KR20040025614A - Curable resin composition and protective coating - Google Patents

Abstract

PURPOSE: A curable resin composition and a protection layer prepared by using the composition are provided, to improve storage stability, alkali resistance, chemical resistance and heat resistance. CONSTITUTION: The curable resin composition comprises a polymer which is prepared by addition polymerizing at least one monomer having a cyclic ether group and an olefin double bond or addition polymerizing the monomer with other monomer having a double bond and having no functional group capable of reacting a cyclic ether group; a thermally curing cation catalyst; optionally an antioxidant; and optionally an oxetane compound having a molecular weight less than 2,000. Preferably the cyclic ether group is an epoxy group and/or an oxetanyl group. Preferably the polymer has a weight average molecular weight of 2,000 or more.

Description

Curable resin composition and protective coating

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 flattening films, protective films, antireflection films, insulating materials and the like in liquid crystal display devices, solid-state imaging devices, and color filters, and a protective film obtained by thermosetting the curable resin composition.

As a protective film for insulation 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 curable resin composition composed of polyglycidyl methacrylate, aromatic carboxylic anhydride and imidazole. A protective film obtained by applying to a complex and thermosetting is proposed. Specifically, a solution (a) in which polyglycidyl methacrylate is dissolved and a solution (b) in which aromatic carboxylic anhydride and imidazole are dissolved are prepared, respectively, immediately before forming a protective film (a) and (b). There is proposed a protective film obtained by mixing two liquids of a mixture, applying the mixed liquid to an adherend, and then thermosetting.

MEANS TO SOLVE THE PROBLEM The present inventors examined the composition of the said publication, and the protective film obtained from this composition, and when mixing two liquids of said (A) and (B), a bubble may mix, and a bubble may be mixed. It turned out that the hole (crater) derived from a bubble is formed in the protective film obtained by apply | coating a composition to a to-be-adhered body in the mixed state, and thermosetting. In addition, it was also found that when the composition after mixing the above two liquids to remove bubbles is stored at room temperature at 23 ° C., the viscosity is remarkably increased and storage stability is 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 chemical resistance, particularly alkali resistance.

That is, the present invention includes the following.

<1> A polymer obtained by addition polymerization of at least one monomer having a cyclic ether group and an olefin double bond or by addition polymerization of the monomer with another monomer having a double bond and not having a functional group capable of reacting with a cyclic ether group. Curable resin composition containing (A) and a thermal cationic curing catalyst (B).

<2> Curable resin composition as described in <1> whose cyclic ether group is an epoxy group and / or an oxetanyl group.

<3> Curable in <1> or <2> whose component (A) is a polymer obtained by addition-polymerizing the monomer which has a cyclic ether group and an olefin double bond, and a (meth) acrylic-type monomer and / or a styrene-type monomer. Resin composition.

<4> Curable resin composition in any one of <1>-<3> whose monomer which has a cyclic ether group and an olefin double bond is glycidyl (meth) acrylate.

<5><1> to <4> according to any one of the components (A) to the structural units 1 to 99mol% of the curable resin composition having a CH ₂ = CH- a group of the structural unit formed in.

<6> The differential scanning according to any one of <1> to <5>, wherein a mixture of 3 parts by weight of the thermal cationic curing catalyst (B) and 100 parts by weight of hexahydrophthalic acid diglycidyl ester is heated at a temperature increase rate of 10 ° C / min. Curable resin composition whose reaction start temperature of a component (B) is the range of 90-200 degreeC when calorie analysis makes the exothermic start temperature of the exothermic peak detected on the lowest temperature side into the reaction start temperature of a thermal cation curing catalyst (B). .

<7> Curable resin composition in any one of <1>-<6> which further contains antioxidant (C).

<8> Curable resin composition as described in <7> whose component (C) is 1 or more types of antioxidant chosen from the group which consists of a phenolic antioxidant, phosphorus antioxidant, sulfur type antioxidant, and lactone type antioxidant.

<9> Curable resin composition in any one of <1>-<8> whose weight average molecular weight of a component (A) is 2000 or more.

<10> Curable resin composition as described in <9> which further contains the oxetane compound (D) whose molecular weight is less than 2000.

<11> Curable resin composition as described in <10> whose component (D) is an aromatic phenol oxetane compound whose molecular weight is less than 2000.

<12> The protective film obtained by thermosetting curable resin composition in any one of <1>-<11> at the temperature of 190 degreeC or more.

<13> The protective film formed by apply | coating curable resin composition in any one of <1>-<11> to a to-be-adhered body, and thermosetting.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In the present invention, component (A) may add-polymerize at least one monomer having a cyclic ether group and an olefin double bond, or add another monomer having a double bond and no other monomer having a functional group capable of reacting with a cyclic ether group. Polymer obtained by polymerization.

In the present specification, the cyclic ether group is an oxacycloalkyl group which may have substituents such as an epoxy group which may have a substituent, an oxetanyl group which may have a substituent, and a tetrahydrofuryl group which may have a substituent. Of these, an epoxy group which may have a substituent and an oxetanyl group which may have a substituent are preferable.

Moreover, as an olefin double bond, the double bond contained in compounds, such as ethylene, propylene, butylene, (meth) acrylic acid ester, and (meth) acrylonitrile, is mentioned, for example.

As a monomer (it describes as this monomer hereafter) which has a cyclic ether group and an olefin double bond, the monomer of following formula (1), etc. are mentioned, for example.

Where

R ₁ is a hydrogen atom or a methyl group,

Y is a -COO- group or a -CH ₂ O- group,

A is a single bond or an alkylene group having 1 to 12 carbon atoms, provided that when A is an alkylene group, CH ₂ may be substituted with -O- in the alkylene group,

E is a chemical formula , And A group selected from any one of wherein R ₂ to R ₉ are each independently a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and m is an integer of 1 to 4;

As a monomer of General formula (1), For example, unsaturated glycidyl ether, such as allyl glycidyl ether and 2-methylallyl glycidyl ether; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate, glycidyl methacrylate and itaconic acid glycidyl ester; Glycidyloxyalkyl (meth) acrylates such as glycidyl oxyethyl (meth) acrylate and glycidyl oxybutyl (meth) acrylate; Epoxy group-containing cycloalkylalkyl (meth) acrylates such as 3,4-epoxycyclohexylmethyl acrylate and 3,4-epoxycyclohexylmethyl methacrylate; Oxetanyl (meth) acrylate, 3-oxetanylmethyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) (Substituted) oxetanyl (meth) acrylates, such as methyl (meth) acrylate, or (substituted) oxetanyl alkyl (meth) acrylate, etc. are mentioned.

