KR20150039551A - Curable composition, cured film and process for forming the same, and compound - Google Patents

Abstract

The object of the present invention is to provide a cured film composition, which has conservation stability and low-temperature curing property and is capable of forming a cured film with excellent solvent resistance. The present invention relates to a curable composition containing at least one selected from the group consisting of compounds represented by formula (1-1) and formula (1-2), and a polymeric compound. R_1 to R_5 and R_11 to R_15 are hydrogen atom, halogen atom, carboxyl group, hydroxyl group, cyano group, sulfo group, formyl group, mercapto group, nitro group, trialkylsilyl group, trialkylsilyl alkyl group, etc. R_6 to R_10 and R_16 to R_18 are hydrogen atom, halogen atom, alkyl group, alicyclic or aromatic hydrocarbon group, heterocyclic group, alkoxy group, phenylthio group, amino group, nitro group, mercapto group, trialkylsilyl group, acyl group, trifluoromethyl group, hydroxyl group, cyano group, nitro group, carboxyl group, sulfo group, etc.

Description

CURABLE COMPOSITION, CURED FILM AND PROCESS FOR FORMING THE SAME, AND COMPOUND Technical Field The present invention relates to a curable composition,

The present invention relates to a curable composition, a cured film, a method for forming the same, and a compound.

The curable composition is widely used in recent years in that a cured film can be formed in a large amount and easily by a simple coating process. In particular, a radiation-curable composition having a radiation-sensitive property is widely used for a photo-curing ink, a photosensitive plate, and the like in addition to a material such as a liquid crystal device or a semiconductor device. Such a curable composition generally contains a resin and a curing agent.

Typical examples of the curing agent include a base generator that generates a base by the action of heat or radiation. According to this base generator, a cured film can be formed by curing the resin by chemical modification with a base generated by the action of heat or radiation as a catalyst. Further, it is also possible to form a pattern using the difference in solubility before and after the chemical modification of the resin. In addition, since the base generator is stably present as long as it does not receive heat or radiation, the curable composition containing the base generator has excellent storage stability.

As such base generators, nitrobenzyl carbamate-based photobase generators such as [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine have been widely used (JP-A-2006-189591 and JP- Patent Publication No. 7-140663). N-allyl-N ', N'-dialkylurea, N-phenylimidazolocarboxamide and the like have been proposed as thermal base generators (Journal of Polymer Science, Part A, Polymer Chemistry, Vol. 48 , 5298-5305, 2010, and Journal of Applied Polymer Science, Vol.104, 3292-3300, 2007).

However, these conventional base generators can not satisfy both the storage stability under a room temperature and a temperature condition close to that at a resin composition for forming a cured film, and a curing property at a relatively low temperature. Further, the cured film formed from the resin composition using the conventional base generator has insufficient properties such as solvent resistance.

Japanese Laid-Open Patent Publication No. 2006-189591 Japanese Patent Application Laid-Open No. 7-140663

 Journal of Polymer Science, Part A, Polymer Chemistry, Vol. 48, 5298-5305, 2010  Journal of Applied Polymer Science, Vol.104, 3292-3300, 2007

The present invention has been made based on the above-described circumstances, and its object is to provide a curable composition capable of both a storage stability and a low temperature curability and capable of forming a cured film excellent in solvent resistance.

The present invention for solving the above problems is characterized in that at least one compound selected from the group consisting of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2) and a curable Composition:

(In formula (1-1) and (1-2) of, R ¹ ~R ⁵ ~R ¹¹ and R ¹⁵ are, each independently, a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a cyano group, an alcohol A nitro group, a nitro group, a phosphate group, a trialkylsilyl group, a trialkylsilylalkyl group, or a hydroxyl group having an alkyl group having 1 to 20 carbon atoms, provided that at least one of R ¹ to R ⁵ R ⁶ to R ¹⁰ and R ¹⁶ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a carbon number A heterocyclic group having 4 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenylthio group, an amino group, a monoalkylamino group, a dialkylamino group, a nitroso group, a mercapto group, A sulfo group, a phosphate group, an acyl group, a trifluoromethyl group, a hydroxyl group, a cyano group, a nitro group, Practical, or alcoholic).

Another invention made to solve the above problems is a cured film formed from the curable composition.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising the steps of: forming a coating film on a substrate; irradiating at least a part of the coating film with radiation; developing the coating film irradiated with the radiation; Wherein the coating film is formed from the curable composition.

Another invention made to solve the above problems is a compound represented by at least one selected from the group consisting of the following formulas (1-3) and (1-4):

(In formulas (1-3) and (1-4), R ^{1 'to} R ^5' and R ^{11 'to} R ^15' each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a cyano group, a sulfo group, a formyl group, a mercapto group, a nitro group, a phosphate group, a trialkylsilyl group, a trialkylsilyl group, or a hydroxyl group and having an alkyl group of 1 to 20 carbon atoms; However, R ^{1 'To} R ^5' and R ^{11 'to} R ^15' are not all hydrogen atoms;

R ^{6 'to} R ^9' and R ^{16 'to} R ^18' each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 24 carbon atoms A heterocyclic group having 4 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenylthio group, an amino group, a monoalkylamino group, a dialkylamino group, a nitroso group, a mercapto group, a trialkylsilyl group, a sulfino group, An acyl group, a trifluoromethyl group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, or a sulfo group; Provided that when at least one of R ^{1 'to} R ^5' is a halogen atom, a hydroxyl group, a nitro group or a methoxy group, all of R ^{6 'to} R ^9' may not be a hydrogen atom;

R ^{10 '} each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 12 to 24 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, a phenylthio group, an amino group, a monoalkylamino group, a dialkylamino group, a nitroso group, a mercapto group, a trialkylsilyl group, a sulfino group, a phosphate group, an acyl group, a trifluoromethyl group, A cyano group, a nitro group, a carboxyl group, or a sulfo group).

The curable composition of the present invention can provide a cured film having excellent storage stability and low temperature curability and having sufficient solvent resistance. The cured film of the present invention has sufficient solvent resistance. The method for forming a cured film of the present invention can provide a cured film having sufficient solvent resistance. The compound of the present invention can provide a curable composition having excellent storage stability and low temperature curability. Therefore, according to the present invention, it is possible to provide a cured film which can be suitably used for various purposes as a material for a liquid crystal device, a semiconductor device and the like.

(Mode for carrying out the invention)

Hereinafter, embodiments of the present invention will be described in detail in the order of a curable composition, a cured film, a method of forming a cured film, and a compound.

≪ Curable composition >

The curable composition of the present invention contains the [A] compound and the [B] polymerizable compound and may contain, as a suitable component, the [C] alkali-soluble resin and the [D] One or the other arbitrary components may be contained. Each component will be described in detail below.

<[A] compound>

The [A] compound exhibits basicity by heating or irradiation with radiation or increases basicity. The [A] compound is represented by at least one selected from the group consisting of the formulas (1-1) and (1-2). The [A] compound is excellent in stability under room temperature and near temperature conditions, and has high sensitivity to heat and radiation. Therefore, the curable composition using the [A] compound exhibits good curability and accurate pattern formation even at a relatively low temperature of about 140 ° C to 200 ° C, and can form a cured film having sufficient solvent resistance.

In formulas (1-1) and (1-2), R ¹ to R ⁵ and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a cyano group, , A formyl group, a mercapto group, a nitro group, a nitroso group, a phosphate group, a trialkylsilyl group, a trialkylsilylalkyl group, or a hydroxyl group having an alkyl group having 1 to 20 carbon atoms. Provided that all of R ¹ to R ⁵ and R ¹¹ to R ¹⁵ are not hydrogen atoms.

