl] succinate, mono[2-(methyl) phthalate Acryloxyethyl] ester and ω-carboxy polycaprolactone mono(meth)acrylate equal to the mono(meth)acrylate of a polymer with carboxyl and hydroxyl groups at both ends; hydroxyethyl (meth)acrylate ‧Maleic acid ester, hydroxypropyl (meth)acrylate ‧maleic acid ester, dicyclopentadiene‧maleic acid ester, and multi-functional ones with 1 carboxyl group and 2 or more (meth)acryl groups Unsaturated monobasic acids such as (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, tertiary butyl (meth)acrylate, cyclohexyl (meth)acrylate, ( n-octyl methacrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxyl (meth)acrylate Dimethylaminomethyl (meth)acrylate, Dimethylaminoethyl (meth)acrylate, Aminopropyl (meth)acrylate, Dimethylaminopropyl (meth)acrylate, Ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate, ( Phenoxyethyl methacrylate, Tetrahydrofuryl (meth)acrylate, Vinyl (meth)acrylate, Allyl (meth)acrylate, Benzyl (meth)acrylate, Ethylene glycol di(meth)acrylate ) 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, trimethylolethane tri(meth)acrylate, trimethylolpropane tri( Meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dihydrolinalool di Esters of unsaturated monobasic acids and polyols or polyphenols such as (meth)acrylates, tris[(meth)acrylethyl]isocyanurate and (meth)acrylic polyester oligomers; base) metal salts of unsaturated polybasic acids such as zinc acrylate and magnesium (meth)acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride Formic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxytetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyl Anhydrides of unsaturated polybasic acids such as tetrahydrophthalic anhydride-maleic anhydride adducts, dodecenyl succinic anhydride, and methylbicycloheptenedicarboxylic anhydride; (meth)acrylamide, methylenebis -(meth)acrylamide, diethylenetriaminetri(meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide and N-2-hydroxyethyl Amides of unsaturated monobasic acids such as ester (meth)acrylamide and polyamines; unsaturated aldehydes such as acrolein; (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide and allyl cyanide, etc. Unsaturated nitriles; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, ethylene Unsaturated aromatic compounds such as benzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone ; Unsaturated amine compounds such as vinylamine, allylamine, N-vinylpyrrolidone and vinylpiperidine; vinyl alcohol such as allyl alcohol and crotyl alcohol; vinyl methyl ether, vinyl ethyl ether, n-butyl ethylene Vinyl ethers such as ether, isobutyl vinyl ether, and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide ; Indene and 1-methylindene and other indenes; 1,3-butadiene, isoprene and chloroprene and other aliphatic conjugated dienes; polystyrene, polymethyl (meth)acrylate , Poly(meth)acrylic n-butyl ester and polysiloxane are macromonomers with mono(meth)acryl group at the end of the polymer molecular chain; vinyl chloride, vinylidene chloride, divinyl succinyl, Diallyl Phthalate, Triallyl Phosphate, Triallyl Isocyanurate, Vinyl Sulfide, Vinylimidazole, Vinyl

Azoline, vinylcarbazole, vinylpyrrolidone, vinylpyridine, hydroxyl-containing vinyl monomer, vinyl urethane compound of polyisocyanate compound, hydroxyl-containing vinyl monomer and polycyclic Vinyl epoxy compounds such as oxygen compounds.

As the above-mentioned radically polymerizable compound, commercially available products can also be used, for example, Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (above, manufactured by Nippon Kayaku); ARONIX M -215, M-350 (above, manufactured by Toa Gosei); NK Ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (above, Shin-Nakamura Chemical Industry manufactured); SPC-1000, SPC-3000 (above, manufactured by Showa Denko); etc.

[chemical 6]

In order to obtain a curable composition with good dispersibility of the colorant (D) and a cured product with good heat resistance, it is preferable that the polymerizable compound (B) is a compound represented by the above general formula (I); An unsaturated compound having a structure in which the compound represented by the above general formula (I) is esterified with an unsaturated monobasic acid; An unsaturated compound with a structure formed by esterification and an unsaturated compound with a structure formed by esterification with a polybasic acid anhydride. In particular, it is desirable that the above-mentioned polymerizable compound (B) has a structure obtained by esterifying the compound represented by the above-mentioned general formula (I) with an unsaturated monobasic acid, and has an unsaturated structure having a structure of [the following (g)] compound; or have the unsaturated compound having the structure that the compound represented by the above general formula (I) is esterified with an unsaturated monobasic acid and further esterified with a polybasic acid anhydride, and have [the following (h)] Unsaturated compounds of the structure.

The composition of the present invention preferably contains "the epoxy compound represented by the general formula (I)" as mentioned above, "the epoxy compound represented by the general formula (I) is esterified with an unsaturated monobasic acid." unsaturated compound of the structure" or "unsaturated compound having the following structure, which is an unsaturated compound having a structure formed by esterifying an epoxy compound represented by general formula (I) with an unsaturated monobasic acid Further, esterification with polybasic acid anhydride is used as a polymerizable compound (B). In the present invention, various compounds can be used as the unsaturated monobasic acid as described below and polyanhydrides. Therefore, the above "unsaturated compound having a structure formed by esterifying an epoxy compound represented by the general formula (I) with an unsaturated monobasic acid" and "an unsaturated compound having a structure such that The epoxy compound represented by the general formula (I) is esterified with an unsaturated monobasic acid, and the unsaturated compound is further esterified with a polybasic acid anhydride." The structure is based on the production of the polymerizable compound (B) The structure of the raw materials used varies greatly. Therefore, in the present situation, it is impossible to uniformly represent the structure of the unsaturated compound which is the ideal polymerizable compound (B) with a certain general formula, which is the technical common sense of the industry. Moreover, if the structure is not specified, it is also difficult to know its material properties determined by its structure, so it cannot be expressed in terms of properties. Therefore, in the present invention, the unsaturated compound that is more desirable as the above-mentioned polymerizable compound (B) has to be defined as the following expression: "the epoxy compound represented by the general formula (I) is esterified with an unsaturated monobasic acid. "unsaturated compound with a structure formed by chemical reaction", "unsaturated compound having a structure obtained by esterifying an epoxy compound represented by the general formula (I) with an unsaturated monobasic acid Unsaturated compounds are then esterified with polybasic acid anhydrides." That is, with regard to the ideal polymerizable compound (B) used in the present invention, there are situations in which "the situation of directly specifying the epoxy acrylate according to its structure or characteristics at the time of patent application" cannot be realized or is not very satisfactory. Reality.

(In the formula, Y ¹ represents the residue of an unsaturated monobasic acid, Y ² represents the residue of a polybasic acid anhydride, * in the formula means that the group represented by the equation is bonded to the adjacent group with the * part).

The hydrocarbon group with 1 to 20 carbon atoms represented by M in the above-mentioned general formula (I) is not particularly limited. Preferably, it represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and the like.

Examples of the above-mentioned alkylene group having 1 to 20 atoms include: methylene, ethylylene, propylylene, butyl, pentylene, hexylene, heptyl, octylene, and nonylene , Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl Alkyl, nonadecanyl, eicosyl, etc.

Examples of the cycloalkylene group having 3 to 20 carbon atoms include a cyclopropylidene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group.

The hydrocarbon group with 1 to 20 carbon atoms represented by R ¹ to R ³⁸ in the above general formula (I) is not particularly limited, and is preferably an alkyl group with 1 to 20 carbon atoms, or a hydrocarbon group with 2 to 20 carbon atoms. Alkenyl, cycloalkyl with 3 to 20 carbon atoms, cycloalkylalkyl with 4 to 20 carbon atoms, aryl with 6 to 20 carbon atoms and aralkyl with 7 to 20 carbon atoms, etc. In terms of good sensitivity when used as a polymerizable compound (B), alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and alkane groups having 1 to 10 carbon atoms are more preferable. Diyl group, cycloalkyl group with 3~10 carbon atoms, cycloalkylalkyl group with 4~10 carbon atoms, aryl group with 6~10 carbon atoms, aralkyl group with 7~10 carbon atoms, etc.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, iso Pentyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, undecyl, Dodecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl, etc. Examples of the above-mentioned alkyl group having 1 to 10 carbon atoms include methyl, ethyl, and propyl , isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, isopentyl, third pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl , the third octyl, nonyl, isononyl, decyl and isodecyl, etc.

Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-heptenyl, 3- Heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2 , 5-cyclohexadienyl-1-methyl, and 4,8,12-tetradecenyl allyl, etc. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl , 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2- Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, etc.

The above-mentioned cycloalkyl group having 3 to 20 carbon atoms refers to a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthalene, octahydropentadiene , bicyclo[1.1.1]pentyl, and tetra-dodecahydroanthracenyl, etc., as the cycloalkyl group having 3 to 10 carbon atoms, examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclo Hexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthalene, octahydropentalene and bicyclo[1.1.1]pentyl, etc.

The aforementioned cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atoms of the alkyl group are substituted by a cycloalkyl group. For example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, 2 -Cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecane Ethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl , 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4- Cyclononylbutyl, 4-cyclodecanylbutyl, 3-3-adamantylpropyl, decahydronaphthylpropyl, etc., as the cycloalkylalkyl group having 4 to 10 carbon atoms, for example, Examples: cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2 -Cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexyl Propyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, etc.

Examples of the above-mentioned aryl group having 6 to 20 carbon atoms include: phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthrenyl, etc., or one or more of the above-mentioned alkyl groups , phenyl, biphenyl, naphthyl, anthracenyl, etc. substituted by the above-mentioned alkenyl or carboxyl, halogen atoms, etc., such as 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methyl Phenyl, 2,4,6-trimethylphenyl, etc. Examples of the aryl group having 6 to 10 carbon atoms include: phenyl, tolyl, xylyl, ethylphenyl, naphthyl, etc. , or phenyl, biphenyl, naphthyl, anthracenyl, etc. substituted by one or more of the above-mentioned alkyl, above-mentioned alkenyl or carboxyl, halogen atoms, etc., such as 4-chlorophenyl, 4-carboxyphenyl, 4- -vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, etc.

The above-mentioned aralkyl group having 7 to 20 carbon atoms refers to a group having 7 to 30 carbon atoms in which hydrogen atoms of the alkyl group are replaced by aryl groups. Examples include: benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl, etc., and the above-mentioned aralkyl group with 7 to 20 carbon atoms means A group having 7 to 20 carbon atoms in which hydrogen atoms of an alkyl group are substituted by an aryl group. For example, benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, phenylethyl group, etc. are mentioned.