Component (A) may be a polymer obtained by addition polymerization of two or more of the present monomers.

As this monomer, the monomer of General formula (1) is preferable. Among the monomers of the general formula (1), monomers having an epoxy group and an olefin double bond are preferred, unsaturated carboxylic acid glycidyl esters and epoxy group-containing cycloalkylalkyl (meth) acrylates are more preferred, glycidyl (meth) acrylates and 3,4 Epoxycyclohexylmethyl acrylate is particularly preferred.

As a component (A), the polymer obtained by addition-polymerizing this monomer and the other monomer which has a double bond and does not have a functional group which can react with a cyclic ether group besides the polymer obtained by addition polymerization of this monomer is mentioned.

Other monomers having the double bond and no functional group capable of reacting with a cyclic ether group (hereinafter referred to as other monomers) contain at least one double bond capable of addition polymerization in a molecule, and also include a carboxylic acid group and an amino group. It is a monomer which does not contain the functional group which can react with the epoxy group of this, Among these, a (meth) acrylic-ester type monomer and / or a styrene monomer are used preferably.

As a (meth) acrylic-ester type monomer, For example, (meth) acrylic-acid linear (C1-20) alkyl esters, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate; (meth) acrylic acid (C3-20) side chain alkyl esters such as t-butyl acrylate and t-butyl methacrylate; (Meth) acrylic acid (C5-20) cycloalkyl esters, such as cyclohexyl acrylate and cyclohexyl methacrylate, etc. are mentioned.

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

As the (meth) acrylic ester monomer, a (meth) acrylic acid alkyl ester or a (meth) acrylic acid cycloalkyl ester is preferable, and a (meth) acrylic acid alkyl ester or (meth) having a linear or branched alkyl group having about 1 to 4 carbon atoms Acrylic acid cycloalkyl esters are preferred.

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

Styrene is particularly suitable as the styrene monomer.

In the case where component (A) is a polymer obtained by addition polymerization of the present monomers and the present other monomers, the structural units derived from the present monomers are usually 5 mol% or more, preferably 100 mol% of the total structural units constituting the component (A). Preferably it is 10 mol% or more, More preferably, it is 20 mol% or more. In addition, the structural unit derived from this other monomer is about 5-95 mol% normally, Preferably it is about 10-90 mol%, More preferably, it is about 20-80 mol%.

Component (A) obtained by addition polymerization of (meth) acrylic ester monomers and / or styrene monomers in the polymer obtained by addition polymerization of the present monomers and the present monomers with (meth) acrylic ester monomers and / or styrene monomers is obtained from the protective film obtained. It is preferable at the point which exists in the tendency to suppress embrittlement.

The other monomers other than the (meth) acrylic ester monomer and the styrene monomer contain one or more double bonds capable of addition polymerization in the molecule, and do not contain a functional group capable of reacting with an epoxy group such as a carboxylic acid group or an amino group. And aliphatic monomers. Examples of such aliphatic monomers include alkanic acid vinyl esters such as vinyl butyrate, vinyl propionate, vinyl pivalate, vinyl laurate, vinyl isononate, and vinyl versatate; Vinyl halides, such as vinyl chloride and vinyl bromide: vinylidene halides, such as vinylidene chloride, etc. are illustrated.

The polymer of component (A) typically is to 1 to 99mol% of the structural unit derived from a monomer forming the polymer of the component (A) is derived from a monomer having a CH ₂ = CH-, the monomer forming the polymer of 1 to 95mol% of the structural units derived from a preferably a polymer of the structural unit derived from a monomer having a CH ₂ = CH-.

If the monomer is 5 to 80 mol% of structural units derived from the monomer forming the polymer of the component (A) is having a CH ₂ = CH-, tends to improve heat resistance is particularly preferred. CH ₂ = CH- groups Specific examples of the monomer having a (meth) having no substituent in position α in the acrylic monomer acrylic monomer having no substituent in α position styrene-based monomer, an alkanoic acid vinyls or vinyl halides, allyl glycidyl ether And glycidyl acrylate.

As a manufacturing method of a component (A), the following method is mentioned, for example.

(1) J. Polym. Sci., Polym. Chem. (1968), 6 (2), 257-267], a monomer and a radical generator are mixed in an organic solvent, and then a chain transfer agent is mixed if necessary to solution polymerization at about 60 to 300 ℃ ;

(2) J. Polym. Sci., Polym. Chem. (1983), 21 (10), 2949-2960 using a solvent in which the monomer is not dissolved, suspension polymerization or emulsion polymerization at about 60 to 300 ℃;

(3) a method of bulk polymerization at about 60 to 200 ° C as described in JP-A-6-80735;

(4) The monomer to be used as described in JP-A-10-195111 is continuously supplied to a polymerizer, and is 5 to 60 at 180 to 300 ° C in the presence or absence of a polymerization initiator in the polymerizer. A method of continuously removing the reaction product obtained by heating for minutes to the outside of the polymerization reactor.

In the manufacturing method using a solvent, when using the organic solvent used as a solvent of the curable resin composition of this invention as a reaction solvent at the time of manufacture of a component (A), the process of melt | dissolving a polymer in the process after combining curable resin composition is carried out. It is preferable because it can be omitted.

As said organic solvent, For example, Alcohol, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, or cyclohexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone or 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, Ethers such as diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol or 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 di Acetate, 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 glycol monomethyl Esters such as ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate or butyrolactone; Aromatic hydrocarbons, such as toluene or xylene, etc. are mentioned.

2 or more types can be used as an organic solvent.

