JP2010126654A - Copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copolymer that can give cured products excellent in adhesiveness to a base material, as well as excellent in heat resistance, chemical resistance, especially in the resistance against heat-coloring. <P>SOLUTION: The copolymer includes at least a monomer unit corresponding to a vinyl monomer A having a blocked isocyanate group represented by formula (1): CH<SB>2</SB>=C(-R<SP>1</SP>)-COO-R<SP>2</SP>-NHCO-R<SP>3</SP>, wherein R<SP>1</SP>is hydrogen atom or methyl, R<SP>2</SP>is a bivalent 1-8C saturated aliphatic hydrocarbon, R<SP>3</SP>indicates a residue of a blocking agent R<SP>3</SP>H of an isocyanate group, a monomer unit corresponding to a vinyl monomer B having a carboxyl group or an acid anhydride group, and a monomer unit corresponding to a specified (meth)acrylate C having a 16-25C hydrocarbon group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a copolymer having an isocyanate group blocked in a side chain, a carboxyl group or an acid anhydride group, and a hydrocarbon group having 16 to 25 carbon atoms. The copolymer of the present invention can be used for paints, coating agents, adhesives, electronic materials (protective films, sealing materials, etc.) and the like.

  Conventionally, as a composition that can be cured by heat or light to form a cured coating film, a curable resin composition containing a polymer having an epoxy group in the side chain, a curable composition containing a polymer having an isocyanate group in the side chain A curable resin composition in which an acid, a base, an organometallic catalyst, or the like is added to a resin composition or a polymer containing an alkoxysilane group is known. However, cured coatings obtained from these curable resin compositions do not satisfy all required performance such as curability, adhesion to substrates, film strength, heat resistance, chemical resistance, and storage stability. Can not.

  JP-A-1-123817 discloses a copolymer comprising an alkoxysilane group-containing vinyl monomer and an oxirane group-containing vinyl monomer as monomer components for the purpose of improving the physical properties of a cured product. Discloses a curable composition containing a chelate compound and a compound having a polyfunctional alicyclic oxirane group. According to this curable composition, crosslinking at a low temperature is possible, and a cured product excellent in various physical properties can be obtained. However, the cured coating film obtained from this curable composition has insufficient performance with respect to chemical resistance, particularly alkali resistance.

  Japanese Patent Application Laid-Open No. 2007-177041 proposes a curable resin composition containing a polymer having a block-type isocyanate group in which the reactivity of the isocyanate group is suppressed and the storage stability is improved. According to this curable resin composition, a cured product having excellent physical properties can be obtained without any problem in the long-term storage stability of the polymer. However, the cured coating film obtained from this curable resin composition also has insufficient performance for adhesion to a substrate, heat resistance, and chemical resistance, which are required in recent years.

JP-A-1-123817 JP 2007-177041 A

  An object of the present invention is to provide a copolymer that provides a cured product that is excellent in adhesion to a substrate and that is excellent in heat resistance, chemical resistance, and particularly in heat-resistant coloring.

  As a result of intensive studies to achieve the above object, the present inventors have found that a vinyl monomer having a blocked isocyanate group, a vinyl monomer having a carboxyl group or an acid anhydride group, and carbonization having 16 to 25 carbon atoms. When a curable resin composition containing a copolymer with a (meth) acrylic acid ester containing a hydrogen group is applied to a substrate and cured, it has excellent adhesion to the substrate, as well as heat resistance, chemical resistance, In particular, the inventors have found that a cured coating film excellent in heat-resistant colorability can be obtained, and completed the present invention.

（式中、Ｒ¹は水素原子又はメチル基を示し、Ｒ²は炭素数１〜８の２価の脂肪族飽和炭化水素基を示す。Ｒ³はイソシアネート基のブロック剤Ｒ³Ｈの残基を示す）
で表されるブロックされたイソシアネート基を有するビニル単量体Ａに対応するモノマー単位と、カルボキシル基又は酸無水物基を有するビニル単量体Ｂに対応するモノマー単位と、下記式（２）

（式中、Ｒ⁴は水素原子又はメチル基を示し、Ｒ⁵は炭化水素基置換オキシ基を有していてもよい炭素数１６〜２５の炭化水素基を示す）
で表される（メタ）アクリル酸エステルＣに対応するモノマー単位を少なくとも含む共重合体を提供する。 That is, the present invention provides the following formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. R ³ is a residue of an isocyanate group blocking agent R ³ H. Indicate)
A monomer unit corresponding to the vinyl monomer A having a blocked isocyanate group, a monomer unit corresponding to the vinyl monomer B having a carboxyl group or an acid anhydride group, and the following formula (2):

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydrocarbon group having 16 to 25 carbon atoms which may have a hydrocarbon-substituted oxy group)
A copolymer containing at least a monomer unit corresponding to (meth) acrylic acid ester C represented by the formula:

（式中、Ｒ⁸は水素原子又はメチル基を示し、Ｒ⁹は炭化水素基置換オキシ基を有していてもよい炭素数１〜１５の炭化水素基を示す）
で表される（メタ）アクリル酸エステルＤ、芳香族ビニル化合物Ｅ、ヒドロキシル基含有単量体Ｆ、及び３〜５員の環状エーテル基を有するビニル単量体Ｇからなる群より選択された少なくとも１種の単量体に対応するモノマー単位を含んでいてもよい。 In addition to the monomer unit corresponding to the vinyl monomer A, the monomer unit corresponding to the vinyl monomer B, and the monomer unit corresponding to the (meth) acrylic ester C, the copolymer has the following formula (3):

(Wherein R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents a hydrocarbon group having 1 to 15 carbon atoms which may have a hydrocarbon group-substituted oxy group)
At least selected from the group consisting of (meth) acrylic acid ester D, aromatic vinyl compound E, hydroxyl group-containing monomer F, and vinyl monomer G having a 3- to 5-membered cyclic ether group A monomer unit corresponding to one kind of monomer may be included.

