KR102374939B1 - Curable composition, cured product, and method for manufacturing cured product - Google Patents

Abstract

A curable composition comprising 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). It is preferable that content of the metal in the said wet silica particle (A) is 1000 ppm or less. In addition, it is preferable that the wet silica particles (A) are colloidally dispersed silica particles.

Description

Curable composition, cured product, and method for manufacturing cured product

The present invention relates to a curable composition containing silica particles and a colorant.

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

Recently, black resist for color filters used in IPS/FFS mode liquid crystal displays are required to have high light blocking properties, high resistance (high insulation), and high definition. There is a problem that there is no compatible color filter.

Patent Documents 1, 2, 3 and 4 disclose a composition capable of producing a cured product having high resistance. Patent Document 1 discloses a photosensitive composition containing a photocurable resin, an acrylic resin particle, and a light-shielding pigment, and a cured product having high resistance is obtained. Patent Document 2 discloses a coloring composition from which a cured product having high resistance is obtained by using a coloring agent coated with silica. Patent Document 3 discloses a coloring composition from which a cured product having high resistance is obtained by using silica contained in carbon black. Patent Document 4 discloses a photosensitive resin composition for black resists from which a cured product having high resistance is obtained by containing granular silica synthesized by a gas phase reaction, a black organic pigment, and a photocurable resin.

Japanese Patent Laid-Open No. 2010-256589 Japanese Patent Laid-Open No. 2001-115043 Japanese Patent Laid-Open No. 2008-150428 Japanese Patent Laid-Open No. 2008-304583

However, the hardened|cured material obtained from the photosensitive composition of patent document 1 had the problem that light-shielding property was low. The hardened|cured material obtained from the coloring photosensitive material described in patent document 2 showed a white color since the surface of the coloring agent was coat|covered with silica, and there existed a problem that it was difficult to obtain a hardened|cured material with high jet-blackness. The hardened|cured material obtained from the coloring composition of patent document 3 had the problem that sufficient electrical resistance was not obtained. The photocurable resin of patent document 4 had a problem of storage stability, and also had a problem with the smoothness of the hardened|cured material obtained.

Accordingly, an object of the present invention is to provide a curable composition capable of producing a cured product that can be achieved at a level that can satisfy high resistance and creation of a high-definition pattern. Moreover, in the case of a curable composition using a black pigment as a coloring agent, the hardened|cured material with high light-shielding can be produced.

The present invention has achieved the above object by providing the following [1] to [8].

[1] A curable composition comprising wet silica particles (A) having 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 colorant (D).

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

[3] a compound in which the polymerizable compound (B) is represented by the following general formula (I);

An unsaturated compound having a structure in which a compound represented by the following general formula (I) and an unsaturated monobasic acid are esterified, or

Curability described in [1] or [2] above, which is an unsaturated compound having a structure in which a polybasic acid anhydride is esterified to an unsaturated compound having a structure in which an epoxy compound represented by the following general formula (I) and an unsaturated monobasic acid are esterified composition.

(wherein M is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SO ₂ -, -SS-, -SO-, -CO-, -OCO-, the following formula ( a), (b), (c) or (d) represents a substituent selected from the group,

A hydrogen atom in the group represented by M may be substituted with 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 ) are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. or a halogen atom,

A methylene group in the group represented by R ¹ to R ⁸ may be substituted with -O- on the condition that oxygen is not adjacent to each other,

n is a number from 0 to 10,

When n is other than 0, a plurality of R ¹ to R ⁸ and M may be the same or different from each other.)

(Wherein, R ⁹ represents a hydrocarbon group having 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 ) are each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocycle, or a halogen atom,

A methylene group in the group represented by R ¹⁰ to R ³⁸ may be substituted with -O- or -S- on the condition that oxygen is not adjacent to each other;

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 , R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ and R ³⁶ and R ³⁷ may combine to form a ring,

* in a formula means that the group represented by these formulas couple|bonds with the adjacent group in * part.)

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

(Wherein, R ⁴¹ and R ⁴² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocycle,

A hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms or the group having 2 to 20 carbon atoms represented by R ⁴¹ and R ⁴² is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, meta It may be substituted with an acryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, or a group having 2 to 20 carbon atoms containing a heterocyclic ring,

The methylene group in the group represented by R ⁴¹ and R ⁴² is -O-, -CO-, -COO-, -OCO-, -NR ⁴³ -, -NR ⁴³ CO-, -S-, -CS-, -SO2-, -SCO-, -COS-, -OCS- or -CSO- may be substituted,

R ⁴³ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,

m represents 0 or 1,

* in a formula means that the group represented by these formulas couple|bonds with the adjacent group in * part.)

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

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

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

[8] A color filter containing the cured product according to [7] above.

1 is a schematic diagram showing an angle θ corresponding to a taper angle between a pattern formed on a substrate and a substrate.

EMBODIMENT OF THE INVENTION Hereinafter, the curable composition of this invention is demonstrated based on preferable embodiment.

The curable composition of this invention contains the wet silica particle (A) whose average particle diameter is 50 nm or less, a polymeric compound (B), a polymerization initiator (C), and a coloring agent (D). Hereinafter, each component is demonstrated in order.

<Silica Particles (A)>

The silica particles (A) used in the curable composition of the present invention are particles made of wet silica having an average particle diameter of 50 nm or less. Wet silica is amorphous silicon dioxide synthesized in a liquid. The silica particles (A) used in the curable composition of the present invention are obtained, for example, by a precipitation method or a gel method for neutralizing sodium silicate with an inorganic acid, or a sol-gel method for hydrolyzing an alkoxysilane.

In the present invention, from the viewpoint of good dispersibility in polymerizable compounds and solvents, silica particles having colloidal dispersion are particularly preferable among wet silica, and surface-treated silica is preferable from the same viewpoint.

Although the silica particle (A) used for the curable composition of this invention does not have a special regulation about content of a metal as an impurity, it is preferable that there is little content of a metal. The metal concentration in the silica particles (A) can be measured with high sensitivity by the ICP-MS method after dispersion in an appropriate dispersion medium.

In addition, the undesirable metals included in the silica particles (A) include iron, sodium, titanium, aluminum, potassium, calcium, zirconium and magnesium. The metal content in the silica particles (A) is preferably 1000 ppm or less, more preferably 100 ppm or less, still more preferably 1 ppm or less.

Silica particles (A) used in the curable composition of the present invention have an average particle diameter of 50 nm or less, a stable curable composition that does not impair the dispersibility of the colorant is obtained, and the cured product obtained from the curable composition has a high fineness The average particle diameter is preferably 30 nm or less, and more preferably 20 nm or less. Although there is no restriction|limiting in particular as a lower limit of the average particle diameter of a silica particle (A), It can be set as 10 nm or more. The average particle diameter of the silica particles can be measured using a laser diffraction type particle size distribution measuring device. As a laser diffraction type particle size distribution measuring device, a Microtrac particle size distribution meter manufactured by Nigisso Co., Ltd. is mentioned.

The surface-treated silica refers to a chemical reaction of a part or all of the silanol groups on the surface of silica particles, for example, silica particles and an organosilicon compound such as an alkoxysilane compound, a solvent, and optionally hydrolyzing the organosilicon compound Silica particles obtained by adding and heating an acid or alkali as a catalyst for this purpose are mentioned.

As said silica particle (A), a commercial item can be used preferably, For example, PL-1-IPA, PL-1-TOL, PL-2L-PGME, PL-2L-MEK (above, Fusoka Chemical Co., Ltd. product) ); YA010C-LDI, YA050C-LHI, YA010C-SP3 (manufactured by Adomatech Co., Ltd.); Organosilicasol 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 (above, Nissan Chemical Industry Co., Ltd. product) etc. are mentioned.

In the curable composition of the present invention, the content of the silica particles (A) is not particularly limited, but with respect to 100 parts by mass of the colorant (D), preferably 0.1 to 70 parts by mass, more preferably 0.5 to 50 parts by mass part, More preferably, it is 5-20 mass parts. When content of a silica particle (A) is the above-mentioned range, since the curable composition excellent in the dispersibility of a silica particle and a colorant, and a hardened|cured material with high resistance are obtained, it is preferable.

For example, when forming a hardened|cured material with a thickness of 1-3 micrometers, Content of the said silica particle (A) is although it does not specifically limit, Preferably it is 0.1-70 mass with respect to 100 mass parts of said coloring agents (D). part, 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 polymerizability such as radical polymerization, cationic polymerization and anionic polymerization, and has good reactivity and has many types of polymerizable compounds. A polymerizable compound can be used preferably.