It is preferable not to contain the functional group which can react with cyclic ether groups, such as a free carboxyl group and an amino group, in an organic solvent.

In addition, the molecular weight per functional group of component (A) is 128 g / equivalent or more normally if epoxy equivalent is taken, Preferably it is about 150-4000 g / equivalent, More preferably, it is about 150-1000 g / equivalent. A functional group equivalent of more than 128 g / equivalent is preferable in that it tends to suppress embrittlement of the protective film obtained, while a content of less than 4000 g / equivalent tends to be excellent in chemical resistance.

Here, the excellent chemical resistance means that the surface of the protective film does not erode even when the protective film of the present invention is immersed in an acidic aqueous solution, an alkaline aqueous solution and an aprotic polar solvent for several tens of minutes, and specifically, the protective film absorbs the chemical. It is excellent in the tendency to suppress the state which swells or decompose | disassembles into a granule.

In the curable resin composition of the present invention, the weight average molecular weight (value obtained by gel permeation chromatography using polystyrene as a standard) of the component (A) is usually about 2,000 to 1,000,000, preferably about 3,000 to 500,000, and more preferably. Preferably 5,000 to 200,000.

As the component (A), for example, blender CP-50M [registered trademark, glycidyl methacrylate methyl methacrylate copolymer, manufactured by Nihon Yushi Chemical Co., Ltd.] or blender CP-50S [registered trademark] , Glycidyl methacrylate styrene copolymer, and Nippon Oil Industries, Ltd.] can be used.

Component (B) used for the curable resin composition of this invention is a curing catalyst which produces | generates an acid by heating and cationically polymerizes a cyclic ether group. As component (B), since the storage stability of curable resin composition of this invention improves further, its reaction start temperature becomes like this. Preferably it is 90 degreeC or more, More preferably, it is 105 degreeC or more.

In addition, the component (B) is not resistant to erosion even when exposed to acid or N-methylpyrrolidone or the like if the reaction start temperature thereof is preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Excellent chemical resistance (hereinafter referred to as NMP resistance).

The reaction start temperature of component (B) is an amount of the active ingredient of the thermal cationic curing catalyst excluding the solvent with respect to 100 parts by weight of liquid epoxy resin AK-601 (hexahydrophthalic acid diglycidyl ester manufactured by Nihon Kayaku Co., Ltd.). For example, when the differential scanning calorimetry (DSC) is performed at a temperature increase rate of 10 ° C./min for a sample to which 3 parts by weight is added, it is the exothermic starting temperature of the exothermic peak detected at the lowest temperature side.

As component (B), organic in which a cation component and an anion component are normally paired

Onium salt compounds are used.

As a cationic component in component (B), organic cations, such as organic sulfonium, organic oxonium, organic ammonium, organic phosphonium, or organic iodonium, are illustrated. Further, component (B) as an anion component B (C ₆ F _{5) 4} in ^{_{-, SbF 6 -, AsF 6}} -, PF 6 -, BF 4 - and the like are exemplified.

As a cation component in the component (B) used for curable resin composition of this invention, organic sulfonium is preferable and aromatic sulfonium is especially preferable. Further, as the anion component a SbF ₆ ^-, AsF ₆ ^- and PF ₆ ^- are preferable.

The ratio of component (B) in curable resin composition of this invention is 0.2-20 weight part normally per 100 weight part of component (A), Preferably it is 1-10 weight part. However, the ratio of component (B) is a ratio based on the amount of active ingredients except the solvent contained in the component (B) to add.

Moreover, when curable resin composition of this invention contains antioxidant (it describes as a component (C) hereafter) in addition to a component (A) and a component (B), the said protective film when making curable resin composition of this invention into a protective film Since the heat resistance of this improves, it is preferable.

The component (C) is preferably at least one antioxidant selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and lactone antioxidants, particularly preferably containing at least one phenolic antioxidant. Do.

As a ratio of component (C) in curable resin composition of this invention, it is 0.001-10 weight part normally per 100 weight part of component (A), Preferably it is 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, dl-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-methylphenylacrylate , 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-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-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-hydroxy Oxybenzyl) 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-octyl Thio) -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, (beta)-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester, etc. are mentioned.

Among these phenolic antioxidants, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester and 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-tetraoxaspiro [5,5] undecane is preferred.

A commercial item can be used as a phenolic antioxidant.

Examples of such commercially available phenolic antioxidants include Irganox 10O (Irganox 10O, manufactured by Ciba Specialty Chemicals), Irganox 1076 (Irganox 1076, manufactured by Ciba Specialty Chemicals), Irganox 1330 (Irganox 1330, Ciba Specialty), and the like. Chemicals), Irganox 3114 (Irganox 3114, Ciba Specialty Chemicals), Irganox 3125 (Irganox 3125, Ciba Specialty Chemicals), Sumifier BHT (Sumilizer BHT, Sumitomo Chemical), Cyanox 1790 (Cyanox 1790, product made by Cytec), Sumizer GA-80 (Sumilizer GA-80, Sumitomo Chemical Co., Ltd.), vitamin E (Ezai agent), etc. are mentioned.

As a phenolic antioxidant, 2 or more types of phenolic antioxidant can be used together.

Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl) diphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tri Phenyl phosphite, tris (butoxyethyl) phosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-t -Butyl-4-hydroxyphenyl) butane diphosphite, tetra (C12 to C15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, tris (mono-di mixed nonylphenyl) phosphite, hydrogenation- 4,4'-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis [4,4'-butylidenebis (3-methyl-6-t-butylphenol)]-1,6-hexanediol Defoss Y, phenyl (4,4'-isopropylidenediphenol) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tris [4,4'-isopropylidenebis (2-t-butylphenol)] phosphite , Di (isodecyl) phenylphosphite, 4,4'-isopropylidenebis (2-t-butylphenol) bis (nonylphenyl) phosphite, 9,10-dihydro-9-oxa-10-phosphape Nsren-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 and 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 following formula (2), the cage form of following formula (3), etc. are mentioned.

Where

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

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 phosphite esters, a mixture of a compound of Formula 2 and a compound of Formula 3 is typically used.