  By curing the curable resin composition containing the copolymer of the present invention, a cured product (cured film, etc.) having high adhesion to a base material and a substrate and excellent in heat resistance and chemical resistance. Obtainable. Moreover, the curable resin composition containing the copolymer of this invention is excellent also in sclerosis | hardenability and storage stability. Therefore, it can be used as a paint, a coating agent, an adhesive, and the like, and can be suitably used particularly in the field of electronic materials.

  The copolymer of the present invention is a monomer unit (repeatedly) corresponding to a vinyl monomer A having a blocked isocyanate group represented by the above formula (1) (hereinafter sometimes referred to as “block isocyanate group”). A structural unit), a monomer unit corresponding to a vinyl monomer B having a carboxyl group or an acid anhydride group (repeating structural unit), and a (meth) acrylic acid ester C represented by the formula (2). It contains at least a monomer unit (repeating structural unit). The blocked isocyanate group is deblocked by heat to produce an active isocyanate group. When the curable resin composition containing the copolymer is cured by heat or active energy rays, the isocyanate group and the carboxyl group or the acid anhydride group contribute to the curing, and various physical properties, in particular, substrate adhesion, heat resistance Gives a cured product with excellent properties and chemical resistance. Further, by including a monomer unit corresponding to (meth) acrylic acid ester C, a cured product with even more flexibility can be obtained.

In the monomer A represented by the formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. R ³ represents a residue of an isocyanate group blocking agent R ³ H.

Examples of the divalent saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ² include linear chains such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene groups. Or a branched divalent saturated aliphatic hydrocarbon group (alkylene group). Among these, C2-C4 bivalent saturated aliphatic hydrocarbon groups, such as ethylene, trimethylene, and a propylene group, are preferable.

As the isocyanate group blocking agent R ³ H, known isocyanate group blocking agents can be used. For example, formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, methylisobutylketoxime, diethylketoxime, cyclohexanone oxime, Oxime-based blocking agents such as diacetyl monooxime and benzophenone oxime; pyrazole-based blocking agents such as 3,5-dimethylpyrazole; alcohol-based blocking agents such as methanol and ethanol; phenol-based blocking agents such as phenol and cresol; butyl mercaptan and the like Mercaptan block agents; acid amide block agents such as acetanilide, ε-caprolactam, γ-butyrolactam; active methyles such as dimethyl malonate and methyl acetoacetate Imide block agents such as succinimide and maleic imide; urea block agents; carbamic acid block agents such as phenyl N-phenylcarbamate; amine block agents such as diphenylamine and aniline; ethyleneimine And imine-based blocking agents such as polyethyleneimine.

  As the isocyanate group blocking agent, a highly stable blocking agent which does not cause gelation in the production line of the curable resin composition is preferable. The deblocking temperature of the blocking agent is, for example, 100 to 300 ° C, preferably 150 to 250 ° C. Of the above blocking agents, oxime blocking agents and pyrazole blocking agents are preferred.

（式中、Ｒ⁶、Ｒ⁷は、同一又は異なって、炭素数１〜８のアルキル基を示す。Ｒ⁶及びＲ⁷は、互いに結合して、隣接する炭素原子とともに環を形成してもよい）
で表されるオキシム系ブロック剤が含まれる。 Particularly preferred blocking agents include the following formula (4)

Wherein R ⁶ and R ⁷ are the same or different and each represents an alkyl group having 1 to 8 carbon atoms. R ⁶ and R ⁷ may be bonded to each other to form a ring with adjacent carbon atoms. Good)
The oxime block agent represented by these is included.

Examples of the alkyl group having 1 to 8 carbon atoms in R ⁶ and R ⁷ include straight chain such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl group and the like. Or a branched alkyl group is mentioned. Among these, a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, and propyl groups is preferable. Examples of the ring in which R ⁶ and R ⁷ are bonded to each other together with adjacent carbon atoms include, for example, about 3 to 12 membered (preferably 5 or 6 membered) cycloalkane such as cyclobutane ring, cyclopentane ring, cyclohexane ring, A ring etc. are mentioned.

  As a typical example of the vinyl monomer A represented by the formula (1), 2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl methacrylate (= 2- (1-methylpropylidene) Aminooxycarbonylaminoethyl) methacrylate) [trade name “Karenz MOI-BM”, manufactured by Showa Denko KK, the following formula (1a)], 2- (3,5-dimethylpyrazol-1-yl) carbonylaminoethyl methacrylate [Product name “Karenz MOI-BP”, manufactured by Showa Denko KK, the following formula (1b)] and the like. As for the deblocking temperature of the trade name “Karenz MOI-BM”, the 50% deblocking temperature is 130 ° C., and the 90% deblocking temperature is 150 ° C. Further, the deblocking temperature of the trade name “Karenz MOI-BP” is 50 ° C. deblocking temperature of 100 ° C. and 90% deblocking temperature of 120 ° C.

In the copolymer of the present invention, the deblocking of the monomer unit corresponding to the vinyl monomer A represented by the formula (1) proceeds as follows. The isocyanate group generated by this deblocking acts as a curable group. The isocyanate group mainly contributes to improvement of adhesion to the substrate.

  As vinyl monomer B which has a carboxyl group or an acid anhydride group, unsaturated carboxylic acid or its acid anhydride is mentioned. Examples of unsaturated carboxylic acids and acid anhydrides include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, and fumaric acid, and acid anhydrides thereof (maleic anhydride). , Itaconic anhydride, etc.). Among these, acrylic acid and methacrylic acid are particularly preferable.