R ⁶ to R ¹⁰ and R ¹⁶ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, a phenylthio group, an amino group, a monoalkylamino group, a dialkylamino group, a nitroso group, a mercapto group, a trialkylsilyl group, a sulfino group, a phosphate group, an acyl group , A trifluoromethyl group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group or a sulfo group.

Examples of the halogen atom represented by R ¹ to R ⁵ and R ¹¹ to R ¹⁵ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the trialkylsilyl group represented by R ¹ to R ⁵ and R ¹¹ to R ¹⁵ include a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group.

Examples of the trialkylsilylalkyl group represented by R ¹ to R ⁵ and R ¹¹ to R ¹⁵ include groups in which a trialkylsilyl group represented by R ¹ to R ⁵ is substituted with a methylene group, And an alkylene group bonded thereto. Among them, a trimethylsilylmethylene group and a triethylsilylmethylene group are preferable, and a trimethylsilylmethylene group is more preferable.

Examples of the hydroxyl group having an alkyl group having 1 to 20 carbon atoms represented by R ¹ to R ⁵ and R ¹¹ to R ¹⁵ include an alkyl group having 1 to 20 carbon atoms represented by R ⁶ to R ¹⁰ , A hydroxyl group and the like.

As R ¹ to R ⁵ and R ¹¹ to R ¹⁵ , a hydrogen atom, a hydroxyl group, a carboxyl group, a trimethylsilyl group, a trimethylsilylmethyl group, a sulfo group and a mercapto group are preferable.

At least one of R ¹ and R ⁵ and R ¹¹ to R ¹⁵ is preferably a halogen atom, a carboxyl group, a hydroxyl group, a cyano group, a sulfo group, a formyl group, a mercapto group, a nitro group, a nitroso group, An alkylsilyl group, a trialkylsilylalkyl group or an alkyl group having 1 to 20 carbon atoms is preferable, and a hydroxyl group, a carboxyl group, a trimethylsilyl group, a trimethylsilylmethylene group, a sulfo group and a mercapto group are more preferable.

Examples of the halogen atom represented by R ⁶ to R ¹⁸ include the same halogen atoms as those represented by R ¹ to R ⁵ .

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁶ to R ¹⁸ include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- Pentyl group, n-hexyl group and the like.

Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ⁶ to R ¹⁸ include monocyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group and cyclohexyl group, cyclobutenyl group, cyclopentenyl group, cyclo A cyclohexyl [2.2.1] heptyl group, a bicyclo [2.2.2] octyl group, a tricyclo [5.2.1.0 ^2,6 ] decyl group and an adamantyl group And cyclic saturated hydrocarbon groups.

Examples of the aromatic hydrocarbon group having ⁶ to ²⁴ carbon atoms represented by R ⁶ to R ¹⁸ include a phenyl group, a naphthyl group, an anthryl group, an anthracenyl group, a tetracenyl group, a phenanthrenyl group, a klycenyl group, a coronenyl group, .

Examples of the heterocyclic group having ⁴ to ²⁰ carbon atoms represented by R ⁶ to R ¹⁸ include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, a benzoxazol-2-yl group, a tetrahydropyranyl group, A thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a piperidyl group, a piperazyl group, a morpholinyl group, an imidazolyl group, a pyrazolyl group, And a polynyl group.

Examples of the alkoxy group having 1 to 12 carbon atoms represented by R ⁶ to R ¹⁸ include a methoxy group, ethoxy group, n-propoxy group, i-propoxy group, butoxy, and pentyloxy group.

Examples of the monoalkylamino group represented by R ⁶ to R ¹⁸ include a methylamino group, ethylamino group, propylamino group, n-butylamino group, tert-butylamino group, sec-butylamino group and the like.

Examples of the dialkylamino group represented by R ⁶ to R ¹⁸ include a dimethylamino group, diethylamino group, dipropylamino group, di-n-butylamino group, di-tert-butylamino group, di- .

Examples of the trialkylsilyl group represented by R ⁶ to R ¹⁸ include the same groups as those exemplified as the trialkylsilyl group represented by R ¹ to R ⁵ .

Examples of the compound [A] include compounds represented by the following formulas (A-1) to (A-16).

&Lt; Synthesis method of [A] compound &gt;

The [A] compound can be synthesized by combining known techniques. For example, as a method for synthesizing the [A] compound represented by the above formula (A-1), a method of reacting o-phenylenediamine with o-hydroxybenzaldehyde can be given. Examples of the method for synthesizing the compound [A] represented by the formula (A-2) include a method of reacting 4-nitro-o-phenylenediamine with 2,4,6-trihydroxybenzaldehyde . The [A] compounds other than these can also be synthesized by the above method or by modifying part of the above method.

The content of the [A] compound is preferably 0.001% by mass or more and 20% by mass or less, more preferably 0.01% by mass or more and 10% by mass or less based on the total solid content of the curable composition. If the content of the [A] compound exceeds the above range, the storage stability of the curable composition may be deteriorated. On the other hand, if the content of the [A] compound is less than the above range, there is a possibility that the storage stability and low temperature curability of the curable composition can not be sufficiently improved.

The term &quot; total solid content of the curable composition &quot; means all components other than the solvent contained in the curable composition.

&Lt; [B] Polymerizable compound &gt;

The polymerizable compound [B] exhibits increased basicity or basicity of the [A] compound by heating or irradiation with radiation, so that a part of the polymerizable compound is modified to contribute to the formation of a cured film. Thus, the curable composition can be used suitably as a composition for negative pattern formation, because it can form a cured film and is hardly dissolved by the alkali developer of the obtained cured film.

[B] The polymerizable compound may generally be in the form of a monofunctional or polyfunctional monomer, oligomer or polymer.

As the polymerizable compound [B], a compound having one or more epoxy groups in one molecule and a compound containing two or more ethylenically unsaturated groups are preferable. In the present invention, the epoxy group is a group having a cyclic ether structure. Representative cyclic ether structures include a 3-membered ring (oxiranyl group) and a 4-membered ring (oxetanyl group).

Examples of the [B] polymerizable compound having one epoxy group in the molecule include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α- Epoxybutyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyhexyl methacrylate, 6,7-epoxyhexyl acrylate, Vinylbenzyl glycidyl ether, 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- ( (Meth) acryloyloxymethyloxetane, phenylglycidyl ether,? -Glycidoxypropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Glycidoxypropyl Diethoxysilane, glycidyl esters of higher fatty acids, and the like.

As the [B] polymerizable compound having two or more epoxy groups in the molecule, for example,

Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglyme Bisphenol-type diglycidyl ethers such as cidyl ether;

Pentaerythritol polyglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, Polyglycidyl ethers of polyhydric alcohols such as cidyl ether and polypropylene glycol diglycidyl ether;

Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;

Phenol novolak type epoxy resins;

Cyclic aliphatic epoxy resins;

Cresol novolak type epoxy resin;

Polyphenol type epoxy resins;

Diglycidyl esters of aliphatic long-chain dibasic acids;

Aliphatic polyglycidyl ethers;

Epoxidized soybean oil, and epoxidized linseed oil.