Here, when the R ¹ to R ⁶ is an alkyl group and is preferably a branched alkyl group, t- butyl group is particularly preferred. In addition, the substitution position of R ¹ to R ⁶ in the benzene ring is preferably 2, 4 or 6 positions.

Specific examples of the phosphite esters 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.

Moreover, as a phosphonate which has the structure which carbon and phosphorus directly couple | bonded, tetrakis (2, 4-di-t-butylphenyl) -4, 4'-biphenylene diphosphonate etc. are mentioned, for example. Can be.

A commercial item can be used as a phosphorus antioxidant.

Examples of such commercial phosphorus antioxidants include Irgafos 168 (Irgafos 168, manufactured by Ciba Specialty Chemicals), Irgafos 12 (manufactured by Ciba Specialty Chemicals), Irgafos 38 (Irgafos 38, Ciba Specialty Chemical), and the like. Zuse), Adeka stave 329K (ADK STAB 329K, Asahi Tenkaze), Adeka stab PEP36 (ADK STAB PEP36, Asahi Denkaze), Adeka stab PEP-8 (ADK STAB PEP-8, Asahi Denkaze ), Sandstar P-EPQ (product made in Sandstab P-EPQ, Clariant), Weston 618 (Weston 618, GE product), Weston 619G (Weston 619G, GE product), Ultra Knox 626 (Ultranox 626, GE product) ) And Sumiizer GP (Sumi1izer GP, Sumitomo Chemical Co., Ltd.) etc. are mentioned.

As phosphorus antioxidant, 2 or more types of phosphorus antioxidant can be used together.

Among the phosphorus antioxidants are tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphonate, distearyl 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] -2,4,8,10- Tetra-t-butyldibenz [d, f] [1.3.2] -dioxaphosphine is preferred.

As a sulfur type antioxidant, For example, Dialkylthio dipropionate, such as a dilauryl thiodipropionate, a dimyristyl thiodipropionate, a distearyl thiodipropionate; Polyhydric alcohol esters of butylthiopropionic acid, polyhydric alcohol esters of octylthiopropionic acid, polyhydric alcohol esters of laurylthiopropionic acid, polyhydric alcohol esters of stearylthiopropionic acid (as the above-mentioned polyhydric alcohols, for example, glycerin, trimethylol ethane, And polyhydric alcohol esters of alkylthiopropionic acids such as trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate, and the like) and pentaerythryl tetrakis-3-laurylthiopropionate. .

Examples of sulfur-based antioxidants include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate and distearyl thiodibutylate. And pentaerythryl tetrakis-3-laurylthiopropionate.

Among these, pentaerythryl tetrakis-3-laurylthiopropionate is particularly preferable.

Commercially available sulfur-based antioxidants include, for example, Smizerizer TPS (Sumilizer TPS, Sumitomo Chemical Co., Ltd.), Smizerizer TPL-R (Sumilizer TPL-R, Sumitomo Chemical), and Sizerizer TPM (Sumilizer TPM, Sumitomo Chemical Co., Ltd., Sumizer TP-D (Sumi1izer TP-D, Sumitomo Chemical Co., Ltd.), etc. are mentioned.

As sulfur type antioxidant, 2 or more types of sulfur type antioxidant can be used together.

As a lactone antioxidant, HP-136 (made by Ciba Specialty Chemicals) etc. which are commercial items are mentioned, for example.

As a lactone antioxidant, 2 or more types of lactone antioxidant can be used together.

In addition, if curable resin composition of this invention contains the oxetane compound (it describes as a component (D) below) of molecular weight less than 2000 in addition to the component (B) and the component (A) whose weight average molecular weight is 2000 or more, Since the heat resistance of the said protective film improves when making curable resin composition of this invention a protective film, it is preferable.

Component (D) is an oxetane compound having a molecular weight of less than 2000 having at least one oxetanyl group in the molecule.

Examples of the oxetane compound having a molecular weight of less than 2000 include 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3- (phenoxymethyl) oxetane and 3-ethyl-3- (2-ethylhexyl Oxymethyl) 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 these, 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- Oxetane compounds having two or more oxetanyl groups in the molecule are preferable, such as oxetanyl) methoxy] biphenyl and bisphenol novolac oxetane. 1,3-bis {(1-ethyl-3-oxetanyl) methoxy} benzene, 4,4 '-[(3-ethyl-3-oxetanyl) methoxy] biphenyl, bisphenol novolac An aromatic phenolic oxetane compound such as oxetane is preferable in view of heat resistance. In the component (D), the molecular weight means a weight average molecular weight (a value obtained by gel permeation chromatography using polystyrene as a standard product) when the component (D) is a polymer having a molecular weight distribution, and does not have a molecular weight distribution. In this case, the conventional molecular weight means the sum of the atomic weights of the atoms constituting the molecule.

As a ratio of a component (D) in curable resin composition of this invention, it is about 1 to 50% normally with respect to the sum total of a component (A) and a component (D), Preferably it is about 5 to 25%.

Moreover, it is more preferable to contain both a component (C) and a component (D) in curable resin composition of this invention.

The curable resin composition of the present invention usually contains an organic solvent, in which component (A) and component (B) and, if necessary, further dissolve component (C) and / or component (D). The composition of the state is used. As an organic solvent used, the thing similar to the organic solvent illustrated by manufacture of component (A) is mentioned. As an organic solvent, 2 or more types of organic solvent can be mixed and used.

Among the organic solvents described above, solvents having no functional group capable of reacting with cyclic ether groups such as free carboxyl groups and amino groups are preferable.

In addition, it is preferable to contain at least 1 type of surfactant chosen from the group which consists of a silicone type surfactant, a fluorine type surfactant, and a silicone type surfactant which has a fluorine atom in curable resin composition of this invention.

As said silicone type surfactant, brand name tresilicone DC3PA, tresilicone SH7PA, tresilicone DC11PA, tresilicone SH21PA, tresilicone SH28PA, tresilicone 29SHPA, or tresilicone SH30PA (made by tresilicone); Polyether modified silicone oil SH8400 [manufactured by Tresilicon Co., Ltd.]; Trade names KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (manufactured by Shin-Etsu Silicone Co., Ltd.); Trade names TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by JI TOSHIBA Silicone Co., Ltd.).