In the (meth) acrylic acid ester C represented by the formula (2), in the formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ may have a hydrocarbon group-substituted oxy group. A hydrocarbon group having 16 to 25 carbon atoms is shown.

Examples of the hydrocarbon group having 16 to 25 carbon atoms in R ⁵ include alkyl groups such as hexadecyl (cetyl), heptadecyl, octadecyl (stearyl), nonadecyl, icosyl and docosyl (behenyl) groups; 10-cyclohexyldecyl, 12-cyclohexyl Groups in which an alicyclic hydrocarbon group such as dodecyl, 14-cyclohexyltetradecyl, 16-cyclohexylhexadecyl group and an alkyl group are bonded; 10-phenyldecyl, 12-phenyldodecyl, 14-phenyltetradecyl, 16-phenyl Examples include aralkyl groups such as a hexadecyl group.

  Examples of the hydrocarbon group-substituted oxy group that the hydrocarbon group having 16 to 25 carbon atoms may have include, for example, alkoxy groups such as methoxy and ethoxy groups (for example, alkoxy groups having 1 to 10 carbon atoms); phenoxy groups Aryloxy groups such as cyclohexyloxy groups, alicyclic hydrocarbon group-substituted oxy groups such as cyclohexyloxy groups, dicyclopentanyloxy groups, etc .; C 1-15 such as aralkyloxy groups such as benzyloxy groups (preferably 1 carbon atoms) -12) hydrocarbon group-substituted oxy groups and the like.

  Typical examples of the (meth) acrylic acid ester represented by the formula (2) include cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, and the like.

  In the copolymer of the present invention, the monomer unit corresponding to the vinyl monomer A, the monomer unit corresponding to the vinyl monomer B, and the monomer unit corresponding to the (meth) acrylic ester C were each one type. Or two or more of them may be present.

  The proportion of the monomer unit corresponding to the vinyl monomer A in the copolymer is, for example, 1 to 99% by weight (for example, 10 to 95% by weight) with respect to all monomer units constituting the copolymer, preferably It is 20 to 90% by weight, more preferably 25 to 88% by weight. If this ratio is too small, the adhesion to the substrate tends to be lowered, and if it is too large, the ratio of the monomer unit corresponding to the vinyl monomer B and the monomer unit corresponding to the (meth) acrylic ester C is relatively reduced. As a result, the heat resistant colorability tends to decrease.

  The proportion of the monomer unit corresponding to the vinyl monomer B in the copolymer varies depending on the type of the monomer unit used, but is usually 0.5 to 98% by weight with respect to all the monomer units constituting the copolymer. % (For example, 2.5 to 70% by weight), preferably 3 to 50% by weight, and more preferably 5 to 40% by weight. If this ratio is too small, the heat resistant colorability tends to be poor, and conversely if too large, the solvent resistance tends to be poor.

  The proportion of the monomer units corresponding to (meth) acrylic acid ester C in the copolymer varies depending on the type of monomer units used, but is usually 0.5- to the total monomer units constituting the copolymer. It is 98 weight% (for example, 2.5 to 70 weight%), Preferably it is 3 to 50 weight%, More preferably, it is 5 to 40 weight%. If this ratio is too small, the flexibility of the cured coating film tends to be lost and brittle, whereas if it is too large, the solvent resistance tends to deteriorate.

  The ratio of the monomer unit corresponding to the vinyl monomer A, the monomer unit corresponding to the vinyl monomer B, and the monomer unit corresponding to the (meth) acrylic ester C to the copolymer is, for example, 30 to 100 % By weight, preferably 40 to 100% by weight, more preferably 50 to 100% by weight.

  In the copolymer of the present invention, the ratio of the monomer unit corresponding to the vinyl monomer A and the monomer unit corresponding to the vinyl monomer B is, for example, the former / the latter (weight ratio) = 2/98 to 98/2. , Preferably 20/80 to 95/5, more preferably 40/60 to 95/5. The ratio of the monomer unit corresponding to the vinyl monomer A and the monomer unit corresponding to the (meth) acrylic ester C is, for example, the former / the latter (weight ratio) = 2/98 to 98/2, preferably 20 / 80 to 95/5, more preferably 40/60 to 95/5.

  The copolymer of the present invention may be composed of only a monomer unit corresponding to the vinyl monomer A, a monomer unit corresponding to the vinyl monomer B, and a monomer unit corresponding to the (meth) acrylic ester C. However, in addition to these monomer units, other monomer units (single repeating structure) may be included. The other monomer unit is a monomer unit corresponding to a polymerizable monomer copolymerizable with vinyl monomer A, vinyl monomer B and (meth) acrylic acid ester C, and has adhesiveness to the substrate. The structural unit is not particularly limited as long as it does not impair the chemical resistance.

  As a monomer capable of forming another monomer unit that may be contained in such a copolymer, (meth) acrylic acid ester D, aromatic vinyl compound E, hydroxyl group represented by the above formula (3) Examples thereof include monomer F, and vinyl monomer G having a 3- to 5-membered cyclic ether group. These monomers can be used alone or in combination of two or more.

In the (meth) acrylic ester D represented by the formula (3), R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ may have a hydrocarbon group-substituted oxy group having 1 to 15 carbon atoms ( Preferably, a C1-C12 hydrocarbon group is shown. Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl group as the hydrocarbon group having 1 to 15 carbon atoms in R ⁹ Alicyclic hydrocarbon groups such as cyclohexyl, dicyclopentanyl and isobornyl groups; aryl groups such as phenyl groups; aralkyl groups such as benzyl, 1-phenylethyl and 2-phenylethyl groups; groups in which two or more of these are bonded Etc.