Examples of commercially available products of the [B] polymerizable compound having two or more epoxy groups in the molecule include "EPIKOTE 1001", "Epikote 1002", "Epikote 1003", " "Epikote 1004", "Epikote 1007", "Epikote 1009", "Epikote 1010", "Epikote 828" (above, Japan Epoxy Resin Co., Ltd.);

As bisphenol F type epoxy resin, "Epikote 807" (Japan Epoxy Resin Co., Ltd.) and the like;

Epicoat 152 "," Epicoat 154 "," Epicoat 157S65 "(trade name, Japan Epoxy Resin Co., Ltd.)," EPPN201 "," EPPN202 "(trade names, manufactured by Nippon Kayaku Co., Ltd.) as the phenol novolak type epoxy resin;

EOCN102S "," EOCN104S "," EOCN1020 "," EOCN1025 "," EOCN1027 "(available from Nippon Kayaku Co., Ltd.)," Epikote 180S75 "(Japan Epoxy Resin Co., Ltd.) as cresol novolak type epoxy resin, Etc;

As the polyphenol type epoxy resin, "Epikote 1032H60", "Epikote XY-4000" (above, Japan Epoxy Resin Co., Ltd.) and the like;

Examples of the cyclic aliphatic epoxy resin include CY-175, CY-177, CY-179, Araldite CY-182, Araldite CY-192, Araldite CY ERL-4234 "," ERL-4221 "," ERL-4206 "(above, UCC Co., Ltd.)," SHOWDYNE " EPICLON 200 &quot;, &quot; Epiclon 400 &quot; (manufactured by Dainippon Ink &amp; Co., Ltd.), Epicote 871, Epicote 872 ED-5661 &quot; and &quot; ED-5662 &quot; (all manufactured by Celanese Coatings);

As the aliphatic polyglycidyl ether, "ED-212", "ED-411" (by Nagase Chemtex Co., Ltd.), "EPOLIGHT 100MF" by Kyowa Kagaku Co., TMP &quot; (niche-like).

As the [B] polymerizable compound having two or more ethylenic unsaturated groups, for example,

Di (meth) acrylates of alkylene glycols such as tripropylene glycol diacrylate, ethylene glycol and propylene glycol;

Di (meth) acrylates of polyalkylene glycols such as tetraethylene glycol diacrylate, EO-modified diacrylate of bisphenol A, polyethylene glycol, and polypropylene glycol;

Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxy polybutadiene, both terminal hydroxy polyisoprene, and both terminal hydroxy polycaprolactone;

Poly (meth) acrylates of polyhydric alcohols having three or more hydroxyl groups such as dipentaerythritol hexaacrylate, glycerin, 1,2,4-butanetriol, trimethylolalkane, tetramethylolalkane, pentaerythritol, dipentaerythritol, Rheology;

Trimethylol propane PO modified triacrylates, poly (meth) acrylates of polyalkylene glycol adducts of polyhydric alcohols having three or more valences, and the like;

Poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzene diols;

(Meth) acrylates such as polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd resin Methacrylate, and the like.

These polymerizable compounds may be used alone or in combination of two or more. Of these, pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether, 3-ethyl-3 - {[(3-ethyloxetan-3- yl) methoxy] methyl} oxetane , Dipentaerythritol hexaacrylate are preferable.

The content of the polymerizable compound [B] is preferably 100 parts by mass or more and 1,000,000 parts by mass or less, more preferably 200 parts by mass or more and 500,000 mass parts or less, per 100 parts by mass of the [A] compound. When the content of the [B] polymerizable compound is within the above range, the sensitivity to heat or radiation is high, and the solvent resistance of the cured film can be further improved.

&Lt; [C] Alkali-soluble resin &gt;

[C] The alkali-soluble resin contributes to the formation of a cured film having a more accurate pattern by improving the developability in the curable composition. The [C] alkali-soluble resin is not particularly limited as long as it is a resin soluble in an alkali developing solution, but an alkali-soluble resin having a carboxyl group is preferable, and at least one kind of compound selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (Hereinafter also referred to as &quot; copolymer (C) &quot;) with an unsaturated compound other than the compound (C1) (hereinafter also referred to as " ).

As the compound (C1), for example,

Acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid And the like;

Dicarboxylic acids such as maleic acid, fumaric acid and citraconic acid;

And the acid anhydrides of the above-mentioned dicarboxylic acids.

Of these, as the compound (C1), from the viewpoint of copolymerization reactivity and solubility of the resulting copolymer in an alkali developing solution, acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid , And maleic anhydride are preferable.

In the synthesis of the copolymer (C), the compound (C1) may be used alone or in combination of two or more. In the copolymer (C), the content of the structural unit derived from the compound (C1) is preferably 5% by mass or more and 60% by mass or less, more preferably 7% by mass or more and 50% by mass or less, And more preferably 40 mass% or less. By setting the content ratio of the structural unit derived from the compound (C1) to the above range, a curable composition having both sensitivity to heat or radiation and alkali developability is obtained.

As the above-mentioned compound (C2), for example,

Acrylic acid alkyl esters such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate and t-butyl acrylate;

Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, ester;

2-methylcyclohexyl acrylate, acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, acrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl , Acrylic acid alicyclic ester such as isobornyl acrylate;

2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] Decane-8-yloxy) ethyl methacrylate, isobornyl methacrylate, and other methacrylic acid alicyclic esters;

Hydroxyalkyl esters of acrylic acid such as 2-hydroxyethyl acrylate and 3-hydroxypropyl acrylate;

Hydroxyalkyl esters of methacrylic acid such as 2-hydroxyethyl methacrylate and 3-hydroxypropyl methacrylate;

Aryl esters or aralkyl esters of acrylic acid such as phenyl acrylate and benzyl acrylate;

Aryl esters or aralkyl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;

Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate and diethyl fumarate;

An oxygen-containing complex five-membered ring or an acrylic acid ester having an oxygen-containing complex 6-member ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, or 2-methyltetrahydropyran-2-yl acrylate;

An oxygen-containing complex 5-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate, Methacrylic acid esters;

Vinyl aromatic compounds such as styrene,? -Methylstyrene, and p-methoxystyrene;

Conjugated diene-based compounds such as 1,3-butadiene and isoprene;

Acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, and the like.

Of these compounds, from the viewpoint of copolymerization reactivity, n-butyl methacrylate, benzyl methacrylate, methacrylic tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, styrene, Methylstyrene, methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene, and 2-hydroxyethyl methacrylate.

In the synthesis of the copolymer (C), the compound (C2) may be used alone or in combination of two or more. In the copolymer (C), the content of the structural unit derived from the compound (C2) is preferably 20% by mass or more and 95% by mass or less, more preferably 30% by mass or more and 90% by mass or less, still more preferably 40% More preferably 85% by mass or less. By setting the content ratio of the structural unit derived from the compound (C2) to the above range, a curable composition having both sensitivity to heat or radiation and alkali developability can be obtained.

The copolymer (C) can be obtained by radical (co) polymerization of the compound (C1) and the compound (C2) in the presence of a radical polymerization initiator. Examples thereof include emulsion polymerization, suspension polymerization, solution polymerization, Lump polymerization method or the like.

The polystyrene reduced weight average molecular weight (hereinafter also referred to as &quot; Mw &quot;) of the copolymer (C) by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. When the Mw of the copolymer (C) is in the above range, a curable composition having both sensitivity to heat or radiation and alkali developability is obtained, and a cured film having high heat resistance can be obtained.

The content of the [C] alkali-soluble resin is preferably 1,000,000 parts by mass or less, and more preferably 100 parts by mass or more and 500,000 parts by mass or less, based on 100 parts by mass of the [A] compound. By setting the content of the [C] alkali-soluble resin within the above range, a curable composition excellent in developability can be obtained.

