JP5180027B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition containing a copolymer having a blocked isocyanate group and a cyclic ether group, and a blocked polyisocyanate compound. The curable resin composition of the present invention is useful for paints, coating agents, adhesives, electronic materials (protective films, sealing materials, nanoimprint 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 films obtained from these curable resin compositions cannot satisfy all required performances such as curability, adhesion to a substrate, chemical resistance, and storage stability.

  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.

JP-A-1-123817

As a result of various investigations to obtain a curable resin composition from which a cured product excellent in chemical resistance, particularly alkali resistance, has been obtained, the present inventors have found that a vinyl monomer having a blocked isocyanate group, an epoxy group, etc. When a curable resin composition containing a copolymer with a vinyl monomer having a cyclic ether group is applied to a substrate and cured, the adhesion to the substrate is excellent, and chemical resistance, particularly alkali resistance is improved. It has been found that an excellent cured coating film can be obtained. However, it has been found that this cured coating film is not necessarily sufficient in hardness.
Accordingly, an object of the present invention is to provide a curable resin composition that is extremely excellent in adhesion to a substrate, excellent in chemical resistance, and capable of obtaining a cured product having high hardness, and curing the curable resin composition. It is in providing the hardened | cured material obtained.

  As a result of intensive studies to achieve the above object, the present inventors have found that a copolymer of a vinyl monomer having a blocked isocyanate group and a vinyl monomer having a cyclic ether group such as an epoxy group, and an isocyanate When a curable resin composition containing a polyisocyanate compound in which a group is blocked is applied to a substrate and cured, the adhesion to the substrate is remarkably excellent, the chemical resistance is excellent, and the hardness is high. The inventors found that a film was 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、３〜５員の環状エーテル基を有するビニル単量体ｂに対応するモノマー単位を少なくとも含む共重合体Ａと、ブロックポリイソシアネート化合物Ｂとを含む硬化性樹脂組成物を提供する。 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 copolymer A comprising at least a monomer unit corresponding to a vinyl monomer a having a blocked isocyanate group and a monomer unit corresponding to a vinyl monomer b having a 3- to 5-membered cyclic ether group And a curable resin composition containing the block polyisocyanate compound B.

（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ｃ、芳香族ビニル化合物ｄ、ヒドロキシル基含有単量体ｅ、及びカルボキシル基含有単量体ｆ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むポリマーであってもよい。 In addition to the monomer unit corresponding to the vinyl monomer a and the monomer unit corresponding to the vinyl monomer b, the copolymer A has the following formula (2):

(Wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydrocarbon group having 1 to 15 carbon atoms which may have a hydrocarbon group-substituted oxy group)
Corresponding to at least one monomer selected from the group consisting of (meth) acrylic acid ester c, aromatic vinyl compound d, hydroxyl group-containing monomer e, and carboxyl group-containing monomer f It may be a polymer containing monomer units.

  Block polyisocyanate compound B is a block product of an organic polyisocyanate, a block product of a prepolymer having an isocyanate group at the terminal obtained by a reaction between the organic polyisocyanate and a compound having two or more active hydrogens, and a large amount of organic polyisocyanate. It may be at least one compound selected from blocked products of the body.

  The present invention also provides a cured product obtained by curing the curable resin composition.

  By curing the curable resin composition of the present invention, it has extremely high adhesion to a substrate and a substrate (especially excellent adhesion to the substrate in contact with a solvent) and solvent resistance. Further, a cured product (cured film or the like) having excellent chemical resistance such as alkali resistance and high hardness and high hardness can be obtained. Moreover, the curable resin composition 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 curable resin composition of the present invention comprises a monomer unit corresponding to the vinyl monomer a having a blocked isocyanate group represented by the formula (1) and a vinyl unit having a 3- to 5-membered cyclic ether group. A copolymer A containing at least a monomer unit corresponding to the monomer b and a block polyisocyanate compound B are included.

[Copolymer A]
In the present invention, the copolymer A is a monomer unit corresponding to the vinyl monomer a having a blocked isocyanate group represented by the formula (1) (hereinafter sometimes referred to as “block isocyanate group”). And a monomer unit corresponding to the vinyl monomer b having a 3- to 5-membered cyclic ether group. The blocked isocyanate group is deblocked by heat to produce an active isocyanate group. When the curable resin composition containing this copolymer is cured by heat or active energy rays, the isocyanate group and the 3- to 5-membered cyclic ether group contribute to the curing, and various physical properties, in particular, substrate adhesion and Gives a cured product with excellent chemical resistance.