It does not specifically limit as a radically polymerizable compound, The compound which has conventionally known radically polymerizable compound can be used, For example, ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride. , unsaturated aliphatic hydrocarbons such as vinylidene fluoride and tetrafluoroethylene; (meth)acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, monosuccinic acid [2-(meth)acryloyloxyethyl], monophthalic acid mono[2-(meth)acryloyloxyethyl] and ω-carboxypolycaprolactone mono(meth)acrylate having a carboxyl group and a hydroxyl group at both terminals Polymer mono (meth) acrylate; Hydroxyethyl (meth)acrylate maleate, hydroxypropyl (meth)acrylate maleate, dicyclopentadiene maleate and polyfunctional (meth) having one carboxyl group and two or more (meth)acryloyl groups unsaturated monobasic acids such as meth)acrylate; (meth)acrylic acid-2-hydroxyethyl, (meth)acrylic acid-2-hydroxypropyl, (meth)acrylic acid glycidyl, the following compound No. A1-No. A4, (meth) methyl acrylate, (meth) butyl acrylate, (meth) acrylate isobutyl, (meth) acrylic acid-t-butyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid n-octyl, (meth) acrylic acid isoox Tyl, (meth) acrylate isononyl, (meth) acrylate stearyl, (meth) acrylate lauryl, (meth) acrylate methoxyethyl, (meth) acrylate dimethylaminomethyl, (meth) acrylate dimethylaminoethyl, (meth) acrylate ) acrylic acid aminopropyl, (meth)acrylic acid dimethylaminopropyl, (meth)acrylic acid ethoxyethyl, (meth)acrylic acid poly(ethoxy)ethyl, (meth)acrylic acid butoxyethoxyethyl, (meth)acrylic acid ethylhexyl, ( Phenoxyethyl (meth)acrylate, tetrahydrofuryl (meth)acrylate, vinyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acryl rate, 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, tricyclodecanedimethyloldi(meth)acrylate, tri[(meth)acryloylethyl]isocyanurate and polyester (meth)acrylate esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as oligomers; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; Maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3 - acid anhydrides of unsaturated polybasic acids such as cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride and methyl hymic anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetris(meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide and N-2-hydroxyethyl ( amides of unsaturated monobasic acids and polyvalent amines such as meth)acrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide and allyl cyanide; Styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid , unsaturated aromatic compounds such as vinyl benzyl methyl ether and vinyl benzyl 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 ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; indene, such as indene and 1-methylindene; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; macromonomers having a mono(meth)acryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate and polysiloxane; Vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalite, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinylimidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone , vinyl pyridine, hydroxyl group-containing vinyl monomers, vinyl urethane compounds of polyisocyanate compounds, vinyl epoxy compounds such as hydroxyl group-containing vinyl monomers and polyepoxy compounds.

Commercially available compounds may be used as the radically polymerizable compound, and for example, Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (above, Nippon Kayaku); Aronix M-215, M-350 (above, manufactured by Toagosei); NK esters A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (above, Shin-Nakamura Chemical Co., Ltd.); SPC-1000, SPC-3000 (above, manufactured by Showa Denko); and the like.

From the viewpoint of obtaining a cured composition having good dispersibility of the colorant (D) and a cured product having good heat resistance, the polymerizable compound (B) is a compound represented by the general formula (I); an unsaturated compound having a structure in which a compound represented by the general formula (I) and an unsaturated monobasic acid are esterified; Or, it is preferable that it is an unsaturated compound which further has a structure obtained by esterifying a polybasic acid anhydride to an unsaturated compound having a structure obtained by esterification of the compound represented by the general formula (I) and an unsaturated monobasic acid. an unsaturated compound in which the polymerizable compound (B) has a structure obtained by esterification of a compound represented by the general formula (I) and an unsaturated monobasic acid, and further has a structure of [the following (g)]; Alternatively, an unsaturated compound having a structure in which a polybasic acid anhydride is esterified to an unsaturated compound having a structure in which a compound represented by the general formula (I) and an unsaturated monobasic acid are esterified, and further having a structure of [the following (h)] It is particularly preferred.

The composition of the present invention is a polymerizable compound (B), and as described above, "the epoxy compound represented by the general formula (I)", "the epoxy compound represented by the general formula (I) and a structure in which an unsaturated monobasic acid is esterified" It is preferable to contain an unsaturated compound having a” or “an unsaturated compound having a structure in which a polybasic acid anhydride is esterified to an unsaturated compound having a structure obtained by esterification of an epoxy compound represented by the general formula (I) and an unsaturated monobasic acid” . In the present invention, a variety of compounds can be used as the unsaturated monobasic acid and polybasic acid anhydride, as will be described later. Therefore, the "unsaturated compound having a structure in which an epoxy compound represented by the general formula (I) and an unsaturated monobasic acid are esterified" and "a structure in which an epoxy compound represented by the general formula (I) and an unsaturated monobasic acid are esterified" The structure of the "unsaturated compound further having a structure in which a polybasic acid anhydride is esterified to an unsaturated compound having For this reason, it is absolutely impossible to represent the structure of the unsaturated compound preferable as said polymeric compound (B) by any kind of general formula uniformly, and this is the technical common knowledge of those skilled in the art. And if the structure is not specified, the properties of the material that are determined accordingly cannot be easily known, so it is impossible to express them in terms of properties. Therefore, in the present invention, an unsaturated compound preferable as the polymerizable compound (B) is defined as “an unsaturated compound having a structure in which an epoxy compound represented by general formula (I) and an unsaturated monobasic acid are esterified”, “general formula (I)” An unsaturated compound having a structure obtained by esterification of a polybasic acid anhydride to an unsaturated compound having a structure obtained by esterification of an epoxy compound and an unsaturated monobasic acid shown cannot but be defined as "an unsaturated compound". That is, with respect to the preferable polymerizable compound (B) used in the present invention, there is a situation in which it is impossible or almost impractical to "specify the epoxy acrylate directly by its structure or properties at the time of filing".

(wherein Y ¹ represents a residue of an unsaturated monobasic acid, Y ² represents a residue of a polybasic acid anhydride,

* in a formula means that the group represented by these formulas couple|bonds with the adjacent group in * part.)

The hydrocarbon group having 1 to 20 carbon atoms represented by M in the general formula (I) is not particularly limited, but preferably an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, etc. indicates.

Examples of the alkylene group having 1 to 20 atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tride. Silene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadexylene, icoxylene group, etc. are mentioned.

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

The hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ³⁸ in the general formula (I) is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. , a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, etc., a polymerizable compound (B ) from the viewpoint of good sensitivity when used as an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkanediyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. , a cycloalkylalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and the like are more preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl and icosyl; Examples of the alkyl group having a number of 1 to 10 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, iso octyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl and isodecyl and the like.

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-tetradecatrienylallyl, and the like, and examples of the alkenyl group having 2 to 10 carbon atoms include For example, 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 and 4-decenyl, and the like.

The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo[1.1.1]fentanyl. and tetradecahydroanthracenyl. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclo decyl, adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]fentanyl; and the like.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with 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-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptyl Propyl, 3-cyclooctylpropyl, 3-cyclononylpropyl, 3-cyclodecylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4-cyclononylbutyl, 4-cyclodecylbutyl, 3-3-adamantylpropyl and decahydronaphthylpropyl, etc. are mentioned, The cycloalkylalkyl group having 4 to 10 carbon atoms is, for example, cyclo Propylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl , 2-cyclooctylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4-cyclopentylbutyl and 4-cyclohexylbutyl, etc. can be heard

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, etc. One or more substituted phenyl, biphenylyl, naphthyl, anthryl, etc., for example, 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, etc. and the aryl group having 6 to 10 carbon atoms is, for example, phenyl, tolyl, xylyl, ethylphenyl and naphthyl, or at least one of the alkyl group, the alkenyl group or carboxyl group, a halogen atom, etc. substituted phenyl, biphenylyl, naphthyl, anthryl and the like, such as 4-chlorophenyl, 4-carboxylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, and the like. can

The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 30 carbon atoms in which a hydrogen atom of the alkyl group is substituted with an aryl group. Examples thereof include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl. The arylalkyl group having 7 to 20 carbon atoms is a hydrogen atom in the alkyl group, substituted with an aryl group. means a group having 7 to 20 carbon atoms. For example, benzyl, α-methylbenzyl, α,α-dimethylbenzyl and phenylethyl and the like are mentioned.

The group having 2 to 20 carbon atoms containing a heterocycle represented by R ¹⁰ to R ³⁸ in the general formula (I) is not particularly limited, and for example, pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, Pyridazyl, piperazil, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, Furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, morphol nyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl and 2,4-dioxazolidine -3-yl and the like, and when specifically described including a substituent, groups having the following structure are exemplified.

(In the formula, R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms. On the other hand, * in the formula is It means that the group represented is bonded to an adjacent group in the * moiety.)

Examples of the 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.

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 in the formula (I) above. 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 combine Examples of the ring to be formed include 5 to 7 of cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone ring and lactam ring. Condensed rings, such as a ring and naphthalene and anthracene, etc. are mentioned.

The unsaturated monobasic acid refers to an acid having an unsaturated bond in its structure and having one hydrogen atom per molecule that can be ionized to become a hydrogen ion. Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, and hydroxyethyl methacrylate maleate, hydroxypropyl methacrylate maleate, and hydroxypropyl acrylic acid. Late maleate, dicyclopentadiene maleate, etc. are mentioned.

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

Examples of the polybasic acid anhydride include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3' -benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydrotrimellitate, glycerol tris anhydrotrimellitate, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydro Phthalic anhydride, hexahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride acid adducts, dodecenyl succinic anhydride and methyl hymic anhydride; and the like.

It is preferable to carry out the reaction molar 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, in the epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, with respect to one hydroxyl group of the epoxy adduct, the polybasic acid of the polybasic acid anhydride It is preferable to make it so that it may become a ratio which becomes 0.1-1.0 number of anhydride structures.