基、哌嗪基、哌啶基、吡喃基、吡喃基乙基、吡唑基、三嗪基、三嗪基甲基、吡咯啶基、喹啉基、異喹啉基、咪唑基、苯并咪唑基、三唑基、呋喃基、呋喃基、苯并呋喃基、噻吩基(thienyl)、苯硫基(thiophenyl)、苯并 噻吩基、噻二唑基、噻唑基、苯并噻唑基、

唑基、苯并

唑基、異噻唑基、異

唑基、吲哚基、嗎啉基、硫代嗎啉基、2-吡咯啶酮-1-基、2-哌啶酮-1-基、2,4-二氧基咪唑啶-3-基及2,4-二氧基

唑啶-3-基等，若包括取代基等在內具體地進行記載，則可列舉具有下述結構之基等。 ^The C2-C20 group containing a heterocyclic ring represented by R10- ^R38 in the above general formula (I) is not particularly limited, for example, pyrrolyl, pyridyl, pyridylethyl, pyrimidyl ,despair

Base, piperazinyl, piperidinyl, pyranyl, pyranylethyl, pyrazolyl, triazinyl, triazinylmethyl, pyrrolidinyl, quinolinyl, isoquinolinyl, imidazolyl, Benzimidazole, triazolyl, furyl, furyl, benzofuryl, thienyl, thiophenyl, benzothienyl, thiadiazolyl, thiazolyl, benzothiazolyl ,

Azolyl, benzo

Azolyl, isothiazolyl, iso

Azolyl, indolyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidinon-1-yl, 2,4-dioxyimidazolidin-3-yl and 2,4-dioxy

Azolidin-3-yl and the like are specifically described including substituents and the like, and examples thereof include groups having the following structures.

(In the above formula, R independently represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, and Z represents a direct bond or an alkylene group with 1 to 6 carbon atoms. Furthermore, * in the formula means that the The group represented by the formula is bonded to the adjacent group with * moiety).

Examples of the above-mentioned alkyl group having 1 to 6 carbon atoms include those having 1 to 6 carbon atoms among those exemplified above as the alkyl group having 1 to 20 carbon atoms.

Examples of the alkylene group having 1 to 6 carbon atoms include those having 1 to 6 carbon atoms among those exemplified as the alkylene group having 1 to 20 carbon atoms represented by M.

Examples of the halogen atom in the general formula (I) include fluorine, chlorine, bromine, and iodine.

、嗎啉、硫代嗎啉、四氫吡啶、內酯環及內醯胺環等5~7員環以及萘及蒽等縮合環等。 R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ²² and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ³⁰ and R ²³ in the above general formula (I) , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ , R ³⁸ and R ³¹ , R ³¹ and R ³² , R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ and R ³⁶ and R ³⁷ are bonded The formed rings include, for example, cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperidine

, morpholine, thiomorpholine, tetrahydropyridine, lactone ring and lactamide ring and other 5-7-membered rings and condensed rings such as naphthalene and anthracene, etc.

The above-mentioned unsaturated monobasic acid refers to an acid having an unsaturated bond in the structure and having one hydrogen atom capable of dissociating to become a hydrogen ion per molecule. Examples of the unsaturated monobasic acid include: acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, hexadienoic acid, hydroxyethyl methacrylate-maleate, hydroxypropyl methacrylate-maleate, Hydroxypropyl acrylate‧maleate and dicyclopentadiene‧maleate, etc.

The term "polybasic acid anhydride" refers to an acid anhydride of a polybasic acid having two or more hydrogen atoms that can dissociate to become hydrogen ions per molecule.

Examples of the polybasic acid anhydride include: biphenyltetracarboxylic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, biphenyltetracarboxylic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, Pyrellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol dianhydrotrimellitic acid Esters, Glyceryl Tridehydrated Trimellitate, Hexahydrophthalic Anhydride, Methyltetrahydrophthalic Anhydride, Resilicate Anhydride, Methyl Resilicate Anhydride, Trialkyl Tetrahydrophthalic Anhydride , 5-(2,5-dioxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride addition substances, dodecenyl succinic anhydride and methyl bicycloheptene dicarboxylic anhydride, etc.

It is preferable to set the reaction ratio of the epoxy compound represented by the said general formula (I), the said unsaturated monobasic acid, and the said polybasic acid anhydride as follows.

That is, it is preferable to set the ratio as follows: in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the above-mentioned unsaturated monobasic acid are added to one epoxy group of the above-mentioned epoxy compound, The polybasic acid anhydride structure of the said polybasic acid anhydride is made into 0.1-1.0 pieces with respect to 1 hydroxyl group of this epoxy adduct.

The reaction example of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride is shown below, However, this invention is not limited to following reaction scheme 1.

As the above-mentioned polymerizable compound (B), it is preferable to use R ¹ to R 1 among the above-mentioned reaction products in terms of ease of acquisition or a high OD value when carbon black is added as a colorant. ⁸ is a hydrogen atom as an epoxy compound represented by the general formula (I). Also, from the same point of view, it is also preferable to use: M is the group represented by (c) and the groups represented by R ¹⁰ to R ¹⁴ are hydrogen atoms or phenyl groups, M is represented by (d) and R ¹⁵ to R ²² are hydrogen atoms or phenyl groups, M is a group represented by (e) and R ²³ to R ³⁰ are hydrogen atoms or phenyl groups, or M is a group represented by (f) and R ³¹ ~ R ³⁸ are hydrogen atoms or phenyl groups. In particular, it is more preferable that M is the group represented by (d) in terms of the high volume resistance of the cured product.

In addition, as the above-mentioned unsaturated monobasic acid, it is preferable to use an unsaturated monobasic acid having 5 or less carbon atoms, and it is particularly preferable to use an unsaturated monobasic acid such as acrylic acid or methacrylic acid. Also, as the polybasic acid anhydride, one having a benzene ring or a saturated aliphatic ring is preferable, and biphenyltetracarboxylic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, biphenyltetracarboxylic anhydride, etc. are preferably used. The polybasic acid anhydride.

As the polymerizable compound (B) of the present invention, a product based on the following production method is preferably used in terms of good dispersibility and curability of the colorant, but is not limited thereto.

Specifically, for example, 1,1-bis[4-(2,3-epoxypropoxy)phenyl]indan is selected as the epoxy compound represented by the above general formula (I), and acrylic acid is selected as the unsaturated monovalent Acid, choose biphenyltetracarboxylic anhydride as the product of polybasic anhydride; choose 1,1-bis[4-(2,3-epoxypropoxy)phenyl]indane as the product of the above general formula (I) For the epoxy compound represented, choose acrylic acid as the unsaturated monobasic acid, choose tetrahydrophthalic anhydride as the product of polybasic acid anhydride; choose 1,1-bis[4-(2,3-epoxypropoxy ) phenyl] indane as the epoxy compound represented by the above general formula (I), select acrylic acid as the unsaturated monobasic acid, select phthalic anhydride as the product formed from the polybasic acid; select 1,1-bis[ 4-(2,3-epoxypropoxy) phenyl] indane is used as the epoxy compound represented by the above general formula (I), acrylic acid is selected as the unsaturated monobasic acid, biphenyltetracarboxylic anhydride and tetrahydro-ortho Phthalic anhydride is a product of polybasic acid anhydride and 1,1-bis[4-(2,3-epoxypropoxy)phenyl]-3-phenylindane is selected as the above general formula (I) The epoxy compound represented is a product obtained by selecting acrylic acid as the unsaturated monobasic acid, biphenyl tetracarboxylic anhydride and tetrahydrophthalic anhydride as the polybasic acid anhydride, etc.

Among the above radical polymerizable compounds, 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 it into 50-99 mass parts with respect to 100 mass parts of polymerizable compounds which have the said radical polymerizability about the usage-amount.

Moreover, the compound which has the said acid value can also be used after adjusting an acid value by making a monofunctional or polyfunctional epoxy compound react further. The alkali developability of the curable composition can be improved by adjusting the acid value of the above-mentioned compound having an acid value. The above-mentioned compound with an acid value (that is, a radically polymerizable polymerizable compound that imparts alkali developability) is preferably in the range of 5 to 120 mgKOH/g in the acid value of the solid content, and the monofunctional or polyfunctional epoxy compound The amount used is preferably selected so as to satisfy the above-mentioned 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, isopropyl glycidyl ether, Butyl glycidyl ether, tertiary butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, ten Monoalkyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethyl Hexyl glycidyl ether, allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxyglycidyl ether, p-butylphenol glycidyl ether 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, cyclo Oxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monoxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, formazan Styrene oxide, cyclohexene oxide, propylene oxide, the above compounds No.A1~No.A4, etc.

It is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers as the polyfunctional epoxy compound because a curable composition with further favorable properties can be obtained.

As said bisphenol type epoxy compound, the bisphenol type epoxy compound represented by the said General formula (I) can be used, for example, the bisphenol type epoxy compound, such as a hydrogenated bisphenol type epoxy compound, can also be used.

In addition, as the glycidyl ethers, 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(glycidyl ether) Glyceryloxymethyl) propane, 1,1,1-tris(glycidyloxymethyl)ethane, 1,1,1-tris(glycidyloxymethyl)methane and 1,1,1,1 -Tetrakis(glycidyloxymethyl)methane and the like.

In addition, phenolic novolak-type epoxy compounds, biphenyl novolac-type epoxy compounds, cresol novolac-type epoxy compounds, bisphenol A novolak-type epoxy compounds, dicyclopentadiene novolac-type epoxy compounds, Novolak-type epoxy compounds such as epoxy compounds; 3,4-epoxy-6-methylcyclohexyl carboxylic acid Hexane carboxylic acid 3,4-epoxy Alicyclic epoxy compounds such as cyclohexyl methyl ester and 1-oxiranyl-3,4-epoxycyclohexane; diglycidyl phthalate, diglycidyl tetrahydrophthalate and di Glycidyl esters such as polyglycidyl esters; glycidyl amines such as tetraglycidyldiaminodiphenylmethane, triglycidyl p-aminophenol and N,N-diglycidylaniline; 1,3- Heterocyclic epoxy compounds such as diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dioxide compounds such as dicyclopentadiene dioxide; naphthalene rings Oxygen compounds; triphenylmethane type epoxy compounds and dicyclopentadiene type epoxy compounds, etc.

As said cationically polymerizable compound, an epoxy compound, an oxetane compound, a vinyl ether compound, etc. are mentioned.

