JP2005089501A - Curable resin composition and protective film composed of the same composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition having excellent preservation stability and to provide a protective film having excellent heat resistance. <P>SOLUTION: The curable resin composition comprises the following components (A), (B) and (C). The protective film is obtained by coating an article to be coated with the curable resin composition and heat-curing the resultant composition. (A) a polymer prepared by carrying out addition polymerization of a monomer having a cyclic ether group such as an epoxy group and an olefinic double bond and having ≥2,000 molecular weight, (B) an aromatic oxetane compound having <2,000 molecular weight and (C) a cationic curing catalyst such as a thermal cationic curing catalyst. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable resin composition and a protective film. Specifically, the present invention relates to a curable resin composition suitable for a flattening film, a protective film, an antireflection film, an insulating material and the like in a liquid crystal display element, a solid-state imaging element, and a color filter, and the curable resin composition It is related with the protective film obtained by thermosetting this.

  Patent Document 1 discloses a solution (a) in which polyglycidyl methacrylate is dissolved and a solution in which aromatic carboxylic acid anhydrides and imidazoles are dissolved as protective films for insulation such as overcoat materials in color filters for liquid crystal display devices. It is disclosed that (a) was prepared, and two liquids (a) and (b) were mixed, coated and heat-cured immediately before coating on a substrate to obtain a protective film.

Japanese Patent Laid-Open No. 4-53879 (refer to the section of Examples)

When the present inventors examined the composition of patent document 1 as said composition for protective films, the composition obtained by mixing said 2 liquid of (A) and (I) was 23 degreeC. It was found that when stored at, the viscosity increased significantly and the storage stability was not sufficient.
An object of the present invention is to provide a curable resin composition having excellent storage stability and a protective film having excellent heat resistance.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention is a curable resin composition containing the following components (A), (B) and (C), and the curable resin composition applied to an article to be coated: A protective film formed by thermosetting is provided.
(A): a polymer having a molecular weight of 2000 or more obtained by addition polymerization of a monomer having a cyclic ether group and an olefin double bond (B): an oxetane compound having a molecular weight of less than 2000 (C): a cationic curing catalyst

The curable resin composition of the present invention has excellent storage stability. Moreover, the curable resin composition of this invention gives the protective film excellent in heat resistance.
Since the composition of the present invention is excellent in storage stability, it does not impair operability even when a large coating is required.

［式中、Ｒ_１は水素原子又はメチル基を表し、Ｙはカルボニルオキシ基又はメチレンオキシ基を表す。Ａは単結合又は炭素数１〜１２のアルキレン基を表す。但し、Ａで表されるアルキレン基における炭素−炭素結合は酸素原子で中断されていてもよい。Ｅは、下記の群から選ばれる環状エーテル基を表す。 Hereinafter, the present invention will be described in detail.
The component (A) in the curable resin composition of the present invention is a polymer having a molecular weight of 2000 or more obtained by addition polymerization of a monomer having a cyclic ether group and an olefin double bond.
Examples of the monomer having a cyclic ether group and an olefin double bond include a monomer represented by the following formula (1).

[Wherein, R ₁ represents a hydrogen atom or a methyl group, and Y represents a carbonyloxy group or a methyleneoxy group. A represents a single bond or an alkylene group having 1 to 12 carbon atoms. However, the carbon-carbon bond in the alkylene group represented by A may be interrupted by an oxygen atom. E represents a cyclic ether group selected from the following group.

（式中、Ｒ_２〜Ｒ_９は、それぞれ独立に水素原子又は炭素数１〜２２の炭化水素基を表す。ｍは１〜４の整数を表す。）］

(Wherein R _{2 to} R ₉ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, m represents an integer of 1 to 4)]

  Examples of the monomer represented by the formula (1) include unsaturated glycidyl ethers such as allyl glycidyl ether and 2-methylallyl glycidyl ether; unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and itaconic acid glycidyl ester; Glycidyl ether (meth) acrylates such as glycidoxyethyl (meth) acrylate and glycidoxybutyl (meth) acrylate; Cycloaliphatic epoxies such as 3,4-epoxycyclohexylmethyl acrylate and 3,4-epoxycyclohexylmethyl methacrylate (Meth) acrylate; oxetanyl (meth) acrylate, 3-oxetanylmethyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-o Setaniru) methyl (meth) oxetanyl (meth) acrylates such as acrylate.

As the monomer having a cyclic ether group and an olefin double bond, two or more kinds of monomers may be mixed and used.
The monomer having a cyclic ether group and an olefin double bond is preferably a monomer represented by the formula (1), more preferably a monomer having an epoxy group and an olefin double bond, and an unsaturated carboxylic acid. Glycidyl ester and cycloaliphatic epoxy (meth) acrylate are more preferable, and glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl acrylate are particularly preferable.