<[D] Solvent>

As the solvent, those in which other components in the curable composition are uniformly dissolved or dispersed and do not react with the other components are suitably used. Examples of such a solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates , Aromatic hydrocarbons, ketones, and other esters.

Examples of the alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

The ethers include, for example, tetrahydrofuran.

As the glycol ether, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like can be given.

Examples of the ethylene glycol alkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and the like.

Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like .

Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.

Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.

Examples of the propylene glycol monoalkyl ether propionate include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate And the like.

Examples of the aromatic hydrocarbons include toluene, xylene, and the like.

Examples of the ketones include methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone.

Examples of the other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- Hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, Propyl methoxyacetate, butyl hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxy Propyl acetate, propyl acetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxy Methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, Ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2- Methoxypropionate, methyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionic acid Propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate.

Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate and butyl methoxyacetate are preferable, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and butyl methoxyacetate are more preferable, and propylene glycol monomethyl ether acetate is more preferable.

In the curable composition, the [D] solvent may be used singly or as a mixture of two or more kinds. The content of the [D] solvent is usually 50,000 parts by mass or less, preferably 100 parts by mass or more and 30,000 parts by mass or less, more preferably 200 parts by mass or more and 15,000 parts by mass or less, based on 100 parts by mass of the total solid content of the curable composition desirable. By setting the content of the solvent [D] within the above range, it is possible to reduce the solubility of each component, the non-reactivity with each component, the ease of forming a film, and the uneven application at the time of forming a coating film on a substrate.

&Lt; Other optional components &gt;

Examples of other arbitrary components include [E] a photopolymerization initiator, [F] a surfactant, and [G] a compound having the same properties as the [A] Compound "), [H] adhesion aid, and the like.

([E] photopolymerization initiator)

The [E] photopolymerization initiator is preferably used when the [B] polymerizable compound is contained in the curable composition.

As the [E] photopolymerization initiator, for example,

Benzoin, benzophenone, camphorquinone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- , 2-methyl- [4 '- (methylthio) phenyl] -2-morpholino-1-propanone, - carbonyl compounds such as &lt; RTI ID = 0.0 &gt;

Azo compounds or azide compounds such as azoisobutylonitrile and 4-azidobenzaldehyde;

Organic sulfur compounds such as mercaptan disulfide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;

Organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide and paramethane hydroperoxide;

(Trichloromethyl) -5- (2'-chlorophenyl) -1,3,5-triazine, 2- [2- (2-furanyl) ethylenyl] Trihalomethanes such as (trichloromethyl) -1,3,5-triazine;

Imidazole dimers such as 2,2'-bis (2-chlorophenyl) 4,5,4 ', 5'-tetraphenyl 1,2'-biimidazole and the like. These may be used alone or in combination of two or more.

The content of the [E] photopolymerization initiator is usually 1 part by mass or more and 200 parts by mass or less, preferably 5 parts by mass or more and 150 parts by mass or less, based on 100 parts by mass of the [B] polymerizable compound.

([F] surfactant)

The [F] surfactant can be used to improve the film formability of the curable composition. Examples of such surfactants include fluorine-based surfactants and silicone-based surfactants.

Specific examples of the fluorine-based surfactant and the silicon-based surfactant include the surfactants described in JP-A-2012-226181 and JP-A-2013-23414, and commercially available surfactants can be used . Examples of commercially available surfactants that can be used include surfactants such as "Eftop EF301", "Eftop EF303", "Eftop EF352" (available from Shin Akita Kasei Co., Ltd.), "Ftergent FT-100 Fotent FT-150, Fotent FT-150, Fotent FT-250, Fotent FT-251, Fotent FT-300, Fluorine surfactants such as "Fotogen FT-310", "Fotent FT-400S", "Fotent FTX-218" and "Fotent FTX-251" . In addition, the SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 (Toray, Dow Corning, Can be used as a surfactant.

These surfactants may be used singly or in combination of two or more. Further, a fluorine-based surfactant and a silicone-based surfactant may be used in combination.

In the curable composition, the [F] surfactant may be used singly or in combination of two or more. The content of the [F] surfactant is usually 1,000 parts by mass or less, more preferably 0.5 parts by mass or more and 500 parts by mass or less, per 100 parts by mass of the [A] compound. When the content of the [F] surfactant is within the above range, it is possible to reduce coating unevenness when a coating film is formed on a substrate.

([G] other compounds)

[G] Other compounds show basicity of the [A] compound increased or basicity by heating or irradiation with radiation. [G] Examples of other compounds include N- (2-nitrobenzyloxycarbonyl) pyrrolidine, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyloxime, 4- Benzoyl) -1-methyl-1 -morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, Phenyl) -butanone, hexamammine cobalt (III) tris (triphenylmethyl borate), and the like.

The content of [G] other compounds is more preferably not less than 10,000 parts by mass and not less than 50 parts by mass and not more than 5,000 parts by mass based on 100 parts by mass of the [A] compound. By setting the content of [G] and other compounds within the above range, the curable composition exhibits high sensitivity even in the case of a low heating amount or a low exposure dose, and a cured film having sufficient solvent resistance can be formed.

([H] adhesion assisting agent)

[H] Adhesion assistant can be used to improve the adhesion between the cured film and the substrate. As such an adhesion aid, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an oxiranyl group is preferable. Examples of such a functional silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, and the like. These adhesion aids may be used singly or in combination of two or more kinds.

The content of the [H] adhesion aid is generally 0 parts by mass or more and 20,000 parts by mass or less, and more preferably 0.05 parts by mass or more and 10,000 parts by mass or less, relative to 100 parts by mass of the [A] compound. By setting the content of the [H] adhesion assistant or the like in the above range, the curable composition can maintain the pattern forming ability at a high level while improving the adhesion of the cured film to the object to be cured film such as a substrate.

The curable composition preferably has a radiation-sensitive property. If the curable composition has a radiation-sensitive property, a cured film having a desired pattern can be formed by irradiation with a radiation through a photomask. The cured film having such a pattern is suitably used as a liquid crystal device or a protective film of a semiconductor device.

<Preparation of Curable Composition>

The curable composition is prepared by uniformly mixing the [A] compound and the [B] polymerizable compound, the [C] alkali-soluble resin as the compatible component, the [D] solvent and other optional components. This curable composition is preferably dissolved in the [D] solvent and used in a solution state, but the solvent may be omitted.

The solid concentration (ratio of components other than the solvent in the composition solution) in the curable composition can be set according to the purpose of use, desired film thickness, and the like. The solution of the curable composition thus prepared may be filtered after using a millipore filter having a pore diameter of about 0.05 to 0.5 mu m and then used for use.

<Cured film>

The cured film of the present invention is formed from the curable composition. This cured film has excellent solvent resistance. Such a cured film can be suitably applied to applications requiring high surface hardness, and can be suitably used for, for example, a protective film for a liquid crystal device or a semiconductor device, an insulating film, a planarizing film, a resist pattern,

&Lt; Method of forming a cured film &

The method for forming a cured film of the present invention includes the following steps. According to this forming method, a cured film having a good pattern and excellent in solvent resistance can be formed. Further, the following irradiation step and the following developing step may be carried out in the case where a pattern formation is required, and may be omitted in the case where there is no need to form a pattern.

The method of forming the cured film,

A step of forming a coating film on a substrate (hereinafter also referred to as a &quot; coating film forming step &quot;),

A step of irradiating at least a part of the coating film with radiation (hereinafter also referred to as a &quot; radiation irradiation step &quot;),

(Hereinafter, also referred to as a &quot; developing step &quot;) for developing the coated film irradiated with the radiation,

And a step of heating the developed coating film (hereinafter also referred to as &quot; heating step &quot;). Hereinafter, each step will be described.

