KR20040007280A - Curable resin composition - Google Patents

Abstract

PURPOSE: A curing resin composition and a protection layer prepared by using the composition are provided, to obtain a composition suitable for the protection layer of a color filter. CONSTITUTION: The curing resin composition comprises a polymer obtained by polymerizing a monomer having an epoxy group and a double bond or addition polymerizing a monomer having an epoxy group and a double bond with a monomer having a double bond and having no functional group capable of reacting with an epoxy group; a carboxylic anhydride; and at least one compound selected from an amidinium tetraaryl borate compound and a urea compound. Preferably the monomer having an epoxy group and a double bond is represented by R-X-CH2-E, wherein R is an alkenyl group of C2-C12; X is a carbonyloxy group or a methyleneoxy group; and E is an epoxy group.

Description

Curable resin composition

The present invention relates to a curable resin composition. More specifically, it is related with curable resin composition suitable for the protective film of a color filter.

As an insulating protective film such as an overcoat material in a color filter for a liquid crystal display device, Japanese Patent Application Laid-Open No. Hei 4-53879 discloses a solution (a) in which polyglycidyl methacrylate is dissolved, an aromatic carboxylic anhydride, and It has been reported that a solution (b) in which imidazole is dissolved is prepared, and two liquids (a) and (b) are mixed, applied and thermoset immediately before being applied to a coated object to obtain a protective film. .

When the present inventors examined the composition of the said publication as a composition for protective films, when the composition obtained by mixing two liquids of said (A) and (B) was preserve | saved at 23 degreeC, a viscosity will remarkably increase, It was found that the storage stability was not sufficient.

In addition, when mixing two liquids of (a) and (b) above, bubbles may be formed inside, and the protective film obtained by coating and thermosetting with bubbles formed therein may be formed from bubbles. It also turned out that craters were created.

An object of the present invention is that when applying the protective film composition to the object to be coated, there is no need to mix, can be treated as a one-component composition excellent in storage stability, and when the composition of the one-liquid type is cured It is providing the curable resin composition from which the protective film excellent in heat resistance or chemical resistance can be obtained.

That is, the present invention

A polymer (A) obtained by polymerizing a monomer having a double bond with an epoxy group alone or by addition polymerization with another monomer having a double bond and having no functional group capable of reacting with an epoxy group,

Carboxylic anhydride (B) and

It provides the curable resin composition (it describes as this resin composition hereafter) containing 1 or more types of compounds (C) chosen from the tetraaryl borate compound (C1) and urea (C2) of amidinium.

Moreover, this invention provides the protective film formed by apply | coating this resin composition to a to-be-coated object and thermosetting.

Component (A) in the present resin composition is a polymer obtained by addition polymerization of a monomer having a double bond with an epoxy group alone, or a functional group capable of reacting a monomer having a double bond with an epoxy group with a epoxy group and having a double bond. A polymer obtained by addition polymerization with another monomer having no.

As a monomer which has a double bond with an epoxy group, the monomer of General formula (1) is mentioned as a preferable example, for example.

RX-CH ₂ -E

In Formula 1 above,

R is an alkenyl group having 2 to 12 carbon atoms,

X is a carbonyloxy group or a methyleneoxy group,

E is , And Epoxy group selected from.

As the monomer of the formula (1), for example, unsaturated glycidyl ether (eg, allyl glycidyl ether, 2-methylallyl glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether), Unsaturated glycidyl esters (e.g. glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters), cyclic aliphatic epoxy (meth) acrylates (e.g. 3,4-epoxycyclohexylmethyl acrylate) And 3,4-epoxycyclohexylmethyl methacrylate).

As the monomer of the formula (1), two or more kinds of monomers of the formula (1) can be used.

As the monomer of the formula (1), unsaturated glycidyl esters and cyclic aliphatic epoxy (meth) acrylates are preferable, and in particular, 3,4-epoxycyclohexylmethyl acrylate and glycidyl methacrylate are suitable.

As content of the structural unit derived from the monomer which has an epoxy group and a double bond in component (A), it is 5-100 mol% normally, Preferably it is 20-90 mol%, More preferably, it is 30-80 mol%.

As the polymer of the component (A), a polymer obtained by addition polymerization of a (meth) acrylic monomer and / or a styrene monomer is preferable as another monomer having a double bond and not having a functional group capable of reacting with an epoxy group.

As a (meth) acrylic-type monomer, the (meth) acrylic-acid alkylester (for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate) which has a C1-C20 linear alkyl group, for example, carbon number (Meth) acrylic acid alkyl ester having a branched alkyl group of about 3 to 20 (e.g., t-butyl acrylate, t-butyl methacrylate), (meth) acrylic acid having a saturated cyclic aliphatic alkyl group of about 5 to 20 carbon atoms Alkyl esters (e.g. cyclohexyl acrylate, cyclohexyl methacrylate), (meth) acrylic acid aralkyl esters with aromatic rings (e.g. benzyl acrylate, benzyl methacrylate), (meth) acrylonitrile (e.g. acryl Nitrile, methacrylonitrile).