The component (A) is obtained by addition polymerization using a (meth) acrylic monomer and / or a styrene monomer in addition to a monomer having a cyclic ether group and an olefin double bond. It may be a polymer.
As said (meth) acrylic-type monomer, (meth) acryl which has C1-C20 linear alkyl groups, such as methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate, for example. Acid alkyl ester; (meth) acrylic acid alkyl ester having a branched alkyl group having 3 to 20 carbon atoms such as t-butyl acrylate and t-butyl methacrylate; carbon number such as cyclohexyl acrylate and cyclohexyl methacrylate Examples include (meth) acrylic acid alkyl esters having about 5 to 20 cyclic aliphatic alkyl groups.
As the (meth) acrylic monomer, two or more kinds of (meth) acrylic monomers may be used.
As the (meth) acrylic monomer, (meth) acrylic acid alkyl ester is preferred.
As a (meth) acrylic monomer, (meth) acrylic acid alkyl ester having a linear alkyl group having 1 to 4 carbon atoms, (meth) acrylic acid having a branched alkyl group having 1 to 4 carbon atoms Alkyl esters and (meth) acrylic acid alkyl esters having saturated cyclic aliphatic alkyl groups are preferred.

Examples of the styrene monomer include styrene, α-methylstyrene, divinylbenzene, and the like. Two or more kinds of styrene monomers may be used as the styrene monomer.
As the styrenic monomer, styrene is particularly suitable.

In the case where the component (A) is obtained by addition polymerization using a (meth) acrylic monomer and / or a styrene monomer in addition to the monomer having a cyclic ether group and an olefin double bond. The total of the structural units derived from the (meth) acrylic monomer and the styrene monomer is usually 5 to 95 mol% with respect to 100 mol% of all the structural units constituting the component (A).
The total of the structural units derived from the (meth) acrylic monomer and the styrene monomer is preferably 10 to 90 mol% with respect to 100 mol% of all the structural units constituting the component (A), Most preferably, it is 20-80 mol%.
Among the polymers obtained by addition polymerization of each of these monomers, the component (A) obtained by addition polymerization of 5 to 95 mol% of a (meth) acrylic monomer and / or a styrene monomer is: It is preferable in that it tends to suppress embrittlement of the protective film obtained.

As a monomer that can be used as a raw material for the component (A) other than the (meth) acrylic monomer or the styrene monomer, it contains at least one double bond that can undergo addition polymerization in the molecule, and Examples include aliphatic monomers that do not contain a functional group capable of reacting with an epoxy group such as a carboxylic acid group and an amino group.
Examples of such aliphatic monomers include vinyl butyrate, vinyl propionate, vinyl pivalate, vinyl laurate, vinyl alkanoate such as vinyl isononanoate and vinyl versatate; vinyl chloride, vinyl bromide and the like. Examples of vinyl halides include vinylidene halides such as vinylidene chloride.

As the polymer of component (A), usually 1 to 99 mol% of the structural units derived from the monomer constituting the polymer of component (A) are derived from a monomer having a CH ₂ ═CH— group. is intended to, polymers of structural units 1 to 95 mol% of structural units derived from a monomer forming the polymer derived from a monomer having a CH 2 ₌ CH- group.
When the structural unit derived from the monomer that forms the polymer of the component (A) is a monomer having a CH ₂ ═CH— group, the heat resistance tends to be improved. preferable. As specific examples of the monomer having a CH ₂ ═CH— group, among the above (meth) acrylic monomers, an acrylic monomer having no substituent at the α-position, and having a substituent at the α-position Styrene monomers, vinyl alkanoates and vinyl halides, allyl glycidyl ether, glycidyl acrylate and the like.

(A) As a manufacturing method of the polymer of a component, the following method is mentioned, for example.
(1) As described in J. Polym. Sci., Polym. Chem. (1968), 6 (2), 257-267, a monomer and a radical generator are mixed in an organic solvent, and further if necessary. , A method in which a chain transfer agent is mixed and solution polymerization is performed at about 60 to 300 ° C .;
(2) As described in J. Polym. Sci., Polym. Chem. (1983), 21 (10), 2949-2960, using a solvent that does not dissolve the monomer, A method of emulsion polymerization;
(3) a method of bulk polymerization at 60 to 200 ° C. as described in JP-A-6-80735;
(4) As described in JP-A No. 10-195111, the monomers to be used are continuously supplied to the polymerization vessel, and in the polymerization vessel at 180 to 300 ° C. in the presence or absence of the polymerization initiator. A method of heating for 5 to 60 minutes and continuously removing the resulting reaction product from the polymerization vessel.

  When an organic solvent used as a solvent for the curable resin composition is used as a reaction solvent during the production of the polymer (A) component, there is a step of dissolving the polymer in the subsequent step of preparing the curable resin composition. This is preferable because it can be omitted.

Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol and cyclohexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone and cyclohexanone; 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 group Ethers such as coal dimethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol and 3-methyl-3-methoxy-1-butanol; ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, Diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene group Glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, esters such as propylene carbonate and butyrolactone; aromatic hydrocarbons such as toluene and xylene, and the like.
As the organic solvent, two or more kinds of organic solvents may be used.
Among organic solvents, those not containing a functional group capable of reacting with a cyclic ether group such as a free carboxyl group or an amino group are preferred.

Further, the molecular weight per functional group of the polymer (A) component is usually 128 g / equivalent or more, preferably 150 to 4000 g / equivalent, more preferably 150 to 1000 g / equivalent, taking epoxy equivalent as an example. It is. When the molecular weight per functional group is larger than 128 g / equivalent, it is preferable from the viewpoint of suppressing embrittlement of the resulting protective film, and when the molecular weight per functional group is smaller than 4000 g / equivalent, the chemical resistance tends to be excellent. This is preferable.
Here, excellent chemical resistance means that the surface of the protective film is not affected even if the protective film of the present invention is immersed in an acidic aqueous solution, an alkaline aqueous solution or an aprotic polar solvent for about several tens of minutes. Specifically, the protective film is excellent in a tendency to suppress a state where the protective film absorbs the chemical and swells or is decomposed into particles.
The weight average molecular weight of the polymer (A) component is usually 2,000 to 1,000,000, preferably 3,000 to 500,000, more preferably 5,000 to 200,000. is there.
Examples of the polymer (A) component include Blenmer CP-50M (registered trademark, glycidyl methacrylate / methyl methacrylate copolymer, manufactured by NOF Corporation), Blemmer CP-50S (registered trademark, glycidyl methacrylate / styrene copolymer). Commercial products such as coalescence, manufactured by NOF Corporation may be used.

The component (B) used in the curable resin composition of the present invention is an oxetane compound having a molecular weight of less than 2000 and having one or more oxetanyl groups in the molecule.
Examples of the oxetane compound having a molecular weight of less than 2000 include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 1 , 4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 1,4-bis {(3-ethyl-3-oxetanyl) methyl} terephthalate, di [1-ethyl (3-oxetanyl) ] Methyl ether, 1,3-bis {(1-ethyl-3-oxetanyl) methoxy} benzene, 4,4 ′-[(3-ethyl-3-oxetanyl) methoxy] biphenyl, bisphenol novolac oxetane and the like.
Among them, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 1,4-bis {(3-ethyl-3-oxetanyl) methyl} terephthalate, di [1-ethyl (3 -Oxetanyl)] methyl ether, 1,3-bis {(1-ethyl-3-oxetanyl) methoxy} benzene, 4,4 '-[(3-ethyl-3-oxetanyl) methoxy] biphenyl, bisphenol novolac oxetane An oxetane compound having two or more oxetanyl groups in the molecule is preferred. In addition, aromatic phenolic compounds such as 1,3-bis {(1-ethyl-3-oxetanyl) methoxy} benzene, 4,4 ′-[(3-ethyl-3-oxetanyl) methoxy] biphenyl, and bisphenol novolac oxetane Oxetane compounds are preferred in terms of heat resistance.
The molecular weight of the component (B) in the curable resin composition of the present invention is less than 2000, preferably 1500 or less, more preferably 1000 or less.
The ratio of the oxetane compound (B) in the curable resin composition of the present invention is usually about 1 to 50%, preferably about 5 to 25% with respect to the total of the polymer (A) and the oxetane compound (B). It is.

  The cationic curing catalyst (C) used in the curable resin composition of the present invention is a curing catalyst capable of cationic polymerization of a cyclic ether group by the action of an acid. It is preferable that the curing catalyst is a latent cation catalyst that generates an acid by heating or radiation, since the storage stability tends to be good, and the thermal cation catalyst (C1) that generates an acid by heating is particularly good. .

As the cation curing catalyst (C), an organic onium salt compound in which a cation component and an anion component are paired is usually used.
Examples of the cation component of the thermal cation curing catalyst (C) include organic cations such as organic sulfonium, organic oxonium, organic ammonium, organic phosphonium, and organic iodonium. As the anionic component of the curing catalyst (C) of ^{_{the, B (C 6 F 5)}} 4 -, SbF 6 -, AsF 6 -, PF 6 - or BF ₄ ^-, and the like.
As a cation component of the cation curing catalyst (C) used in the curable resin composition of the present invention, organic sulfonium is preferable, and aromatic sulfonium is particularly preferable among organic sulfoniums. As the anionic component of the curing catalyst ^{_{(C), SbF 6 -,}} AsF 6 - or PF ₆ ^- is preferred, PF ₆ ^- are particularly preferred.