  Examples of the hydrocarbon group-substituted oxy group that the hydrocarbon group having 1 to 15 carbon atoms may have include, for example, alkoxy groups such as methoxy and ethoxy groups (for example, alkoxy groups having 1 to 10 carbon atoms); phenoxy groups Aryloxy groups such as cyclohexyloxy groups, alicyclic hydrocarbon group-substituted oxy groups such as cyclohexyloxy groups, dicyclopentanyloxy groups, etc .; C 1-15 such as aralkyloxy groups such as benzyloxy groups (preferably 1 carbon atoms) -12) hydrocarbon group-substituted oxy groups and the like.

  As typical examples of the (meth) acrylic acid ester D represented by the formula (3), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate Etc.

  Examples of the aromatic vinyl compound E include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, vinyl biphenyl, and the like.

  Examples of the hydroxyl group-containing monomer F include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6- Polyhydric alcohols and acrylics such as hydroxyalkyl (meth) acrylates such as hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 4-hydroxymethylcyclohexyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, etc. A compound obtained by ring-opening polymerization of ε-caprolactone to a monoesterified product of acid or methacrylic acid or a monoesterified product of polyhydric alcohol and acrylic acid or methacrylic acid (product of Daicel Chemical Industries, Ltd. Le FA series, PLACCEL FM series, etc.), ethylene oxide, or propylene oxide ring-opening polymerization with hydroxyl group-containing compounds, and the like.

  The vinyl monomer G having a 3- to 5-membered cyclic ether group includes an oxirane ring (epoxy group) -containing polymerizable unsaturated compound, an oxetane ring (oxetanyl group) -containing polymerizable unsaturated compound, and an oxolane ring (oxolanyl group). Contains polymerizable unsaturated compounds.

Examples of the oxirane ring (epoxy group) -containing polymerizable unsaturated compound include oxiranyl (meth) acrylate, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, and 2-oxy Polymerizable unsaturated compounds containing an oxirane ring (monocyclic) such as ranylethyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxypropyl (meth) acrylate, glycidyloxyphenyl (meth) acrylate, etc. ((Meth) acrylic acid ester derivatives, etc.); 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate Epoxy group-containing fats such as 3,4-epoxycyclohexane rings such as 2- (3,4-epoxycyclohexylmethyloxy) ethyl (meth) acrylate and 3- (3,4-epoxycyclohexylmethyloxy) propyl (meth) acrylate Polymerizable unsaturated compounds containing a cyclic carbocycle (such as (meth) acrylic acid ester derivatives); 5,6-epoxy such as 5,6-epoxy-2-bicyclo [2.2.1] heptyl (meth) acrylate Polymerizable unsaturated compounds containing a 2-bicyclo [2.2.1] heptane ring (such as (meth) acrylic acid ester derivatives); epoxidized dicyclopentenyl (meth) acrylate [3,4-epoxytricyclo [5] .2.1.0 ^2,6 ] decan-9-yl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] decan-8-yl (meth) acrylate, or a mixture thereof], epoxidized dicyclopentenyloxyethyl (meth) acrylate [2- (3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] decan-9-yloxy) ethyl (meth) acrylate, 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl (meth) acrylate, or these , Epoxidized dicyclopentenyloxybutyl (meth) acrylate, epoxidized dicyclopentenyloxyhexyl (meth) acrylate, etc. 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring Polymerizable unsaturated compounds containing (such as (meth) acrylic acid ester derivatives) and the like. As another oxirane ring (epoxy group) -containing polymerizable unsaturated compound, a vinyl ether compound containing an epoxy group, an allyl ether compound containing an epoxy group, an aromatic vinyl compound containing an epoxy group, or the like can also be used. Examples of the aromatic vinyl compound containing an epoxy group include styrene derivatives such as 4-vinylbenzylglycidyl ether, 4-vinylbenzyloxirane, 4-vinylphenethyloxirane.

  Examples of the oxetane ring (oxetanyl group) -containing polymerizable unsaturated compound include oxetanyl (meth) acrylate, 3-methyl-3-oxetanyl (meth) acrylate, 3-ethyl-3-oxetanyl (meth) acrylate, (3- Methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, 2- (3-methyl-3-oxetanyl) ethyl (meth) acrylate, 2- (3-ethyl -3-Oxetanyl) ethyl (meth) acrylate, 2-[(3-methyl-3-oxetanyl) methyloxy] ethyl (meth) acrylate, 2-[(3-ethyl-3-oxetanyl) methyloxy] ethyl (meta ) Acrylate, 3-[(3-Methyl-3-oxetanyl) methyloxy] propyl Pill (meth) acrylate, 3 - and [(3-ethyl-3-oxetanyl) methyloxy] propyl (meth) acrylate, vinyl ether compounds containing oxetanyl group, and allyl ether compounds containing oxetanyl group.

  Examples of the oxolane ring (oxolanyl group) -containing polymerizable unsaturated compound include tetrahydrofurfuryl (meth) acrylate, vinyl ether compounds containing an oxolanyl group, and allyl ether compounds containing an oxolanyl group.

  When the copolymer of the present invention has a 3- to 5-membered cyclic ether group [oxirane ring (epoxy group), oxetane ring (oxetanyl group), oxolane ring (oxolanyl group)], these groups are used as curable groups. Works. The 3- to 5-membered cyclic ether group mainly contributes to improvement of chemical resistance (solvent resistance, alkali resistance, etc.).

  From the group consisting of (meth) acrylic acid ester D represented by formula (3), aromatic vinyl compound E, hydroxyl group-containing monomer F, and vinyl monomer G having a 3- to 5-membered cyclic ether group The proportion of monomer units corresponding to the selected at least one monomer in the copolymer is generally 0 to 60% by weight (for example, 2 to 60% by weight), preferably 0 to 50% by weight. % (For example, 2 to 50% by weight), more preferably 0 to 40% by weight (for example, 5 to 40% by weight).