As the (meth) acrylic monomer, two or more kinds of (meth) acrylic monomers can be used.

As a (meth) acrylic-type monomer, (meth) acrylic-acid alkylester is preferable, Especially the (meth) acrylic-acid alkylester which has a linear or branched alkyl group of about 1-4 carbon atoms, (meth) which has a saturated cyclic aliphatic alkyl group (Meth) acrylic-acid aralkyl ester which has an acrylic acid alkyl ester and an aromatic ring is preferable.

As a styrene-type monomer, styrene, (alpha) -methylstyrene, divinylbenzene, etc. are mentioned, for example. As the styrene monomer, two or more kinds of styrene monomers can be used.

Among these, styrene is suitable as a styrene monomer.

In component (A), as content of the structural unit derived from the other monomer which has a double bond and does not have a functional group which can react with an epoxy group, for example, a (meth) acrylic monomer and / or a styrene monomer, it is usual About 0-95 mol%, Preferably it is about 10-80 mol%, Especially preferably, it is about 20-70 mol%.

In addition to other monomers having a double bond in component (A) and no functional groups capable of reacting with epoxy groups, vinyl alkane esters such as vinyl butyrate, vinyl propionate, vinyl pivalate, and vinyl laurate And vinyl isononate, vinyl basatate, vinyl halides (vinyl chloride, vinyl bromide), and vinylidene halides (for example, vinylidene chloride).

If 1 to 99 mol%, especially 5 to 95 mol% of the structural units derived from the monomer which forms component (A) are structural units derived from the monomer which has a monocyclic double bond, it exists in the tendency for heat resistance to improve and it is preferable. As a specific example of the monomer which has a monocyclic double bond, the acryl-type monomer which does not have a substituent in the (alpha) position among the said (meth) acrylic-type monomers, the styrene-type monomer which does not have a substituent in the (alpha) position, vinyl alkanes, vinyl halides, allyl glycidyl Ether, glycidyl acrylate, and the like.

As component (A), a polymer obtained by addition polymerization of a monomer having a double bond with an epoxy group alone, or another monomer having a double bond with an epoxy group has a double bond and no other functional group capable of reacting with the epoxy group. Two or more kinds of polymers obtained by addition polymerization with a monomer can be used.

The epoxy equivalent of the component (A) is usually 128 g / equivalent or more, preferably about 150 to 4500 g / equivalent, and more preferably about 150 to 1000 g / equivalent.

Moreover, as a molecular weight of a component (A), it is about 1000 to 1,000,000 normally, Preferably it is about 2000-200,000, More preferably, it is about 5000 to 50,000.

As the component (A), for example, blender CP-50M [glycidyl methacrylate methyl methacrylate copolymer, manufactured by Nihon Yushi Co., Ltd.] (NOF Corp.)] and blender CP-50S [gly Commercially available products, such as a cyl methacrylate styrene copolymer and the Nippon Oil Industries, Ltd. product] can be used.

The manufacturing method of component (A) is not specifically limited. See, eg, J. Poll. As described in Sci., Polm. Chem. (1968), 6 (2), 257-267, the monomer and radical generator used are mixed in an organic solvent, and a chain transfer agent is further mixed as necessary. And solution polymerization at about 60 to 300 ° C., as described in J. Polm. Sci., Polm. Chem. (1983), 21 (10), 2949-2960. Suspension polymerization or emulsion polymerization at about 60 to 300 ° C. using a solvent which is not used, and a method of bulk polymerization at 60 to 200 ° C. as described in JP-A-6-80735. , As described in Japanese Patent Application Laid-Open No. Hei 10-195111, the monomers to be used are continuously fed to the polymerization reactor, and the mixture is prepared in the polymerization reactor in the presence or absence of a polymerization initiator. Reaction obtained by heating at 180 to 300 ° C. for 5 to 60 minutes The method of taking out a substance continuously out of a mixer etc. is mentioned.

When using the organic solvent used as a solvent of this resin composition for manufacture of component (A), since the process of dissolving a polymer can be skipped in the post process of combining a composition, it is preferable.

As an organic solvent which can be used for manufacture of component (A), for example, alcohols (for example, methanol, ethanol, isopropyl alcohol, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-) Butanol), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone), ethers (e.g. ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol Monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, Tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether), esters (e.g. ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, butyl lactate, 3-methoxybutyl Acetate, 3-methyl-3-methoxy-1-butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetates) and aromatic hydrocarbons such as toluene and xylene.

As an organic solvent, 2 or more types of organic solvent can be used.

Component (B) used for this resin composition is carboxylic anhydride.