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

As the polymerizable compound (B), among the above reaction products, it is easy to obtain to use an epoxy compound represented by the general formula (I), wherein R ¹ to R ⁸ are hydrogen atoms, but when carbon black is added as a colorant. Since it becomes a high OD value, it is preferable. Further, from the same viewpoint, M is the group represented by (c), the group represented by R ¹⁰ to R ¹⁴ is a hydrogen atom or a phenyl group, M is the group represented by (d), and R ¹⁵ to R ²² are a hydrogen atom or a phenyl group It is also preferable to use a group in which M is a group represented by (e) and R ²³ to R ³⁰ are a hydrogen atom or a phenyl group, or a group in which M is a group represented by (f) and R ³¹ to R ³⁸ is a hydrogen atom or a phenyl group. Do. Especially when M is group represented by (d), since the volume resistance of hardened|cured material is high, it is more preferable.

Moreover, it is preferable to use a C5 or less thing as said unsaturated monobasic acid, and it is especially preferable to use acrylic acid, methacrylic acid, etc. As the polybasic acid anhydride, those having a benzene ring or a saturated fatty ring are preferable, and in particular, those using biphenyltetracarboxylic dianhydride, phthalic anhydride, tetrahydrophthalic anhydride, biphthalic anhydride, and the like are preferable.

As the polymerizable compound (B) of the present invention, a product produced by the following production method is preferable from the viewpoint of good dispersibility and curability of the colorant, but it is not limited thereto.

Specifically, for example, 1,1-bis[4-(2,3-epoxypropyloxy)phenyl]indane as the epoxy compound represented by the general formula (I), acrylic acid as the unsaturated monobasic acid, and polybasic acid anhydride A product formed by selecting nonphthalic anhydride as

Select 1,1-bis[4-(2,3-epoxypropyloxy)phenyl]indane as the epoxy compound represented by the general formula (I), acrylic acid as the unsaturated monobasic acid, and tetrahydrophthalic anhydride as the polybasic acid anhydride product made by

A product obtained by selecting 1,1-bis[4-(2,3-epoxypropyloxy)phenyl]indane as the epoxy compound represented by the general formula (I), acrylic acid as the unsaturated monobasic acid, and phthalic anhydride as the polybasic acid ,

1,1-bis[4-(2,3-epoxypropyloxy)phenyl]indane as the epoxy compound represented by the general formula (I), acrylic acid as the unsaturated monobasic acid, and biphthalic anhydride and tetrahydrous as the polybasic acid anhydride a product made by selecting phthalic anhydride and

1,1-bis[4-(2,3-epoxypropyloxy)phenyl]-3-phenylindane as the epoxy compound represented by the general formula (I), acrylic acid as the unsaturated monobasic acid, and biphthalic acid as the polybasic acid anhydride The product etc. which consist of selecting anhydride and tetrahydrophthalic anhydride are mentioned.

When the compound which has an acid value is used among the said radically polymerizable compound, alkali developability can be provided to the curable composition of this invention. When using the compound which has the said acid value, it is preferable to use it so that it may become 50-99 mass parts with respect to 100 mass parts of polymeric compounds which have the said radical polymerizability.

In addition, the compound which has the said acid value can also be used, after adjusting an acid value by further reacting a monofunctional or polyfunctional epoxy compound. The alkali developability of a curable composition can be improved by adjusting the acid value of the compound which has the said acid value. The compound having the above acid value (that is, the polymerizable compound having radical polymerizability imparting alkali developability) preferably has an acid value of 5 to 120 mgKOH/g of solid content, and a monofunctional or polyfunctional epoxy compound It is preferable that the amount used is selected to satisfy the above acid value.

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, Dil ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether Cidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether Cydyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether Dil ether, 2-methylcresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl Methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monoxide, 1,2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, Propylene oxide, the compound No. A1-No. A4 etc. are mentioned.

As said polyfunctional epoxy compound, when 1 or more types of compounds chosen from the group which consists of a bisphenol-type epoxy compound and glycidyl ethers are used, since a curable composition with much better characteristics can be obtained, it is preferable.

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

Further, examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether , triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri ( glycidyloxymethyl)propane, 1,1,1-tri(glycidyloxymethyl)ethane, 1,1,1-tri(glycidyloxymethyl)methane and 1,1,1,1-tetra( glycidyloxymethyl)methane, etc. can be used.

In addition, novolak-type epoxy compounds, such as a phenol novolak-type epoxy compound, a biphenyl novolak-type epoxy compound, a cresol novolak-type epoxy compound, a bisphenol A novolak-type epoxy compound, and a dicyclopentadien novolak-type epoxy compound; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 1- alicyclic epoxy compounds such as epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester and dimer acid glycidyl ester; glycidylamines such as tetraglycidyldiaminodiphenylmethane, triglycidylP-aminophenol and N,N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds, such as dicyclopentadiene dioxide; naphthalene type epoxy compound; A triphenylmethane type epoxy compound, a dicyclopentadiene type epoxy compound, etc. can also be used.

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

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-sec-butylphenyl glycidyl ether, p-tert-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, methoxy polyethylene glycol monoglycidyl ether, ethoxy polyethylene glycol monoglycidyl ether, butoxy polyethylene glycol mono Glycidyl ether, phenoxypolyethylene glycol monoglycidyl ether, dibromophenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6 -Glycidyl such as hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,1,2,2-tetrakis (glycidyloxyphenyl) ethane and pentaerythritol tetraglycidyl ether etheride; glycidyl esters such as glycidyl acetate and glycidyl stearate; 2-(3,4-Epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane- metadioxane, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl- Bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, ethylenebis(3,4-epoxycyclohexanecarboxylate), bis(3,4-epoxycyclohexyl) Hexylmethyl) adipate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl 6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl 3,4-epoxy-3-methylcyclohexane Carboxylate, 3,4-epoxy-5-methylcyclohexylmethyl 3,4-epoxy-5-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy- Epoxycycloalkyl such as 2-epoxyethylcyclohexane, dicyclopentadiene diepoxide, 3,4-epoxy-6-methylcyclohexylcarboxylate, α-pinene oxide, styrene oxide, cyclohexene oxide and cyclopentene oxide type compound and N-glycidyl phthalimide, and the like.

As the epoxy compound, an epoxidized polyolefin may be used. The epoxidized polyolefin is a polyolefin in which an epoxy group is introduced by modifying the polyolefin with an epoxy group-containing monomer. It can be produced by copolymerizing ethylene or an α-olefin having 3 to 20 carbon atoms, an epoxy group-containing monomer, and, if necessary, other monomers by either a copolymerization method or a graft method. Ethylene or ?-olefin having 3 to 20 carbon atoms, epoxy group-containing monomers and other monomers may be polymerized individually, or may be polymerized in plurality with other monomers. Further, the double bond of non-conjugated polybutadiene having a hydroxyl group at the terminal may be obtained by epoxidation by the peracetic acid method, or one having a hydroxyl group in the molecule may be used. Alternatively, an epoxy group may be introduced by urethanizing the hydroxyl group with isocyanate and reacting the epoxy compound containing a primary hydroxyl group therewith.

Examples of the ethylene or α-olefin having 3 to 20 carbon atoms include ethylene, propylene, butylene, isobutylene, 1,3-butadiene, 1,4-butadiene, 1,3-pentadiene, 2,3-dimethyl- 1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, and the like.

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

Examples of the other monomer 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, hymic acid, crotonic acid, isocrotonic acid, vinylacetic acid, allylacetic acid, cinnamic acid, sorbic acid, mesaconic acid, monosuccinic acid [2-(meth)acryloyloxyethyl], monophthalic acid [2-(meth)acryloyloxyethyl], ω-carboxypolycaprolactone mono(meth)acrylate having a carboxyl group and a hydroxyl group at both terminals Polymer mono (meth) acrylate, hydroxyethyl (meth) acrylate maleate, hydroxypropyl (meth) acrylate maleate, dicyclopentadiene maleate and one carboxyl group and two or more (meth) ) Unsaturated polybasic acids, such as polyfunctional (meth)acrylate which has an acryloyl group; (meth)acrylic acid-2-hydroxyethyl, (meth)acrylic acid-2-hydroxypropyl, (meth)acrylic acid methyl, (meth)acrylate butyl, (meth)acrylate isobutyl, (meth)acrylic acid-t-butyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid n-octyl, (meth)acrylic acid isooctyl, (meth)acrylic acid isononyl, (meth)acrylic acid stearyl, (meth)acrylic acid lauryl, (meth)acrylic acid methoxy Ethyl, (meth)acrylate dimethylaminomethyl, (meth)acrylate dimethylaminoethyl, (meth)acrylate aminopropyl, (meth)acrylate dimethylaminopropyl, (meth)acrylate ethoxyethyl, (meth)acrylic acid poly(ethoxy) Ethyl, (meth) acrylate butoxyethoxyethyl, (meth) acrylate ethylhexyl, (meth) acrylate phenoxyethyl, (meth) acrylate tetrahydrofuryl, (meth) acrylate vinyl, (meth) acrylate allyl, (meth) Benzyl 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, tricyclodecanedimethyloldi(meth)acrylate, tri[ esters of unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols such as (meth)acryloylethyl]isocyanurate and polyester (meth)acrylate oligomers; metal salts of unsaturated polybasic acids such as zinc (meth)acrylate and magnesium (meth)acrylate; Maleic anhydride, itaconic anhydride, citraconic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3 -acid anhydrides of unsaturated polybasic acids such as cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, dodecenyl succinic anhydride and methyl hymic anhydride; (meth)acrylamide, methylenebis-(meth)acrylamide, diethylenetriaminetris(meth)acrylamide, xylylenebis(meth)acrylamide, α-chloroacrylamide, N-2-hydroxyethyl ( amides of unsaturated monobasic acids and polyvalent amines such as meth)acrylamide; unsaturated aldehydes such as acrolein; unsaturated nitriles such as (meth)acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, and allyl cyanide; Styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid , unsaturated aromatic compounds such as vinyl benzyl methyl ether and vinyl naphthalene; 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 ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether and isobutyl vinyl ether; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; indene, such as indene and 1-methylindene; macromonomers having a mono(meth)acryloyl group at the terminal of the polymer molecular chain, such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate and polysiloxane; Vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triaryl phosphate, triallyl isocyanurate, vinyl thioether, vinylimidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, Hydroxyl group-containing polyfunctional acrylics such as vinyl pyridine, vinyl urethane compounds of hydroxyl group-containing vinyl monomers and polyisocyanate compounds, vinyl epoxy compounds of hydroxyl group-containing vinyl monomers and polyepoxy compounds, pentaerythritol triacrylate and dipentaerythritol pentaacrylate rate; reaction products of polyfunctional isocyanates such as tolylene diisocyanate and hexamethylene diisocyanate; A polyfunctional acrylate having an acid value, which is a reaction product of a hydroxyl group-containing polyfunctional acrylate such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and a dibasic acid anhydride such as succinic anhydride, phthalic anhydride and tetrahydrophthalic anhydride can be heard