烷、亞甲基雙(3,4-環氧環己烷)、丙烷- 2,2-二基雙(3,4-環氧環己烷)、2,2-雙(3,4-環氧環己基)丙烷、伸乙基雙(3,4-環氧環己烷羧酸酯)、己二酸雙(3,4-環氧環己基甲基)酯、3,4-環氧環己烷羧酸3,4-環氧環己基甲酯、3,4-環氧-1-甲基己烷羧酸3,4-環氧-1-甲基環己酯、6-甲基-3,4-環氧環己烷羧酸6-甲基-3,4-環氧環己基甲酯、3,4-環氧-3-甲基環己烷羧酸3,4-環氧-3-甲基環己基甲酯、3,4-環氧-5-甲基環己烷羧酸3,4-環氧-5-甲基環己基甲酯、1-環氧乙基-3,4-環氧環己烷、1,2-環氧-2-環氧乙基環己烷、二環氧化二環戊二烯、羧酸3,4-環氧-6-甲基環己酯、α-氧化蒎烯、環氧苯乙烷、氧化環己烯及氧化環戊烯等環氧環烷基型化合物及N-縮水甘油基鄰苯二甲醯亞胺等。 Examples of the epoxy compound include: methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, C12~13 mixed alkyl glycidyl ether, phenyl- 2-Methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether, p-2-butylphenyl glycidyl ether, p-3-butylphenyl glycidyl ether, glycidyl methacrylate , isopropyl glycidyl ether, allyl glycidyl ether, ethyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, 4-n-butylphenyl glycidyl ether, 4- Phenylphenol glycidyl ether, cresyl glycidyl ether, dibromocresyl glycidyl ether, decyl glycidyl ether, methoxypolyethylene glycol monoglycidyl ether, ethoxypolyethylene glycol monoglycidyl ether , butoxy polyethylene glycol monoglycidyl ether, phenoxy polyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentane Diol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2,2-tetra(glycidyloxyphenyl)ethane and pentaerythritol tetra Glycidyl ether compounds such as glycidyl ether; glycidyl esters such as glycidyl acetate and glycidyl stearate; 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy ) Cyclohexane-1,3-di

alkane, methylenebis(3,4-epoxycyclohexane), propane-2,2-diylbis(3,4-epoxycyclohexane), 2,2-bis(3,4-cyclohexane Oxycyclohexyl) propane, ethylidene bis(3,4-epoxycyclohexanecarboxylate), adipate bis(3,4-epoxycyclohexylmethyl)ester, 3,4-epoxycyclohexane 3,4-epoxycyclohexylmethyl hexanecarboxylate, 3,4-epoxy-1-methylcyclohexylhexanecarboxylate, 6-methyl- 3,4-epoxycyclohexanecarboxylic acid 6-methyl-3,4-epoxycyclohexyl methyl ester, 3,4-epoxy-3-methylcyclohexanecarboxylic acid 3,4-epoxy- 3-Methylcyclohexyl methyl ester, 3,4-epoxy-5-methylcyclohexyl carboxylic acid 3,4-epoxy-5-methylcyclohexyl methyl ester, 1-oxiranyl-3, 4-epoxycyclohexane, 1,2-epoxy-2-oxiranylcyclohexane, diepoxidized dicyclopentadiene, 3,4-epoxy-6-methylcyclohexyl carboxylate , α-pinene oxide, styrene oxide, cyclohexene oxide, cyclopentene oxide and other epoxy cycloalkyl compounds and N-glycidyl phthalimide, etc.

As the above-mentioned epoxy compound, epoxidized polyolefin can also be used. The so-called epoxidized polyolefin refers to the polyolefin introduced with epoxy group by modifying polyolefin with monomer containing epoxy group. It can be produced by copolymerizing ethylene or α-olefins with 3 to 20 carbons, monomers containing epoxy groups, and other monomers as needed by any method of copolymerization or grafting. Ethylene or α-olefins with 3 to 20 carbons, epoxy group-containing monomers and other monomers can be polymerized individually, or can be polymerized with other monomers in multiples. Moreover, it can also be obtained by epoxidizing the double bond of the non-conjugated polybutadiene which has a hydroxyl group at the terminal by the peracetic acid method, and the thing which has a hydroxyl group in a molecule|numerator can also be used. Moreover, it is also possible to urethanize a hydroxyl group with an isocyanate, and to introduce an epoxy group by making it react with the epoxy compound containing a primary hydroxyl group here.

Examples of ethylene or α-olefins having 3 to 20 carbon atoms include ethylene, propylene, butene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-Dimethyl-1,3-butadiene, pentadiene, 3-butyl-1,3-octadiene and isoprene, etc.

Examples of the epoxy group-containing monomer include glycidyl esters of α,β-unsaturated acids, vinylbenzyl glycidyl ether, and allyl glycidyl ether. As an α,β-unsaturated acid Specific examples of glycidyl esters include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, and glycidyl methacrylate is particularly preferred.

唑啉、乙烯基咔唑、乙烯基吡咯啶酮、乙烯基吡啶、含羥基之乙烯基單體及聚異氰酸酯化合物之乙烯基胺基甲酸酯化合物、含羥基之乙烯基單體及多聚環氧化合物之乙烯基環氧化合物、季戊四醇三丙烯酸酯及二季戊四醇五丙烯酸酯等含羥基之多官能丙烯酸酯；甲苯二異氰酸酯及六亞甲基二異氰酸酯等多官能異氰酸酯之反應物；作為季戊四醇三丙烯酸酯及二季戊四醇五丙烯酸酯等含羥基之多官能丙烯酸酯與琥珀酸酐、鄰苯二甲酸酐及四氫鄰苯二甲酸酐等二元酸酐之反應物的具有酸值之多官能丙烯酸酯。 Examples of the above-mentioned other monomers include: unsaturated aliphatic hydrocarbons such as vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid , citraconic acid, fumaric acid, bicycloheptenedicarboxylic acid, crotonic acid, methacrylic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, hexadienoic acid, mesaconic acid, succinic acid mono[2-(methyl) Acryloxyethyl] ester, phthalate mono[2-(meth)acryloxyethyl] ester, ω-carboxy polycaprolactone mono(meth)acrylate are equal to having carboxyl and Mono(meth)acrylate of hydroxyl polymer, hydroxyethyl (meth)acrylate‧maleate, hydroxypropyl(meth)acrylate‧maleate, dicyclopentadiene‧maleic acid Esters and unsaturated polyacids such as polyfunctional (meth)acrylates with one carboxyl group and two or more (meth)acryl groups; (meth)acrylate-2-hydroxyethyl ester, (meth)acrylic acid -2-Hydroxypropyl, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, cyclohexyl (meth)acrylate , n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylic acid Methoxyethyl ester, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminopropyl (meth)acrylate ester, ethoxyethyl (meth)acrylate, poly(ethoxy)ethyl (meth)acrylate, butoxyethoxyethyl (meth)acrylate, ethylhexyl (meth)acrylate , phenoxyethyl (meth)acrylate, 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, trimethylolethane tri(meth)acrylate, trimethylolpropane Tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dihydrolinalyl Esters of unsaturated monobasic acids and polyols or polyphenols such as alcohol di(meth)acrylate, tris[(meth)acrylethyl]isocyanurate and (meth)acrylic polyester oligomers; Metal salts of unsaturated polyacids such as zinc (meth)acrylate and magnesium (meth)acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride Anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxytetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrofuryl Hydrogen phthalic anhydride-maleic anhydride adduct, dodeca Anhydrides of unsaturated polybasic acids such as alkenyl succinic anhydride and methylbicycloheptenedicarboxylic anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetri( Meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth)acrylamide and other unsaturated monobasic acids and polyamines Amide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, allyl cyanide, etc.; styrene, 4-methylstyrene, 4-ethyl Styrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzene Unsaturated aromatic compounds such as sulfonic acid, vinyl benzyl methyl ether and vinyl naphthalene; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone and vinyl piperidine Unsaturated amine compounds such as allyl alcohol and crotyl alcohol and other vinyl alcohols; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether and isobutyl vinyl ether; maleimide, N-phenyl Unsaturated imides such as maleimide and N-cyclohexylmaleimide; indene such as indene and 1-methylindene; polystyrene, poly(meth)acrylate, poly(meth) Base) n-butyl acrylate and polysiloxane are macromonomers with mono(meth)acryl groups at the end of the polymer molecular chain; vinyl chloride, vinylidene chloride, divinyl succinyl, phthalic acid Diallyl ester, triallyl phosphate, triallyl isocyanurate, vinyl sulfide, vinylimidazole, vinyl

Azoline, vinylcarbazole, vinylpyrrolidone, vinylpyridine, hydroxyl-containing vinyl monomers and vinyl urethane compounds of polyisocyanate compounds, hydroxyl-containing vinyl monomers and polycyclic rings Oxygen compounds such as vinyl epoxy compounds, pentaerythritol triacrylate and dipentaerythritol pentaacrylate and other hydroxyl-containing polyfunctional acrylates; reactants of polyfunctional isocyanates such as toluene diisocyanate and hexamethylene diisocyanate; as pentaerythritol triacrylate Polyfunctional acrylates with acid value that are reactants of hydroxyl-containing polyfunctional acrylates such as esters and dipentaerythritol pentaacrylate and dibasic anhydrides such as succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride.

Commercially available products can also be used as the above-mentioned epoxidized polyolefin, for example, Epolead PB3600, Epolead PB4700 (the above, manufactured by Daicel); BF-1000, FC-3000 (the above, manufactured by ADEKA); Bondfast 2C, Bondfast E, Bondfast CG5001, Bondfast CG5004, Bondfast 2B, Bondfast 7B, Bondfast 7L, Bondfast 7M, Bondfast VC40 (above, manufactured by Sumitomo Chemical); JP-100, JP-200 (above, manufactured by Nippon Soda); Poly bd R-45HT, Poly bd R-15HT (above, manufactured by Idemitsu Kosan); and Ricon657 (manufactured by Arkema); etc.

Examples of the oxetane compound include: 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[(3-ethyl-3- Oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl -3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxa Cyclobutylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl- 3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl ) Oxetane, 3-ethyl-3-(chloromethyl)oxetane, etc.

Examples of the vinyl ether compound include diethylene glycol monovinyl ether, triethylene glycol divinyl ether, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloro Ethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monoethylene ether, ethylene glycol divinyl ether, 1,4-butanediol divinyl ether and 1,6-cyclohexanedimethanol divinyl ether, etc.

As the above-mentioned cationically polymerizable compound, commercially available products can also be used, for example: Epolight 40E, 1500NP, 1600, 80MF, 4000 and 3002 (above, manufactured by Kyoeisha Chemical); ADEKA Glycyrol ED-503, ED-503D, ED-503G, ED-523T, ED-513, ED-501, ED-502, ED-509, ED-518, ED-529, Adeka Resin EP-4000, EP-4005, EP-4080 and EP-4085( above, manufactured by ADEKA); DENACOL EX-201, EX-203, EX-211, EX-212, EX-221, EX-251, EX-252, EX-711, EX-721, DENACOL EX-111, EX- 121, EX-141, EX-142, EX-145, EX-146, EX-147, EX-171, EX-192 and EX-731 (above, manufactured by Nagase Kasei); EHPE-3150, Celloxide 2021P, 2081 , 2000 and 3000 (above, manufactured by Daicel); EPIOLM, EH, L-41, SK, SB, TB and OH (above, manufactured by NOF); Epolight M-1230 and 100MF (above, manufactured by Kyoeisha Chemical); ARONE OXETANE OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211 and OXT-212 (above, manufactured by Toagosei); ETERNACOLL OXBP and OXTP (above, manufactured by Ube Industries); 2- Hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical); DENACOL EX-121, EX-141, EX-142, EX-145, EX-146 , EX-147, EX-201, EX-203, EX-711, EX-721, Oncoat EX-1020, EX-1030, EX-1040, EX- 1050, EX-1051, EX-1010, EX-1011, and 1012 (above, manufactured by Nagase Chemicals); OGSOL PG-100, EG-200, EG-210, and EG-250 (above, manufactured by Osaka Gas Chemicals); HP4032 , HP4032D and HP4700 (above, manufactured by DIC); ESN-475V (manufactured by Tohto Kasei); Epikote YX8800 (manufactured by Mitsubishi Chemical); Marproof G-0105SA and G-0130SP (above, manufactured by NOF); EPICLON N-665 and HP -7200 (above, manufactured by DIC); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H and NC-7000L (above , manufactured by Nippon Kayaku); etc.