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 R ³ H, the same blocking agent as in the block polyisocyanate compound B described later can also be used.

  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 (3)

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 and the like. 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 A, 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.

  The vinyl monomer b 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], epoxidized dicyclopentenyloxyethyl (meth) acrylate [2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9. -Yloxy) ethyl (meth) acrylate; 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl (meth) acrylate], epoxidized dicyclopentenyloxy Polymerizable unsaturated compounds containing a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring such as butyl (meth) acrylate and epoxidized dicyclopentenyloxyhexyl (meth) acrylate ((meta ) Acrylic acid ester derivatives, etc.). 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, or the like can also be used.

  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.

  In the copolymer A, a 3- to 5-membered cyclic ether group [oxirane ring (epoxy group), oxetane ring (oxetanyl group), oxolane ring (oxolanyl group)] acts as a curable group. The 3- to 5-membered cyclic ether group mainly contributes to improvement of chemical resistance (solvent resistance, alkali resistance, etc.).

  In the copolymer A, the monomer unit corresponding to the vinyl monomer a and the monomer unit corresponding to the vinyl monomer b may each be one type or may exist in two or more types. For example, as a monomer unit corresponding to the vinyl monomer b, a monomer unit corresponding to a polymerizable unsaturated compound (such as a (meth) acrylic acid ester derivative) containing a monocyclic oxirane ring, and 3,4-epoxycyclohexane A monomer unit corresponding to a polymerizable unsaturated compound (such as a (meth) acrylic acid ester derivative) containing an epoxy group-containing alicyclic carbocycle such as a ring can be used in combination.

  The proportion of the monomer unit corresponding to the vinyl monomer a in the copolymer A is, for example, 1 to 95% by weight, preferably 3 to 70% by weight, based on all monomer units constituting the copolymer A. More preferably, it is 5 to 50% 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 monomer units corresponding to the vinyl monomer b is relatively reduced, so that the chemical resistance tends to be lowered.

  The proportion of the monomer unit corresponding to the vinyl monomer b in the copolymer A is, for example, 5 to 99% by weight, preferably 30 to 97% by weight, based on all monomer units constituting the copolymer A. More preferably, it is 50 to 95% by weight. If this ratio is too small, the chemical resistance tends to decrease, and if it is too large, the ratio of the monomer units corresponding to the vinyl monomer a is relatively small, so that the adhesion to the substrate tends to decrease.

  The ratio of the monomer units corresponding to the vinyl monomer a and the monomer units corresponding to the vinyl monomer b to the copolymer A is, for example, 40% of the total monomer units constituting the copolymer A. % By weight to 100% by weight, preferably 50 to 100% by weight, more preferably 60 to 100% by weight.

  In the copolymer A, 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) = 1/99 to 99/1, preferably Is about 3/97 to 70/30, more preferably about 5/95 to 50/50.

  The copolymer A may be composed of only a monomer unit corresponding to the vinyl monomer a and a monomer unit corresponding to the vinyl monomer b, but the monomer unit corresponding to the vinyl monomer a and the vinyl unit In addition to the monomer unit corresponding to the monomer b, other monomer units may be included. The other monomer unit is a monomer unit corresponding to a polymerizable monomer copolymerizable with the vinyl monomer a and the vinyl monomer b, and does not impair the adhesion and chemical resistance to the substrate. There is no particular limitation as long as it is a structural unit.

  As a monomer capable of forming another monomer unit which may be contained in such a copolymer A, a (meth) acrylic acid ester c represented by the formula (2), an aromatic vinyl compound d, a hydroxyl group. And group-containing monomer e and carboxyl group-containing monomer f. These monomers can be used alone or in combination of two or more.

In the (meth) acrylic acid ester c represented by the formula (2), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ 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 ⁵ 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 An aryloxy group such as cyclohexyloxy group, an alicyclic hydrocarbon group-substituted oxy group such as a cyclohexyloxy group or a dicyclopentanyloxy group; an aralkyloxy group such as a benzyloxy group having 1 to 15 carbon atoms (preferably 1 carbon atom -12) hydrocarbon group-substituted oxy groups and the like.