The thermal cation curing catalyst (C1) preferably has a reaction start temperature of 90 ° C. or higher, particularly 105 ° C. or higher because the storage stability of the curable resin composition tends to be further improved. Moreover, when the reaction start temperature is 200 ° C. or lower, particularly 150 ° C. or lower, there is a tendency to be excellent in acid resistance and chemical resistance (NMP resistance, etc.) that it is not attacked by exposure to an acid or N-methylpyrrolidone. .
The reaction start temperature of the thermal cation curing catalyst (C1) is the thermal cation curing catalyst (C1) with respect to 100 parts by weight of the liquid epoxy resin AK-601 (hexahydrophthalic acid diglycidyl ester manufactured by Nippon Kayaku Co., Ltd.). Exotherm of the exothermic peak detected at the lowest temperature when differential scanning calorimetry (DSC) was performed on the sample to which 3 parts by weight of the active ingredient excluding the solvent was added at a rate of temperature increase of 10 ° C./min. This is the starting temperature.

  The ratio of the cationic curing catalyst (C) in the curable resin composition of the present invention is usually represented by the amount of the active ingredient excluding the solvent in the catalyst (C) per 100 parts by weight of the polymer (A). Is 0.2 to 20 parts by weight, preferably 1 to 10 parts by weight.

The curable resin composition of the present invention preferably contains an antioxidant (D). The antioxidant is preferably at least one antioxidant selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants, and one or more phenolic antioxidants. It is particularly preferable to contain
The ratio of the antioxidant (D) in the curable resin composition of the present invention is usually 0 per 100 parts by weight of the total of the polymer (A) having a molecular weight of 2000 or more and the oxetane compound (B) having a molecular weight of less than 2000. 0.001 to 10 parts by weight, preferably 0.01 to 1 part by weight.

  Examples of the phenolic antioxidant in the present invention include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, and 2,6-dicyclohexyl-4. -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, dl-α-tocopherol, t-butylhydroquinone, 2,2'-methylenebis (4-methyl- -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 2,2'-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-pentylphenyl acrylate, 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-hexanediol bis [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-hydrocinnamide), 3,5-di-t- Butyl-4-hydroxybenzylphosphonate diethyl ester, tris (2,6-dimethyl-3-hydroxy-4-tert-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-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,2'-methylenebis (4-methyl-6-tert-butylphenol) terephthalate 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,9 Bis [1,1-dimethyl-2- {β- (3-tert-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 and β- (3,5-di-t- Butyl-4-hydroxyphenyl) propionic acid stearyl ester and the like.

  Among these phenolic antioxidants, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester, tetrakis [methylene-3- (3,5-di-t-butyl- 4-hydroxyphenyl) 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, dl-α-tocopherol, tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, tris [(3,5-di-t -Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate and 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl) 4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-spiro [5,5] undecane is preferred.

A commercially available product may be used as the phenolic antioxidant.
Examples of such commercially available phenolic antioxidants include Irganox 1010 (Irganox 1010, manufactured by Ciba Specialty Chemicals), Irganox 1076 (Irganox 1076, manufactured by Ciba Specialty Chemicals), Irga Knox 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), Smither BHT ( Sumilizer BHT (manufactured by Sumitomo Chemical), Cyanox 1790 (Cyanox 1790, manufactured by Cytec), Sumilizer GA-80 (Sumiliz) er GA-80, manufactured by Sumitomo Chemical Co., Ltd.) and vitamin E (manufactured by Eisai).
A phenolic antioxidant may use together 2 or more types of phenolic antioxidants.

  Examples of the phosphorus antioxidant in the present invention include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl) diphenyl phosphite, and tris (2,4-di-t-butylphenyl) phosphite. , Triphenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-t -Butyl-4-hydroxyphenyl) butanediphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyldiphosphite, tetra (tridecyl) -4,4'-butylidenebis (3-methyl) -6-tert-butylphenol) diphospha Tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, tris (mono-dimixed nonylphenyl) phosphite, hydrogenated-4,4′-isopropylidenediphenol polyphosphite, Bis (octylphenyl) bis [4,4′-butylidenebis (3-methyl-6-tert-butylphenol)]-1,6-hexanediol diphosphite, phenyl (4,4′-isopropylidenediphenol) pentaerythritol Diphosphite, distearyl pentaerythritol diphosphite, tris [4,4′-isopropylidenebis (2-t-butylphenol)] phosphite, di (isodecyl) phenyl phosphite, 4,4′-isopropylidenebis ( 2-t-butylphenol) bis (nonylphenyl) phos 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, 2-[{2 , 4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] -dioxaphosphin-6-yl} oxy] -N, N-bis [2-[{2, 4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] -dioxaphosphin-6-yl} oxy] ethyl] ethanamine or 6- [3- (3-t- Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1.3.2] -dioxaphosphine.