It is preferable that component (B) is a mixture containing dicarboxylic anhydride (B1) and the compound (B2) which has 2 or more of cyclic acid anhydride structures in a molecule | numerator.

Examples of the compound (B1) include aromatic dicarboxylic acid anhydrides (such as phthalic anhydride and tetrabromophthalic anhydride), alicyclic dicarboxylic acid anhydrides (such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. , Methyl hexahydrophthalic anhydride, 5-norbornane-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, methyl norbornane-2,3-dicarboxylic acid anhydride, methylnor Borneen-2,3-dicarboxylic acid anhydride, reactant of maleic anhydride with C ₁₀ diene (manufactured by Japan Epoxy Resins Co., Ltd., YH-306, etc.), cycloaliphatic dicarboxylic acid Anhydrides such as 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid anhydride, aliphatic dicarboxylic acid anhydrides (such as dodecenyl anhydride succinic acid) do.

It is also preferable to use compound (B2). Examples of the compound (B2) include aromatic tetracarboxylic dianhydrides such as pyromellitic anhydride, 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-oxydiphthalic acid dianhydride, and 3,3'. , 4,4'-biphenyltetracarboxylic dianhydride, ethylene glycol bistrimelate [Ref .: New Japan Chemicals Co., Ltd. make, brand name: TMEG], Glycerol tristrimellitate [ Reference: Shin-Nihon Rica Co., Ltd., trade name: TMTA], cycloaliphatic tetracarboxylic dianhydride (e.g. 5- (2,5-dioxotetrahydro-3-pranil) -3-methyl-3-cyclohexene) -1,2-dicarboxylic acid anhydride, 5- (2,5-dioxotetrahydro-3-praylmethyl) norbornane-2,3-dicarboxylic acid anhydride), copolymer of styrene maleic anhydride, etc. The polymer etc. of the monomer containing a cyclic acid anhydride structure and a polymerizable unsaturated bond in a molecule | numerator are illustrated.

As the compound (B2), two or more kinds of compounds can be used.

As component (B), it is preferable that one part or all part is compound (B2). The particularly preferable content of compound (B2) in the carboxylic anhydride of component (B) is about 10 to 80% by weight.

As a compound (B2), alicyclic tetracarboxylic dianhydride is preferable.

Component (B) preferably contains 0.1 mol or less, particularly preferably 0.05 mol or less, in terms of -COOH group of free carboxylic acid per 100 g. When free carboxylic acid is 0.05 mol or less, the storage stability of curable resin composition becomes favorable and it is especially preferable.

The content of component (B) in the present resin composition is usually about 0.3 to 1.2 mol, preferably about 0.6 to 1.0 mol, in terms of acid anhydride groups per 1 mol of the total of the epoxy groups contained in component (A). .

Component (C) in this resin composition is a hardening accelerator, and is 1 or more types chosen from the tetraaryl borate compound (C1) and urea (C2) of amidinium.

Amidiniums in the compound (C1) are cations having a partial structure of formula (2) in the molecule. As said amidinium, the cation which has a partial structure of general formula (2a) in a molecule | numerator is preferable, and the cation which has a partial structure of general formula (2b) in a molecule | numerator is especially preferable.

Said amidinium is used in the form which formed the salt with tetraaryl borate in this resin composition.

In Formula 2, Formula 2a and Formula 2b above,

Dotted line part D is a 5- to 8-membered hetero ring containing one nitrogen atom,

Dotted line part E is a 5-8 membered hetero ring containing two nitrogen atoms.

Among the above amidiniums, the chemical formula 2a having a ring structure in the molecule, and imidazolium having a raw number of 5 is preferable.

As said imidazolium, for example, imidazolium (for example, imidazolium, 2-methyl imidazolium, 2-ethyl-4-methyl imidazolium, 2-undecyl imidazolium, 2-hepta Decylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-sia Noethyl-2-ethyl-4-ethylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-phenylimidazolium), and the nitrogen atom of such imidazolium Furthermore, quaternary imidazolium substituted by the alkyl group, the aryl group, or the arylalkyl group etc. are mentioned.

Furthermore, amidiniums having two rings in the molecule (formula 2b) are also preferable. As such polycyclic amidinium, for example, 1,8-diaza-bicyclo (5.4.0) undeca-7-enium and 1,5-diazabicyclo (4.3.0) nona-5-enium Tertiary amidiniums having two such rings, and quaternary amidis obtained by quaternization of nitrogen atoms of such amidiniums with alkyl having 1 to 20 carbon atoms, arylalkyl having 7 to 20 carbon atoms, or phenyl group; Iums are mentioned. Among these, 8-methyl-1,8-diaza-bicyclo (5.4.0) undeca-7-enium and 8-benzyl-1,8-diaza-bicyclo (quaternary amidinium) 5.4.0) undeca-7-enium and the like are particularly preferred.