In the curable composition of the present invention, the content of the polymerizable compound (B) is not particularly limited, relative to the silica particles (A), the polymerizable compound (B), the polymerization initiator (C) and the coloring agent (D) is preferably 10 to 70 parts by mass, more preferably 20 to 50 parts by mass, and still more preferably 30 to 50 parts by mass, in terms of good curability for 100 parts by mass in total. When the content of the polymerizable compound (B) is within the above range, the obtained cured product is excellent in curability and light-shielding properties, which is preferable.

For example, when forming a cured product with a thickness of 1 to 3 μm, the content of the polymerizable compound (B) is not particularly limited. ) in a total of 100 parts by mass, preferably 10 to 70 parts by mass, more preferably 30 to 60 parts by mass, further preferably 30 to 50 parts by mass.

<Polymerization initiator (C)>

As the polymerization initiator (C) used in the curable composition of the present invention, conventionally known radical polymerization initiators and cationic polymerization initiators can be used.

The radical polymerization initiator mentioned above refers to a photo radical polymerization initiator and a thermal radical polymerization initiator. A photoradical polymerization initiator is more preferable in terms of high reactivity.

系化合物及肟酯系化合物等作為較佳者。 The photoradical polymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and previously known compounds can be used, for example, acetophenone-based compounds, benzoyl-based compounds, diphenyl Methanone compounds, 9-oxosulfur

Compounds and oxime ester compounds are preferred.

Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2 -Methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone , p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzylidene acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-(Methylthio)phenyl]-2-morpholinoacetone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 , benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- Methyl-1-propan-1-one, etc.

Examples of the benzoyl compound include benzoyl and the like.

Examples of benzophenone-based compounds include benzophenone, methyl o-phthalbenzoate, michelerone, 4,4'-bisdiethylaminobenzophenone, 4,4 '-Dichlorobenzophenone and 4-benzoyl-4'-methyl diphenyl sulfide, etc.

系化合物，可列舉：9-氧硫

、2-甲基9-氧硫

、2-乙基9-氧硫

、2-氯9-氧硫

、2-異丙基9-氧硫

、2,4-二乙基9-氧硫

等。 as 9-oxosulfur

series compounds, such as: 9-oxosulfur

, 2-methyl 9-oxosulfur

, 2-Ethyl 9-oxosulfur

, 2-chloro 9-oxysulfur

, 2-isopropyl 9-oxosulfur

, 2,4-Diethyl 9-oxosulfur

Wait.

The so-called oxime ester compound means a compound having a group represented by the above-mentioned general formula (II). Among the above-mentioned photoradical polymerization initiators, the oxime ester compound has good sensitivity, so it can be preferably used in this invention. The curable composition of the invention.

The hydrocarbon groups with 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴³ in the above general formula (II) are the same as the hydrocarbon groups with 1 to 20 carbon atoms represented by R ¹ to R ³⁸ respectively.

R ⁴¹ and R ⁴² in the above general formula (II) and the group represented by R ⁴¹ or R ⁴² are modified, and the group with 2 to 20 carbon atoms containing a heterocyclic ring is represented by R ¹⁰ to R ³⁸ The group having 2 to 20 carbon atoms containing a heterocyclic ring is the same.

The halogen atom in the above general formula (II) is the same as the halogen atom in the above general formula (I).

Among the compounds having a group represented by the above-mentioned general formula (II), the compound represented by the following general formula (III) has a high sensitivity and is therefore more suitable for use in the curable composition of the present invention.

(In the formula, R ⁴¹ , R ⁴² and m are respectively the same as R ⁴¹ , R ⁴² and m in the general formula (II), and R ⁵¹ and R ⁵² independently represent a hydrogen atom, a cyano group, and a carbon atom number of 1 to 20 Alkyl group with 6~20 carbon atoms, aryl group with 6~20 carbon atoms, aralkyl group with 7~20 carbon atoms or heterocyclic group with ² ~20 carbon atoms, X1 represents oxygen atom, sulfur atom, selenium atom, CR ⁵³ R ⁵⁴ , CO, NR ⁵⁵ or PR ⁵⁶ , R ⁵¹ to R ⁵⁶ independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms or a group with 2 to 20 carbon atoms containing a heterocyclic ring, R ⁵³ to R ⁵⁶ The hydrogen atoms in the groups represented may also be substituted by halogen atoms, nitro, cyano, hydroxyl, carboxyl or heterocyclic groups, and the methylene groups in the groups represented by R ⁵¹ ~ R ⁵⁶ may also be present in different In the case of being substituted with -O- under the condition of being adjacent to oxygen, R ⁵¹ ~ R ⁵⁶ may also independently form a ring with any adjacent benzene ring, g represents the number from 0 to 5, h represents number from 0 to 4).

R ⁵¹ and R ⁵² in the general formula (III) represent alkyl groups with 1 to 20 carbon atoms, aryl groups with 6 to 20 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, and heterocyclic ring-containing A group with 2 to 20 carbon atoms is an alkyl group with 1 to 20 carbon atoms represented by R ¹ to R ³⁸ , an aryl group with 6 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, and a group containing The groups having 2 to 20 carbon atoms of the heterocycle are the same.

The halogen atom in the general formula (III) is the same as the halogen atom in the above-mentioned general formula (I).

The hydrocarbon groups with 1 to 20 carbon atoms represented by R ⁵³ to R ⁵⁶ in the above general formula (III) are the same as the hydrocarbon groups with 1 to 20 carbon atoms represented by R ¹ to R ³⁸ respectively.

R ⁵³ ~ R ⁵⁶ in the above-mentioned general formula (III) represent the group containing 2 ~ 20 carbon atoms of the heterocycle and the group represented by R ¹⁰ ~ R ³⁸ containing the group of 2 ~ 20 carbon atoms containing the heterocycle same.

Examples of the compound represented by the above-mentioned general formula (III) include the compounds shown below. However, the present invention is not limited in any way by the following compounds.

[chemical 12]

Examples of other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(cyclopentadienyl)-bis[2,6 - titanocene-based compounds such as difluoro-3-(pyrrol-1-yl)]titanium, and the like.

Examples of commercially available free radical initiators include: Adeka Optomer N-1414, N-1717, N-1919, Adeka Arkls NCI-831, NCI-930 (above, manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907 , IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (the above, manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309, and TR-PBG-314 (the above, manufactured by Tronly); etc.

The thermal radical polymerization initiator is not particularly limited as long as it generates free radicals by heating, and previously known compounds can be used, for example, azo compounds, peroxides, and persulfates can be exemplified as comparative examples. the best.

Examples of the azo compound include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(methylisobutyrate), 2,2'-azobis-2,4 -Dimethylvaleronitrile, 1,1'-azobis(1-acetyloxy-1-phenylethane) and the like.

Examples of peroxides include: benzoyl peroxide, di-tert-butyl benzoyl peroxide, tert-butyl peroxypivalate, and di(4-tert-butyl peroxydicarbonate) Cyclohexyl) ester, etc.

Examples of persulfates include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

The above-mentioned cation initiator refers to a photocation initiator and a thermal cation initiator.

The above-mentioned photocationic polymerization initiator is not particularly limited as long as it is a compound that can release a substance that initiates cationic polymerization by light irradiation. Existing compounds can be used. Double salts of onium salts of Lewis acids, or derivatives thereof. Representative examples of this compound include salts of cations and anions represented by the following general formula: [A] ^r+ [B] ^r- .

The above-mentioned cation [A] ^r+ is preferably onium, and its structure can be represented by the following general formula: [(R ⁵⁸ ) _e Q] ^r+ .

Furthermore, here, ^R58 is an organic group having 1 to 60 carbon atoms and may contain atoms other than some carbon atoms. e is any integer from 1 to 5. The e R ^58s are independently independent, and may be the same or different. Also, at least one of R ⁵⁸ is preferably the above-mentioned organic group having an aromatic ring. Examples include: alkyl, alkoxy, hydroxyl, hydroxyalkoxy, halogen atom, benzyl, thiophenoxy, 4-benzoylphenylthio, 2-chloro-4-benzyl Phenyl substituted with acylphenylthio, etc. Q is an atom or group of atoms selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N=N. Also, when the atomic valence of Q in the cation [A] ^r+ is set to q, the relationship of r=eq must be established (wherein, N=N is regarded as atomic valence 0).

Also, the anion [B] ^r- is preferably a halide complex, and its structure can be represented by, for example, the following general formula [LX _f ] ^r- .

Furthermore, here, L is a metal or semimetal (Metalloid) as the central atom of a halide complex, and is B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn and Co, etc. X is a halogen atom or a phenyl group which may be substituted by a halogen atom or an alkoxy group. f is an integer from 3 to 7. Also, when the atomic valence of L in the anion [B] ^r- is set to p, the relationship of r=fp must be established.

Specific examples of the anion [LX ^f ] ^r- of the above general formula include tetrakis (pentafluorophenyl) borate, tetrakis (3,5-difluoro-4-methoxyphenyl) borate, tetrakis Fluoroborate (BF ₄ ) ^- , hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- and hexachloroantimonate (SbCl ₆ ) ^- wait.

Also, the anion [B] ^r- can also preferably use the following general formula: [LX _f-1 (OH)] ^r-

the structure represented. The L, X, and f systems are the same as above. In addition, other usable anions include: perchlorate ion (ClO ₄ ) ^- , trifluoromethylsulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonate ion (FSO ₃ ) ^- , toluenesulfonate Acid anion, trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraaryl borate and tetrakis(pentafluorophenyl)borate, etc.

In the present invention, among such onium salts, it is particularly effective to use the following aromatic onium salts (1) to (3). Among them, one type may be used alone, or two or more types may be used in combination.

(1) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, and 4-methylphenyldiazonium hexafluorophosphate.

(2) Diphenyliodonium hexafluoroantimonate, bis(4-methylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate and tolylcumene Diaryl iodonium salts such as base iodonium tetrakis (pentafluorophenyl) borate.

(3) Percilium salts represented by the following groups I or II, such as percite cations, hexafluoroantimony ions, tetrakis(pentafluorophenyl)borate ions, etc.

[chemical 13]

[chemical 14]

As other preferred ones, it is also possible to enumerate: (η5-2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methylethyl ) Benzene]-iron-hexafluorophosphate and other iron-aromatic complexes; aluminum complexes such as tris(acetylacetonate)aluminum, tris(ethylacetylacetonate)aluminum, tris(salicyloxylate)aluminum, etc. substances; mixtures with silanols such as triphenylsilanol, etc.

As said photocationic polymerization initiator, you may use a commercial item, For example, IRUGACURE261 (made by BASF); Adeka Optomer SP-150, SP-151, SP-152, SP-170, SP-171, SP- 172 (above, manufactured by ADEKA); UVE-1014 (manufactured by General Electronics); CD-1012 (manufactured by Sartomer); CI-2064, CI-2481 (above, manufactured by Nippon Soda); Uvacure1590, 1591 (above, manufactured by Daicel UCB); CYRACURE UVI-6990 (above, manufactured by Union Carbide); BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, and NDS-103 (above, manufactured by Midori Kagaku); etc.