（式中、Ｒ^１、Ｒ^２、およびＲ^３は、それぞれ独立に、水素原子又は炭素数１〜９のアルキル基を表す。）
で示されるスピロ型のもの、又は、下記式（３）

（式中、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に水素原子又は炭素数１〜９のアルキル基を表す。）
で示されるケージ形のものなどが挙げられる。
このようなホスファイトエステルは、通常、上記式（２）の化合物と式（３）の化合物との混合物が使用される。
ここで、Ｒ^１〜Ｒ^６がアルキル基である場合は、分枝状のアルキル基が好ましく、ｔ−ブチル基が特に好ましい。また、ベンゼン環におけるＲ^１〜Ｒ^６の置換位置は、２位、４位又は６位が好ましい。 Moreover, as bis (dialkylphenyl) pentaerythritol diphosphite ester, following formula (2)

^(Wherein, R 1, ^{R 2,} and ^{R 3} each independently represent a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.)
Spiro type represented by the following formula (3)

(In formula, R < ⁴ >, R < ⁵ > and R < ⁶ > represent a hydrogen atom or a C1-C9 alkyl group each independently.)
The cage type shown by is mentioned.
As such a phosphite ester, a mixture of the compound of the above formula (2) and the compound of the formula (3) is usually used.
Here, when R ^{1 to} R ⁶ are alkyl groups, a branched alkyl group is preferable, and a t-butyl group is particularly preferable. Further, the substitution positions of R ^{1 to} R ⁶ in the benzene ring are preferably the 2-position, 4-position or 6-position.

Specific examples of phosphite esters include bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite. And bis (nonylphenyl) pentaerythritol diphosphite.
Examples of the phosphonite having a structure in which carbon and phosphorus are directly bonded include tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite.

A commercial item can also be used as a phosphorus antioxidant.
Examples of such commercially available phosphorous antioxidants include Irgafos 168 (Irgafos 168, manufactured by Ciba Specialty Chemicals), Irgafos 12 (Irgafos 12, manufactured by Ciba Specialty Chemicals), Irgafos 38 ( Irgafos 38, manufactured by Ciba Specialty Chemicals), ADK STAB 329K (ADK STAB 329K, manufactured by Asahi Denka), ADK STAB PEP36 (ADK STAB PEP36, manufactured by Asahi Denka), ADK STAB PEP-8 (ADK STAB PEP-8, manufactured by Asahi Denka) ), Sandstab P-EPQ (Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultra) ox 626, manufactured by GE) and Sumilizer GP (Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd.) and the like.
Two or more phosphorus antioxidants may be used in combination as the phosphorus antioxidant.

  Among phosphorus antioxidants, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphonite, Distearyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, 2-[{2,4,8,10-tetra-t-butyldibenz [d, f] [ 1.3.2] -Dioxaphosphin-6-yl} oxy] -N, N-bis [2-[{2,4,8,10-tetra-t-butyldibenz [d, f] [1 3.2] -Dioxaphosphin-6-yl} oxy] ethyl] ethanamine and 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4, 8,10-tetra- - butyldibenz [d, f] [1.3.2] - dioxaphosphepin are preferred.

  Examples of the sulfur-based antioxidant in the present invention include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate; polyhydric alcohol ester of butylthiopropionic acid , Polyhydric alcohol ester of octylthiopropionic acid, polyhydric alcohol ester of lauryl thiopropionic acid, polyhydric alcohol ester of stearyl thiopropionic acid (for example, glycerin, trimethylolethane, trimethylolpropane, Such as pentaerythritol and trishydroxyethyl isocyanurate) and polyhydric alcohols of alkylthiopropionic acid such as pentaerythryltetrakis-3-laurylthiopropionate. Le, and the like.

Examples of the sulfur antioxidant include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, distearyl thiodibutyrate and pentaerythryl tetrakis. -3-Laurylthiopropionate is preferred.
Of these, pentaerythryltetrakis-3-laurylthiopropionate is particularly preferred.

Examples of commercially available sulfur-based antioxidants include Sumitizer TPS (Sumilizer TPS, manufactured by Sumitomo Chemical), Sumitizer TPL-R (Sumizer TPL-R, manufactured by Sumitomo Chemical), Sumitizer TPM (Sumizer TPM, manufactured by Sumitomo Chemical) and Sumitizer. TP-D (Sumilizer TP-D, manufactured by Sumitomo Chemical Co., Ltd.) and the like can be mentioned.
As the sulfur-based antioxidant, two or more kinds of sulfur-based antioxidants may be used in combination.