As tetraaryl borate in a compound (C1), the compound of General formula (3) is mentioned.

In Formula 3 above,

Ar ¹ to Ar ⁴ are each independently an aryl group which may be substituted with one or more substituents selected from alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms and halogen.

Specific examples of the tetraaryl borate of the formula (3) include tetraphenylborate, tetratoluylborate and the like.

As a compound (C2), the compound which has the partial structure of general formula (4) in a molecule | numerator is mentioned, for example.

N-CO-N

As said urea, Preferably, the compound which has one or more trisubstituted urea structure of general formula (4a) or tetrasubstituted urea structure of general formula (4b) is preferable in a molecule | numerator.

-NH-CO-N <

> N-CO-N <

Examples of the compound having at least one trisubstituted urea structure represented by the formula (4a) or tetrasubstituted urea structure represented by the formula (4b) in the molecule include aliphatic ureas (e.g., tributylurea, 1,1-dimethyl-3-cyclohexylurea). , Tricyclohexyl urea, tetracyclohexyl urea), aromatic urea (e.g. 3- (4-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethyl Urea, 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea).

Particularly preferred are compounds having at least two trisubstituted urea structures of the formula 4a or tetrasubstituted urea structures of the formula 4b in the molecule. Examples of the compound having two or more trisubstituted urea structures of the general formula (4a) or tetrasubstituted urea structures of the general formula (4b) in the molecule include aromatic ureas (for example, toluenebisdimethylurea, methylenebis (phenyldimethylurea)), alicyclic compounds. Group urea (for example, isophoronebisdimethylurea).

The content of component (C) is usually about 0.05 to 30 parts by weight, preferably about 0.5 to 10 parts by weight, per 100 parts by weight of component (A).

This resin composition is normally used in the state dissolved in an organic solvent. As an organic solvent, it is preferable that it does not have a functional group which can react with epoxy groups and acid anhydride groups, such as a free carboxyl group and an amino group, and the said organic solvent is mentioned.

As the organic solvent, two or more organic solvents can be used.

In addition, the present resin composition can contain an antioxidant (hereinafter, referred to as component (D)).

The component (D) is preferably one or more selected from the group consisting of phenolic antioxidants, phosphorus antioxidants and sulfur antioxidants, and more preferably phenolic antioxidants. As content of the component (D) in this resin composition, it is about 0.001-10 weight part normally per 100 weight part of components (A), Preferably it is about 0.01-1 weight part.

As a phenolic antioxidant, 2, 6- di- t- butyl- 4-methyl phenol, 2, 6- di- t- butyl- 4-ethyl phenol, 2, 6- dicyclohexyl-4-, for example Methylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2 -Cyclohexyl-4-n-butyl-6-isopropylphenol, d1-α-tocopherol, t-butylhydroquinone, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4, 4′-butylidenebis (3-methyl-6-t-butylphenol), 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-thiobis (4- Methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p- Cresol], 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-butylidenebis (2-t-butyl-4-methylphenol), 2-t- Butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl Acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenylacrylate, 1,1,3-tris (2 -Methyl-4-hydroxy-5-t-butylphenyl) butane, triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6- Hexanediolbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate], N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamid), 3,5-di-t-butyl-4 -Hydroxybenzylphosphonate diethyl ester, tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, tris (3,5-di-t-butyl-4- Hydroxybenzyl) isocyanurate, Tris

[(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris

(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di- t-butylanilino) -1,3,5-triazine, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2,2- Methylenebis (4-methyl-6-t-butylphenol) terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene , 3,9-bis [[1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10- Tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- (3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)) ethoxyphenyl] propane, β -(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester etc. are mentioned.

In these, (beta)-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester and tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxy] Phenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, d1-α-tocopherol, tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, tris [(3 , 5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane is preferred.

As a phenolic antioxidant, a commercially available phenolic antioxidant can be used, for example, Irganox 1010 (manufactured by Irganox 10O, manufactured by Ciba Specialty Chemicals.Co.), Irganox 1076 [Irganox 1076, manufactured by Ciba Specialty Chemicals], Irganox 1330 [Irganox 1330, manufactured by Ciba Specialty Chemicals], Irganox 3114 [Irganox 3114, manufactured by Ciba Specialty Chemicals], Irganox 3125 [Irganox 3125, manufactured by Ciba Specialty Chemicals], Smallizer BHT [Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.], Cyanox 1790 [Cyanox 1790, manufactured by Psytec Inc. ], Smillizer GA-80 [Sumilizer GA-80, Sumitomo Kagaku make], vitamin E (Eisai Co., Ltd. make), etc. are mentioned.

Two or more kinds of phenolic antioxidants can be used as a phenolic antioxidant.