As said epoxidized polyolefin, a commercially available item can also be used, For example, Epollide PB3600, Epolid PB4700 (above, Daicel product); BF-1000, FC-3000 (above, manufactured by ADEKA); Bond First 2C, Bond First E, Bond First CG5001, Bond First CG5004, Bond First 2B, Bond First 7B, Bond First 7L, Bond First 7M, Bond First 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 (from Arcma); and the like.

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 glycolbis(3 -Ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, 1; 4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-[(phenoxy)methyl]ox Cetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane and 3-ethyl -3-(chloromethyl)oxetane and the like.

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-chloroethyl vinyl ether, Ethyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,6-cyclohexanedimethanol monovinyl ether, ethylene glycol divinyl ether, 1 and 4-butanediol divinyl ether and 1,6-cyclohexanedimethanol divinyl ether.

As the cationic polymerizable compound, a commercially available compound may be used, for example, Eporite 40E, 1500NP, 1600, 80MF, 4000 and 3002 (above, manufactured by Kyoeisha Chemical); Adecaglycerol ED-503, ED-503D, ED-503G, ED-523T, ED-513, ED-501, ED-502, ED-509, ED-518, ED-529, Adekaresin 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 Chemicals); EHPE-3150, Celoxide 2021P, 2081, 2000 and 3000 (or higher, manufactured by Daicel); Epiol M, EH, L-41, SK, SB, TB and OH (above, manufactured by Nichiyu); Eporite M-1230 and 100MF (above, manufactured by Kyoeisha Chemical); Aronoxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211 and OXT-212 (above, manufactured by Toagosei); etanacol OXBP and OXTP (above, from Ube Kosan); 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether (above, manufactured by Maruzen Seki Chemical); 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 Chemical); HP4032, HP4032D and HP4700 (or higher, DIC products); ESN-475V (manufactured by Toto Kasei); Epicoat YX8800 (manufactured by Mitsubishi Chemical); Mapproof G-0105SA and G-0130SP (above, manufactured by Nichiyu); Epiclone 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); and the like.

The curable composition of the present invention WHEREIN: Although content of a polymeric compound (B) is not specifically limited, A total of 100 mass parts of a silica particle (A), a polymeric compound (B), a polymerization initiator (C), and a coloring agent (D) To that, from the viewpoint of good sclerosis, it is preferably 10 to 70 parts by mass, more preferably 20 to 50 parts by mass, still more preferably 30 to 50 parts by mass. When content of a polymeric compound (B) exists in said range, since the hardened|cured material obtained is excellent in sclerosis|hardenability and light-shielding property, it is preferable.

For example, although content of a polymeric compound (B) is not specifically limited when forming a 1-3 micrometers-thick cured film, The sum total of a silica particle (A), a polymeric compound (B), and a polymerization initiator (C) Preferably it is 10-70 mass parts with respect to 100 mass parts, More preferably, it is 30-60 mass parts, More preferably, it is 30-50 mass parts.

<Polymerization Initiator (C)>

As the polymerization initiator (C) used in the curable composition of the present invention, it is possible to use conventionally known radical polymerization initiators and cationic polymerization initiators.

The said radical polymerization initiator is an optical radical polymerization initiator and a thermal radical polymerization initiator. From the viewpoint of high reactivity, a radical photopolymerization initiator is more preferable.

The photoradical polymerization initiator is not particularly limited as long as it generates radicals by irradiation with light, and a conventionally known compound can be used. For example, an acetophenone-based compound, a benzyl-based compound, a benzophenone-based compound, and thioxane Tone-based compounds, oxime ester-based compounds, and the like can be exemplified as preferable ones.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 4'-isopropyl-2-hydroxy-2-methylpropiophenone. , 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p -tertbutyltrichloroacetophenone, p-azidebenzalacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone- 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, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, etc. are mentioned.

Benzyl etc. are mentioned as a benzyl type compound.

As the benzophenone-based compound, for example, benzophenone, o-benzoyl methyl benzoate, Michler ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 4-benzoyl-4' -Methyldiphenyl sulfide, etc. are mentioned.

As a thioxanthone-based compound, thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc. can be heard

An oxime ester-type compound means the compound which has group represented by the said General formula (II), and since a sensitivity is favorable among the said radical photopolymerization initiator, it can use it suitably for the curable composition of this invention.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴³ in the general formula (II) is the same as the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ³⁸ , respectively.

The group having 2 to 20 carbon atoms containing a heterocycle which may be modified by R ⁴¹ and R ⁴² and the group represented by R ⁴¹ or R ⁴² in the general formula (II) is a heterocycle represented by R ¹⁰ to R ³⁸ It is the same as the group containing 2-20 carbon atoms.

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

Among the compounds having a group represented by the general formula (II), the compound represented by the following general formula (III) is more preferably used for the curable composition of the present invention from the viewpoint of particularly high sensitivity.

(wherein R ⁴¹ , R ⁴² and m are the same as R ⁴¹ , R ⁴² and m in general formula (II), respectively;

R ⁵¹ and R ⁵² are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an arylalkyl group having 2 to carbon atoms 20 represents a heterocyclic group,

X ¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁵³ R ⁵⁴ , CO, NR ⁵⁵ or PR ⁵⁶ ;

R ⁵¹ to R ⁵⁶ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocycle, and a hydrogen atom in the group represented by R ⁵³ to R ⁵⁶ is , may be substituted with a halogen atom, a nitro group, a cyan group, a hydroxyl group, a carboxyl group or a heterocyclic group,

A methylene group in the group represented by R ⁵¹ to R ⁵⁶ may be substituted with -O- on the condition that oxygen is not adjacent to each other,

R ⁵¹ to R ⁵⁶ may each independently form a ring by forming one with a benzene ring of any adjacent one,

g represents a number from 0 to 5,

h represents a number from 0 to 4.)

The number of carbon atoms containing an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms and a heterocycle represented by R ⁵¹ and R ⁵² in the general formula (III) The group of 2 to 20 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and a heterocycle-containing carbon atom represented by R ¹ to R ³⁸ . It is the same as the group of 2~20.

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

The hydrocarbon group having 1 to 20 carbon atoms represented by R ⁵³ to R ⁵⁶ in the general formula (III) is the same as the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ³⁸ , respectively.

The group having 2 to 20 carbon atoms containing a heterocycle represented by R ⁵³ to R ⁵⁶ in the general formula (III) is the same as the group having 2 to 20 carbon atoms containing a heterocycle represented by R ¹⁰ to R ³⁸ .

As a compound represented by the said general formula (III), the compound shown below is mentioned, for example. However, the present invention is not limited at all by the following compounds.

Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(phyll -1-yl)] titanocene compounds such as titanium; and the like.

Commercially available radical initiators include Adeka Optomers N-1414, N-1717, N-1919, Adeka Acools NCI-831, NCI-930 (above, manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE784 (above, manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (above, Tronly products); and the like.

The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and conventionally known compounds can be used. For example, azo-based compounds, peroxides and persulfates can be exemplified as preferable ones. .

Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1, 1'-azobis(1-acetoxy-1-phenylethane) etc. are mentioned.

Examples of the peroxide include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxyfivalate and di(4-t-butylcyclohexyl)peroxydicarbonate.

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

The said cationic initiator shows a photocationic initiator and a thermal cationic initiator.