The curable resin composition of the present invention is usually used after being dissolved in an organic solvent. Examples of the organic solvent used in the curable resin composition of the present invention include the organic solvents described above. Two or more organic solvents may be mixed and used as the organic solvent.
Among the above organic solvents, a solvent having no functional group capable of reacting with a cyclic ether group such as a free carboxyl group or an amino group is preferable.

Moreover, the curable resin composition of the present invention contains at least one surfactant selected from the group consisting of silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. It is preferable.
As the above-mentioned silicone surfactant, trade names: Tore Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA and SH30PA (manufactured by Torresilicone); trade name: polyether-modified silicone oil SH8400 (Made by Torre Silicone Co., Ltd.); trade names KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (made by Shin-Etsu Silicone); trade names TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446 , TSF4452 and TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.).

Examples of the fluorosurfactant include Fluorinert (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited); MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183 R30 (Dainippon Ink Chemical Co., Ltd.); Ftop (registered trademark) EF301, EF303, EF351 and EF352 (manufactured by Shin-Akita Kasei); Surflon (registered trademark) S381, S382 SC101 and SC105 (manufactured by Asahi Glass Co., Ltd.); trade name E5844 (manufactured by Daikin Fine Chemical Laboratory); trade names BM-1000 and BM-1100 (manufactured by BM Chemie).
Examples of the silicone surfactant having a fluorine atom include Megafac (registered trademark) R08, BL20, F475, F477 and F443 (Dainippon Ink & Chemicals, Inc.).
These surfactants can be used alone or in combination of two or more.

Furthermore, you may use together other surfactants, such as an acrylic polymer type surfactant and a vinyl polymer type surfactant, in the curable resin composition of this invention.
As the acrylic polymer surfactant, Disparon (registered trademark) OX-880, OX-881, OX-883, OX-70, OX-77, OX-77HF, OX-60, OX-710, OX-720, OX-740, OX-750, OX-8040, 1970, 230, L-1980-50, L-1982-50, L-1983-50 L-1984-50, L-1985-50, LAP-10, LAP-20, LAP-30 and LHP-95 (manufactured by Enomoto Kasei Co., Ltd.); trade names BYK-352, BYK -354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-361 and BYK-390 (manufactured by BYK Chemie Japan); EFKER (registered trademark) L 3778 (Efka Chemicals Co., Ltd.), and the like.

  Examples of the vinyl polymer surfactant include Disparon (registered trademark) 1922, 1927, 1950, 1951, P-410, P-410HF, P-420, P-425, and PD-7. And LHP-90 (manufactured by Enomoto Kasei Co., Ltd.).

  Furthermore, as long as the storage stability of the curable resin composition of the present invention and the chemical resistance of the protective film obtained by thermosetting the composition are not impaired, the curable resin composition of the present invention may have other cationic curing. Sexual compounds may be mixed. Examples of the cationic curable compound to be mixed include epoxy resins such as aromatic epoxy resins, hydrogenated aromatic epoxy resins, aliphatic epoxy resins, glycidyl esters of carboxylic acids, spiro ring-containing epoxy resins, and alicyclic epoxy resins. Cyclic lactones, cyclic carbonates; spiro orthoesters; spiro ortho carbonates; vinyl ethers; polyols and the like.

  Examples of the aromatic epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and biphenyl type epoxy resin.

  Examples of the hydrogenated aromatic epoxy resin include hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated phenol novolac type epoxy resin, hydrogenated cresol novolak type epoxy resin, or hydrogenated biphenyl type. An epoxy resin etc. are mentioned.

Examples of the aliphatic epoxy resin include butyl glycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, or trimethylolpropane triglycidyl. Examples include ether.
Examples of the glycidyl ester of the carboxylic acid include neodecanoic acid glycidyl ester and hexahydrophthalic acid diglycidyl ester.

  Examples of the spiro ring-containing epoxy resin or alicyclic epoxy resin include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3,4. -Epoxycyclohexanecarbochelate, bis (3,4-epoxycyclohexyl) adipate, 1,2: 8,9-diepoxy limonene and the like.

  Examples of the polyols include polycaprolactone diol, polycaprolactone triol, polycaprolactone polyol, polyester diol, polyester triol, polyester polyol, polycarbonate diol, polycarbonate triol, and polycarbonate polyol.

The ratio of the cationic curing catalyst that can be mixed with the curable resin composition of the present invention is usually mixed with respect to a total of 100 parts by weight of the polymer (A) having a molecular weight of 2000 or more and the oxetane compound (B) having a molecular weight of less than 2000. The possible cationic curing catalyst is about 20 parts by weight or less. Preferably, the cationic curing catalyst (C) that can be mixed is 10 parts by weight or less with respect to a total of 100 parts by weight of the polymer (A) having a molecular weight of 2000 or more and the oxetane compound (B) having a molecular weight of less than 2000.
In the curable resin composition of the present invention, two or more kinds of cationic curing catalysts may be used.