[Coating film forming step]

This coating film forming step is a step of forming a coating film on a substrate by using the curable composition of the present invention. The substrate is not particularly limited, and examples thereof include a transparent substrate and a metal substrate. Examples of the transparent substrate include a glass substrate and a resin substrate. Examples of the glass substrate include substrates made of soda lime glass, alkali-free glass, and the like. Examples of the resin substrate include substrates made of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, and the like.

The coating method of the curable composition on the substrate is not particularly limited and examples of the coating method include a spraying method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, Method can be adopted. Among these coating methods, a spin coating method and a slit die coating method are particularly preferable.

The solid content concentration of the curable composition used for forming the coating film is preferably 5 mass% or more and 50 mass% or less, more preferably 10 mass% or more and 40 mass% or less, and still more preferably 15 mass% or more and 35 mass% .

After the application of the curable composition onto the substrate, it is preferable that the coated surface is heated (prebaked).

The conditions for the prebaking differ depending on the kind of each component and blending ratio, and preferably about 70 to 120 캜 for about 1 minute to about 15 minutes. The film thickness of the film after pre-baking is preferably 0.3 mu m to 10 mu m, and more preferably 1.0 mu m to 7.0 mu m or so.

[Irradiation Process]

This irradiation step is a step of irradiating at least a part of the coating film with radiation. Irradiation of a part of the coating film with radiation can be performed, for example, through a photomask having a predetermined pattern.

Examples of the radiation used for irradiation include visible light, ultraviolet light, far ultraviolet light, and the like. The wavelength of the radiation is preferably in the range of 250 nm to 550 nm.

As the radiation dose (exposure dose), the intensity of the irradiated radiation at a wavelength of 365 nm is a value measured by a light meter (OAI model 356, manufactured by Optical Associates Inc.) of 100 J / m 2 to 5,000 J / m 2 , More preferably from 200 J / m 2 to 3,000 J / m 2, and still more preferably from 250 J / m 2 to 2,000 J / m 2. According to this formation method, since the radiation sensitivity of the curable composition is high, the radiation dose can be further reduced.

[Development process]

This developing step is a step of developing the coated film irradiated with the radiation. By this developing step, a predetermined pattern can be formed by removing an unnecessary portion.

Examples of the developing solution used in the development include aqueous solutions of alkaline (basic compounds) such as inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide . To such an aqueous alkali solution, an appropriate amount of at least one of a water-soluble organic solvent such as methanol and ethanol and a surfactant may be added. The concentration of the alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of achieving adequate developability. Examples of the developing method include a puddle method, a dipping method, and a shower method.

[Heating process]

This heating step is a step of heating (post-baking) the developed coating film. After the development process, the patterned coating film is preferably subjected to water-repellent cleaning for 30 seconds to 90 seconds, followed by air drying with compressed air or compressed nitrogen. Next, by heating at a temperature of usually 120 ° C to 250 ° C, preferably 130 ° C to 230 ° C, and more preferably 140 ° C to 200 ° C by a suitable heating apparatus such as a hot plate or an oven, A cured film can be obtained. The heating time is, for example, 5 minutes to 60 minutes in the case of heating by a hot plate, and 30 minutes to 180 minutes in the case of heating by an oven.

<Compound>

The compound of the present invention (hereinafter also referred to as "compound (A ')") is represented by at least one selected from the group consisting of the above formulas (1-3) and (1-4).

In the formulas (1-3) and (1-4), R ^{1 'to} R ^5' and R ^{11 'to} R ^15' each independently represent a hydrogen atom, a halogen atom, a carboxyl group, A nitro group, a nitro group, a phosphate group, a trialkylsilyl group, a trialkylsilylalkyl group, or a hydroxyl group having an alkyl group of 1 to 20 carbon atoms. Provided that all of R ^{1 'to} R ^5' and R ^{11 'to} R ^15' are not hydrogen atoms.

R ^{6 'to} R ^9' and R ^{16 'to} R ^18' each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 24 carbon atoms A heterocyclic group having 4 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenylthio group, an amino group, a monoalkylamino group, a dialkylamino group, a nitroso group, a mercapto group, a trialkylsilyl group, a sulfino group, An acyl group, a trifluoromethyl group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, or a sulfo group. Provided that when at least one of R ^{1 'to} R ^5' is a halogen atom, a hydroxyl group, a nitro group, or a methoxy group, R ^{6 'to} R ^9' are not all hydrogen atoms.

R ^{10 '} each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 12 to 24 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, a phenylthio group, an amino group, a monoalkylamino group, a dialkylamino group, a nitroso group, a mercapto group, a trialkylsilyl group, a sulfino group, a phosphate group, an acyl group, a trifluoromethyl group, A cyano group, a nitro group, a carboxyl group, or a sulfo group.

Wherein R ^{1 '~R 5'} and R ^{11 '~R 15'} a halogen atom, a carboxyl group, a hydroxyl represented by the rock group, a cyano group, a sulfo group, a formyl group, a mercapto group, a nitro group, a phosphate group, Examples of the hydroxyl group having a trialkylsilyl group, a trialkylsilylalkyl group or an alkyl group having 1 to 20 carbon atoms include R ¹ to R ⁵ and R ¹¹ to R ^{15 in} the formulas (1-1) and (1-2) And the like.

Wherein ^{R 6 '~R 9', R} 16 ' and R ^17' be a hydrogen atom, a halogen atom, a group of the alicyclic hydrocarbon group of 1 to 20 carbon atoms, 3 to 20 carbon atoms, an aromatic hydrocarbon group having a carbon number of 6-24 represented by, An alkoxy group having 1 to 12 carbon atoms, a phenylthio group, an amino group, a monoalkylamino group, a dialkylamino group, a nitroso group, a mercapto group, a trialkylsilyl group, a sulfino group, a phosphate group, R ⁶ to R ⁹ , R ¹⁶ and R (7) in the formulas (1-1) and (1-2) are preferably the same as or different from each other, ¹⁷ may be mentioned.

Examples of the aromatic hydrocarbon group having 12 to 24 carbon atoms represented by R ^{10 '} include anthracenyl, tetracenyl, phenanthrenyl, chrysenyl and coronenyl groups.

Examples of the aromatic hydrocarbon group having 6 to 24 carbon atoms represented by R ^{18 '} include the same ones exemplified as R ¹⁸ in the formula (1-4).

Examples of the compound (A ') include compounds represented by the following formulas (A-2) to (A-16).

Compound (A ') can be synthesized by the same method as compound (A).

(Example)

Hereinafter, the present invention will be described more specifically based on examples. The present invention is not limited in any way by these examples.

First, the measurement method and evaluation method of physical properties will be described.

[Measurement of ¹ H-NMR]

&Lt; ¹ &gt; H-NMR was measured at 25 DEG C using a nuclear magnetic resonance apparatus (JNM-ECS400 (400 MHz), manufactured by JEOL).

[Measurement of weight average molecular weight Mw]

The weight average molecular weight Mw is the polystyrene reduced molecular weight measured using a gel permeation chromatography (GPC) apparatus ("GPC-101" manufactured by Showa Denko K.K.). GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko K.K.) as GPC columns And THF (tetrahydrofuran) was used as a solvent, and the measurement was carried out at a temperature of 40 ° C.

&Lt; Synthesis of [A] compound &gt;

[Synthesis Example 1]

(Hereinafter also referred to as "compound (A-1)") represented by the following formula (A-1) was synthesized according to the following synthesis reaction formula.