Examples of the fluorine-based surfactants include Florinate® FC430 and Florinate FC431 (manufactured by Sumitomo Chemical Co., Ltd.); MegaPak® F142D, MegaPak F171, MegaPak F172, MegaPak F173, MegaPak F177, MegaPak F183 or MegaPak R30 (manufactured by Dainiphon Ink Chemical Co., Ltd.); F-top (trademark) EF301, F-top EF303, F-top EF351, and F-top EF352 (made by Shin-Akiga Chemical Co., Ltd.); Saffron (registered trademark) S381, saffron S382, saffron SC101 and saffron SC105 (manufactured by Asahi Glass Co., Ltd.); Trade name E5844 [manufactured by Daikai Chemical Co., Ltd.]; Trade names BM-1000 and BM-1100 (manufactured by BM Chemie).

Examples of the silicone-based surfactant having a fluorine atom include MegaPak® R08, MegaPark BL20, MegaPak F475, MegaPak F477, and MegaPak F443 (manufactured by Dainiphon Ink Chemical Co., Ltd.).

These surfactant can be used individually or in combination of 2 or more types.

Moreover, other surfactant, such as an acrylic polymer type surfactant and a vinyl polymer type surfactant, can be used together with curable resin composition of this invention.

As the acrylic polymer-based surfactant, Dispalon (registered trademark) OX-880, Dispalon OX-881, Dispalon OX-883, Dispalon OX-70, Dispalon OX-77, Dispalon OX-77HF, Dispalon OX- 60, Dispalon OX-710, Dispalon OX-720, Dispalon OX-740, Dispalon OX-750, Dispalon OX-8040, Dispalon 1970, Dispalon 230, Dispalon L-1980-50, Dispalon L-1982-50, Dispalon L-1983-50, Dispalon L-1984-50, Dispalon L-1985-50, Dispalon LAP-10, Dispalon LAP-20, Dispalon LAP-30 or Dispalon LHP-95 [Kusumoto Kasei Co., Ltd.]; Brand names BYK-352, BYK-354, BYK-355, BYK-356, BYK-357, BYK-358, BYK-359, BYK-361, and BYK-390 (manufactured by Big Chemi Japan Co., Ltd.); Efka (trademark) LP3778 (made by Efka Chemicals), etc. are mentioned.

Examples of the vinyl polymer-based surfactants include Dispalon® 1922, Dispalon 1927, Dispalon 1950, Dispalon 1951, Dispalon P-410, Dispalon P-410HF, Dispalon P-420, Dispalon P-425, Dispalon PD-7 and Dispalon LHP-90 (manufactured by Kusumoto Chemical Co., Ltd.).

Moreover, another cationically curable compound can be mixed with the curable resin composition of this invention, unless the storage stability of the curable resin composition of this invention and the chemical-chemical resistance of the protective film obtained by thermosetting the said composition are impaired. As a cation curable compound which can be mixed, For example, epoxy resins, such as an aromatic epoxy resin, a hydrogenated aromatic epoxy resin, an aliphatic epoxy resin, the glycidyl ester of carboxylic acid, a spiro ring containing epoxy resin, or an alicyclic epoxy resin; Oxetane resins; Cyclic lactones and cyclic carbonates; Spirorthoesters; Spirorthocarbonates; Vinyl ethers; Polyols; and the like.

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

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

Examples of the aliphatic epoxy resins include butyl glycidyl ether, 1,6-hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and polypropylene glycol di. Glycidyl ether, trimethylolpropanetriglycidyl ether, and the like.

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

As said spiro ring containing epoxy resin or alicyclic epoxy resin, it is 3, 4- epoxycyclohexyl methyl-3, 4- epoxy cyclohexane carboxylate, (epsilon) -caprolactone modified 3, 4- epoxy cyclohexyl methyl, for example. -3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexyl) adipate, or 1,2: 8,9-diepoxylimonene.

Examples of the polyols include polycaprolactone diol, polycaprolactone triol, polycaprolactone polyol, polyester diol, polyester triol, polyester polyol, polycarbonate diol, polycarbonate triol, polycarbonate polyol, and the like. Can be mentioned.

As a mixing ratio of cation curable compounds other than a component (A), about 100 weight part of cation curable compounds other than a component (A) is about 100 weight part or less normally with respect to 100 weight part of components (A). Preferably it is 50 weight part or less.

In the present invention, two or more kinds of cationically curable compounds may be used as the cationically curable compound other than the component (A).

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

Curable resin composition of this invention is a method of manufacturing a component (A) in an organic solvent, for example, and then adding a component (B) and other components suitably; Component (A) is prepared in an organic solvent and the organic solvent is removed to obtain a polymer, followed by dissolving component (A), component (B) and other components in a solvent.

Thus, the protective film of this invention can be obtained by apply | coating curable resin composition obtained to the to-be-adhered body (for example, base material which needs protection, such as a glass substrate and a color filter substrate), and heating.

As the coating method in the present specification, for example, a method using a spin coater, a slit coater, a bar coater, a spray coater, a roll coater, flexo printing, offset printing, or the like and a slit and spin coating The method which combined 2 or more types of coating methods, such as group, a bar and spin coating machine, etc. is mentioned.

As the heating method, for example, a heating plate, a clean oven, an infrared heating device or the like is used, and is usually 150 ° C. or higher, preferably 190 to 260 ° C., more preferably 220 to 250 ° C. for 10 to 120 minutes. The heating method 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 hardened | cured material will hardly be colored that heating temperature is 260 degrees C or less, it is preferable.

Insulate the solvent at a temperature of room temperature to 150 ° C, preferably 50 to 120 ° C under atmospheric pressure or reduced pressure for 0.5 to 5 minutes to remove the solvent, and then to 150 ° C or more using the heating plate, clean oven, or infrared heater. The method of heating is also preferable.

In addition, the thickness of the obtained protective film is usually about 0.07 to 20 µm, and in such a range, the physical properties of the protective film, in particular, flattening and surface strength tend to be excellent.