  The curable resin composition of the present invention includes, for example, a silane cup, in addition to the organic solvent and the surfactant, as long as the storage stability of the composition and the chemical resistance of the protective film of the present invention are not impaired. You may contain additives, such as a ring agent, an antifoamer, a thixotropy imparting agent, a dye, and an ultraviolet absorber.

  In the curable resin composition of the present invention, for example, after the component (A) is produced in an organic solvent, an oxetane compound (B) having a molecular weight of less than 2000, a cationic curing catalyst (C) and other components are appropriately added; After producing the component (A) in the organic solvent, the organic solvent is once removed, and then the oxetane compound (B) having a molecular weight of less than 2000, the cationic curing catalyst (C) and other components are dissolved and mixed in the organic solvent. Manufactured by a method or the like.

The protective film of the present invention can be obtained by applying the curable resin composition thus obtained to a substrate that needs to be protected, such as a glass substrate or a color filter substrate, followed by heating.
Here, as the coating method, for example, there are two types such as a method using a spin coater, a slit coater, a bar coater, a spray coater, a roll coater, a flexographic printing, an offset printing, a slit and spin coater, a bar and spin coater, etc. The method etc. which combined the above coating method are mentioned.

As a heating method, for example, a hot plate, a clean oven, an infrared heating device or the like is used, and a method of heating at 150 ° C. or higher, preferably 190 to 260 ° C., more preferably 220 to 250 ° C. for 10 to 120 minutes, etc. Is mentioned.
A heating temperature of 150 ° C. or higher is preferred because the heat resistance tends to be improved.
Moreover, since the hardened | cured material is hard to color if heating temperature is 260 degrees C or less, it is preferable.
After removing the solvent by heating at room temperature to 150 ° C., preferably about 50 to 120 ° C. under normal or reduced pressure for about 0.5 to 5 minutes, the above hot plate, clean oven, infrared heating device, etc. A method of heating using is also preferred.
Further, the thickness of the protective film to be obtained is usually about 0.07 to 20 μm, and when it is within this range, the physical properties of the protective film, in particular, flattening and surface strength tend to be excellent.

In addition, the curable resin composition of the present invention is silicone-coated on the surface in contact with a layer made of, for example, a polyolefin film such as a film made of 4-methyl-1-pentene copolymer, a cellulose acetate film, or a curable resin composition. This is applied to release paper coated with release agent or fluorine release agent, release polyethylene terephthalate (PET) film, etc., and the organic solvent is removed to produce an adhesive film. The protective film may be bonded to a substrate that needs to be protected and then thermally cured to form the protective film of the present invention.
The above film or release paper may be bonded to a substrate that needs to be protected and peeled before thermosetting or after thermosetting.
Moreover, you may laminate | stack another resin and a base | substrate further as needed to the protective film before thermosetting.

The material of the substrate is usually a material that can adhere to the protective film of the present invention.
Specific examples of the base material include gold, silver, copper, iron, tin, lead, metals such as aluminum and silicone; inorganic materials such as glass and ceramics; cellulosic polymer materials such as paper and cloth; melamine resins , Acrylic / urethane resins, urethane resins, (meth) acrylic resins, styrene / acrylonitrile copolymers, polycarbonate resins, phenol resins, alkyd resins, synthetic polymer materials such as epoxy resins and silicone resins It is done.

As the substrate, two or more different materials may be mixed or combined.
If necessary, the substrate may be subjected to a coating treatment such as a release agent, a coating such as plating, or a coating made of a resin composition other than the present invention. Surface treatment such as oxidation and etching may be performed.
As the substrate, an integrated circuit which is a composite material of a synthetic polymer material and a metal, a printed wiring board, a liquid crystal display element, a solid-state imaging element, a color filter, or other electronic / electrical parts are preferably used.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited by these. In the examples, “parts” means parts by weight unless otherwise specified.

  In the following example, as a polymer (A) having a molecular weight of 2000 or more obtained by addition polymerization of a monomer having a cyclic ether group and an olefin double bond, a registered trademark Blemmer CP-50S (manufactured by NOF Corporation) Glycidyl methacrylate-styrene copolymer; epoxy equivalent was 292, Mw was 19000).

  As the oxetane compound (B) having a molecular weight of less than 2000, Aron Oxetane RSOX (1,3-bis {(1-ethyl-3-oxetanyl) methoxy} benzene) manufactured by Toagosei Co., Ltd. was used.

Further, (C1) as the thermal cationic curing catalyst component, Sanshin Chemical Co., Ltd. of San-Aid SI-110L (aromatic sulfonium PF ₆ ^- was 49% gamma-butyrolactone solution of the salt, the reaction starting temperature is 120 ° C.) Was used.