Among them, it is preferable to use an aromatic iodonium salt, an aromatic cerium salt, and an iron-arene complex from the viewpoint of practicality and photosensitivity.

鹽等鹽；二伸乙基三胺、三伸乙基三胺及四伸乙基五胺等聚烷基聚胺類；1,2-二胺基環己烷、1,4-二胺基-3,6-二乙基環己烷及異佛爾酮二胺等脂環式聚胺類；間苯二甲胺、二胺基二苯基甲烷及二胺基二苯基碸等芳香族聚胺類；藉由常規方法使上述聚胺類與苯基縮水甘油醚、丁基縮水甘油醚、雙酚A-二縮水甘油醚及雙酚F-二縮水甘油醚等縮水甘油醚類或羧酸之縮水甘油酯類等各種環氧樹脂進行反應而製造之多聚環氧加成改性物；藉由常規方法使上述有機聚胺類與鄰苯二甲酸、異鄰苯二甲酸及二聚酸等羧酸類進行反應而製造之醯胺化改性物；藉由常規方法使上述聚胺類與甲醛等醛類；苯酚、甲酚、二甲苯酚、第三丁基苯酚及間苯二酚等於核具有至少一個醛化反應性部位之苯酚類進行反應而製造之曼尼希化改性物；多元羧酸(草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、2-甲基琥珀酸、2-甲基己二酸、3-甲基己二酸、3-甲基戊二酸、2-甲基辛二酸、3,8-二甲基癸二酸、3,7-二甲基癸二酸、氫化二聚酸及二聚酸等脂肪族二羧酸類；鄰苯二甲酸、對苯二甲酸、異鄰苯二甲酸及萘二羧酸等芳香族二羧酸類；環己烷二羧酸等脂環式二羧酸類；偏苯三甲酸、均苯三酸及蓖麻油脂肪酸等三聚物等之三羧酸類；均苯四甲酸等四羧酸類等)之酸酐；雙氰胺、咪唑類、羧酸酯、磺酸酯及胺醯亞胺等。 The above-mentioned thermal cation initiator is not particularly limited as long as it is a compound that generates a cationic species or a Lewis acid by heating, and an existing compound can be used. Typical examples of such compounds include: permeic acid salts, thiophenium salts, thiolanium salts, benzylamine, pyridinium salts, and

salt and other salts; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diaminocyclohexane -3,6-diethylcyclohexane and isophorone diamine and other alicyclic polyamines; m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylmethane and other aromatics Polyamines; make the above polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether or carboxylate by conventional methods Polymerized epoxy addition modification produced by reacting various epoxy resins such as glycidyl esters of acid; the above-mentioned organic polyamines are mixed with phthalic acid, isophthalic acid and dimerization by conventional methods. Amidated modified products produced by reacting carboxylic acids such as acid; by conventional methods, the above-mentioned polyamines and aldehydes such as formaldehyde; phenol, cresol, xylenol, tert-butylphenol and resorcinol It is equal to Mannich modified products produced by reacting phenols with at least one hydroformylation reactive site; polycarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid , suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylglutaric acid, Aliphatic dicarboxylic acids such as 2-methylsuberic acid, 3,8-dimethylsebacic acid, 3,7-dimethylsebacic acid, hydrogenated dimer acid and dimer acid; phthalic acid, Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid, trimellitic acid and castor oil fatty acid, etc. Tricarboxylic acids such as trimers; acid anhydrides of tetracarboxylic acids such as pyromellitic acid); dicyandiamide, imidazoles, carboxylates, sulfonates, and amidoimides, etc.

Commercially available products can also be used as the above-mentioned thermal cationic initiator, for example, Adekaopton CP-77, Adekaopton CP-66 (above, manufactured by ADEKA); CI-2639, CI-2624 (above, manufactured by Nippon Soda); San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L (the above, manufactured by Sanshin Chemical Industry); etc.

The above-mentioned polymerization initiator (C) can be used in combination of one type or two or more types exemplified above.

In the curable composition of the present invention, the content of the above-mentioned polymerization initiator (C) is not particularly limited, and relative to the silica particles (A), polymerizable compound (B), polymerization initiator (C) and The total amount of 100 parts by mass of the coloring agent (D) is preferably 0.3 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, in terms of good curability. When the content of the polymerizable compound (B) is within the above range, a curable composition having good curability and excellent storage stability without precipitation of the polymerization initiator can be obtained, which is preferable.

For example, when forming a cured film with a thickness of 1 to 3 μm, the content of the polymerization initiator (C) is not particularly limited, relative to the silica particles (A), the polymerizable compound (B) and the polymerization initiator ( C) is 100 mass parts in total, Preferably it is 0.3-20 mass parts, More preferably, it is 0.5-10 mass parts, More preferably, it is 1-5 mass parts.

<Colorant (D)>

Pigments and dyes can be used as the coloring agent (D) used in the curable composition of the present invention. As a pigment and a dye, an inorganic coloring material or an organic coloring material can be used, respectively, and these can be used individually or in mixture of 2 or more types. Here, the so-called pigment refers to a colorant that is insoluble in the following solvents, among inorganic or organic colorants, it also includes those that are insoluble in solvents, or those obtained by laking inorganic or organic dyes.

Examples of the above-mentioned pigment include: carbon black obtained by the furnace method, channel method or thermal method, or carbon black such as acetylene black, Ketjen black or lamp black, the above-mentioned carbon black adjusted or coated with epoxy resin, pre-treated The above-mentioned carbon black is dispersed into the resin in a solvent and coated with 20~200mg/g of resin, and the above-mentioned carbon black is treated with an acidic or alkaline surface, the average particle size is above 8nm, and the DBP oil absorption is 90ml Carbon ^black per _100g or less, carbon black, graphitized carbon black, graphite, activated carbon, carbon fiber, nano Black pigments represented by carbon tubes, spiral carbon fibers, carbon nanohorns, carbon aerogels, fullerenes, aniline black, pigment black 7, titanium black, lactam black, and black, chromium oxide green, Milo Li blue, cobalt green, cobalt blue, manganese series, ferrocyanide, ultramarine phosphate, iron blue, ultramarine blue, sky blue, dark green, emerald green, lead sulfate, yellow lead, zinc yellow, iron red (red iron oxide ( III)), cadmium red, synthetic iron black, umber, lake pigments and other organic or inorganic pigments, in terms of high light-shielding properties, it is better to use black pigments, and it is better to use carbon black as black pigments .

Among the above-mentioned carbon blacks, carbon blacks adjusted or coated with epoxy resin, carbon blacks previously dispersed in a solvent into a resin and coated with 20-200 mg/g of resin can be preferably used.

In addition, among carbon blacks, it is preferable to use carbon black on the surface of carbon black in terms of obtaining a colorant dispersion liquid with excellent dispersibility, and obtaining a cured product with excellent light-shielding properties and good adhesion to substrates such as glass. Carbon black with sulfonic acid groups.

Examples of methods for imparting sulfonic acid groups to the surface of the carbon black include the method (1) of oxidizing carbon black with peroxodisulfuric acid or its salt, and the method (2) of treating carbon black with a sulfonating agent.

The above-mentioned method (1) of oxidizing carbon black with peroxodisulfuric acid or its salt can be carried out by any known method, for example, it can be carried out by the following method: if necessary, use a surfactant or a dispersant to dissolve carbon black, Peroxodisulfuric acid or its salt, aqueous medium (water or the mixture of water and water-soluble solvent) Mixing, heating the mixture at less than 100°C, preferably at 40-90°C for less than 24 hours, preferably at 2-20 hours, and neutralizing to pH≧7 if necessary.

Examples of the salt of the above-mentioned peroxodisulfuric acid include metal salts or ammonium salts of lithium, sodium, potassium, aluminum, and the like.

The usage-amount of peroxodisulfuric acid or its salt is preferably in the range of 0.5-5 mass parts with respect to 1 mass part of carbon black.

The method (2) of treating the above-mentioned carbon black with a sulfonating agent can be carried out by any known method, for example, it can be carried out by the following method: mixing the carbon black and the sulfonating agent or dissolving the carbon black and the sulfonating agent in a solvent, and stirred at below 200°C, preferably at 0-100°C.

烷錯合物、SO₃-酮錯合物、胺基磺酸、磺化吡啶鹽等。 Examples of the above-mentioned sulfonating agent include: concentrated sulfuric acid, oleum, sulfur trioxide, halogenated sulfuric acid, amide sulfuric acid, bisulfite, sulfite, SO3 _- di

Alkane complexes, SO ₃ -keto complexes, sulfamic acid, sulfonated pyridinium salts, etc.

烷、二乙醚等醚類；二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮、環丁碸、硝基甲烷、丙酮、乙腈、苯甲腈等極性溶劑；乙酸乙酯、乙酸丁酯等酯類；苯、甲苯、二甲苯、硝基苯等芳香族系溶劑；甲醇、乙醇、異丙醇等醇系溶劑；氯仿、三氯氟甲烷、二氯甲烷、氯苯等氯系溶劑等，亦可使用該等之混合溶劑。 As the solvent, water; acidic solvents such as sulfuric acid, oleum, formic acid, acetic acid, propionic acid, and acetic anhydride; basic solvents such as pyridine, triethylamine, and trimethylamine; tetrahydrofuran,

Ethers such as alkane and diethyl ether; polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, cyclobutane, nitromethane, acetone, acetonitrile, benzonitrile, etc.; acetic acid Esters such as ethyl ester and butyl acetate; Aromatic solvents such as benzene, toluene, xylene and nitrobenzene; Alcohol solvents such as methanol, ethanol and isopropanol; Chloroform, trichlorofluoromethane, dichloromethane, chlorine Chlorinated solvents such as benzene, etc., and mixed solvents of these can also be used.

The amount of sulfonating agent used is preferably in the range of 0.5 to 20 parts by mass relative to 1 part by mass of carbon black. When using multiple sulfonating agents, it is preferable that the total amount of the multiple sulfonating agents falls within the above range .

Also, in order to suppress the formation of the well-known sulfonation as a side reaction of the sulfonation reaction, the Add 0.01~5% of known inhibitors within the range that will inhibit the reaction, such as fatty acids, organic peracids, acid anhydrides, acetic acid, ketones, etc.

Commercially available products can also be used as the above-mentioned pigments, 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, 254, 228, 240 and 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64 , 65 and 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 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 and 185; Pigment Green 7 , 10, 36 and 58; pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62 and 64; pigment Purple 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50 etc.

化合物、喹啉化合物、蒽醌化合物、香豆素化合物、花青化合物、酞菁化合物、異吲哚啉酮化合物、異吲哚啉化合物、喹吖啶酮化合物、蒽締蒽酮化合物、紫環酮化合物、苝化合物、吡咯并吡咯二酮化合物、硫靛藍化合物、二

化合物、三苯甲烷化合物、喹酞酮化合物、萘四羧酸、偶氮染料、花青染料之金屬錯合物化合物等。 Examples of the dyes include: nitroso compounds, nitro compounds, azo compounds, diazo compounds,

Compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, cyanine compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, quinacridone compounds, anthracenthone compounds, purple rings Keto compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, di

Compounds, triphenylmethane compounds, quinophthalone compounds, naphthalene tetracarboxylic acid, azo dyes, metal complex compounds of cyanine dyes, etc.