The curable resin composition of this invention is apply | coated to a to-be-adhered body, an organic solvent is removed, the film which has adhesiveness is produced, it is paste | laminated to the base material which needs protection, it is thermosetted, and can be used as the protective film of this invention. The adherend can be peeled off after heat curing the film pasted onto the substrate or before heat curing. Here, as a to-be-adhered body, the release paper by which the silicone mold release agent or the fluorine mold release agent was apply | coated to the surface which contact | connects the layer which consists of polyolefin films, such as a film which consists of 4-methyl-1- pentene copolymer, a cellulose acetate film, and curable resin composition, for example. And a release polyethylene terephthalate (PET) film.

Moreover, another resin or base material can be further laminated | stacked on the film which has adhesiveness before thermosetting as needed.

The material of the substrate is usually a material that can be adhered to the protective film of the present invention.

Specific examples of the material for the base material include metals such as gold, silver, copper, iron, tin, lead, aluminum and silicon; Inorganic materials such as glass and ceramics; Cellulose polymer materials such as paper and textiles; Synthetic polymer materials such as melamine resin, acrylic urethane resin, urethane resin, (meth) acrylic resin, styrene acrylonitrile copolymer, polycarbonate resin, phenol resin, alkyd resin, epoxy resin and silicone resin Can be heard.

As the substrate, two or more different materials can be mixed or combined.

The base material can be subjected to a coating film treatment with a coating film made of a resin composition other than the present invention or a coating film such as a release agent or plating, if necessary, and surface treatment such as surface modification, surface oxidation, etching, etc. by plasma or laser. Can be carried out.

As the substrate, electronic circuits such as integrated circuits, printed wiring boards, liquid crystal display devices, solid-state imaging devices, color filters, etc. which are composite materials of synthetic polymer materials and metals are preferably used.

Hereinafter, although an Example etc. demonstrate this invention in detail, this invention is not limited by these examples. The parts in the examples mean parts by weight unless otherwise specified.

The following polymer is used as component (A).

A1: Blenmer CP-50S [registered trademark, manufactured by Nihon Yushi Co., Ltd.] (glycidyl methacrylate-styrene copolymer, epoxy equivalent = 292, Mw = 19000)

A2: Blenmer CP-50M (registered trademark, manufactured by Nihon Yushi Co., Ltd.) (glycidyl methacrylate-methyl methacrylate copolymer, epoxy equivalent = 297, Mw = 8200)

A3: polymer prepared by the following preparation example

<Production Example of Polymer A3>

165 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) was added to a four-necked flask, and the temperature was raised to 80 ° C under stirring under a stream of nitrogen.

81 parts of (3-ethyl-3-oxetanyl) methacrylate, 111 parts of cyclohexyl methacrylate, and 192 parts of PGMEA were added to a separate container, and 4 parts of 2,2-azobisisobutyronitrile were added and dissolved at room temperature. To obtain a solution. This solution is then added dropwise over 1 hour while maintaining the liquid temperature in the four neck flask at 80 to 90 ° C. After completion of the dropwise addition, the temperature is kept at the temperature for 3 hours. After the end of the thermal insulation, a PGMEA solution of (3-ethyl-3-oxetanyl) methylmethacrylate-cyclohexylmethacrylate copolymer having a weight ratio of solid components except PGMEA is 35% is obtained. The weight average molecular weight of the polymer is 15000 (value obtained by gel permeation chromatography using polystyrene as a standard) in terms of polystyrene.

The obtained PGMEA solution was again diluted with PGMEA to give polymer A3 with a solid component concentration of 25%.

As component (B), the following is used.

B1: Adeka Offton CP-66 [registered trademark, product made by Asahi Denka Kogyo Co., Ltd.]

Propylene carbonate solution containing 66% 2-butenyltetramethylenesulfonium hexafluoroantimonate

B2: Adeka Offton CP-77 (registered trademark, manufactured by Asahi Denka Kogyo Co., Ltd.)

Propylene carbonate solution containing 66% 3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimonate

B3: Adeka Optomer SP-150 (registered trademark, manufactured by Asahi Denka Kogyo Co., Ltd.)

Propylene carbonate solution containing 50% of 4,4-bis [di- (β-hydroxyethoxy) phenylsulfonio] -phenylsulfide-bis-hexafluorophosphate

B4: Sunaid SI-60L [32% solution of Sanshin Chemical Co., Ltd., aromatic sulfonium, SbF ₆ ^- salt]

B5: Sunade SI-80L [49% solution of Sanshin Chemical Co., Ltd., aromatic sulfonium, SbF ₆ ^- salt]

B6: Sunaid SI-100L [49% solution of aromatic sulfonium SbF ₆ ^- salt made by Sanshin Chemical Co., Ltd.]

B7: Sun-Aid SI-110L [A 49% solution of aromatic sulfonium PF ₆ ^- salt made by Sanshin Chemical Co., Ltd.]

B8: CI-2624 [50% γ-butyrolactone solution of aromatic sulfonium SbF ₆ ^- salt, manufactured by Nihon Soda Co., Ltd.]

B9: CI-2639 (50% γ-butyrolactone solution of Nippon Soda Co., Ltd., aromatic sulfonium PF ₆ ^- salt)

The reaction start temperature of component (B) is measured as follows.

A sample obtained by adding an amount of 3 parts of the active ingredient except for the solvent of the thermal cation curing catalyst to 100 parts of liquid epoxy resin AK-601 [hexahydrophthalic acid diglycidyl ester, manufactured by Nihon Kayaku Co., Ltd.] was added. The lowest temperature side is added to a 10 mg aluminum pan and measured at an elevated temperature rate of 10 ° C / min per minute using an EXSTAR 6000 DSC 6200 type differential scanning calorimetry (DSC) device manufactured by Seiko Instruments Co., Ltd. The exothermic onset temperature of the exothermic peak observed at is measured.

The reaction start temperature of the component (B) measured as mentioned above is shown in Tables 2-3.

As the component (C), the following are used.