  Further, Irganox 1010 (phenolic antioxidant) manufactured by Ciba Specialty Chemicals was used as the antioxidant of component (D).

Examples 1-2
<Example of production of curable resin composition>
The amount of 80 parts of the component (A), 20 parts of the component (B) and 3 parts of the active ingredient excluding the solvent in the component (C1) described in Table 2 is propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA). ) Dissolved in 480 parts. Furthermore, the antioxidant of (D) component was added and the curable resin composition was obtained.

Comparative Example 1
100 parts of the component (A) shown in Table 2 and an amount of 3 parts of the active ingredient excluding the solvent of the component (C1) were dissolved in 480 parts of PGMEA.
A part of the curable resin composition was subjected to the following storage stability test.

Comparative Example 2
100 parts of the above (A), 33 parts of trimellitic anhydride (curing agent) of (E), and Curazole 1B2MZ (F) of Shikoku Kasei Co., Ltd. 2 parts of methylimidazole) was dissolved in 450 parts of PGMEA to obtain a curable resin composition.
This curable resin composition was subjected to a storage stability test, but gelled after 10 days.

<Storage stability test>
After the curable resin composition obtained in the production example of the preceding paragraph is hermetically stored in an incubator at 23 ° C. for 10 days, the composition whose viscosity change rate (%) is less than ± 10% is changed to ○, ± 10 to 20 For compositions showing% changes, compositions showing changes greater than Δ and ± 20% were evaluated as x.
The results are summarized in Table 2.

<Example of production of protective film>
The curable resin composition before being subjected to the storage stability test was spin-coated on a slide glass, baked for 2 minutes in a heating and drying furnace at 85 ° C to remove the solvent, and then heated in a heating and curing furnace at 230 ° C for 40 minutes. A protective film was obtained. When the thickness of this protective film was measured using a contact-type film thickness meter, it was 1.5 to 2.0 μm.

<Chemical resistance test>
Three of the protective films obtained in the previous section were immersed in the immersion liquid described in Table 1 for the time described in Table 1. Next, the thickness of the protective film was measured, and the remaining film ratio was determined by the following mathematical formula (2) to evaluate acid resistance, alkali resistance and NMP resistance (N-methyl-2-pyrrolidone resistance).
Residual film rate = [film thickness after immersion / film thickness before immersion] × 100 (2)
In the judgment, the change in the residual film rate in the chemical resistance test was ± 5% or less, and the change was more than ± 5%, and the change was ×.
The results are summarized in Table 2.

<Heat resistance test>
After heat-treating the protective film obtained in the previous item at 250 ° C. for 1 hour, the film thickness of the protective film was measured, and the remaining film ratio represented by the following mathematical formula (3) was obtained to evaluate the heat resistance.
The results are summarized in Table 2.
Residual film ratio = [film thickness after heating / film thickness before heating] × 100 (3)
In Table 2, the heat resistance is expressed as “heat resistant residual film ratio”.

<Heat resistance transparency test>
Using the protective film heat-treated under the same conditions as in the heat resistance test of the previous paragraph, a minimum value of transmittance at 400 to 700 nm was obtained with a V-560 spectrophotometer manufactured by JASCO Corporation. The results are summarized in Table 2.
In Table 2, the transmittance is expressed as “heat-resistant transmittance”.

The protective film of the present invention has, for example, a flattening film, a protective film, and an antireflection film in liquid crystal display elements, solid-state imaging elements and color filters; electronic parts such as insulating materials and solder resists; It is suitably used for adhesives and the like.

Claims (9)

A curable resin composition comprising the following components (A), (B), and (C):
(A): a polymer having a molecular weight of 2000 or more obtained by addition polymerization of a monomer having a cyclic ether group and an olefin double bond (B): an oxetane compound having a molecular weight of less than 2000 (C): a cationic curing catalyst   The curable resin composition according to claim 1, wherein the component (C) is a thermal cation curing catalyst (C1).   The curable resin composition according to claim 1 or 2, wherein the component (B) is an aromatic oxetane compound having a molecular weight of less than 2000.   The cyclic ether group in (A) component is an epoxy group, The curable resin composition in any one of Claims 1-3.   The (A) component is a polymer obtained by addition polymerization using a (meth) acrylic monomer and / or a styrene monomer, and the curability according to any one of claims 1 to 4. Resin composition.   The curable resin composition according to any one of claims 1 to 5, wherein the monomer having a cyclic ether group and an olefin double bond in component (A) is glycidyl methacrylate.   Furthermore, the curable resin composition in any one of Claims 1-6 containing antioxidant of (D) component.   The curable resin composition according to claim 7, wherein the antioxidant of component (D) contains a phenolic antioxidant. The protective film formed by applying the curable resin composition in any one of Claims 1-8 to a to-be-coated article, and thermosetting.