In the curable composition of the present invention, the content of the above-mentioned colorant (D) is not particularly limited, but it is preferably 50-500 parts by mass, more preferably 150-500 parts by mass relative to 100 parts by mass of the above-mentioned polymerizable compound (B). 350 parts by mass, more preferably 150 to 300 parts by mass. The content of the coloring agent is the above When it falls within the range, it becomes a curable composition having excellent storage stability without aggregation of the colorant, and the cured product of the curable composition has high light-shielding properties, so it is preferable.

For example, when forming a cured film with a thickness of 1 to 3 μm, the content of the colorant (D) is not particularly limited, but it is preferably 50 to 500 parts by mass, more preferably 50 to 500 parts by mass relative to 100 parts by mass of the polymerizable compound (B) above. It is 150-350 mass parts, More preferably, it is 150-300 mass parts.

Moreover, the curable composition of this invention may contain the compound which does not have radical polymerizability but imparts alkali developability, As long as it is a compound which is soluble in alkaline aqueous solution by having an acid value, it is free. Particularly limited, alkali-soluble novolak resins (hereinafter, simply referred to as "novolac resins") are mentioned as typical ones. Novolac resin is obtained by polycondensing phenols and aldehydes in the presence of an acid catalyst.

As the above-mentioned phenols, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butyl Phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol Base phenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,5-xylenol, , 3,5-trimethylphenol, resorcinol, 2-methylresorcinol and bisphenol A, etc. These phenols can be used individually or in mixture of 2 or more types.

As the above-mentioned aldehydes, for example, formaldehyde, p-formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, Benzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-tolualdehyde, m-tolualdehyde, p-formaldehyde phenylbenzaldehyde, p-ethylbenzaldehyde and p-n-butylbenzaldehyde, among these compounds, formaldehyde, acetaldehyde and benzene Formaldehyde, etc. These aldehydes can be used individually or in mixture of 2 or more types. The aldehydes are used at a ratio of 0.7-3 moles, more preferably 0.7-2 moles per 1 mole of phenols.

烷等環狀醚類。關於該等反應介質之使用量，通常反應原料每100質量份，為20~1000質量份。縮合反應之反應溫度可視反應原料之反應性而適當進行調整，但通常為10~200℃，較佳為70~150℃。於縮合反應結束後，為了將存在於系統內之未反應原料、酸觸媒及反應介質去除，一般而言，使內溫上升至130~230℃，於減壓下將揮發分蒸餾去除，繼而使已熔融之酚醛清漆樹脂於鋼製傳送帶等之上進行流涎而回收。 As the acid catalyst, for example, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid can be used. The usage amount of these acid catalysts is per 1 mole of phenol, preferably 1×10 ^-4 ~5×10 ^-1 mole. In the condensation reaction, water is usually used as the reaction medium, but when the phenols used in the condensation reaction are not dissolved in the aqueous solution of the aldehydes, and it becomes a heterogeneous system from the initial stage of the reaction, the hydrophilic The solvent serves as the reaction medium. As such hydrophilic solvents, for example, alcohols such as methanol, ethanol, propanol, and butanol; or tetrahydrofuran and dihydrofuran

Alkanes and other cyclic ethers. The usage-amount of these reaction media is 20-1000 mass parts per 100 mass parts of reaction raw materials normally. The reaction temperature of the condensation reaction can be appropriately adjusted depending on the reactivity of the reaction raw materials, but it is usually 10-200°C, preferably 70-150°C. After the condensation reaction is completed, in order to remove the unreacted raw materials, acid catalyst and reaction medium in the system, generally speaking, the internal temperature is raised to 130~230°C, and the volatile matter is distilled off under reduced pressure, and then The melted novolac resin is salivated on a steel conveyor belt and recovered.

In addition, after the condensation reaction is completed, the reaction mixture is dissolved in the above-mentioned hydrophilic solvent, and added to a precipitant such as water, n-hexane, and n-heptane, whereby novolak resin is precipitated, and the precipitate is separated and heated. Drying, whereby recycling is also possible.

Examples other than the above-mentioned novolac resins include polyhydroxystyrene and derivatives thereof, styrene-maleic anhydride copolymers, polyethylene hydroxybenzoate, and the like.

烷、四氫呋喃、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷及二丙二醇二甲醚等醚系溶劑；乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸環己酯、乳酸乙酯、琥珀酸二甲酯及TEXANOL等酯系溶劑；乙二醇單甲醚及乙二醇單乙醚等溶纖劑系溶劑；甲醇、乙醇、異或正丙醇、異或正丁醇及戊醇等醇系溶劑；乙二醇單乙酸甲酯、乙二醇單乙酸乙酯、丙二醇-1-單甲醚(PGM)、丙二醇-1-單甲醚-2-乙酸酯(PGMEA)、二丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯及丙酸乙氧基乙酯等醚酯系溶劑；苯、甲苯及二甲苯等BTX(Benzene-Toluene-Xylene)系溶劑；己烷、庚烷、辛烷及環己烷等脂肪族烴系溶劑；松節油、D-檸檬烯及蒎烯等萜烯系烴油；礦油精、Swasol # 310(以上，科斯莫松山石油製造)；及Solvesso # 100(以上，Exxon化學製造)；等石蠟系溶劑；四氯化碳、氯仿、三氯乙烯、二氯甲烷及1,2-二氯乙烷等鹵化脂肪族烴系溶劑；氯苯等鹵化芳香族烴系溶劑；卡必醇系溶劑、苯胺、三乙胺、吡啶、乙酸、乙腈、二硫化碳、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、二甲基亞碸及水等，該等溶劑可單獨地使用，或者以2種以上之混合溶劑之形式使用。該等之中，酮類及醚酯系溶劑等、尤其是PGMEA及環己酮等由於在硬化性組合物中與抗蝕劑及聚合起始劑之相溶性良好，故而較佳。 The curable composition of the present invention may further contain a solvent. Examples of the solvent include solvents that can generally dissolve or disperse the above-mentioned components (silicon dioxide particles (A), polymerizable compound (B), polymerization initiator (C) and colorant (D)) as needed. , such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone and other ketones; ether, two

Ether solvents such as alkane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, n-propyl acetate, acetic acid Ester solvents such as isopropyl ester, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and TEXANOL; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol , ethanol, iso-or n-propanol, iso-or n-butanol and amyl alcohol and other alcohol solvents; ethylene glycol monoacetate methyl ester, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol -1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate and other ether ester solvents; benzene, toluene and xylene and other BTX (Benzene-Toluene-Xylene) solvents; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene and pinene; Olein, Swasol # 310 (above, manufactured by Cosmo Matsuyama Oil); and Solvesso # 100 (above, manufactured by Exxon Chemical); and other paraffin-based solvents; carbon tetrachloride, chloroform, trichloroethylene, dichloromethane and 1, Halogenated aliphatic hydrocarbon solvents such as 2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethyl Dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and water, etc., these solvents can be used alone, or as a mixture of two or more solvents Form use. Among them, ketones, ether ester solvents, and the like, especially PGMEA, cyclohexanone, and the like are preferable because they have good compatibility with resists and polymerization initiators in curable compositions.

In the curable composition of the present invention, the amount of the solvent used is not particularly limited, but is preferably 70 to 95% by mass based on the total amount of the curable composition. When the content of the solvent is within the above range, it can properly control the operability (viscosity or wettability of the curable composition) and excellent liquid stability (without precipitation or precipitation of the components contained in the composition). The curable composition and the thickness of the hardened product are better.

A dispersant may further be used in the curable composition of the present invention. As the dispersant, as long as it is capable of dispersing and stabilizing the colorant (D), commercially available dispersants such as BYK series produced by BYK-Chemie can be used. Polymer dispersants for polyesters, polyethers, and polyurethanes, with nitrogen atoms as basic functional groups and functional groups with nitrogen atoms are amines and/or their quaternary salts, and the amine value is 1~ 100mgKOH/g.

In the curable composition of this invention, an inorganic compound may be contained further. 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, silicon dioxide, and aluminum oxide; layered clay minerals, rice Lori blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminosilicates, calcium silicates , aluminum hydroxide, platinum, gold, silver, copper, etc., among these, titanium oxide, silicon dioxide, layered clay minerals, and silver are preferred. In the curable composition of the present invention, the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the above-mentioned polymerizable compound, and one of these inorganic compounds can be used or 2 or more.

By making the curable composition of this invention contain an inorganic compound, it can be used as a photosensitive paste composition. The photosensitive paste composition can be used to form baked product patterns such as partition wall patterns, dielectric patterns, electrode patterns, and black matrix patterns between plasma display panels.

In addition, these inorganic compounds can also be preferably used as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength enhancers, special wavelength absorbers, and ink repelling agents, for example.

等熱聚合抑制劑；塑化劑；助黏劑；填充劑；消泡劑；調平劑；表面調整劑；抗氧化劑；紫外線吸收 劑；分散助劑；抗凝集劑；觸媒；效果促進劑；交聯劑；増黏劑等慣用之添加物。 Also, in the curable composition of the present invention, p-anisole, hydroquinone, catechol, tertiary butylcatechol and phenanthrene may be added as needed.

Isothermal polymerization inhibitor; plasticizer; adhesion promoter; filler; defoamer; leveling agent; surface regulator; antioxidant; ultraviolet absorber; dispersion aid; anticoagulant; catalyst; effect promotion Agents; crosslinking agents; thickeners and other commonly used additives.

In the curable composition of the present invention, a coupling agent, a chain transfer agent, a sensitizer, a surfactant, melamine, and the like may further be used in combination.

It is preferable to increase the adhesion between the cured product and the base material by adding the above-mentioned coupling agent. For example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyl Alkyl functional alkoxysilanes such as triethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane , Allyltrimethoxysilane and other alkenyl functional alkoxysilanes; 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropylmethyltrimethoxysilane, etc. (Meth)acrylate functional alkoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-cyclo Oxycyclohexyl)ethyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane and other epoxy-functional alkoxysilanes; N-β(aminoethyl)- Amino-functional alkoxysilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; γ- Mercapto-functional alkoxysilanes such as mercaptopropyltrimethoxysilane; Isocyanato-functional alkoxysilanes such as 3-isocyanatopropyltriethoxysilane; 3-ureidopropyltrialkoxy Urea-functional alkoxysilanes such as urea-based silane; isocyanurate-functional alkoxysilanes such as tri-(trimethoxysilylpropyl) isocyanurate; titanium tetraisopropoxide, tetra-n-butanol Titanium alkoxides such as titanium; titanium chelates such as dioctyloxytitanium bis(octanediol) and diisopropoxide titanium bis(ethyl acetate); zirconium tetraacetylpyruvate, tributoxy Zirconium chelates such as zirconium monoacetylpyruvate; zirconium tributoxy monostearate Zirconium compounds such as methyltriisocyanatosilane and other isocyanatosilanes, etc.