The photocationic initiator is not particularly limited as long as it is a compound capable of releasing a substance that initiates cationic polymerization by irradiation with light, and it is possible to use an existing compound, preferably releasing a Lewis acid by irradiation with an energy ray. double salt, which is an onium salt, or a derivative thereof. Representative examples of such compounds include the following general formula,

[A] ^r+ [B] ^r-

and salts of cations and anions represented by

The cation [A] ^r+ is preferably onium, and the structure thereof is, for example, the following general formula,

[(R ⁵⁸ ) _e Q] ^r+

can be expressed as

Here, R ⁵⁸ is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms. e is an integer in any one of 1-5. e pieces of R ⁵⁸ may be each independently the same or different. In addition, at least one of R ⁵⁸ is preferably an organic group as described above having an aromatic ring. For example, it is substituted with an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkoxy group, a halogen atom, a benzyl group, a thiophenoxy group, a 4-benzoylphenylthio group, a 2-chloro-4-benzoylphenylthio group, etc. The phenyl group which may exist is mentioned. Q is an atom or group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N=N. In addition, when the valence of Q in the cation [A] ^r+ is set to q, the relationship r=eq must be established (however, N=N is treated as valence 0).

In addition, it is preferable that the anion [B] ^r- is a halide complex, and the structure can be represented by the following general formula, [LX _f ] ^r- , for example.

Moreover, where L is a metal or metalloid, which is the central atom of the halide complex, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn and Co, and the like. X is a halogen atom or a phenyl group which may be substituted with a halogen atom, an alkoxy group, or the like. f is an integer from 3 to 7. In addition, when the valence of L in the anion [B] ^r- is set to p, it is necessary that the relationship r=fp is established.

Specific examples of the anion [LX _f ] ^r- of the above general formula include tetrakis(pentafluorophenyl)borate, tetra(3,5-difluoro-4-methoxyphenyl)borate, tetrafluoroborate ( BF ₄ )-, hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- and hexachloroantimonate (SbCl ₆ ) ^- etc. can be heard

In addition, the anion [B] ^r- is represented by the following general formula,

[LX _{f - 1} (OH)] ^{r -}

A structure represented by can also be preferably used. L, X and f are the same as above. In addition, as other anions that can be used, perchlorate ion (ClO ₄ )-, trifluoromethylsulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonic acid ion (FSO ₃ ) ^- , toluenesulfonic acid anion, trinitrobenzenesulfonic acid anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate and tetrakis(pentafluorophenyl)borate; and the like.

In the present invention, it is particularly effective to use the following aromatic onium salts (a) to (c) among such onium salts. Among these, 1 type can be used individually or in mixture of 2 or more types.

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

(B) Diphenyliodonium hexafluoroantimonate, di(4-methylphenyl)iodonium hexafluorophosphate, di(4-tert-butylphenyl)iodonium hexafluorophosphate and tolylcumyliodo Diaryliodonium salts, such as nium tetrakis (pentafluorophenyl) borate.

(C) Sulfonium salts, such as a sulfonium cation represented by the following group I or group II, a hexafluoroantimony ion, and a tetrakis (pentafluorophenyl) borate ion.

As other preferred, (η5-2,4-cyclopentadien-1-yl)[(1,2,3,4,5,6-η)-(1-methylethyl)benzene]-iron-hexa iron-arene complexes such as fluorophosphate; aluminum complexes such as tris(acetylacetonato)aluminum, tris(ethylacetonatoacetato)aluminum, and tris(salicylaldehyde aldehyde)aluminum; Mixtures with silanols, such as triphenylsilanol: etc. are mentioned.

A commercially available product may be used as the photocationic initiator, for example, IRUGACURE261 (manufactured by BASF); Adekaoptomers SP-150, SP-151, SP-152, SP-170, SP-171, SP-172 (above, manufactured by ADEKA); UVE-1014 (manufactured by General Electronics); CD-1012 (product of Sartomer); CI-2064, CI-2481 (above, manufactured by Nippon Soda); Uvacure1590, 1591 (above, manufactured by Daicel UCB); CYRACURE UVI-6990 (above, Union Carbide products); BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103 and NDS-103 (above, manufactured by Midori Chemical); and the like.

Among these, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, and an iron- arene complex from a viewpoint of practical use and photosensitivity.

The thermal cationic 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. Representative examples of such compounds include salts such as sulfonium salts, thiophenium salts, thioranium salts, benzylammonium, pyridinium salts and hydrazinium salts; polyalkyl polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone; The above polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether and bisphenol F-diglycidyl ether or glycidyl ester of carboxylic acid polyepoxy addition-modified products produced by reacting various types of epoxy resins such as those by conventional methods; amidation-modified products produced by reacting the organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid by a conventional method; aldehydes such as the polyamines and formaldehyde; a Manich-modified product produced by reacting phenols having at least one aldehyde-reactive site with a nucleus such as phenol, cresol, xylenol, tert-butylphenol and resorcin by a conventional method; 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 acid, 3-methyladipic acid, 3-methylpentanoic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid, etc. aliphatic dicarboxylic acids; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid, trimesic acid and pima acid anhydrides of tricarboxylic acids such as trimers such as free fatty acids and tetracarboxylic acids such as pyromellitic acid; and dicyandiamide, imidazoles, carboxylate esters, sulfonic acid esters and amine imides.

As said thermal cationic initiator, a commercial item can also be used, For example, Adecaopton CP-77, Adecaopton CP-66 (above, ADEKA product); CI-2639, CI-2624 (above, manufactured by Nippon Soda); Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L (above, Sanshin Chemical Co., Ltd.); and the like.

The polymerization initiator (C) may be used alone or as a mixture of two or more of the above examples.

In the curable composition of the present invention, the content of the polymerization initiator (C) is not particularly limited, but 100 parts by mass in total of the silica particles (A), the polymerizable compound (B), the polymerization initiator (C) and the colorant (D) With respect to , it is preferably 0.3-20 mass parts, More preferably, it is 0.5-10 mass parts, More preferably, it is 1-5 mass parts from sclerosis|hardenability favorable. When content of a polymeric compound (B) exists in said range, since curable composition excellent in storage stability which sclerosis|hardenability is favorable and is not accompanied by precipitation of a polymerization initiator is obtained, it is preferable.

For example, when forming a cured film with a thickness of 1-3 micrometers, Content of a polymerization initiator (C) is although it does not specifically limit, The sum total of a silica particle (A), a polymeric compound (B), and a polymerization initiator (C) With respect to 100 mass parts, 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 colorant (D) used in the curable composition of the present invention. As the pigment and dye, an inorganic color material or an organic color material may be used, respectively, and these may be used alone or in combination of two or more. Here, the pigment refers to a colorant that is insoluble in a solvent to be described later, and also includes an inorganic or organic colorant that is insoluble in a solvent, or a raked inorganic or organic dye.

As the pigment, carbon black obtained by furnace method, channel method or thermal method, carbon black such as acetylene black, Ketjen black or lamp black, the carbon black adjusted or coated with an epoxy resin, the carbon black Dispersion treatment in a resin in advance in a solvent and coating with a resin of 20 to 200 mg/g, carbon black having an acidic or alkaline surface treatment, carbon having an average particle size of 8 nm or more and DBP oil absorption of 90 ml/100 g or less Black, carbon black, graphitized carbon black, graphite, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon with total oxygen content calculated from CO and CO ₂ in volatile matter at 950° C. of 9 mg or more per 100 m 2 of surface area Black pigments represented by nanohorn, carbon airgel, fullerene, aniline black, pigment black 7, titanium black, perylene black, lactam black, chromium oxide rust, milory blue, cobalt rust, cobalt blue, manganese-based, ferro Cyanide, Phosphate Ultramarine Blue, Blue Blue, Ultramarine, Cellulian Blue, Viridian, Emerald Green, Lead Sulfate, Yellow Lead, Zinc Sulfur, Bengal (Red Iron(III) Oxide), Cadmium Red, Synthetic Iron Black, Umber, Lake Pigment, etc. of organic or inorganic pigments, it is preferable to use a black pigment from the viewpoint of high light-shielding property, and it is more preferable to use carbon black as the black pigment.

Among the above carbon blacks, those in which carbon black is adjusted or coated with an epoxy resin, and those in which carbon black is previously dispersed in a resin in a solvent and coated with a resin of 20 to 200 mg/g are preferably used.

Also, among carbon black, carbon black having a sulfonic acid group on the carbon black surface is preferable from the viewpoint of obtaining a colorant dispersion having excellent dispersibility and of obtaining a cured product having excellent light-shielding property and good adhesion to a substrate such as glass.

As a method of imparting a sulfonic acid group to the surface of the carbon black, a method (1) for oxidizing carbon black with peroxodisulfuric acid or a salt thereof or a method (2) for treating carbon black with a sulfonating agent is mentioned.

Method (1) for oxidizing the carbon black with peroxodisulfuric acid or a salt thereof can be carried out by any known method, for example, carbon black, peroxodisulfuric acid or a salt thereof, an aqueous medium (water or (a mixture of water and a water-soluble solvent) is mixed with a surfactant or a dispersing agent as needed, and the mixture is heated at less than 100 ° C, preferably 40 to 90 ° C for less than 24 hours, preferably 2 to 20 hours, If necessary, it can be carried out by neutralizing to pH≥7.

Examples of the salt of peroxodisulfuric acid include metal salts or ammonium salts such as lithium, sodium, potassium, and aluminum.

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.

Method (2) of treating the carbon black with a sulfonating agent can be carried out by any known method, for example, mixing or dissolving carbon black and a sulfonating agent in a solvent, 200° C. or less, preferably It can carry out by stirring at 0-100 degreeC.