C1: Irganox 1010 [phenol-type antioxidant] made by Ciba Specialty Chemicals

C2: Irgafos 168 [phosphorus antioxidant] made by Ciba Specialty Chemicals

C3: Sumitizer TP-D [sulfur antioxidant] made by Sumitomo Chemical Co., Ltd.

As the component (D), the following are used.

D1: 1, 3-bis {(1-ethyl-3- oxetanyl) methoxy} benzene [Toga Seisakusho make, brand name: alon oxetane RSOX)

Examples 1-15

<Production Example of Curable Resin Composition>

100 parts of components (A) shown in Tables 2 and 3 and 3 parts of active ingredients except the solvent of the components (B) shown in Tables 3 are dissolved in 400 parts of PGMEA to obtain a curable resin composition.

A part of curable resin composition provides for the following storage stability test.

<Storage stability test>

The viscosity at 23 degreeC (henceforth an initial viscosity) is measured for the curable resin composition obtained by said manufacture example using the Toki Sangyo TV-30L type | mold viscosity meter (N0.1 rota).

Next, the curable resin composition is kept sealed for 10 days in an incubator at 23 ° C. Thereafter, the viscosity after storage (hereinafter referred to as storage viscosity) is measured in the same manner as the initial viscosity.

Storage stability is evaluated as (circle) when the viscosity change rate (%) calculated | required by following formula (1) is less than +/- 10%, (triangle | delta) when +/- 10 to 20%, and x when it is larger than +/- 20%. The results are shown in Tables 2-4.

Viscosity Change Rate (%) = [Storage Viscosity-Initial Viscosity] x 100 / [Initial Viscosity]

<Production Example of Protective Film>

The curable resin composition obtained in the preparation example of the curable resin composition is spin-coated on the slide glass as it is, and baked in a heat drying furnace at 85 ° C. for 2 minutes to remove the solvent. Subsequently, it heats for 40 minutes in 200 degreeC heat curing furnace, and obtains a protective film. It was 2-3 micrometers when the film thickness of such a protective film was measured by the contact type thickness gage.

<Chemical resistance test>

The protective films (three) obtained in the preparation example of a protective film are immersed in the immersion liquid shown in Table 1, respectively, for the time shown in Table 1. Next, the film thickness of the protective film is measured, and the residual film rate is obtained by the following formula (2) to evaluate acid resistance, alkali resistance and NMP resistance.

Residual film ratio (%) = [film thickness after immersion / film thickness before immersion] × 100

In the determination of the alkali resistance test, the above-described residual film ratio within the range of 100 ± 5% is ○ and 100 ± 5% is said to be x. The results are shown in Tables 2-3.

However, about the protective film of Example 9, when an acid resistance or NMP resistance test is performed, a protective film will decompose into a granule and a film thickness cannot be measured, and it describes in Table 3 as "peeling."

Comparative Example 1

100 parts of A2, 33 parts of trimellitic anhydride (curing agent) and 2 parts of cursol 1B2MZ (a curing accelerator made by Shikoku Chemical Co., Ltd., 1-benzyl-2-methylimidazole) are dissolved in 450 parts of PGMEA. To obtain a curable resin composition.

This curable resin composition is subjected to a storage stability test but gelled for 10 days as described in Table 4.

Comparative Example 2

100 parts of A2, 50 parts of HN-5500 (hardener made by Hitachi Chemical Co., Ltd., methylhexahydrophthalic anhydride), and curing agent 2E4MZ (hardening accelerator made by Shikoku Chemical Co., Ltd.), 2-ethyl-4 2-methylimidazole) is dissolved in 450 parts of PGMEA to obtain a curable resin composition. This curable resin composition is provided to a storage stability test.

The results are shown in Table 4.

From the obtained curable resin composition, a protective film is prepared in the same manner as above and used for chemical resistance testing in the same manner as above.

The results are shown in Table 4.

Examples 16 and 17

In the same manner as in Examples 1 to 15, 100 parts of the component (A) described in Table 5 and 3 parts of the active ingredient except for the solvent of the component (B) described in Table 5 were dissolved in 400 parts of PGMEA to obtain a curable resin composition. .

The obtained curable resin composition was spin-coated on slide glass in the same manner as in Examples 1 to 15 and baked in a heat drying furnace at 85 ° C. for 2 minutes to remove the solvent. Subsequently, it heats for 40 minutes in 200 degreeC or 230 degreeC heat curing furnace, and obtains a protective film. It was 2-3 micrometers when the protective film measured the film thickness with the contact thickness meter.

<Heat resistance test>

The protective film obtained above was heated at 250 ° C. for 1 hour, and then the film thickness of the protective film was measured. Subsequently, the residual film rate is calculated by the following Equation 3 to evaluate the heat resistance of the protective film.

The results are shown in Table 5.

Residual film ratio (%) = [film thickness after heating / film thickness before heating] × 100

In addition, evaluation of heat resistance is described as "heat resistant residual film ratio."

<Heat resistance transparency test>

Using a protective film treated under the same heating conditions as the above heat resistance test, using a V-560 spectrophotometer manufactured by Nippon Bunko Co., Ltd., the lowest transmittance was obtained at 400 to 700 nm. The results are shown in Table 5.

Examples 18-20

<Production Example of Curable Resin Composition>

480 parts of propylene glycol monomethyl ether acetate (PGMEA) was added in an amount of 3 parts of the thermal cationic curing catalyst (active ingredient) excluding 100 parts of the component (A) shown in Table 6 and the solvent of the component (B) shown in Table 6. After dissolving, antioxidant (component (C)) is added to obtain a curable resin composition.

In addition, a part of curable resin composition is given to the following storage stability test.

<Storage stability test>

The curable resin composition obtained in the above preparation was kept in an incubator at 23 ° C. for 10 days, and then for a composition having a change in viscosity (%) of less than ± 10%, a change of ○, ± 10 to 20% was observed. About the composition shown, (triangle | delta), the composition which shows a change larger than +/- 20% is evaluated as x.

The results are shown in Table 6.