Examples of the phosphorus antioxidant include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl) diphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tri Phenylphosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5- t-butyl-4-hydroxyphenyl) butanediphosphite, tetra (C12 to C15 mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, tetra (tridecyl) -4,4'-butylidene Bis (3-methyl-6-t-butylphenol) diphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, tris (monodi mixed nonylphenyl) phosphite, hydrogenation -4,4'-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4'-butylidenebis (3-methyl-6-t-butylphenol)]-1,6-hexane Dior Diphospha , Phenyl (4,4'-isopropylidenediphenol) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris [4,4'-isopropylidene bis (2-t-butylphenol)] Phosphite, di (isodecyl) phenylphosphite, 4,4′-isopropylidenebis (2-t-butylphenol) bis (nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide, bis (2,4-di-t-butyl-6-methylphenyl) ethylphosphite, 2-[{2,4,8,10-tetra-t-butyldibenz [d , f] [1.3.2] -dioxaphosphine-6-yl} oxy]

-N, N-bis [2-[{2,4,8,10-tetra-t-butyldibenz [d, f] [1,3.2] -dioxaphosphine-6-yl} oxy] ethyl] Ethanamine, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1.3 .2] -dioxaphosphine etc. are mentioned.

Moreover, as a bis (dialkylphenyl) pentaerythritol diphosphite ester, the spiro form of Formula (10) or the cage form of Formula (11) is mentioned.

In Formula 10 and Formula 11 above,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

As such a phosphite ester, a mixture of the formulas (10) and (11) is usually used.

Here, when R ¹ to R ⁶ are alkyl groups, alkyl groups with side chains are preferred, among which t-butyl group is suitable.

In addition, the substitution positions of R ¹ to R ⁶ in the phenyl group are preferably 2, 4, 6 positions.

Specific examples of the phosphite ester include bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis ( Nonylphenyl) pentaerythritol diphosphite etc. are mentioned, As a phosphonite which has a structure which carbon and phosphorus directly couple | bonded, it is tetrakis (2, 4-di-t-butylphenyl)-, for example. And compounds such as 4,4'-biphenylenediphosphonite.

As a phosphorus antioxidant, a commercial item can be used, for example, Irgafos 168 [Irgafos 168, Ciba Specialty Chemicals make], Irgafos 12 [Irgafos 12, Ciba Specialty Chemicals make], Irga POS 38 [manufactured by Irgafos 38, Shiva Specialty Chemicals], Adecasta 329K [manufactured by ADK STAB 329K, Asahi Denka Co., Ltd.], Adecasta PEP36 [ADK STAB PEP36, manufactured by Asahi Denka ], Adecastar PEP-8 [ADK STAB PEP-8, manufactured by Asahi Denka], Sandstar P-EPQ [Sandstab P-EPQ, Clariant], Western 618 [Weston 618, GE manufactured], Western 619G [Weston 619G, GE make], Ultra Knox 626 [Ultranox 626, GE make], Sumilizer GP [Sumilizer GP, Sumitomo Kagaku make], etc. are mentioned.

As the phosphorus antioxidant, two or more phosphorus antioxidants can be used.

Among the phosphorus antioxidants, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite and dis Tearyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, 2-[{2,4,8, 10-tetra-t-butyldibenz [d, f ] [1.3.2] -dioxaphosphine-6-yl} oxy] -N, N-bis [2-[{2,4,8,10-tetra-t-butyldibenz [d, f] [ 1.3.2] -dioxaphosphine-6-yl} oxy] ethyl] ethanamine, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4, Preference is given to 8,10-tetra-t-butyldibenz [d, f] [1.3.2] -dioxaphosphine.

Examples of sulfur-based antioxidants include dialkylthiodipropionate (e.g. dilauryl-, dimyristyl-, distearyl-) and alkylthiopropionic acid (e.g. butyl-, octyl-, lauryl-, Esters of polyhydric alcohols (e.g., glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) of stearyl-) (e.g., pentaerythritol tetrakis-3- Laurylthiopropionate), and the like.

More specifically, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodibutylate, etc. are mentioned. have.

Among these, pentaerythritol tetrakis-3-laurylthiopropionate is preferable.

Examples of sulfur-based antioxidants include, for example, smilizer TPS [Sumilizer TPS, manufactured by Sumitomo Kagaku], Smizer TPL-R [Sumilizer TPL-R, manufactured by Sumitomo Kagaku], and Smizerizer TPM [Sumilizer TPM, Sumitomo Kagaku Co. ], Smillizer TP-D [Sumilizer TP-R, Sumitomo Kagaku make], etc. are mentioned.

As the sulfur-based antioxidant, two or more sulfur-based antioxidants can be used.

In addition, it is recommended that the present resin composition contains at least one surfactant selected from the group consisting of silicone surfactants, fluorine-based surfactants and silicone-based surfactants having fluorine atoms.