Examples of the sulfonating agent include concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, halogenated sulfuric acid, amide sulfuric acid, hydrogen sulfite, sulfite, SO ₃ -dioxane complex, SO ₃ -ketone complex, sulfamic acid, and sulfonated pyridine salt. .

As the solvent, water; acidic solvents such as sulfuric acid, fuming sulfuric acid, formic acid, acetic acid, propionic acid, and acetic anhydride; basic solvents such as pyridine, triethylamine, and trimethylamine; ethers such as tetrahydrofuran, dioxane, and diethyl ether; Polar solvents, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfolane, nitromethane, acetone, acetonitrile, and benzonitrile; esters such as ethyl acetate and butyl acetate; aromatic solvents such as benzene, toluene, xylene, and nitrobenzene; alcohol solvents such as methanol, ethanol and isopropanol; Chlorine solvents, such as chloroform, trichlorofluoromethane, methylene chloride, and chlorobenzene, etc. can be used, and these mixed solvents may be used.

The amount of the sulfonating agent used is preferably in the range of 0.5 to 20 parts by mass based on 1 part by mass of carbon black, and when a plurality of sulfonating agents are used, the total amount is preferably within the above range.

In addition, in order to suppress the formation of a known sulfone as a side reaction of the sulfonation reaction, 0.01 to 5% of a known sulfone inhibitor, for example, fatty acid, organic peracid, acid anhydride, acetic acid, ketone, etc. may be added.

A commercially available product may be used as the pigment, 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 Violet 1, 19, 23, 27, 29, 30, 32, 37, 40 and 50, and the like.

As the dye, for example, a nitroso compound, a nitro compound, an azo compound, a diazo compound, a xanthene compound, a quinoline compound, an anthraquinone compound, a coumarin compound, a cyanine compound, a phthalocyanine compound, an isoindolinone compound, isoin Doline compound, quinacridone compound, ananthrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid, and metal complex compounds of azo dyes and cyanine dyes.

In the curable composition of the present invention, the content of the colorant (D) is not particularly limited, but with respect to 100 parts by mass of the polymerizable compound (B), preferably 50 to 500 parts by mass, more preferably 150 to 350 parts by mass. It is a mass part, More preferably, it is 150-300 mass parts. When content of a coloring agent is in said range, it becomes a curable composition excellent in storage stability without aggregation of a coloring agent, and the hardened|cured material of a curable composition is preferable at the point with high light-shielding property.

For example, when forming a cured film of thickness 1-3 micrometers, content of a coloring agent (D) is although it does not specifically limit, To 100 mass parts of said polymeric compound (B), Preferably 50-500 mass parts, More preferably, it is 150-350 mass parts, More preferably, it is 150-300 mass parts.

In addition, the curable composition of the present invention does not have radical polymerizability and may contain a compound that imparts alkali developability. As such a compound, if it is a compound that is soluble in aqueous alkali solution by having an acid value, it is particularly Although not limited, an alkali-soluble novolak resin (hereinafter simply referred to as "novolak resin") is mentioned as a typical example. A novolak resin is obtained by polycondensing phenols and aldehydes in the presence of an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and p-butylphenol. , 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester and gallic acid ester are used, and among these phenols, phenol, o -Cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methylresorcinol and bisphenol A, etc. This is preferable. These phenols are used individually or in mixture of 2 or more types.

The aldehydes include, for example, formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde , p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methyl Benzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, etc. are used, and among these compounds, formaldehyde, acetaldehyde, benzaldehyde, etc. are preferable. These aldehydes are used individually or in mixture of 2 or more types. Aldehydes are used in a ratio of preferably 0.7 to 3 moles, particularly preferably 0.7 to 2 moles per mole of phenols.

As the acid catalyst, for example, an inorganic acid such as hydrochloric acid, nitric acid, or sulfuric acid, or an organic acid such as formic acid, oxalic acid or acetic acid is used. The amount of the acid catalyst used is preferably 1×10 ^-4 to 5×10 ^-1 mol per 1 mol of phenols. In the condensation reaction, water is usually used as the reaction medium, but when the phenols used in the condensation reaction are not soluble in the aqueous solution of aldehydes and become a heterogeneous system from the beginning of the reaction, a hydrophilic solvent may be used as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The usage-amount of these reaction medium 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 according to the reactivity of the reaction raw material, and is usually 10 to 200°C, preferably 70 to 150°C. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalysts and reaction medium present in the system, the internal temperature is generally raised to 130-230 ° C., and the volatiles are distilled off under reduced pressure. Then, the molten novolak resin is recovered by casting it on a steel belt or the like.

In addition, after completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane and n-heptane to precipitate a novolak resin, and the precipitate can be separated and recovered by heating and drying. .

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

A solvent can further be added to the curable composition of this invention. As the solvent, a solvent capable of dissolving or dispersing each component (silica particles (A), polymerizable compound (B), polymerization initiator (C), colorant (D), etc.) as needed, for example, Ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2- Ether solvents such as dimethoxyethane, 1,2-diethoxyethane and dipropylene glycol dimethyl ether: methyl acetate, ethyl acetate, acetate-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, and ethyl lactate , ester solvents such as 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 solvents such as alcohol: ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether (PGM), propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol Ether ester solvents such as monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane ; Terpene hydrocarbon oils such as turpentine, D-limonene and pinene; Mineral spirit, Swasol #310 (above, manufactured by Cosmo Matsuyama Sekiyu); and Solvesso #100 (above, manufactured by Exxon Chemical); Paraffins such as solvents: halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine , acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide and water, and these solvents are one or two Can be used as a mixed solvent of more than one species can Among these, ketones, ether ester solvents, etc., especially PGMEA and cyclohexanone, etc. are preferable because they have good compatibility between the resist and the polymerization initiator in the curable composition.

In the curable composition of this invention, although the usage-amount of the said solvent is not specifically limited, It is preferable that it will be 70-95 mass % with respect to the curable composition whole quantity. When the content of the solvent is within the above range, the curable composition excellent in handling properties (viscosity or wettability of the curable composition) and liquid stability (not accompanied by precipitation or sedimentation of components contained in the composition) and the thickness of the cured product can be appropriately controlled. It is preferable that there is

A dispersing agent can further be used for the curable composition of this invention. As the dispersant, any dispersing agent capable of dispersing and stabilizing the colorant (D) may be used, and a commercially available dispersing agent, for example, a product of Bikkuchemi, BYK series, etc. may be used, and polyester, polyether, poly having a basic functional group A polymer dispersing agent made of urethane, having a nitrogen atom as a basic functional group, a functional group having a nitrogen atom is an amine and/or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH/g is suitably used.

The curable composition of the present invention may further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica and alumina; Layered clay mineral, milory blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfide, selenide, aluminum silicate, calcium Silicate, aluminum hydroxide, platinum, gold, silver, copper, etc. are mentioned, Among these, titanium oxide, silica, a layered clay mineral, silver, etc. are preferable. 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, with respect to 100 parts by mass of the polymerizable compound, and these inorganic compounds are one or two More than one species can be used.

By containing an inorganic compound in the curable composition of the present invention, it can be used as a photosensitive paste composition. The photosensitive paste composition is used to form a fired product pattern such as a barrier rib pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.

In addition, these inorganic compounds are suitably used as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellent agents, and the like, for example.

In addition, in the curable composition of the present invention, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol and phenothiazine; plasticizer; adhesion promoter; filler; antifoam; leveling agent; surface conditioning agent; antioxidants; UV absorbers; dispersing aid; anti-aggregation agent; catalyst; effect promoter; crosslinking agent; Conventional additives, such as a thickener, can be added.

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

Since the adhesiveness between hardened|cured material and a base material is improved by adding the said coupling agent, it is preferable. For example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, etc. Alkenyl-functional alkoxysilane, 3-methacryloxypropyltriethoxysilane, such as alkyl-functional alkoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane, etc. (meth)acrylic acid ester function Sexual alkoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-(3,4- Epoxy functional alkoxysilane such as epoxycyclohexyl)propyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-amino Amino-functional alkoxysilane such as propyltrimethoxysilane, mercapto-functional alkoxysilane such as γ-mercaptopropyltrimethoxysilane, isocyanate-functional alkoxysilane such as 3-isocyanatepropyltriethoxysilane, 3-urethane Ureido-functional alkoxysilanes such as idopropyltrialkoxysilane, isocyanurate-functional alkoxysilanes such as tris-(trimethoxysilylpropyl)isocyanurate, titanium tetraisopropoxide, and titanium tetranormal butoxide Titanium alkoxides, such as titanium dioctyloxybis (octylene glycolate), titanium chelates, such as titanium diisopropoxybis (ethylacetoacetate), zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, etc. zirconium chelates, zirconium acylates such as zirconium tributoxy monostearate, and isocyanate silanes such as methyl triisocyanate silane can be used.

Commercially available products may 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 (above, manufactured by Shin-Etsu Silicone).

As the chain transfer agent and the sensitizer, a compound containing a sulfur atom is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3 -[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amino]propionic acid, N-(3-mercaptopropionyl)alanine, 2-mercaptoethane Sulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio)phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto- 2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercaptobenzoimidazole, 2-mercapto-3-pyridinol , 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropanetris(3-mercaptopropionate), and mercapto compounds such as pentaerythritoltetrakis(3-mercaptopropionate); an alkyl iodide compound such as a disulfide compound obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid; Trimethylolpropane tris (3-mercaptoisobutyrate), butanediolbis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4-dimethyl mercaptobenzene, butanediol bisthiopropionate; Butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakis Thiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, compound No. C1, Showa Denko Carlens PE1, NR1, etc. are mentioned.