  As a preferred embodiment of the copolymer of the present invention, (i) a monomer unit corresponding to vinyl monomer A, a monomer unit corresponding to vinyl monomer B, and a monomer unit corresponding to (meth) acrylic ester C are combined. (Ii) a monomer unit corresponding to the vinyl monomer A, a monomer unit corresponding to the vinyl monomer B, and (meth) acrylic In addition to the monomer unit corresponding to the acid ester C, the monomer unit corresponding to the (meth) acrylic acid ester represented by the formula (3) (particularly methyl methacrylate) is 2 to 60% by weight (preferably Is a copolymer containing 2 to 50% by weight, more preferably 5 to 40% by weight), (iii) a monomer unit corresponding to vinyl monomer A, and a monomer unit corresponding to vinyl monomer B In addition to the monomer unit corresponding to (meth) acrylic ester C, the monomer unit corresponding to the aromatic vinyl compound is 2 to 60% by weight of the total monomer unit (preferably 2 to 50% by weight, more preferably 5 to 5% by weight). 40% by weight), a copolymer containing (iv) a monomer unit corresponding to vinyl monomer A, a monomer unit corresponding to vinyl monomer B, and a monomer unit corresponding to (meth) acrylate C, A copolymer containing 2 to 60% by weight (preferably 2 to 50% by weight, more preferably 5 to 40% by weight) of the monomer units corresponding to the hydroxyl group-containing monomer, (v) vinyl monomer In addition to the monomer unit corresponding to the body A, the monomer unit corresponding to the vinyl monomer B, and the monomer unit corresponding to the (meth) acrylic ester C, a 3- to 5-membered cyclic amine Monomer units corresponding to the vinyl monomer having an Le group 2-70% by weight of the total monomer units include (preferably 2 to 60% by weight, more preferably 5 to 50 wt%) containing the copolymer.

  The copolymer of the present invention includes a vinyl monomer A having a blocked isocyanate group represented by the formula (1), a vinyl monomer B having a carboxyl group or an acid anhydride group, and a formula (2). It can manufacture by attaching | subjecting the monomer mixture containing the (meth) acrylic acid ester C represented, and another copolymerizable monomer as needed to copolymerization (vinyl polymerization).

  As the polymerization initiator used for polymerization, a normal radical initiator can be used. For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), Dimethyl-2,2'-azobis (2-methylpropionate), 2,2-azobis (isobutyric acid) dimethyl, diethyl-2,2'-azobis (2-methylpropionate), dibutyl-2,2 Azo compounds such as' -azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, organic peroxides such as 1,1-bis (t-butylperoxy) cyclohexane, peroxide Examples include hydrogen. When a peroxide is used as a radical polymerization initiator, a redox initiator may be combined with a reducing agent. Of these, azo compounds are preferred, and in particular, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2-azobis (isobutyric acid) dimethyl. preferable.

  The amount of the polymerization initiator used can be appropriately selected within a range that does not impair smooth copolymerization, but is usually about 1 to 30% by weight, preferably based on the total amount of all monomer components and polymerization initiator. It is about 5 to 25% by weight.

  In the present invention, a chain transfer agent generally used in radical polymerization may be used in combination. Specific examples include thiols (such as n-dodecyl mercaptan, n-octyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, triethylene glycol dimercaptan). Mercaptopropionic acid, thiobenzoic acid, thioglycolic acid, thiomalic acid, etc.), alcohols (isopropyl alcohol, etc.), amines (dibutylamine, etc.), hypophosphites (sodium hypophosphite, etc.), α-methylstyrene dimer , Terbinolene, myrcene, limonene, α-pinene, β-pinene and the like, and the amount of the chain transfer agent is preferably 0.001 to 3% by weight based on the amount of the total radical polymerizable monomer. is there. When using a chain transfer agent, it is preferable to mix with a polymerizable vinyl monomer in advance.

  The polymerization can be performed by a conventional method used for producing a styrene polymer or an acrylic polymer, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization. Among these, solution polymerization is preferable. The monomer and the polymerization initiator may be supplied all at once to the reaction system, or a part or all of them may be dropped into the reaction system. For example, a method in which a solution in which a polymerization initiator is dissolved in a polymerization solvent is dropped into a mixed solution of a monomer and a polymerization solvent kept at a constant temperature, or the monomer and the polymerization initiator are dissolved in the polymerization solvent in advance. A method in which the solution is dropped into a polymerization solvent maintained at a constant temperature for polymerization (drop polymerization method) can be employed.

The polymerization solvent can be appropriately selected according to the monomer composition and the like. As a polymerization solvent, for example, ether (diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether (diethylene glycol dialkyl ether such as diethylene glycol methyl ethyl ether), propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, Dipropylene glycol mono or dialkyl ether (such as dipropylene glycol dialkyl ether such as dipropylene glycol dimethyl ether), tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl Ether, 1,4-butanediol mono- or dialkyl Chain ethers such as glycol ethers such as ether, glycerin mono, di or trialkyl ethers; cyclic ethers such as tetrahydrofuran and dioxane), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, 3- Carboxylic acid esters such as methyl methoxypropionate, ethyl 3-ethoxypropionate, C _5-6 cycloalkanediol mono- or diacetate, C _5-6 cycloalkane dimethanol mono- or diacetate; ethylene glycol monoalkyl ether acetate, Ethylene glycol mono or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol Rumono or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono or diacetate, 1,3-propanediol monoalkyl ether acetate, 1,3-propanediol mono or diacetate, 1,3-butanediol mono Alkyl ether acetate, 1,3-butanediol mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-butanediol mono or diacetate, 1,6-hexanediol mono or diacetate, glycerin mono , Di or triacetate, glycerin mono or di C _1-4 alkyl ether di or mono acetate, tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono or diacetate Glycol acetates or glycol ether acetates, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, etc.), amides (N, N-dimethyl) Acetamide, N, N-dimethylformamide, etc.), sulfoxide (dimethylsulfoxide, etc.), alcohol (methanol, ethanol, propanol, C _5-6 cycloalkanediol, C _5-6 cycloalkanedimethanol, etc.), hydrocarbon (benzene, Aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, and a mixed solvent thereof. The polymerization temperature can be appropriately selected within a range of about 30 to 150 ° C., for example.