(30.0 mmol) of o-phenylenediamine (Sigma Aldrich), 3.67 g (30.0 mmol) of salicylaldehyde (Sigma Aldrich) and 5.70 g (30.0 mmol) of sodium pyrosulfite (Sigma Aldrich) And 270 mL of N, N-dimethylformamide (Sigma Aldrich) were charged, and the mixture was heated to 80 DEG C in an oil bath and reacted for 24 hours. After the reaction, the temperature was returned to room temperature, and the reaction solution was added to 300 mL of water at 0 캜. The precipitate was collected by filtration and then purified by silica gel column chromatography to obtain a compound (A-1).

The results of ¹ H-NMR measurement of the compound (A-1) were as follows.

^{1 H-NMR (DMSO-d} 6);

? 7.00-7.04 (2H, m),? 7.24-7.40 (3H, m),? 7.59-7.73 (2H, m),? 8.05 (1H, d).

[Example 1]

(Hereinafter also referred to as "compound (A-2)") represented by the following formula (A-2) was synthesized according to the following synthesis reaction formula.

In a one-necked flask, 0.766 g (5.00 mmol) of 4-nitro-o-phenylenediamine (Sigma Aldrich), 0.771 g (5.00 mmol) of 2,4,6-trihydroxybenzaldehyde (Sigma Aldrich) 0.951 g (5.00 mmol) of sodium (Sigma Aldrich) and 50 mL of N, N-dimethylformaldehyde (Sigma Aldrich) were charged and heated in an oil bath at 80 DEG C for 24 hours. After the reaction, the reaction mixture was returned to room temperature and the reaction solution was added to 100 mL of water at 0 ° C. The precipitate was collected by filtration and then purified by silica gel column chromatography to obtain a compound (A-2).

The results of ¹ H-NMR measurement of the compound (A-2) were as follows.

_{^{1 H-NMR (CD 3 OD}} );

? 5.98 (2H, s),? 7.53 (1H, d),? 7.91 (1H, d),? 8.23 (1H, d).

[Example 2]

(Hereinafter also referred to as "compound (A-3)") represented by the following formula (A-3) was synthesized according to the following synthesis reaction formula.

(5.00 mmol) of salicylaldehyde (5.00 mmol), 0.430 g (5.00 mmol) of diacetyl (Sigma Aldrich), 2.31 g (30.0 mmol) of ammonium acetate (Sigma Aldrich) Aldrich), and the mixture was stirred in an oil bath at 120 DEG C for 5 hours. After the reaction, the reaction solution was returned to room temperature and the reaction solution was added to a 3% aqueous ammonia solution. The precipitate was removed by filtration and the filtrate was concentrated. The residue was purified by recrystallization with ethyl acetate to obtain a compound (A-3).

The results of ¹ H-NMR measurement of the compound (A-3) were as follows.

^{1 H-NMR (DMSO-d} 6);

? 2.15 (6H, s),? 6.89 (2H, m),? 7.15 (1H, t),? 7.72 (1H, d).

[Example 3]

(Hereinafter also referred to as "compound (A-4)") represented by the following formula (A-4) was synthesized according to the following synthesis reaction formula.

2.58 g (9.96 mmol) of 2-bromobenzaldehyde diethyl acetal (Sigma Aldrich) and 15.0 mL of diethyl ether (Sigma Aldrich) were placed in a two-necked flask which had been heated and dried. 7.50 mL (1.6 M, 11.9 mmol) of n-hexane solution (Sigma Aldrich) was added. After stirring at -78 ° C for 1 hour, 1.46 g (13.4 mmol) of chlorotrimethylsilane (Sigma Aldrich) was added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was concentrated and purified by silica gel column chromatography to obtain 2-trimethylsilylbenzaldehyde dimethyl acetal.

To the two-necked flask after heating and drying were added 2.00 g (7.92 mmol) of the obtained 2-trimethylsilylbenzaldehyde dimethylacetal, 20 mL of trifluoroacetic acid (Sigma Aldrich) and 30 mL of dichloromethane (Sigma Aldrich) Stirring time. After confirming the formation of the compound by thin layer chromatography (TLC), purification by silica gel column chromatography gave 2-trimethylsilylbenzaldehyde.

(5.61 mmol) of the obtained 2-trimethylsilylbenzaldehyde, 0.607 g (5.61 mmol) of 1,2-phenylenediamine (Sigma Aldrich) and 1.07 g (5.61 mmol) of sodium pyrosulfite (Sigma Aldrich) ) And 50 mL of N, N-dimethylformamide (Sigma Aldrich) were charged, and the mixture was heated to 80 DEG C in an oil bath and reacted for 24 hours. After the reaction, the reaction mixture was returned to room temperature and the reaction solution was added to 100 mL of water at 0 ° C. The precipitate was collected by filtration and then purified by silica gel column chromatography to obtain a compound (A-4).

The results of ¹ H-NMR measurement of the compound (A-4) were as follows.

^{1 H-NMR (DMSO-d} 6);

(1H, m),? 7.92 (1H, d).

[Example 4]

(A-5) was obtained in the same manner as in Example 3, except that 1.64 g (13.4 mmol) of (chloromethyl) trimethylsilane (Sigma Aldrich) was used in place of chlorotrimethylsilane (Hereinafter also referred to as &quot; compound (A-5) &quot;) was synthesized.

The results of ¹ H-NMR measurement of the compound (A-5) were as follows.

^{1 H-NMR (DMSO-d} 6);

(2H, m),? 7.32-7.44 (4H, m),? 7.62 (1H, m),? .89 (1H, d).

[Example 5]

(Hereinafter also referred to as "compound (A-6)") represented by the following formula (A-6) was synthesized according to the following synthesis reaction formula.

(5.00 mmol) of N-methyl-1,2-phenylenediamine (Sigma Aldrich), 0.771 g (5.00 mmol) of thiosalicylic acid (Sigma Aldrich) and 10 g of polyphosphoric acid (Sigma Aldrich) And the mixture was heated to 200 DEG C in an oil bath and reacted for 4 hours. After the reaction, the reaction mixture was added to 100 mL of water and adjusted to pH = 6 with aqueous sodium hydroxide solution. The precipitate was collected by filtration and recrystallized from ethanol to obtain a compound (A-6).

The results of ¹ H-NMR measurement of the compound (A-6) were as follows.

_{^{1 H-NMR (CDCl 3)}} ;

? 3.60 (3H, s),? 7.17-7.32 (6H, m),? 7.50 (1H, d),? 8.01 (1H, d).

[Example 6]

(Hereinafter also referred to as "compound (A-7)") represented by the following formula (A-7) was synthesized according to the following synthesis reaction formula.

(30.0 mmol) of 4,5-dimethyl-o-phenylenediamine (Sigma Aldrich), 3.67 g (30.0 mmol) of salicylaldehyde (Sigma Aldrich) and sodium pyrosulfite (Sigma Aldrich) 5.70 g (30.0 mmol) of N, N-dimethylformamide (Sigma Aldrich) were placed, and the mixture was heated to 80 DEG C in an oil bath and reacted for 24 hours. After the reaction, the temperature was returned to room temperature, and the reaction solution was added to 300 mL of water at 0 캜. The precipitate was collected by filtration and then purified by silica gel column chromatography to obtain a compound (A-7) as a thermal latent base.

The results of ¹ H-NMR measurement of the compound (A-7) were as follows.

^{1 H-NMR (DMSO-d} 6);

(2H, m),? 7.48 (1H, s),? 8.00 (1H, d).