As a silicone type surfactant, toray silicon DC3PA, toray silicon SH7PA, toray silicon DC11PA, toray silicon SH21PA, toray silicon SH28PA, toray silicon 29SHPA, toray silicon SH30PA, polyether modified silicone oil SH8400 [brand name, Toray silicon Co., Ltd. Silicone Co., Ltd.)], KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Silicones Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Reference: GE Toshiba Silicone Co., Ltd.), etc. are mentioned.

Examples of the fluorine-based surfactant include Florinite® FC430, Florinite FC431 (manufactured by Sumitomo 3M Ltd.), MegaPak® F142D, MegaPak F171, MegaPak F172, MegaPak F173, Megapak F177, Megapak F183, Megapak R30 (manufactured by Dainippon Ink and Chemicals, Inc.), F-Top® EF301, F-top EF303, F-top EF351, f Top EF352 [manufactured by Shin-Akita Kasei Co., Ltd.], Saffron (registered trademark) S381, Saffron S382, Saffron SC101, Saffron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Kenkyujo), BM-1OOOO, BM-1100 (brand name, the BM Chemie company make), etc. are mentioned. Examples of the silicone-based surfactant having a fluorine atom include Megapak® R08, Megapak BL20, Megapak F475, Megapak F477, and Megapak F443 (manufactured by Dainippon Inking Chemical Co., Ltd.).

Such surfactant can be used individually or in combination of 2 or more types. Content in the case of containing such surfactant is 0.0001-1 weight% normally with respect to component (A), Preferably it is 0.001-0.1 weight%.

A polymer obtained by addition polymerization of a monomer having a double bond with an epoxy group alone or a double with an epoxy group, so long as the storage stability of the resin composition or the heat resistance and chemical resistance of the protective film obtained using the resin composition are not impaired. The monomer having the bond may contain an epoxy resin different from the polymer obtained by addition polymerization with another monomer having a double bond and not having a functional group capable of reacting with an epoxy group (hereinafter also referred to as another epoxy resin). .

As such another epoxy resin, an aromatic epoxy resin, a heterocyclic containing epoxy resin, a hydrogenated aromatic epoxy resin, an aliphatic epoxy resin, glycidyl ester of a carboxylic acid, a spiro ring containing epoxy resin, alicyclic, for example Epoxy resin etc. are mentioned.

Here, the chemical resistance means that the protective film of the present invention does not penetrate the surface even if it is immersed in an acidic aqueous solution, an alkaline aqueous solution or an aprotic polar solvent for several minutes, and specifically, the protective film absorbs the chemical and does not swell. In addition, it means that it will not be further broken down into granular form.

As an aromatic epoxy resin, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a biphenyl type epoxy resin, etc. are mentioned, for example.

As a heterocyclic containing epoxy resin, a hydantoin type | mold epoxy resin, a triglycidyl isocyanurate, etc. are mentioned, for example.

Examples of the hydrogenated aromatic epoxy resin include hydrogenated bisphenol A epoxy resins, hydrogenated bisphenol F epoxy resins, hydrogenated phenol novolac epoxy resins, hydrogenated cresol novolac epoxy resins, hydrogenated biphenyl epoxy resins, and the like. Can be.

As an aliphatic epoxy resin, for example, butyl glycidyl ether, 1, 6- hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, polypropylene glycol di Glycidyl ether, a trimethylol propane triglycidyl ether, etc. are mentioned.

As glycidyl ester of carboxylic acid, neodecanoic acid glycidyl ester, hexahydrophthalic acid diglycidyl ester, etc. are mentioned, for example.

As the alicyclic epoxy resin, for example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane Carboxylate, bis (3,4-epoxycyclohexyl) adipate, 1,2: 8,9-diepoxylimonene and the like.

Content of another epoxy resin is about the same weight or less normally with respect to component (A), Preferably it is about 0 to 20%.

In the present resin composition, in addition to an organic solvent and a surfactant, for example, a silane coupling agent, an antifoaming agent, a thixotropic imparting agent, a dye, in a range that does not impair the storage stability of the present resin composition and the chemical resistance of the protective film of the present invention. Additives, such as antioxidant and a ultraviolet absorber, can be contained.

As a manufacturing method of this resin composition, For example, the method of manufacturing a component (A) in an organic solvent, and adding a component (B) and a component (C) suitably further as needed further; Component (A) is prepared in an organic solvent, and the organic solvent is removed to obtain a polymer, and then components (A), (B) and (C), and, if necessary, other components are further dissolved in the organic solvent. The method etc. are mentioned.

The protective film of this invention can be obtained by apply | coating curable resin composition obtained in this way to to-be-coated objects, such as a glass substrate and a color filter substrate, and heating.

As a coating method, For example, the method of using a spin coater, a slit coater, a bar coater, a spray coater, a roll coater, flexographic printing, offset printing, etc .; The method which combined two or more types of coating methods, such as a slit and spin coating machine and a bar and spin coating machine, is mentioned.