  The copolymer of this invention produces | generates by the said method. The weight average molecular weight of the copolymer is, for example, about 500 to 100,000, preferably 1000 to 40000, and more preferably about 2000 to 30000. The degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the copolymer is about 1 to 3.

  The polymerization solution obtained by the above method is prepared by adjusting the solid content concentration as necessary, exchanging the solvent, performing filtration treatment, and further, if necessary, a curing catalyst [thermal acid generator (thermosetting Catalyst, thermal cationic polymerization initiator), photoacid generator (photocuring catalyst, photocationic polymerization initiator)], photoradical initiator, curing agent, curing accelerator, additive (filler, antifoaming agent, flame retardant) , Antioxidants, ultraviolet absorbers, stress reducing agents, flexibility imparting agents, waxes, resins, crosslinking agents, halogen trapping agents, leveling agents, wetting improvers, etc.) You can get things. Moreover, the polymer produced | generated by superposition | polymerization can be refine | purified by precipitation or reprecipitation, etc., The curable resin composition can also be obtained by melt | dissolving this refine | purified polymer in the solvent according to a use with the said appropriate additive. . As the solvent constituting the curable resin composition, those exemplified as the polymerization solvent can be used.

  Among the curing catalysts, as the thermal acid generator, for example, Sun-Aid SI-45, Same as left SI-47, Same as left SI-60, Same as left SI-60L, Same as left SI-80, Same as left SI-80L, Same as left SI-100, Same as SI-100L, Same as left SI-145, Same as left SI-150, Same as left SI-160, Same as left SI-110L, Same as left SI-180L (above, Sanshin Chemical Co., Ltd., product name), CI-2921, CI-2920 CI-2946, CI-3128, CI-2624, CI-2638, CI-2064 (product of Nippon Soda Co., Ltd., product name), CP-66, CP-77 (product of Asahi Denka Kogyo Co., Ltd., product) Name), FC-520 (product of 3M, product name), diazonium salt, iodonium salt, sulfonium salt, phosphonium salt, selenium salt, oxonium salt Ammonium salts, and the like can be used.

  Examples of the photoacid generator include Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, trade name of Union Carbide, USA), Irgacure 261 (Ciba Specialty Chemicals) Product name), SP-150, SP-151, SP-170, Optomer SP-171 (above, manufactured by Asahi Denka Kogyo Co., Ltd., product name), CG-24-61 (manufactured by Ciba Specialty Chemicals, Product name), DAICATII (manufactured by Daicel Chemical Industries, Ltd., product name), UVAC1591 (manufactured by Daicel-Cytec Co., Ltd., product name), CI-2064, CI-2639, CI-2624, CI-2481, CI-2734 , CI-2855, CI-2823, CI-2758 , Nippon Soda Co., Ltd., trade name), PI-2074 (Rhone-Poulenc, trade name, pentafluorophenyl borate toluylcumyl iodonium salt), FFC509 (3M product, trade name), BBI-102, BBI-101 , BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (trade name, manufactured by Midori Chemical Co., Ltd.), CD-1012 (trade name, manufactured by Sartomer, USA) ) And the like, and diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts, and the like can be used.

  Examples of the photo radical initiator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfite, orthobenzoylbenzoate. Methyl 4-ethylaminobenzoate (Nippon Kayaku Co., Ltd. Kayacure EPA), 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd. Kayacure DETX etc.), 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba-Gigi-Irgacure 907, etc.), tetra (t-butylperoxycarbonyl) benzophenone, benzyl, -Hydroxy-2-methyl-1-phenyl-propan-1-one, 4,4-bisdiethylaminobenzophenone, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl- 1,2′-biimidazole (B-CIM, etc., manufactured by Hodogaya Chemical Co., Ltd.) or the like can be used alone or in combination, and a photosensitizer can be added as necessary.

  The addition amount of the curing catalyst is, for example, 0.05 to 10% by weight, preferably 0.5 to 5% by weight with respect to the copolymer (resin component) in the curable resin composition. A curing catalyst can be used individually or in combination of 2 or more types.

  As said crosslinking agent, a polyfunctional alcohol compound, polyfunctional thiol compounds, etc. can be used.

  The polyfunctional alcohol compound may be a compound having two or more hydroxyl groups. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4- Multivalents such as butylene glycol, glycerin, diglycerin, D-glucose, D-glucitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol Polyalkylene glycols such as alcohols, polyethylene glycols, polypropylene glycols, polybutylene glycols, polytetramethylene glycols, polycaprolactone diols, polycaprolacs Examples include tontriols and polycarbonate diols.

  The polyfunctional thiol compound may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglyco Rate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthio Glycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2, 4, -Trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, tetraethylene glycol bis3-mercaptopropionate, trimethylolpropane tris3-mercaptopropionate , Tris (3-mercaptopropynyloxyethyl) isocyanurate, pentaerythritol tetrakis 3-mercaptopropionate, dipentaerythritol tetrakis 3-mercaptopropionate, 1,4-bis (3-mercaptobutyryloxy) butane, , 3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate), etc. Is mentioned. One type of polyfunctional alcohol compound or polyfunctional thiol compound may be used alone, or two or more types may be present.