Commercially available products can be used as the coupling agent, for example: KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502 , KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM -6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007, KBM-04, KBE-04, KBM-13, KBE-13, KBE-22, KBE-103 , HMDS-3, KBM-3063, KBM-3103C, KPN-3504, and KF-99 (the above, manufactured by Shin-Etsu Silicones), etc.

As the above-mentioned chain transfer agent and sensitizer, compounds containing sulfur atoms are generally used. Examples include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine Acid, 2-mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)aminoformyl]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-mercapto Ethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzo Mercapto compounds such as imidazole, 2-mercapto-3-hydroxypyridine, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate); Alkyl iodide compounds such as disulfide compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid obtained by oxidizing the mercapto compound; trimethylolpropane trimethylolpropane (3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol dithio Propionate, Butylene Glycol Dithioglycolate, Ethylene Glycol Bisthioglycolate, Trimethylolpropane Trithioglycolate, Butylene Glycol Dithiopropionate, Trimethylol Propane trithiopropionic acid Esters, trimethylolpropane trithioglycolate, pentaerythritol tetrathiopropionate, pentaerythritol tetrathioglycolate, trihydroxyethyl trithiopropionate, the following compound No.P1, Showa Denko Manufacture Karenz PE1 and NR1 etc.

Fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates can be used as the above-mentioned surfactants. ; Higher amine hydrohalide salt, quaternary ammonium salt and other cationic surfactants; Polyethylene glycol alkyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, fatty acid monoglyceride and other non-ionic interface Surfactants; surfactants such as amphoteric surfactants and polysiloxane-based surfactants, which may also be used in combination.

Examples of the above-mentioned melamine compound include active methylol in nitrogen compounds such as (poly)methylol melamine, (poly)methylol glycoluril, (poly)methylol benzoguanamine, and (poly)methylol urea. A compound in which all or part (at least 2) of groups (CH ₂ OH groups) are etherified with an alkyl group. 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. In addition, the methylol group that has not been etherified by an alkyl group can self-condense within one molecule or condense between two molecules, resulting in the formation of an oligomer component. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, etc. can be used. Among them, alkyl-etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

In the curable composition of the present invention, the content of optional components other than silica particles (A), polymerizable compound (B), polymerization initiator (C), colorant (D) and solvent depends on It is appropriately selected for the purpose of use, and there is no particular limitation, but it is preferably 100 mass relative to the total value of silica particles (A), polymerizable compound (B), polymerization initiator (C) and colorant (D) parts, a total of 20 parts by mass or less.

The curable composition of the present invention can be used in curable paints, varnishes, curable adhesives, printed substrates, or color filters in liquid crystal display panels for color display such as color TVs, PC monitors, portable information terminals, and digital cameras. , black spacers in liquid crystal display panels for color display such as portable information terminals and digital cameras, black spacers for various display purposes, black spacers for organic EL, CCD (Charge Coupled Device, Charge Coupled Device) image sensing Color filters for devices, touch panels, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, gel coatings, photoresists for electronics, plating resists , etch resist, solder resist, insulating film, black matrix, color filters for various display applications, plasma display panels, electroluminescent display devices, and resists used to form structures in LCD manufacturing steps , Compositions for sealing electrical and electronic parts, solder resists, magnetic recording materials, micromechanical parts, waveguides, optical switches, masks for plating, etching masks, color test systems, glass fiber cable coatings, sieves Stencils for screen printing, materials for producing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, microcapsules Decolorizing materials for image recording materials, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, dielectric layer formation in sequential build-up of printed circuit boards Various applications such as photoresist materials and protective films are not particularly limited.

Regarding the production method of the cured product using the curable composition of the present invention, the preferred coating The cloth method and curing conditions are shown below.

The coating method of the curable composition is a well-known method such as roll coating, curtain coating, various printing, and dipping, and is applied to support substrates such as glass, metal, paper, and plastic. In addition, it can also be temporarily applied to a support substrate such as a film, and then transferred to other support substrates, that is, used in the form of a dry film, and the application method is not limited.

Also, as a light source of active light used for curing the curable composition of the present invention, one that emits light with a wavelength of 300 to 450 nm can be used, such as ultra-high pressure mercury, mercury vapor arc, carbon arc, and xenon arc.

Furthermore, the laser direct writing method, which uses laser light as an exposure light source without using a mask, and directly forms an image based on digital information such as a computer, not only improves productivity, but also improves resolution and positional accuracy. As the laser light, light with a wavelength of 340~430nm is preferably used, but argon ion laser, helium-neon laser, YAG laser, and semiconductor laser can also be used to emit visible light to infrared light. The light of the light range. When using such lasers, a sensitizing pigment that absorbs visible light to infrared light may be added.

Using the curable composition of the present invention, the following steps (1) to (4) are repeated to combine patterns of two or more colors to manufacture color filters for liquid crystal display panels and the like.

(1) Step of forming a coating film of the colored polymerizable composition of the present invention on a substrate

(2) Step of irradiating the coating film with active light through a mask having a pattern shape

(3) The step of developing the hardened coating with a developer (especially an alkaline developer)

(4) The step of heating the film after development

The cured product formed by using the curable composition of the present invention can be used for curable coatings, varnishes, curable adhesives, printed substrates, or color televisions, PC monitors, portable information terminals Color filters in liquid crystal display panels for color displays such as mobile phones and digital cameras, color filters for CCD image sensors, touch panels, electrode materials for plasma display panels, powder coating, printing inks, printing Plate, adhesive, gel coat, photoresist for electronics, plating resist, etch resist, solder resist, insulating film, black matrix, color filter for various display purposes, plasma display Panels, electroluminescent display devices, and resists for forming structures in LCD manufacturing steps, compositions for encapsulating electrical and electronic parts, solder resists, magnetic recording materials, micromechanical parts, waveguides, optical switches, Masks for plating, masks for etching, color test systems, coatings for glass fiber cables, stencils for screen printing, materials for the manufacture of three-dimensional objects by stereolithography, materials for holographic recording, image recording Materials, microelectronic circuits, decolorizing materials, decolorizing materials for image recording materials, decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and visible laser direct imaging systems The photoresist material used, the photoresist material used in the formation of the dielectric layer in the sequential build-up of the printed circuit board, and various uses such as protective films, etc. These uses are not particularly limited.

When the curable composition of the present invention uses a black pigment as the colorant (D), it is used to form a black matrix. The black matrix is especially a color filter for display devices such as liquid crystal display panels. Tablets are useful.

The above-mentioned black matrix is preferably formed by the following steps: (1) the step of forming the coating film of the curable composition of the present invention on the substrate, (2) forming the coating film through a mask having a specific pattern shape The step of irradiating active light, (3) the step of developing the exposed film with a developer (especially an alkaline developer), and (4) the step of heating the developed film. In addition, the curable composition of the present invention is also useful as an inkjet system composition without a developing step.

With regard to the manufacture of color filters used in liquid crystal display panels, etc., the curable compositions of the present invention or other ones can be used, and the above steps (1) to (4) can be repeated to combine two or more colors Created by combining patterns.

A specific method for producing a cured product using the curable composition of the present invention is shown below.

That is, the curable composition of the present invention 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, exposure was performed at an exposure amount of 40 mJ/cm ² (gap 100 μm) through a negative mask formed with a pattern of 1 to 20 μm using a proximity exposure machine manufactured by Microtec Corporation. The exposed film was developed for 40 seconds with a 0.04% by mass KOH aqueous solution at 23° C., and then baked at 230° C. for 30 minutes.

[Example]

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

[Manufacturing example 1] Preparation of PGMEA solution of polymerizable compound No.1

Add 1,1-bis[4-(2,3-epoxypropoxy)phenyl]indan 184g, acrylic acid 58g, 2,6-di-tert-butyl-p-cresol 0.26g, tetra-n- 0.11 g of butylammonium bromide and 105 g of PGMEA were stirred at 120° C. for 16 hours. The reaction liquid was cooled to room temperature, 160 g of PGMEA, 59 g of biphenyl tetracarboxylic anhydride, and 0.24 g of tetra-n-butylammonium bromide were added, and it stirred at 120 degreeC for 4 hours. Furthermore, 20 g of tetrahydrophthalic anhydride was added, and stirred 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. Thereafter, PGMEA 128 g was added to obtain a PGMEA solution (Mw=5000, Mn=2100, acid value (solid content) 92.7 mgKOH/g) of polymerizable compound No. 1.

[Manufacturing example 2] Preparation of PGMEA solution of polymerizable compound No.2

Add 1,1-bis[4-(2,3-epoxypropoxy)phenyl]indane 43g, acrylic acid 13.5g, 2,6- 0.05 g of di-tert-butyl-p-cresol, 0.11 g of tetrabutylammonium acetate, and 23 g of PGMEA were stirred at 120° C. for 16 hours. After cooling to room temperature, 35 g of PGMEA and 11.5 g of biphenyltetracarboxylic anhydride were added, and stirred at 120° C. for 8 hours. Furthermore, 7.4 g of tetrahydrophthalic anhydride was added, and stirred 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. After one hour, 34.4 g of PGMEA was added to obtain a PGMEA solution (Mw=4000, Mn=2100, acid value (solid content) 86 mgKOH/g) of polymerizable compound No. 2.

[Production Example 3] Production of PGMEA solution of polymerizable compound No.3

Add 75.0 g of 9,9-bis(4-glycidyloxyphenyl) terpene, 23.8 g of acrylic acid, 0.273 g of 2,6-di-tert-butyl-p-cresol, 0.585 g of tetrabutylammonium chloride, and PGMEA 65.9g, stirred at 90°C for 1 hour, at 100°C for 1 hour, at 110°C for 1 hour and at 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 stirred at 100° C. for 5 hours. Furthermore, 30.0 g of 9,9-bis(4-glycidyloxyphenyl) terpene, 0.269 g of 2,6-di-tert-butyl-p-cresol, and 1.50 g of PGMEA were added, and stirred at 90° C. for 90 minutes After stirring at 120° C. for 4 hours, 122.2 g of PGMEA was added to obtain a PGMEA solution of polymerizable compound No. 3 (Mw=4190, Mn=2170, acid value (solid content) 52 mg‧KOH/g).

[Manufacture Example 4] Manufacture of Carbon Black No.1

150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 3000 ml of a deionized aqueous solution of sodium peroxodisulfate (concentration: 2.0 N) were mixed, and stirred at 60° C. for 10 hours. Filtration was performed, the obtained slurry was neutralized with sodium hydroxide, treated by membrane diafiltration, and the obtained solid was dried at 75° C. overnight to obtain Carbon Black No. 1 as a black powder.

[Manufacture Example 5] Manufacture of Carbon Black No.2

150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 400 ml of cyclobutane were mixed, 15 g of amide sulfuric acid was added, and the mixture was stirred at 140 to 150° C. for 10 hours. The obtained slurry was neutralized with lithium hydroxide, treated by membrane diafiltration, and the obtained solid was dried at 75° C. overnight to obtain carbon black No. 2 as a black powder.