[Example 7]

(Hereinafter also referred to as "compound (A-8)") represented by the following formula (A-8) was synthesized according to the following synthesis reaction formula.

(30.0 mmol) of 4-methoxy-o-phenylenediamine (Sigma Aldrich), 3.67 g (30.0 mmol) of salicylaldehyde (Sigma Aldrich) and 5.20 g of sodium pyrosulfite (Sigma Aldrich) g (30.0 mmol) and N, N-dimethylformamide (Sigma Aldrich) were placed and heated in an oil bath at 80 占 폚 for 24 hours. After the reaction, the temperature was returned to room temperature, and the reaction solution was added to 300 mL of water at 0 캜. The precipitate was collected by filtration and then purified by silica gel column chromatography to obtain a compound (A-8) as a thermal latent base.

The results of ¹ H-NMR measurement of the compound (A-8) were as follows.

^{1 H-NMR (DMSO-d} 6);

? 3.82 (3H, s), 6.89-7.54 (6H, m),? 8.01 (1H, d).

[Example 8]

(Hereinafter also referred to as "compound (A-9)") represented by the following formula (A-9) was synthesized according to the following synthesis reaction formula.

(30.0 mmol) of 4-tert-butyl-o-phenylenediamine (hydroschemistry), 3.67 g (30.0 mmol) of salicylaldehyde (Sigma Aldrich) and sodium pyrosulfite (Sigma Aldrich) 5.70 g (30.0 mmol) of N, N-dimethylformamide (Sigma Aldrich) were placed, and the mixture was heated to 80 DEG C in an oil bath and reacted for 24 hours. After the reaction, the temperature was returned to room temperature, and the reaction solution was added to 300 mL of water at 0 캜. The precipitate was collected by filtration and then purified by silica gel column chromatography to obtain a compound (A-9) as a thermal latent base.

The results of ¹ H-NMR measurement of the compound (A-9) were as follows.

^{1 H-NMR (DMSO-d} 6);

? 1.34 (9H, s), 6.66-7.39 (6H, m),? 7.98 (1H, d).

[Example 9]

A compound represented by the following formula (A-10) (hereinafter also referred to as &quot; compound (A-10) &quot;) was synthesized according to the following synthesis reaction formula.

(30.0 mmol) of 4-propoxy-o-phenylenediamine (Nacalai Tesque), 3.67 g (30.0 mmol) of salicylaldehyde (Sigma Aldrich) and sodium pyrosulfite (Sigma Aldrich) 5.70 g (30.0 mmol) of N, N-dimethylformamide (Sigma Aldrich) were placed, and the mixture was heated to 80 DEG C in an oil bath and reacted for 24 hours. After the reaction, the temperature was returned to room temperature, and the reaction solution was added to 300 mL of water at 0 캜. The precipitate was collected by filtration and then purified by silica gel column chromatography to obtain a compound (A-10) as a thermal latent base.

The results of ¹ H-NMR measurement of the compound (A-10) were as follows.

^{1 H-NMR (DMSO-d} 6);

(1H, d), 1.99 (2H, m), 3.99 (2H, t), 7.00-7.62 (6H, m),? 8.03 (1H, d).

[Example 10]

(Hereinafter also referred to as "compound (A-11)") represented by the following formula (A-11) was synthesized according to the following synthesis reaction formula.

(30.0 mmol) of 4-phenylthio-o-phenylenediamine (Nacalai Tesque), 3.67 g (30.0 mmol) of salicylaldehyde (Sigma Aldrich) and sodium pyrosulfite (Sigma Aldrich) 5.70 g (30.0 mmol) of N, N-dimethylformamide (Sigma Aldrich) were placed, and the mixture was heated to 80 DEG C in an oil bath and reacted for 24 hours. After the reaction, the temperature was returned to room temperature, and the reaction solution was added to 300 mL of water at 0 캜. The precipitate was collected by filtration and then purified by silica gel column chromatography to obtain a compound (A-11) as a thermal latent base.

The results of ¹ H-NMR measurement of the compound (A-11) were as follows.

^{1 H-NMR (DMSO-d} 6);

[delta] 6.85-7.40 (10H, m), 7.66-7.82 (2H, m).

[Synthesis Example 2]

(Hereinafter also referred to as "compound (a-1)") represented by the following formula (a-1) was synthesized according to the following synthesis reaction formula.

To the two-necked flask after heating and drying were added 2.68 g (20.0 mmol) of 2-coumaranone (Sigma Aldrich), 3.24 g (30.0 mmol) of 4-aminomethylpyridine (Sigma Aldrich) and 10 mL of dioxane (Sigma Aldrich) And the mixture was refluxed at 100 ° C for 24 hours. Subsequently, after the formation of the compound (a-1) was confirmed by thin layer chromatography (TLC), the compound (a-1) was obtained by purification by silica gel column chromatography.

The results of ¹ H-NMR measurement of the compound (a-1) were as follows.

&Lt; ¹ &gt; H-NMR (DMSO-d6);

(2H, d),? 7.32 (2H, s),? 4.35 (2H, d),? 6.69-7.09 (1H, s), 810.30 (1H, s).

<Synthesis of [C] alkali-soluble resin>

[Synthesis Example 3]

4 parts by mass of 2,2'-azobisisobutyronitrile (Sigma Aldrich) and 220 parts by mass of propylene glycol monomethyl ether acetate (Sigma Aldrich) were fed into a flask equipped with a stirrer, a cooling tube and a stirrer. Subsequently, 5 parts by mass of styrene (Sigma Aldrich), 10 parts by mass of methacrylic acid (Sigma Aldrich), 4 parts by mass of acrylic acid (Sigma Aldrich), 31 parts by mass of benzyl methacrylate (Sigma Aldrich) And 45 parts by mass of n-butyl acrylate (Sigma Aldrich) were charged, and after replacing with nitrogen, 5 parts by mass of 1,3-butadiene (Sigma Aldrich) was further added thereto. (C-1) at a solid content concentration of 31.0% by mass was obtained by maintaining the temperature for 4 hours and further maintaining the temperature at 100 DEG C for 1 hour to allow the reaction to proceed . The polymer (C-1) as the [C] alkali-soluble resin was measured for Mw using the apparatus and conditions described above and found to be 13,000.

<Preparation of Curable Composition>

Components constituting the curable composition of this embodiment will be described below.

([A] compound)

A-1: The compound synthesized in Synthesis Example 1

A-2 to A-11: The compounds synthesized in Examples 1 to 10

A-12: A compound represented by the following formula (A-12) (Sigma Aldrich)

A-13: A compound represented by the following formula (A-13) (Sigma Aldrich)

A-14: A compound represented by the following formula (A-14) (Sigma Aldrich)

([a] compound)

a-1: Compound synthesized in Synthesis Example 2

a-2: 2-phenyl-4-methylimidazole ("PMI" manufactured by Sigma-Aldrich)

a-3: 2-phenyl-1H-benzimidazole ("PBI" from Sigma-Aldrich)

([B] polymerizable compound)

B-1: Pentaerythritol polyglycidyl ether ("EX-411" manufactured by Nagase Chemtex Co., Ltd.)

B-2: 1,6-hexanediol diglycidyl ether ("EX-212" manufactured by Nagase Chemtex Co., Ltd.)

B-3: 3-ethyl-3 - [(3-ethyloxetan-3-yl) methoxy] methyl} oxetane (OXT-

B-4: dipentaerythritol hexaacrylate ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.)