  As typical examples of the (meth) acrylic acid ester c represented by the formula (2), 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 d include styrene, α-methylstyrene, vinyl toluene, vinyl naphthalene, vinyl biphenyl, and the like.

  Examples of the hydroxyl group-containing monomer e 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.

  Examples of the carboxyl group-containing monomer f include acrylic acid and methacrylic acid.

  At least one simple substance selected from the group consisting of (meth) acrylic acid ester c represented by formula (2), aromatic vinyl compound d, hydroxyl group-containing monomer e, and carboxyl group-containing monomer f. The proportion of monomer units corresponding to the monomer in the copolymer A is generally 0 to 60% by weight (for example, 5 to 60% by weight) with respect to all the monomer units constituting the copolymer A, preferably It is 0 to 50% by weight (for example, 5 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 A, (i) a monomer unit corresponding to the vinyl monomer a and a monomer unit corresponding to the vinyl monomer b total 50% by weight or more (particularly 60% by weight or more) of the total monomer units. ) Containing copolymer, (ii) a monomer unit corresponding to vinyl monomer a and a monomer unit corresponding to vinyl monomer b, and (meth) acrylic acid ester represented by formula (2) (particularly , Methyl methacrylate) a copolymer containing 5-60 wt% (preferably 5-50 wt%, more preferably 5-40 wt%) of monomer units corresponding to c, (iii) vinyl monomer In addition to the monomer unit corresponding to the body a and the monomer unit corresponding to the vinyl monomer b, the monomer unit corresponding to the hydroxyl group-containing monomer e is added in an amount of 5 to 60% by weight (preferably 5%). A copolymer containing 50 wt%, more preferably 5 to 40 wt%), (iv) in addition to the monomer unit corresponding to vinyl monomer a and the monomer unit corresponding to vinyl monomer b, Examples thereof include a copolymer containing 5 to 60% by weight (preferably 5 to 50% by weight, more preferably 5 to 40% by weight) of monomer units corresponding to the monomer f.

  The copolymer A includes a vinyl monomer a having a blocked isocyanate group represented by the formula (1), a vinyl monomer b having a 3- to 5-membered cyclic ether group, and other monomers as necessary. It can be produced by subjecting a monomer mixture containing a copolymerizable monomer to polymerization (copolymerization).

  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, t-butylperoxyoctoate, 1,1-bis (t-butylperoxy) cyclohexane, etc. An organic peroxide, hydrogen peroxide, etc. are mentioned. 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, 2-ethylhexyl mercaptoacetate, 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. 001-3 weight It is. 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, propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, dipropylene glycol mono or dialkyl ether, tripropylene glycol mono Or glycol ethers such as dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether, glycerol mono, di or trialkyl ether Chain ethers such as tetrahydrofuran, cyclic ethers such as dioxane, etc.), esters (methyl acetate, ethyl acetate) , Butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C _5-6 cycloalkane diol mono- or diacetate, C _5-6, such as cycloalkane monovinyl or diacetate Carboxylic acid esters; 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 mono 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 monoalkyl ether acetate, 1,3-butanediol mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-butanediol mono Or glycol acetates or glycol ether acetates such as diacetate, glycerol mono, di or triacetate, glycerol mono or di C _1-4 alkyl ether di or mono acetate, tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono or diacetate ), Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, etc.), amides (N, N-di) Methylacetamide, N, N-dimethylformamide, etc.), sulfoxide (dimethylsulfoxide, etc.), alcohol (methanol, ethanol, propanol, _C5-6 cycloalkanediol, _C5-6 cycloalkanedimethanol, etc.), hydrocarbon (benzene) , Aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, and the like, and mixed solvents thereof. The polymerization temperature can be appropriately selected within a range of about 30 to 150 ° C., for example.

  By the above method, the copolymer A in the present invention is produced. The weight average molecular weight of the copolymer A is, for example, 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 A is about 1 to 3.

[Block Polyisocyanate Compound B]
The blocked polyisocyanate compound B is a compound in which the isocyanate group of the polyisocyanate compound is blocked with a blocking agent. The blocked isocyanate group is deblocked by heat, and the active isocyanate group generated by the deblocking acts as a curable group. The block polyisocyanate compound B mainly contributes to the improvement of the hardness of the cured product when the curable resin composition is cured. Moreover, it may contribute to the improvement of the adhesiveness with respect to the base material of this hardened | cured material.