[Manufacture Example 6] Manufacture of Carbon Black Dispersion No.1

16 g of carbon black No. 1, 3.6 g of PGMEA solution of polymerizable compound No. 1, 2.4 g of DISPERBYK-161 (manufactured by BYK-Chemie, dispersant) and 78 g of PGMEA were weighed and mixed, and processed by a bead mill Thus, carbon black dispersion liquid No. 1 was obtained.

[Manufacturing Example 7] Manufacture of Carbon Black Dispersion No.2

16g of carbon black No.2, 3.6g of PGMEA solution of polymerizable compound No.1, 2.4g of DISPERBYK-161 and 78g of PGMEA were weighed and blended, and processed by a bead mill to obtain carbon black dispersion No.2 .

[Examples 1-16 and Comparative Examples 1-4] Preparation of curable composition

Each component was mixed according to the formulation of [Table 2]-[Table 4], and curable compositions were obtained (Examples 1-16 and Comparative Examples 1-4). In addition, the numerical values prepared in the table represent parts by mass.

In addition, the symbol of each component in a table|surface represents the following component.

A-1 PL-2L-PGME (colloidal silica; manufactured by Fuso Chemical Co., Ltd.)

A-2 YA010C-LDI (colloidal silicon dioxide; manufactured by Admatechs Corporation)

A-3 PMA-ST (colloidal silicon dioxide; manufactured by Nissan Chemical Co., Ltd.)

A-4 YA050C-LHI (colloidal silica; manufactured by Admatechs Corporation)

A-5 YA010C-SP3 (powdered silica; manufactured by Admatechs Corporation)

A'-1 AEROSIL 100 (powdered silicon dioxide; manufactured by Aerosil Corporation)

A'-2 AEROSIL OX-50 (powdered silicon dioxide; manufactured by Aerosil Corporation)

A'-3 SC2050-MB (colloidal silicon dioxide; manufactured by Admatechs Corporation)

B-1 PGMEA solution of polymerizable compound No.1 (solid content 45wt%)

B-2 PGMEA solution of polymerizable compound No.2 (solid content 45wt%)

B-3 PGMEA solution of polymerizable compound No.3 (solid content 45wt%)

B-4 Kayarad DPHA (polymerizable compound; manufactured by Nippon Kayaku Co., Ltd.)

C-1 Compound No.C1

C-2 Compound No.C2

D-1 Carbon black dispersion No.1

D-2 Carbon black dispersion No.2

E-1 PGMEA

F-1 KBM-403 (coupling agent; manufactured by Shin-Etsu Chemical Co., Ltd.)

The parameters of the above-mentioned silica particles are summarized in [Table 1].

[Evaluation Examples 1-16 and Comparative Evaluation Examples 1-4]

For the curable compositions No.1~No.16 obtained in Examples 1~16 and the comparison curable compositions No.1~No.4 obtained in Comparative Examples 1~4, the following method was used Evaluation of minimum dense line width, surface roughness Ra, volume resistivity, inclination angle and OD value. The results are shown in [Table 5] to [Table 7].

(Minimum tight line width)

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 coating film of 1.0 μm on the surface of the glass substrate. Thereafter, exposure was performed at an exposure amount of 40 mJ/cm ² (gap 100 μm) through a negative mask formed with a pattern of 1 to 20 μm using a proximity exposure machine manufactured by Microtec Corporation. The exposed film was developed for 40 seconds with a 0.04% by mass KOH aqueous solution at 23° C., and then baked at 230° C. for 30 minutes. Observe with an optical microscope, and set the minimum mask pattern remaining on the glass substrate as the minimum dense line width. If the minimum dense line width is 6 μm or less, it is high-definition. On the other hand, when the minimum dense line width is 7 μm or more, it cannot be called high definition.

(surface roughness Ra)

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 coating film of 1.0 μm on the surface of the glass substrate. Thereafter, baking treatment was performed at 230° C. for 30 minutes. The surface roughness Ra of the film was measured using a surface profiler (DEKTAK 6M) from ULVAC Company. If the surface roughness Ra is less than 100Å, it means that the colorant and silicon dioxide are fully dispersed, the surface becomes smooth, and sufficient light-shielding properties are obtained. On the other hand, when the surface roughness Ra is 100Å or more, the colorant and silica are not sufficiently dispersed, the surface is rough, and sufficient light-shielding properties (OD value) cannot be obtained.

(volume resistivity)

Spin-coat the curable composition on a chromium-sputtered substrate so that the film thickness of the curable composition becomes 4 μm. As a pre-baking, bake at 110°C for 2 minutes, and then use a high-pressure mercury lamp as a light source to heat at 100mJ/cm ² Exposure was performed, followed by post-exposure baking, and baking was performed at 230° C. for 180 minutes to produce a cured product. Platinum electrodes are formed on the hardened body by sputtering. Connect the chromium part to the platinum electrode with a wire, and connect the resistance measuring device to measure the volume resistivity. The unit is Ω‧cm.

Hardened products with a volume resistivity of 10 ¹⁰ Ω‧cm or higher can be used as high-resistance black matrices for color filters of IPS liquid crystal displays, and cured products with a volume resistivity of 10 ¹¹ Ω‧cm or higher can be better used as black matrices matrix.

(OD value)

The curable composition or the comparative curable composition was spin-coated (1300 rpm, 50 seconds) on the substrate and dried, and then pre-baked at 100° C. for 100 seconds. After exposure at 100 mJ/cm ² using an ultra-high pressure mercury lamp as a light source, it was baked at 230° C. for 30 minutes to produce a hardened product. The OD value of the obtained film was measured using a McBeth transmission densitometer, and the OD value per unit thickness was calculated by dividing the OD value by the thickness after exposure and baking.

A cured product with an OD value per unit thickness of 3.0 or more can be used as a black matrix, and a cured product with an OD value per unit thickness of 3.5 or more can be preferably used as a black matrix.

(Tilt angle)

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 coating film of 1.0 μm on the surface of the glass substrate. Thereafter, exposure was performed at an exposure amount of 40 mJ/cm ² (gap 100 μm) through a negative mask on which a pattern of 6 μm was formed using a proximity exposure machine manufactured by Microtec Corporation. The exposed film was developed with 0.04 mass% KOH aqueous solution at 23°C for 40 seconds, then baked at 230°C for 30 minutes, and the bonding angle (tilt angle) between the pattern and the substrate was measured using a scanning electron microscope. Determination. This inclination angle corresponds to the angle θ in (a) and (b) of Fig. 1 shown below. When (a) the inclination angle is an acute angle, it means that there is no undercut in the pattern, and when (b) the inclination angle is an obtuse angle, it means that there is an undercut in the pattern. When the inclination angle is 70° to 90°, the pattern of the obtained hardened product becomes high-definition, so it is good.

From the above results, it is clear that the curable composition of the present invention can provide a cured product with high volume resistance and high light-shielding properties (OD value) and a high-definition (minimum dense line width, inclination angle) pattern shape. it works. Therefore, the curable resin and cured product of the present invention are useful for curable resin compositions for electronic materials, especially black matrices.

[Industrial availability]

The curable composition of the present invention is useful as a resist for color filters since it can obtain a cured product at a level satisfying high resistance and high-definition pattern formation. Moreover, in the case of a curable composition using a black pigment as a colorant, a highly light-shielding cured product can be produced, so it is particularly useful as a black matrix forming material.

Claims (8)

A curable composition comprising: wet-type silica particles (A) with an average particle diameter of 50 nm or less, a polymerizable compound (B), a polymerization initiator (C) and a colorant (D). For 100 parts by mass of the coloring agent (D), the content of the wet-type silica particles (A) is 0.1 to 70 parts by mass. The curable composition according to claim 1, wherein the content of the metal in the above-mentioned wet silica particles (A) is 1000 ppm or less. The curable composition as in Claim 1, wherein the polymerizable compound (B) is a compound represented by the following general formula (I); it has the ability to esterify the compound represented by the following general formula (I) with an unsaturated monobasic acid An unsaturated compound with a chemically formed structure; or an unsaturated compound with the following structure, which is a structure formed by esterifying an epoxy compound represented by the following general formula (I) with an unsaturated monobasic acid The unsaturated compound is then esterified with polybasic acid anhydride,

(In the formula, M represents a direct bond, a hydrocarbon group with 1 to 20 carbon atoms, -O-, -S-, -SO ₂ -, -SS-, -SO-, -CO-, -OCO-, selected from the following For the substituents in the group represented by the above formula (a), (b), (c) or (d), the hydrogen atom in the group represented by M may be replaced by a halogen atom, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ (hereinafter also referred to as R ¹ to R ⁸ ) each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms or a halogen atom, and R ¹ The methylene group in the group represented by ~R ⁸ may also be substituted with -O- under the condition that it is not adjacent to oxygen, n is a number from 0 to 10, and when n is other than 0, there is Plural R ¹ ~ R ⁸ and M have the same and different cases respectively),

(In the formula, R ⁹ represents a hydrocarbon group with 1 to 20 carbon atoms, 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 , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ (hereinafter also referred to as R ¹⁰ to R ³⁸ ) each independently represent a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, a group with 2 to 20 carbon atoms containing a heterocyclic ring, or a halogen atom, and R ¹⁰ to The methylene group in the group represented by R ³⁸ may be substituted with -O- or -S- under the condition that it is not adjacent to oxygen, R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ²² and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ³⁰ and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ , R ³⁸ and R ³¹ , R ³¹ and R ³² , When R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ and R ³⁶ and R ³⁷ are bonded to form a ring, the * in the formula means that the group represented by the equation has the * part and the adjacent basis for bonding). The curable composition as claimed in item 1, wherein the polymerization initiator (C) is a compound having a group represented by the following general formula (II),

(wherein, R ⁴¹ and R ⁴² independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group with 1 to 20 carbon atoms or a group with 2 to 20 carbon atoms containing a heterocyclic ring, R ⁴¹ and The hydrogen atom in the hydrocarbon group with 1 to 20 carbon atoms represented by R ⁴² or the group with 2 to 20 carbon atoms containing a heterocyclic ring is substituted by halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, In the case of methacryl group, acryl group, epoxy group, vinyl group, vinyl ether group, mercapto group, isocyanate group or a group with 2 to 20 carbon atoms containing a heterocyclic ring, R ⁴¹ and R ⁴² represent The methylene group in the base is also substituted by -O-, -CO-, -COO-, -OCO-, -NR ⁴³ -, -NR ⁴³ CO-, -S-, -CS-, -SO ₂ In the case of -, -SCO-, -COS-, -OCS- or CSO-, R ⁴³ represents a hydrogen atom, a hydrocarbon group with 1 to 20 carbon atoms, m represents 0 or 1, and * in the formula means The base indicated is bonded with the adjacent base by the * moiety). The curable composition according to claim 1, wherein the colorant (D) is a black pigment. A method for producing a cured product, which uses the curable composition according to claim 1. A cured product, which is a cured product of the curable composition according to claim 1. A color filter containing the cured product according to claim 7.

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