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

Examples of the melamine compound include an active methylol group (CH ₂ OH group) in nitrogen compounds such as (poly) methylolmelamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea) and compounds in which all or part (at least two) of are alkyletherified. Here, as the alkyl group constituting the alkyl ether, a methyl group, an ethyl group, and a butyl group are exemplified, and may be the same as or different from each other. In addition, the methylol group which is not alkyl-etherified may self-condensate within 1 molecule, and may condense between 2 molecules, and as a result, the oligomer component may be formed. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril, or the like can be used. Among these, alkyl-etherified melamines, such as hexamethoxymethylmelamine and hexabutoxymethylmelamine, are preferable.

In the curable composition of the present invention, the content of optional components other than the silica particles (A), the polymerizable compound (B), the polymerization initiator (C), the colorant (D) and the solvent is appropriately selected according to the purpose of use and is not particularly limited. However, Preferably, it is 20 mass parts or less in total with respect to 100 mass parts of total values of a silica particle (A), a polymeric compound (B), a polymerization initiator (C), and a coloring agent (D).

The curable composition of the present invention is a curable paint, varnish, curable adhesive, printed circuit board, or color filter for color display liquid crystal display panels such as color TVs, PC monitors, portable information terminals and digital cameras, portable information terminals and digital cameras. Black column spacer in liquid crystal display panel for color display such as, black column spacer for various display applications, black barrier rib for organic EL, color filter for CCD image sensor, touch panel, electrode material for plasma display panel, powder coating, printing Manufacturing of inks, printing plates, adhesives, gel coats, photoresists for electronics, electroplating resists, etching resists, solder resists, insulating films, black matrices, color filters for various display applications, plasma display panels, electroluminescent displays, and LCDs Resist for forming a structure in the process, composition for encapsulating electrical and electronic components, solder resist, magnetic recording material, micro-mechanical component, waveguide, optical switch, plating mask, etching mask, color Test systems, glass fiber cable coatings, stencils for screen printing, materials for manufacturing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronic circuits, bleaching materials, discoloration materials for image recording materials, microcapsules Various uses such as discoloration materials for image recording materials used, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, photoresist materials used to form dielectric layers in sequential lamination of printed circuit boards, protective films, etc. can be used, and there is no particular limitation on its use.

About the manufacturing method of the hardened|cured material using the curable composition of this invention, a preferable application|coating method and hardening conditions are shown below.

The application method of the curable composition is a known means such as a roll coater, a curtain coater, various types of printing and immersion, and is applied on a supporting substrate such as glass, metal, paper, or plastic. In addition, it may be used once on a supporting substrate such as a film and then transferred onto another supporting substrate, that is, in the form of a dry film, and there is no limitation on the application method.

In addition, as a light source of the actinic light used when curing the curable composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc, etc. can be used

Furthermore, by using laser light as the exposure light source, the laser direct drawing method, which forms an image directly from digital information such as a computer without using a mask, can improve not only productivity but also resolution and positional accuracy. It is useful in that it is useful, and as the laser beam, light with a wavelength of 340 to 430 nm is suitably used. Argon ion lasers, helium neon lasers, YAG lasers, and semiconductor lasers that emit light in the visible to infrared range are also used. . When these lasers are used, a sensitizing dye that absorbs the above-mentioned region from visible to infrared is added.

Using the curable composition of the present invention, the following steps (1) to (4) are repeated, and a color filter used for a liquid crystal display panel or the like can be manufactured by combining patterns of two or more colors.

(1) The process of forming the coating film of the colored polymeric composition of this invention on a board|substrate

(2) step of irradiating actinic light to the coating film through a mask having a pattern shape

(3) A step of developing the cured film with a developer (especially an alkali developer)

(4) The process of heating the said coating film after image development

A cured product using the curable composition of the present invention is a curable paint, varnish, curable adhesive, printed circuit board, or color filter in a color display liquid crystal display panel such as a color TV, PC monitor, portable information terminal and digital camera, CCD image Sensor color filter, touch panel, electrode material for plasma display panel, powder coating, printing ink, printing plate, adhesive, gel coat, photoresist sheet for electronic engineering, electroplating resist, etching resist, solder resist, insulating film, black matrix, various Resists for forming structures in the manufacturing process of color filters for display, plasma display panels, electroluminescent display devices, and LCDs, compositions for encapsulating electrical and electronic components, solder resists, magnetic recording materials, micromechanical components, Waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for manufacturing three-dimensional objects by stereolithography, materials for holographic recording, image recording materials, microelectronic circuits, discoloration Materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, dielectric layers in sequential lamination of printed circuit boards It can be used for various uses, such as a photoresist material used for formation and a protective film, There is no restriction|limiting in particular in the use.

The curable composition of the present invention is used for the purpose of forming a black matrix when a black pigment is used as the colorant (D), and the black matrix is particularly useful for a color filter for display devices for image display devices such as liquid crystal display panels. .

The black matrix includes (1) a step of forming a coating film of the curable composition of the present invention on a substrate, (2) a step of irradiating the coating film with actinic light through a mask having a predetermined pattern shape, (3) a film after exposure is preferably formed by a step of developing with a developer (especially an alkali developer) and (4) heating the above-mentioned coating film after development. Moreover, the curable composition of this invention is useful also as an inkjet system composition without a developing process.

Production of a color filter used in a liquid crystal display panel or the like can be produced by repeating the steps (1) to (4) above using the present invention or a curable composition other than that, and combining patterns of two or more colors.

The specific manufacturing method of the hardened|cured material using the curable composition of this invention is shown below.

That is, the curable composition of this invention was spin-coated to a glass substrate (10 cm x 10 cm), and a 1.0 micrometers coating film was formed in the surface of a glass substrate by heating at 100 degreeC for 100 second. Thereafter, using a proximity exposure machine manufactured by Microtech, it was exposed at an exposure amount of 40 mJ/cm 2 (Gap 100 μm) through a negative mask having a pattern of 1-20 μm formed thereon. After developing the film after exposure for 40 seconds with a 0.04 mass % KOH aqueous solution at 23°C, baking treatment is performed at 230°C for 30 minutes.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples and the like.

[Production Example 1] Polymeric compound No. 1 PGMEA solution preparation

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

[Production Example 2] Polymeric compound No. 2 PGMEA solution preparation

43 g 1,1-bis[4-(2,3-epoxypropyloxy)phenyl]indane, 13.5 g acrylic acid, 0.05 g 2,6-di-tert-butyl-p-cresol, 0.11 g tetrabutylammonium acetate and PGMEA 23 g was added, and the mixture was stirred at 120° C. for 16 hours. After cooling to room temperature, 35 g of PGMEA and 11.5 g of nonphthalic anhydride were added, followed by stirring 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, at 40° C. for 11 hours, and then 34.4 g of PGMEA was added, followed by polymerization. Sex compound No. A PGMEA solution of 2 was obtained (Mw=4000, Mn=2100, acid value (solid content) 86 mgKOH/g).

[Production Example 3] Polymeric compound No. 3 Preparation of PGMEA solution

75.0 g of 9,9-bis(4-glycidyloxyphenyl)fluorene, 23.8 g of acrylic acid, 0.273 g of 2,6-di-t-butyl-p-cresol, 0.585 g of tetrabutylammonium chloride, and 65.9 g of PGMEA and 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, followed by stirring at 100°C for 5 hours. Furthermore, 30.0 g of 9,9-bis (4-glycidyloxyphenyl) fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol, and 1.50 g of PGMEA were added and heated to 90° C. for 90 minutes; After stirring at 120°C for 4 hours, 122.2 g of PGMEA was added, and polymerizable compound No. A PGMEA solution of 3 was obtained (Mw=4190, Mn=2170, acid value (solid content) 52 mg·KOH/g).

[Production Example 4] Carbon black No. 1, Manufacturing

150 g of MA100 (carbon black manufactured by Mitsubishi Chemical) and 3000 ml of a deionized sodium peroxodisulfate aqueous solution (concentration of 2.0 N) were mixed, and the mixture was stirred at 60° C. for 10 hours. After filtration, the obtained slurry was neutralized with sodium hydroxide, treated by diafiltration, and the obtained solid was dried at 75° C. overnight, and carbon black No. 5 as a black powder. got 1

[Production Example 5] Carbon black No. 2, Manufacturing

150 g of MA100 (carbon black manufactured by Mitsubishi Chemical) and 400 ml of sulfolane 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 diafiltration, and the obtained solid was dried at 75° C. overnight, and as a black powder, carbon black No. got 2

[Preparation Example 6] Carbon black dispersion No. 1, Manufacturing

Carbon Black No. 1 for 16 g, polymerizable compound No. 3.6 g of PGMEA solution of 1, 2.4 g of DISPERBYK-161 (manufactured by Bikkuchemi, dispersant) and 78 g of PGMEA, respectively, were weighed and combined, treated with a bead mill to obtain carbon black dispersion No. got 1

[Preparation Example 7] Carbon black dispersion No. 2, Manufacturing

Carbon Black No. 2 for 16 g, polymerizable compound No. 3.6 g of the PGMEA solution of 1, 2.4 g of DISPERBYK-161 and 78 g of PGMEA, respectively, were weighed and combined, treated with a bead mill to obtain carbon black dispersion No. got 2

[Examples 1 to 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 (Examples 1-16 and Comparative Examples 1-4) were obtained. In addition, the numerical value of compounding in a table|surface represents a mass part.