  As the block polyisocyanate compound B, an isocyanate group at the terminal obtained by the reaction of a blocked product x of an organic polyisocyanate (isocyanate monomer), an organic polyisocyanate (isocyanate monomer) and a compound having two or more active hydrogens. And a blocked product z of a prepolymer having a polymer and a multimer (multimerized product) of an organic polyisocyanate (isocyanate monomer). These compounds can be used alone or in combination of two or more.

  The organic polyisocyanate in the blocked product x of the organic polyisocyanate is an isocyanate having at least two isocyanate groups in the molecule, such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene. Diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 2,6-diisocyanate methyl caproate, etc. 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (= isophorone diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6- Such as cyclohexane diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, trans-cyclohexane-1,4-diisocyanate, etc. Cycloalkylene diisocyanate (alicyclic diisocyanate); m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene Aromatic diisocyanates such as socyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate; ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, α, α, α ′, α′-tetra Aromatic aliphatic diisocyanates such as methyl metaxylylene diisocyanate, α, α, α ′, α′-tetramethyl paraxylylene diisocyanate; triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5 -Triisocyanate benzene, 2, 4, -Triisocyanates such as triisocyanate toluene, ω-isocyanatoethyl-2,6-diisocyanatocaproate; tetras such as 4,4'-diphenyldimethylmethane-2,2 ', 5,5'-tetraisocyanate An isocyanate etc. are mentioned.

  Among these, when weather resistance is required, such as when used as a precoat metal, hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (= isophorone diisocyanate), 1,4- Isocyanates such as bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4'-methylenebis (cyclohexyl isocyanate), α, α, α ', α'-tetramethylmetaxylylene diisocyanate It is preferable to use a compound.

  The organic polyisocyanate in the blocked product y of the prepolymer having an isocyanate group at the terminal obtained by the reaction of the organic polyisocyanate with the compound having two or more active hydrogens is the same as the organic polyisocyanate in the blocked product x of the organic polyisocyanate. Yes, and preferred examples are the same as described above.

  Examples of the compound having two or more active hydrogens include ethylene glycol, propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, diethylene glycol, diethylene glycol, Dihydric alcohols such as propylene glycol, neopentyl glycol, neopentyl glycol hydroxypivalate, triethylene glycol, hydrogenated bisphenol A, xylylene glycol; glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexane Trihydric alcohols such as triols; Low molecular weight polyols such as tetrahydric alcohols such as pentaerythritol; Propylene oxide or ethylene oxide adducts of the above low molecular weight polyols, etc. Polyether polyols; polyols such as high molecular weight polyols, such as those fatty acid modified in making the polyester polyols or polyester polyols obtained by a reaction of the low molecular weight polyol and a dicarboxylic acid. In addition to the above, examples of the compound having two or more active hydrogens include water; polyamines such as low molecular weight polyamines (such as low molecular weight diamine) such as ethylenediamine, hexamethylenediamine, and isophoronediamine. Compounds having two or more active hydrogens can be used alone or in combination of two or more.

  The prepolymer having an isocyanate group at the terminal can be obtained by reacting an organic polyisocyanate (isocyanate monomer) with a compound having two or more active hydrogens in an excess of isocyanate groups. In general, the equivalent ratio of isocyanate group / active hydrogen group (for example, hydrogen atom of hydroxyl group) is about 2.0 to 15, preferably about 4 to 8. The reaction temperature is usually 40 to 140 ° C, preferably 70 to 100 ° C. After completion of the reaction, if necessary, unreacted organic polyisocyanate can be removed by a conventional thin film distillation method or extraction method. In the above reaction, organometallic catalysts such as tin, lead, zinc and iron may be used.

  The prepolymer having an isocyanate group at the terminal is a biuret compound obtained by reacting water or a lower polyamine such as ethylenediamine with an excess of an organic polyisocyanate (isocyanate monomer), or the above low molecular weight polyol or high molecular weight polyol. And an allophanate compound obtained by reacting an excess of organic polyisocyanate (isocyanate monomer).