<Production Example of Protective Film>

The curable resin composition before providing to the storage stability test was spin-coated on slide glass and baked in a heat drying furnace at 85 ° C. for 2 minutes to remove the solvent, and then heated in a heat curing furnace at 230 ° C. for 40 minutes to obtain a protective film. It was 1.5-2.0 micrometers when the film thickness of such a protective film was measured using the contact type thickness meter.

<Chemical resistance test>

Each of the three protective films obtained above was used, and chemical resistance tests were conducted in the same manner as in Examples 1 to 15, and acid resistance, alkali resistance and NMP resistance were evaluated.

The results are shown in Table 6.

<Heat resistance test>

Using the protective film obtained above, the heat resistance test was carried out in the same manner as in Examples 16 to 17 to evaluate the heat resistance.

The results are shown in Table 6.

<Heat resistance transparency test>

The heat resistance transparency test was carried out in the same manner as in Examples 16 to 17 using the protective film heat-treated under the same conditions as the above heat resistance test to evaluate the transmittance.

The results are shown in Table 6.

In Table 6, the transmittance is referred to as "heat resistance transmittance".

<Checker board peeling test>

Using a protective film heat-treated under the same conditions as the heat resistance test above, a cutter knife and a cross-cut gauge are scratched at 1 mm intervals on a checkerboard scale and a tape peeling test is performed.

Peeling state is determined based on JIS K5400 8.5.1 Table 18.

The results are shown in Table 6.

Examples 21 and 22

<Production Example of Curable Resin Composition>

80 parts of the Al component, 20 parts of the D1 component, and B7 components shown in Table 7 were dissolved in 480 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) in an amount of 3 parts by weight of the active ingredient excluding the solvent. Furthermore, C1 component is added and curable resin composition is obtained.

A part of curable resin composition provides for the following storage stability test.

<Storage stability test>

Using the curable resin composition obtained in the above Preparation Example, the storage stability test was carried out by the same method and evaluation as in Examples 18 to 20.

The results are shown in Table 7.

<Production Example of Protective Film>

The protective film is obtained by the same method as Examples 18-20 using curable resin composition before providing to a storage stability test. It was 1.5-2.0 micrometers when the film thickness of such a protective film was measured using the contact type thickness meter.

<Chemical resistance test>

Using three protective films obtained above, chemical resistance tests were carried out in the same manner as in Examples 1 to 15, and acid resistance, alkali resistance and NMP resistance were evaluated.

The results are shown in Table 7.

<Heat resistance test>

Using the protective film obtained above, the heat resistance test was carried out in the same manner as in Examples 16 to 17 to evaluate the heat resistance.

The results are shown in Table 7.

<Heat resistance transparency test>

The heat resistance transparency test was carried out in the same manner as in Examples 16 to 17 using the protective film heat-treated under the same conditions as the above heat resistance test, and the transmittance was evaluated.

The results are shown in Table 7.

In Table 7, the transmittance is referred to as "heat resistance transmittance".

Curable resin composition of this invention is excellent in storage stability. Moreover, curable resin composition of this invention provides the protective film excellent in alkali resistance.

And the curable resin composition of this invention whose reaction start temperature of a component (B) is the range of 90-200 degreeC improves storage stability further.

In addition, the protective film obtained from the curable resin composition has acid resistance in addition to alkali resistance, and also has excellent chemical resistance to aprotic polar solvents (N-methylpyrrolidone and the like).

Moreover, when a protective film is manufactured using curable resin composition containing a component (C) in addition to a component (A) and a component (B), its heat resistance also improves.

In addition to the component (B) and the component (A) having a weight average molecular weight of 2000 or more, when the protective film is produced using the curable resin composition containing the component (D), its heat resistance is also improved.

Since curable resin composition of this invention is excellent in storage stability, even when a large application | coating is required, operability is not impaired.

In addition, the protective film of the present invention, from the excellent properties thereof, for example, a flattening film, a protective film, an antireflection film in a liquid crystal display device, a solid-state imaging device and a color filter; Electronic components such as insulating materials and solder resists; varnish; It is suitably used for an adhesive or the like.

Claims (13)

Polymer (A) obtained by addition polymerization of at least one monomer having a cyclic ether group and an olefin double bond or by addition polymerization of the monomer with another monomer having a double bond and not having a functional group capable of reacting with a cyclic ether group And a curable resin composition containing a thermal cationic curing catalyst (B). The curable resin composition according to claim 1, wherein the cyclic ether group is an epoxy group and / or an oxetanyl group. The curable resin composition according to claim 1 or 2, wherein the component (A) is a polymer obtained by addition polymerization of a monomer having a cyclic ether group and an olefin double bond with a (meth) acrylic monomer and / or a styrene monomer. The curable resin composition according to any one of claims 1 to 3, wherein the monomer having a cyclic ether group and an olefin double bond is glycidyl (meth) acrylate. Any one of claims 1 to 4 according to any one of wherein the component (A) to the structural unit 1 to a curable resin composition having 99mol% is CH ₂ = CH- a group of the structural unit to form. The differential scanning calorimetry according to any one of claims 1 to 5, wherein a mixture of 3 parts by weight of the thermal cationic curing catalyst (B) and 100 parts by weight of hexahydrophthalic acid diglycidyl ester is heated at a temperature increase rate of 10 ° C / min. Curable resin composition whose reaction start temperature of a component (B) is the range of 90-200 degreeC when the exothermic start temperature of the exothermic peak detected at the lowest temperature side is made into the reaction start temperature of a thermal cation curing catalyst (B). Curable resin composition of any one of Claims 1-6 which further contains antioxidant (C). The curable resin composition according to claim 7, wherein component (C) is at least one antioxidant selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and lactone antioxidants. Curable resin composition in any one of Claims 1-8 whose weight average molecular weights of a component (A) are 2000 or more. Curable resin composition of Claim 9 which further contains the oxetane compound (D) whose molecular weight is less than 2000. Curable resin composition of Claim 10 whose component (D) is an aromatic phenol oxetane compound whose molecular weight is less than 2000. The protective film obtained by thermosetting the curable resin composition of any one of Claims 1-11 at 190 degreeC or more. The protective film formed by apply | coating curable resin composition of any one of Claims 1-11 to a to-be-adhered body, and thermosetting.