  A radiation sensitive component can also be mix | blended with curable resin composition. Examples of radiation sensitive components include polyfunctional (meth) acrylates, polyfunctional epoxy compounds, polyfunctional urethane (meth) acrylates, polyfunctional epoxy (meth) acrylates (types in which acrylic acid is added to epoxy groups), and the like. Can be mentioned. A polyfunctional (meth) acrylate and a heat or radiation polymerization initiator, or a polyfunctional epoxy compound and a heat or radiation acid generator may be combined. Each of these radiation-sensitive components, heat or radiation polymerization initiators, and heat or radiation acid generators may be used alone or in combination of two or more.

  Specific examples of polyfunctional (meth) acrylates include di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol, di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol, both ends Di (meth) acrylates of both end hydroxylated polymers such as hydroxypolybutadiene, both end hydroxypolyisoprene and both end hydroxypolycaprilactone, glycerin, 1,2,4, -butanetriol, trimethylolalkane, tetramethylolalkane , Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as pentaerythritol, dipentaerythritol, poly (polyalkylene glycol adducts of trihydric or higher polyhydric alcohols ( ) Acrylates, poly (meth) acrylates of cyclic polyols such as 1,4-cyclohexanediol, 1,4-benzenediols, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, Examples thereof include oligo (meth) acrylates such as alkyd resin (meth) acrylate, silicon resin (meth) acrylate, and spirane resin (meth) acrylate. These may be used alone or in combination of two or more.

  As the multifunctional epoxy compound, for example, the trade name “Celoxide 2021”, the trade name “Celoxide 2081”, the trade name “Celoxide 3000”, the trade name “EHPE3150”, the trade name “Epolide GT401” (above, Daicel Chemical Industries Ltd.) Company name), trade name "Epolite 4000" (manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more.

  The curable resin composition thus obtained has a high adhesion to a substrate or a substrate by curing, and obtains a cured product (cured film, etc.) excellent in chemical resistance such as solvent resistance and alkali resistance. Can do. Therefore, it is useful as a paint, a coating agent, an adhesive, and the like, and can be suitably used particularly in the field of electronic materials.

  By curing the curable resin composition, a cured product having excellent physical properties can be obtained. For example, the curable resin composition is applied to various substrates or substrates by a method such as a spin coater or a slit coater to form a coating film, and then a cured product is obtained by curing the coating film. Can do. Examples of the base material or substrate include glass, ceramic, silicon wafer, metal, and plastic. Coating with a spin coater, slit coater, or the like can be performed by a known method.

  Curing of the coating film is performed by heating, irradiating and irradiating active energy rays, or heating after exposure. When the curable resin composition is cured by heat, the heating temperature is in the range of 50 ° C to 260 ° C, preferably in the range of 80 ° C to 240 ° C. When the curable resin composition is cured by light, light of various wavelengths, for example, ultraviolet rays, X-rays, g-rays, i-rays, excimer lasers, etc. are used for exposure. Although the thickness of the coating film after hardening can be suitably selected according to a use, generally it is 0.1-40 micrometers, Preferably it is 0.3-20 micrometers, More preferably, it is about 0.5-10 micrometers.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In addition, the weight average molecular weight (polystyrene conversion) and dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of the produced | generated copolymer were measured on condition of the following.
Device: Detector: RID-10A (Shimadzu Corporation)
Pump: LC-10ADVP (Shimadzu Corporation)
System controller: SCL-10AVP (Shimadzu Corporation)
Degasser: DGU-14A (Shimadzu Corporation)
Autoinjector: SIL-10AF (Shimadzu Corporation)
Column: Waters Styragel HR3, Styragel HR4, Styragel HR5, 3 in total Mobile phase: THF
Flow rate: 1mL / min
Temperature: Oven (40 ° C), RI (40 ° C)
Detector: RI POLARITY (+)
Injection volume: 50μL

Example 1
An appropriate amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 100 parts by weight of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, in the flask, 60 parts by weight of 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz MOI-BM”, Showa Denko KK), 20 parts of methacrylic acid A solution in which 20 parts by weight of stearyl methacrylate and 20 parts by weight of stearyl methacrylate were dissolved in 30 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over about 4 hours using a dropping pump. On the other hand, a solution prepared by dissolving 5 parts by weight of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 90 parts by weight of propylene glycol monomethyl ether acetate was added to a flask using another dropping pump for about 4 hours. It was dripped in. After completion of the dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 4 hours, and then cooled to room temperature to obtain a copolymer solution having a solid content of 31.4% by weight. The produced copolymer had a weight average molecular weight Mw of 14,000 and a dispersity of 2.72.

Example 2
The monomer composition is 50 parts by weight of 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz MOI-BM”, Showa Denko KK), 20 weights of methacrylic acid. Part of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 -Mixture of yl acrylate [50:50 (molar ratio)] (trade name "E-DCPA", manufactured by Daicel Chemical Industries, Ltd.) 10 parts by weight, with the exception of changing to 20 parts by weight of stearyl methacrylate. The same operation was performed to obtain a copolymer solution having a solid content of 32.6% by weight. The produced copolymer had a weight average molecular weight Mw of 15000 and a dispersity of 2.86.

Example 3
The monomer composition is 50 parts by weight of 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz MOI-BM”, Showa Denko KK), 20 weights of methacrylic acid. The copolymer solution having a solid content of 32.3% by weight was obtained in the same manner as in Example 1 except that the content was changed to 10 parts by weight of styrene and 20 parts by weight of stearyl methacrylate. The produced copolymer had a weight average molecular weight Mw of 14,000 and a degree of dispersion of 2.70.

Example 4
The monomer composition was 60 parts by weight of 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate (trade name “Karenz MOI-BM”, Showa Denko KK), 20 weights of methacrylic acid. Parts, epoxidized dicyclopentenyl acrylate (trade name “E-DCPA”, manufactured by Daicel Chemical Industries, Ltd.) 10 parts by weight, except for changing to 10 parts by weight of behenyl methacrylate, the same operation as in Example 1, A copolymer solution having a solid content of 33% by weight was obtained. The produced copolymer had a weight average molecular weight Mw of 15000 and a dispersity of 2.86.