([C] alkali-soluble resin)

C-1: Polymer synthesized in Synthesis Example 3

([D] solvent)

D-1: Propylene glycol monomethyl ether acetate

([E] photopolymerization initiator)

E-1: 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (IRG-

([F] surfactant)

F-1: Fluorine-based surfactant ("FTX-218" manufactured by NEOS Corporation)

[Example 11]

5 g of compound (A-1) as compound [A], 29 g of pentaerythritol polyglycidyl ether (B-1) as polymerizable compound, 30 g of dipentaerythritol hexaacrylate (B- (Dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) propionic acid] as a photopolymerization initiator, 1 g of a fluorine-containing surfactant (F-1) as a surfactant was mixed to give a solid concentration of 10 mass%. [D] Propylene glycol mono 900 g of methyl ether acetate (D-1) was added, followed by filtration through a membrane filter with a pore size of 0.2 탆 to prepare a solution of the curable composition.

[Examples 12 to 28 and Comparative Examples 1 to 7]

The curable compositions of Examples 12 to 28 and Comparative Examples 1 to 7 were prepared by carrying out the same operations as in Example 11 except that each kind and amount of the components described in Table 1 were used.

[Table 1]

"-" in Table 1 indicates that the corresponding component is not used.

<Evaluation>

In this example, storage stability, gelation time and solvent resistance were evaluated by the following methods. The evaluation results are shown in Table 2.

[Evaluation of storage stability]

The storage stability was evaluated by measuring the time until the viscosity of the solution of the curable composition at 25 占 폚 was maintained at 10 times the viscosity at the time of preparation. For viscosity measurement, an ELD type viscometer (Tokyo Keiki Co., Ltd.) was used. The longer this time, the better the storage stability.

[Evaluation of gelation time]

The gelation time was evaluated as the time until the gelation of the solution of the curable composition was heated at 100 캜 and 140 캜. The longer the gelation time at 100 占 폚 and the shorter the gelation time at 140 占 폚, the better the curing temperature contrast and the lower the temperature curability.

[Evaluation of solvent resistance]

The solvent resistance was evaluated as a change rate of the film thickness before and after immersion in acetone with respect to the cured film formed of the curable composition.

(Production of a cured film)

First, a solution of the curable composition was coated on a non-alkali glass substrate by a spinner, and then prebaked on a hot plate at 90 DEG C for 3 minutes to form a coating film having a thickness of 3 mu m. The obtained coating film was adjusted to have a size of 30 mu m x 30 mu m, and this coating film was exposed to light through a pattern mask with a high-pressure mercury lamp having an exposure gap of 200 mu m and an exposure intensity of 300W / .

Subsequently, the resist film was developed with a 0.05 mass% aqueous solution of potassium hydroxide at 25 DEG C for 120 seconds, and then rinsed with pure water for 1 minute. Further, the film was heated in an oven at 200 DEG C for 30 minutes to form a cured film.

(Measurement of Film Thickness Change Rate)

The film thickness change ratio (%) was calculated by measuring the film thickness (T1) of the cured film after fabrication and the film thickness (T2) after immersing in acetone for 20 minutes. When the film thickness change ratio is 5% or less, it can be said that the solvent resistance is good.

Film thickness change rate (%) = {(T1-T2) / T1} x 100

[Table 2]

As is clear from the results of Table 2, the curable compositions of Examples 11 to 28 were excellent in storage stability, and had a short curing time at relatively low temperatures (100 ° C to 180 ° C). Further, the cured films formed from the curable compositions of Examples 11 to 28 were excellent in solvent resistance.

On the other hand, the curable compositions and the cured films of Comparative Examples 1 to 7 were inferior in storage stability, curing temperature contrast (gel time) and solvent resistance.

The curable composition of the present invention can provide a cured film having excellent storage stability and low temperature curability and having sufficient solvent resistance. The cured film of the present invention is a cured film having sufficient solvent resistance. The method for forming a cured film of the present invention can provide a cured film having sufficient solvent resistance. The compound of the present invention can provide a cured film composition having excellent storage stability and low temperature curability. Therefore, according to the present invention, it is possible to provide a cured film which can be suitably used for various purposes as a material for a liquid crystal device, a semiconductor device and the like.

Claims (8)

At least one compound selected from the group consisting of a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2)
A curable composition containing a polymerizable compound:

(In formula (1-1) and (1-2) of, R ¹ ~R ⁵ ~R ¹¹ and R ¹⁵ are, each independently, a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a cyano group, an alcohol A nitro group, a nitro group, a phosphate group, a trialkylsilyl group, a trialkylsilylalkyl group, or a hydroxyl group having an alkyl group having 1 to 20 carbon atoms, provided that at least one of R ¹ to R ⁵ And not all of them are hydrogen atoms;
R ⁶ to R ¹⁰ and R ¹⁶ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, a phenylthio group, an amino group, a monoalkylamino group, a dialkylamino group, a nitroso group, a mercapto group, a trialkylsilyl group, a sulfino group, a phosphate group, an acyl group , A trifluoromethyl group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, or a sulfo group). The method according to claim 1,
At least one of R ¹ and R ⁵ in the formula (1-1) or at least one of R ¹¹ and R ¹⁵ in the formula (1-2) is a halogen atom, a carboxyl group, a hydroxyl group, a cyano group, A hydroxyl group having an alkyl group having 1 to 20 carbon atoms, a formyl group, a mercapto group, a nitro group, a nitroso group, a phosphate group, a trialkylsilyl group, a trialkylsilylalkyl group or an alkyl group having 1 to 20 carbon atoms. The method according to claim 1,
Wherein the polymerizable compound is a compound having an oxiranyl group, an oxetanyl group or an ethylenically unsaturated group. The method according to claim 1,
Wherein the curable composition further contains an alkali-soluble resin. 5. The method according to any one of claims 1 to 4,
A radiation curable curable composition. A cured film formed from the curable composition according to any one of claims 1 to 4. A step of forming a coating film on the substrate, a step of irradiating at least a part of the coating film with radiation, a step of developing the coating film irradiated with the radiation, and a step of heating the developed coating film,
Wherein the coating film is formed from the curable composition according to claim 5. A compound represented by at least one selected from the group consisting of the following formulas (1-3) and (1-4):

(In the formulas (1-3) and (1-4), R ^{1 'to} R ^5' And R ^{11 'to} R ^15' each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a hydroxyl group, a cyano group, a sulfo group, a formyl group, a mercapto group, a nitro group, a nitroso group, An alkylsilyl group, a trialkylsilylalkyl group, or a hydroxyl group having an alkyl group having 1 to 20 carbon atoms; Provided that not all of R ^{1 'to} R ^5' and R ^{11 'to} R ^15' are hydrogen atoms;
R ^{6 'to} R ^9' and R ^{16 'to} R ^18' each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic group having 6 to 24 carbon atoms A heterocyclic group having 4 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a phenylthio group, an amino group, a monoalkylamino group, a dialkylamino group, a nitroso group, a mercapto group, a trialkylsilyl group, a sulfino group, An acyl group, a trifluoromethyl group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, or a sulfo group; Provided that when at least one of R ^{1 'to} R ^5' is a halogen atom, a hydroxyl group, a nitro group or a methoxy group, all of R ^{6 'to} R ^9' may not be a hydrogen atom;
R ^{10 '} each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 12 to 24 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, a phenylthio group, an amino group, a monoalkylamino group, a dialkylamino group, a nitroso group, a mercapto group, a trialkylsilyl group, a sulfino group, a phosphate group, an acyl group, a trifluoromethyl group, A cyano group, a nitro group, a carboxyl group, or a sulfo group).