As said heating method, a hotplate, a clean oven, an infrared heating apparatus, etc. are used, for example, Usually 150 degreeC or more, Preferably it is 190-260 degreeC, More preferably, it is 220-250 degreeC, 10-120 The heating method for minutes, etc. are mentioned.

If heating temperature is 150 degreeC or more, it exists in the tendency for heat resistance to improve and it is preferable.

Moreover, since a hardened | cured material tends to be difficult to color, when heating temperature is 260 degreeC or less, it is preferable.

The method of performing said heating is also preferable after heating at normal temperature or about 150 degreeC, Preferably it is about 50-120 degreeC, heating about 0.5 to 5 minutes under normal pressure or reduced pressure, and removing an organic solvent.

The protective film of the present invention usually has a thickness of about 0.07 to 20 µm, and if it is in this range, the physical properties of the protective film, in particular, flattening and surface strength tend to be improved.

Release paper to which the silicone mold release agent or the fluorine mold release agent was apply | coated to the surface which contact | connects this resin composition to the layer which consists of polyolefin films, such as a film which consists of 4-methyl-1- pentene copolymer, a cellulose acetate film, and a thermosetting resin composition, for example And coated with a coated object such as a release polyethylene terephthalate (PET) film, and then, an organic solvent is removed, a film having an adhesive property, affixed to a substrate that needs to be protected, and coalesced. Next, the protective film of the present invention can be obtained by thermal curing.

The to-be-coated object, such as a mold release agent, a release paper, a release PET film, can be peeled after thermosetting or before thermosetting to gas.

In addition, other resins or substrates can be laminated on the protective film of the present invention as needed.

Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited by these examples. The part in an example means a weight part unless there is particular notice.

Example 1

[Production Example of Curable Resin Composition]

100 parts by weight of component (A), 50 parts by weight of component (B1) and 2 parts by weight of component (C) shown below are dissolved in 450 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) to form a curable resin composition. To obtain.

Component (A):

Blender CP-5OM (glycidyl methacrylate-methyl methacrylate copolymer, Mw = 10,000, epoxy equivalent = 310 g / equivalent, manufactured by Nihon Yushi Co., Ltd.)

Component (B1):

HN-5500 [Methyl hexahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd.]

Component (C):

U-CAT 5002 [1,8-diazabicyclo (5.4.0) -7-undecene-based tetraphenylborate salt, manufactured by San-Apro, Ltd.]

[Storage Stability Test]

The viscosity at 23 degreeC is measured for said curable resin composition using the TV-30L type | mold viscosity meter (No. 1 rotor) manufactured by Toki Sangyo Co., Ltd. (Hereinafter, it is referred to as initial viscosity. List).

Then, the composition is kept sealed for 10 days in an incubator at 23 ° C., and then the viscosity is measured in the same manner as the initial viscosity (hereinafter, referred to as storage viscosity).

As for storage stability, the viscosity change rate (%) calculated by the formula (5) is changed by more than ± 5% to 0 that only changes of ± 5% or less, but the result is zero.

The results are summarized in Table 2.

(Viscosity change rate) = 100 x [(preservation viscosity)-(initial viscosity)] / (initial viscosity)

[Production Example of Protective Film]

The composition before storage obtained in the production example of the curable resin composition was spin-coated on a slide glass (alkali glass), baked for 2 minutes in a heat curing furnace at 85 ° C. to remove the solvent, and then 40 minutes in a heat curing furnace at 230 ° C. Heating to obtain three protective films. The thickness of the said protective film is 1.5 micrometers (measured by a contact film thickness meter).

[Heat resistance test]

The protective film obtained in the above production example is heated in an oven at 250 ° C. for 1 hour, and heat resistance is evaluated by measuring the thickness of the film before and after heating.

The evaluation of the heat resistance was performed in the case where the residual heat-resistance ratio of Equation 6 exceeded 95% in [◎], in the case of exceeding 90% [O], in the case of 80-90% [△], and in the case of less than 80% It is set to [X].

The heat resistance of the protective film of Example 1 is O. The results are summarized in Table 2.

(Heat resistance residual film rate) = 100 * (thickness of film after heating) / (thickness of film before heating)

[Chemical Resistance Test]

Three protective films (1.5 micrometers in thickness of a film) obtained by the said preparation example are immersed in the immersion liquid of Table 1 for the time of Table 1, respectively. The thickness of the film of each protective film after immersion is measured to evaluate acid resistance, alkali resistance and NMP resistance. That is, the protective film which shows the change larger than 0 and +/- 10% is evaluated by X regarding the protective film which stayed in the change of the chemical-resistance residual film ratio of (10) below +/- 10%. The protective film of Example 1 is O in all of acid resistance, alkali resistance and NMP resistance. The results are summarized in Table 2.