Comparative Example 1
A copolymer solution having a solid content of 32.0% by weight was obtained by performing the same operation as in Example 1 except that all the monomer compositions were changed to “Karenz MOI-BM”. The weight average molecular weight Mw of the produced copolymer was 9500, and the degree of dispersion was 1.85.

Comparative Example 2
Except for changing the monomer composition to 80 parts by weight of methyl methacrylate and 20 parts by weight of methacrylic acid, the same operation as in Example 1 was performed to obtain a copolymer solution having a solid content of 32.5% by weight. The produced copolymer had a weight average molecular weight Mw of 12,000 and a dispersity of 1.78.

Comparative Example 3
Except for changing the monomer composition to 70 parts by weight of methyl methacrylate, 20 parts by weight of methacrylic acid, 10 parts by weight of epoxidized dicyclopentenyl acrylate (trade name “E-DCPA”, manufactured by Daicel Chemical Industries, Ltd.) The same operation as in Example 1 was performed to obtain a copolymer solution having a solid content of 33% by weight. The resulting copolymer had a weight average molecular weight Mw of 9,500 and a dispersity of 1.80.

Comparative Example 4
Except for changing the monomer composition to 80 parts by weight of styrene and 20 parts by weight of methacrylic acid, the same operation as in Example 1 was performed to obtain a copolymer solution having a solid content of 32.5% by weight. The produced copolymer had a weight average molecular weight Mw of 9000 and a dispersity of 1.76.

Evaluation test (1) Preparation of test piece for evaluation After applying the copolymer solution (curable resin composition) obtained in each Example and Comparative Example to a base material with a spin coater, on a hot plate at 100 ° C. After heating for 3 minutes, each test piece for evaluation was produced by heating in an oven at 80 ° C. for 10 minutes and further heating in an oven at 230 ° C. for 60 minutes. A glass plate and a stainless steel plate were used as the base material.

(2) Adhesiveness In Examples and Comparative Examples, the adhesiveness was measured by peeling from the substrate in accordance with JIS K-5600-5-6 for the places where the solvent resistance test was performed. Moreover, it evaluated based on the following reference | standard in accordance with the classification | category prescribed | regulated by the classification | category of JIS K5600-5-6 8.3 Table 1 test result classification.
A: The test result classification was “0”.
○: It was “1” in the classification of the test results.
Δ: “2” in the classification of test results.
X: “3” and “4” in the classification of the test results.

(3) Solvent resistance In Examples and Comparative Examples, isopropyl alcohol (IPA), methyl ethyl ketone (MEK), and N-methylpyrrolidone (NMP) were dropped on each of the test pieces prepared with glass plates, Left for 10 minutes. After washing with water, if the location where the solvent has been dripped has not changed at all ◎, a trace of the solvent will remain, but if it disappears if wiped off, ○ will leave a trace of the solvent and will not disappear even if wiped off. △, if it was completely discolored, x. Similar results were obtained when using test specimens made of stainless steel plates.

(4) Heat resistance (heat resistance coloring)
In the examples and comparative examples, the transmittance at wavelengths of 400 nm to 800 nm was measured using a spectrophotometer for the test specimens made of glass plates. The cured coating film was again heated in a clean oven at 250 ° C. for 1 hour, and the presence or absence of cracks in the coating film and the transmittance were measured. For the transmittance after heat curing at 220 ° C. for 30 minutes, the change rate of the transmittance after the reheating treatment is calculated as the transmittance reduction rate, and when the transmittance reduction rate is less than 5%, The case of 10% was evaluated as Δ, and the case of exceeding 10% was evaluated as ×.

The results of the evaluation test are shown in Table 1. In the table, 2- [O- (1′-methylpropylideneamino) carboxyamino] ethyl methacrylate is represented by “Karenz MOI-BM” and 3,4-epoxytricyclo [5.2.1.0]. The mixture [50:50 (molar ratio)] of ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate is referred to as “E -DCPA ".

  As is clear from the table, the cured coating films obtained from the copolymer solutions of the examples were excellent in any of adhesion to the base materials (glass and stainless steel), solvent resistance, and heat-resistant coloring. On the other hand, the cured coating film obtained from the copolymer solution of Comparative Example 1 has heat resistant colorability, and the cured coating film obtained from the copolymer solutions of Comparative Examples 2 and 4 has adhesion and solvent resistance. The cured coating film obtained from the copolymer solution of Comparative Example 3 was inferior in solvent resistance.

Claims (2)

Following formula (1)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. R ³ is a residue of an isocyanate group blocking agent R ³ H. Indicate)
A monomer unit corresponding to the vinyl monomer A having a blocked isocyanate group, a monomer unit corresponding to the vinyl monomer B having a carboxyl group or an acid anhydride group, and the following formula (2):

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydrocarbon group having 16 to 25 carbon atoms which may have a hydrocarbon-substituted oxy group)
A copolymer containing at least a monomer unit corresponding to (meth) acrylic ester C represented by: In addition to the monomer unit corresponding to vinyl monomer A, the monomer unit corresponding to vinyl monomer B, and the monomer unit corresponding to (meth) acrylic acid ester C, the following formula (3)

(Wherein R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents a hydrocarbon group having 1 to 15 carbon atoms which may have a hydrocarbon group-substituted oxy group)
At least selected from the group consisting of (meth) acrylic acid ester D, aromatic vinyl compound E, hydroxyl group-containing monomer F, and vinyl monomer G having a 3- to 5-membered cyclic ether group The copolymer according to claim 1, comprising monomer units corresponding to one kind of monomer.