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

A-1 PL-2L-PGME (colloidal silica; manufactured by Fusoka Chemical)

A-2 YA010C-LDI (Colloidal Silica; Adomatech Co., Ltd.)

A-3 PMA-ST (colloidal silica; Nissan Chemical Co., Ltd.)

A-4 YA050C-LHI (Colloidal Silica; Adomatech Co., Ltd.)

A-5 YA010C-SP3 (Powdered silica; Adomatech Co., Ltd.)

A'-1 AEROSIL 100 (Powdered Silica; manufactured by Aerosil)

A'-2 AEROSIL OX-50 (Powdered Silica; manufactured by Aerosil)

A'-3 SC2050-MB (Colloidal Silica; Adomatech Co., Ltd.)

B-1 Polymerizable compound No. 1 PGMEA solution (45wt% solids)

B-2 Polymerizable compound No. 2 PGMEA solution (45wt% solids)

B-3 Polymerizable compound No. 3 PGMEA solution (45wt% solids)

B-4 Kayarad DPHA (polymerizable compound; Nippon Kayakusa)

C-1 compound No. C1

C-2 compound No. C2

D-1 Carbon Black Dispersion No. One

D-2 Carbon Black Dispersion No. 2

E-1 PGMEA

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

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

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

Curable composition No. obtained in Examples 1-16. 1 to No. 16 and Comparative Curable Composition Nos. obtained in Comparative Examples 1-4. 1 to No. About 4, evaluation of the minimum adhesion line|wire width, surface roughness Ra, volume resistivity, a taper angle, and OD value was performed as follows. A result is shown to [Table 5] - [Table 7].

(Minimum tight line width)

A coating film of 1.0 µm was formed on the surface of the glass substrate by spin-coating the curable composition to a glass substrate (10 cm × 10 cm) and heating it at 100°C for 100 seconds. Thereafter, using a proximity exposure machine manufactured by Microtech, it was exposed at an exposure amount of 40 mJ/cm 2 (Gap 100 μm) through a negative mask having a pattern of 1-20 μm formed thereon. The film after exposure was developed with a 0.04 mass % KOH aqueous solution at 23°C for 40 seconds, and then fired at 230°C for 30 minutes. The optical microscope was observed, and the minimum photomask pattern remaining on the glass substrate was used as the minimum adhesion line width. If the minimum adhesion line width is 6㎛ or less, it is high definition. On the other hand, when it is 7 micrometers or more, it cannot be said that it is high definition.

(Surface roughness Ra)

A coating film of 1.0 µm was formed on the surface of the glass substrate by spin-coating the curable composition to a glass substrate (10 cm × 10 cm) and heating it at 100°C for 100 seconds. Thereafter, baking treatment was performed at 230°C for 30 minutes. The surface roughness Ra of the film was measured using an Aruba surface level meter (DEKTAK 6M). When the surface roughness Ra is 100 angstroms or less, it shows that the coloring agent and silica are well disperse|distributed, the surface becomes smooth and sufficient light-shielding property is acquired. On the other hand, when it is 100 angstroms or more, the colorant and silica are not well dispersed, the surface becomes rough, and sufficient light-shielding property (OD value) is not obtained.

(volume resistivity)

The chrome sputtered substrate was spin-coated so that the thickness of the curable composition was 4 μm, and after baking at 110° C. for 2 minutes as a pre-baking, exposure was performed at 100 mJ/cm 2 using a high-pressure mercury lamp as a light source, followed by 230 as a post-baking A cured product was prepared by baking at 180°C for 180 minutes. A platinum electrode was produced on the cured product by sputtering. A conducting wire was attached to the chrome portion and the platinum electrode, and a resistance measuring device was connected to measure the volume resistivity. The unit is Ω·cm.

A cured product having a volume resistivity of 10 ¹⁰ Ω·cm or more can be used as a high-resistance black matrix for a color filter of an IPS liquid crystal display, and a cured product having a volume resistivity of 10 ¹¹ Ω·cm or more can be more preferably used as a black matrix.

(OD value)

After spin-coating (1300rpm, 50 seconds) of the said curable composition or comparative curable composition on a board|substrate and drying, prebaking was performed at 100 degreeC for 100 second. 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 prepare a cured product. The OD value of the obtained film was measured using a Macbeth permeation densitometer, and the OD value was divided by the thickness after post-baking to calculate the OD value per thickness.

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

(taper angle)

A coating film of 1.0 µm was formed on the surface of the glass substrate by spin-coating the curable composition to a glass substrate (10 cm × 10 cm) and heating it at 100°C for 100 seconds. Thereafter, using a proximity exposure machine manufactured by Microtech, it was exposed at an exposure dose of 40 mJ/cm 2 (Gap 100 μm) through a negative mask having a 6 μm pattern formed thereon. The film after exposure was developed with a 0.04 mass % KOH aqueous solution at 23° C. for 40 seconds, then fired at 230° C. for 30 minutes, and the bonding angle (taper angle) between the pattern and the substrate was measured with a scanning electron microscope. This taper angle corresponds to the angle [theta] in Figs. 1 (a) and (b) shown below. (a) When the taper angle is an acute angle, it means that there is no undercut in the pattern, and (b) when the taper angle is an obtuse angle, it means that there is an undercut in the pattern. The presence of undercuts in the pattern is not preferable because display defects may occur. When a taper angle is 70-90 degrees, since the hardened|cured material pattern obtained becomes high definition, it is favorable.

From the above results, it is clear that the curable composition of the present invention is useful because it can provide a cured product having an excellent solid resistance and high light-shielding property (OD value) and having a high-definition (minimum adhesion line width, tapered angle) pattern shape. Accordingly, the curable resin and cured product of the present invention are useful in a curable resin composition for electronic materials, particularly a black matrix.

The curable composition of the present invention is useful as a resist for color filters because a cured product that satisfies the high resistance and formation of a high-definition pattern can be obtained. Moreover, in the case of the curable composition using a black pigment as a coloring agent, since the hardened|cured material with high light-shielding can be produced, it is especially useful as a black matrix formation material.

Claims (8)

It 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),
Curable composition whose content of the said silica particle (A) is 0.1-20 mass parts with respect to 100 mass parts of said coloring agents (D). According to claim 1,
The curable composition whose metal content in the said wet silica particle (A) is 1000 ppm or less. According to claim 1,
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) and an unsaturated monobasic acid are esterified, or
A curable composition, which is an unsaturated compound having a structure in which a polybasic acid anhydride is esterified to an unsaturated compound having a structure in which an epoxy compound represented by the following general formula (I) and an unsaturated monobasic acid are esterified.

(wherein M is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SO ₂ -, -SS-, -SO-, -CO-, -OCO-, the following formula ( a), (b), (c) or (d) represents a substituent selected from the group,
A hydrogen atom in the group represented by M may be substituted with 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 ) are each independently a hydrogen atom, a hydrocarbon having 1 to 20 carbon atoms. represents a group or a halogen atom,
A methylene group in the group represented by R ¹ to R ⁸ may be substituted with -O- on the condition that oxygen is not adjacent to each other,
n is a number from 0 to 10,
When n is other than 0, a plurality of R ¹ to R ⁸ and M may be the same or different from each other.)

(wherein R ⁹ represents a hydrocarbon group having 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 ) are each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a group having 2 to 20 carbon atoms containing a heterocycle, or a halogen atom,
A methylene group in the group represented by R ¹⁰ to R ³⁸ may be substituted with -O- or -S- on the condition that oxygen is not adjacent to each other;
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 , R ³² and R ³³ , R ³⁴ and R ³⁵ , R ³⁵ and R ³⁶ and R ³⁶ and R ³⁷ may combine to form a ring,
* in a formula means that the group represented by these formulas couple|bonds with the adjacent group in * part.) According to claim 1,
The curable composition wherein the polymerization initiator (C) is a compound having a group represented by the following general formula (II).

(Wherein, R ⁴¹ and R ⁴² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocycle,
A hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms or the group having 2 to 20 carbon atoms represented by R ⁴¹ and R ⁴² is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a carboxyl group, meta It may be substituted with an acryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group, or a group having 2 to 20 carbon atoms containing a heterocyclic ring,
The methylene group in the group represented by R ⁴¹ and R ⁴² is -O-, -CO-, -COO-, -OCO-, -NR ⁴³ -, -NR ⁴³ CO-, -S-, -CS-, -SO ₂ - , -SCO-, -COS-, -OCS- or -CSO- may be substituted,
R ⁴³ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
m represents 0 or 1,
* in a formula means that the group represented by these formulas couple|bonds with the adjacent group in * part.) According to claim 1,
The curable composition wherein the colorant (D) is a black pigment. The manufacturing method of the hardened|cured material using the curable composition in any one of Claims 1-5. A cured product of the curable composition according to any one of claims 1 to 5. A color filter containing the cured product according to claim 7.

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