(Resistance of drug resistance) = 100 * (thickness of film after immersion) / (thickness of film before immersion)

Example 2, Comparative Example 1 and Comparative Example 2

Except using the component (B), component (C), and component (D) of Table 2, it carried out similarly to Example 1, and manufactures a curable resin composition and a protective film, and performs the same experiment.

Examples 3 to 5

The curable resin composition was used in the same manner as in Example 1 except that the component (B), the component (C) and the component (D) shown in Table 2 were used, and # 1737 manufactured by Corning Corporation was used as the substrate glass. A protective film was prepared and tested in the same manner. The results are summarized in Table 3.

Comparative Example 3

The composition of Comparative Example 1, which has good storage safety, is prepared and tested in the same manner as in Examples 3 to 7. The results are summarized in Table 3.

Component (A):

A1; Blender CP-50M (glycidyl methacrylate-methyl methacrylate copolymer, Mw = 10,000, epoxy equivalent = 310 g / equivalent, manufactured by Nihon Yushi Co., Ltd.)

A2; Blender CP-50S (glycidyl methacrylate-styrene copolymer, Mw = 16,800, epoxy equivalent = 297 g / equivalent, manufactured by Nihon Yushi Co., Ltd.)

Component (B):

B1; HN-5500 (Methylhexahydrophthalic anhydride, Hitachi Kasei Co., Ltd.)

B2; 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, Tokyo Kasei Kogyo Co., Ltd. Produce)

Component (C);

C1; 1,8-diazabicyclo (5,4,0) -7-undecene-based tetraphenylborate salt, U-CAT 5002, manufactured by San Afro Co., Ltd.)

C2; 2,4-toluenebisdimethyl urea (Omicure 24, manufactured by CVC Specialty Chemicals)

C3; 2-ethyl-4-methylimidazole (cuazole 2E4MZ, Shikoku Chemical Co., Ltd.)

(Shikoku Corp.) manufacture)

Curable resin composition of this invention can be handled as a one-component composition which does not require mixing, and is excellent in stability even if it preserve | save as one liquid. And the protective film obtained by thermosetting this composition is excellent in heat resistance, and also shows the outstanding chemical-resistance also about an acid, an alkali, an aprotic polar solvent, etc.

Moreover, since curable resin composition of this invention is excellent in storage stability, even when large application | coating is required, it can apply | coat without impairing operability.

The protective film of this invention is used suitably for electronic components, such as a flattening film, a protective film, an antireflection film, an insulating material, a soldering resist, etc. in a liquid crystal display element, a solid-state image sensor, and a color filter from such an outstanding characteristic. In addition, the protective film of this invention is used also for paint, an adhesive agent, etc.

Claims (10)

A polymer (A) obtained by polymerizing a monomer having a double bond with an epoxy group alone or by addition polymerization with another monomer having a double bond and having no functional group capable of reacting with an epoxy group, Carboxylic anhydride (B) and Curable resin composition containing the at least 1 sort (s) of compound (C) chosen from the tetraaryl borate compound (C1) and urea (C2) of amidinium. The curable resin composition of Claim 1 whose monomer which has a double bond with the epoxy group in component (A) is a monomer of General formula (1). Formula 1 RX-CH ₂ -E In Formula 1 above, R is an alkenyl group having 2 to 12 carbon atoms, X is a carbonyloxy group or a methyleneoxy group, E is , And Epoxy group selected from. Curable resin composition of Claim 1 or 2 which further contains antioxidant (D) other than a component (A), a component (B), and a component (C). The curable resin composition according to any one of claims 1 to 3, wherein the component (B) is a mixture containing a dicarboxylic acid anhydride (B1) and a compound (B2) containing two or more cyclic acid anhydride structures in the molecule. . The curable resin composition according to any one of claims 1 to 4, wherein the component (A) is a polymer obtained by addition polymerization of a monomer having a double bond with an epoxy group, a (meth) acrylic monomer and / or a styrene monomer. . The curable resin composition according to any one of claims 1 to 4, wherein 1 to 99 mol% of the structural units derived from the monomer forming the component (A) is a structural unit derived from a monomer having a monocyclic double bond. The curable resin composition according to any one of claims 1 to 5, wherein the component (B) contains 0.1 mol or less of free carboxylic acid per 100 g in terms of -COOH group. The compound according to any one of claims 1 to 7, wherein the urea (C2) has one or two substituted urea structures selected from -NH-CO-N <and> N-CO-N <in the molecule. Phosphorus curable resin composition. The curable resin composition according to any one of claims 1 to 6, wherein the compound (C1) is a tetraaryl borate compound of an onium having a heterocyclic group. The protective film formed by apply | coating the resin composition of any one of Claims 1-9 to a to-be-coated object, and thermosetting.