  The organic polyisocyanate in the blocked product z of the multimer (multimerized product) of the organic polyisocyanate is the same as the organic polyisocyanate in the blocked product x of the organic polyisocyanate. Dimers or trimers obtained by reacting organic polyisocyanate (isocyanate monomer) with a dimerization or trimerization catalyst of organic diisocyanate as a polymer (multimerization product) of organic polyisocyanate. And the like.

  The block polyisocyanate compound B is a compound having two or more isocyanate groups in the molecule [for example, the organic polyisocyanate (isocyanate monomer), the prepolymer having an isocyanate group at the terminal, the organic polyisocyanate (isocyanate monomer) Body) multimers (multimerized products)] and a blocking agent.

As the blocking agent, a blocking agent known to be used for blocking isocyanate, such as phenol, lactam, active methylene, alcohol, mercaptan, acid amide, imide, amine, Any blocking agent such as imidazole, urea, carbamate, imine, oxime, or sulfite may be used. Among these, blocking agents such as phenol-based, oxime-based, lactam-based, and imine-based are advantageously used. As the blocking agent, those exemplified as the aforementioned blocking agent R ³ H of isocyanate group can also be used. The blocking agent is preferably a highly stable blocking agent that does not cause gelation in the production line of the curable resin composition. The deblocking temperature of the blocking agent is, for example, 100 to 300 ° C, preferably 150 to 250 ° C. Specific examples of the blocking agent include the following.

  Phenol-based blocking agent: phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, p-hydroxydiphenyl, t-butylphenol, o-isopropylphenol, o-sec-butylphenol, p-nonylphenol, pt-octylphenol, Hydroxybenzoic acid, hydroxybenzoic acid ester, etc.

  Lactam blocking agents: ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam, etc.

  Active methylene blocking agent: diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, acetylacetone, etc.

  Alcohol-based blocking agent: methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol Glycolic acid esters such as monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, methoxymethanol, glycolic acid, methyl glycolate, ethyl glycolate, butyl glycolate, lactic acid , Lactate esters such as methyl lactate, ethyl lactate and butyl lactate, methylo Urea, methylol melamine, diacetone alcohol, ethylene chlorohydrin, ethylene epibromohydrin, 1,3-dichloro-2-propanol, .omega. hydroperoxide fluoroalcohol, aceto cyanohydrin such as

  Mercaptan blocking agents: butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol, ethylthiophenol, etc.

  Acid amide blocking agents: acetanilide, acetanisidide, acetolide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide, benzamide, etc.

  Imide blocking agent: Succinimide, phthalic imide, maleic imide, etc.

  Amine blocking agent: Diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine, butylphenylamine, etc.

  Imidazole-based blocking agents: imidazole, 2-ethylimidazole, etc.

  Urea blocking agent: urea, thiourea, ethylene urea, ethylene thiourea, 1,3-diphenylurea, etc.

  Carbamate block agent: phenyl N-phenylcarbamate, 2-oxazolidone, etc.

  Imine block agent: Ethyleneimine, propyleneimine, etc.

  Oxime-based blocking agents: formamidoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexanone oxime, etc.

  Sulphite blocking agents: sodium bisulfite, potassium bisulfite, etc.

  Compound having two or more isocyanate groups in the molecule [the organic polyisocyanate (isocyanate monomer), prepolymer having an isocyanate group at the terminal, multimer of the organic polyisocyanate (isocyanate monomer) (multimer) As a specific method of the reaction between the blocking agent and the blocking agent, for example, (1) a compound having two or more isocyanate groups in the molecule and the blocking agent are combined with an active hydrogen group (equivalent ratio) in the isocyanate group / blocking agent. ) = A method of reacting at about 0.9 to 1.0, preferably about 0.95 to 1.0, (2) a compound having two or more isocyanate groups in the molecule (for example, an isocyanate monomer) and a block Active agent group in isocyanate group / blocking agent (equivalent ratio) = 1.1 to 3.0, preferably about 1.2 to 2.0 (3) a method of reacting with a low molecular weight polyol, a high molecular weight polyol, water or a low molecular weight polyamine as used in the preparation of the prepolymer, and (3) two or more isocyanate groups in the molecule. A compound having a low molecular weight polyol, a high molecular weight polyol, water or a low molecular weight polyamine (isocyanate group / active hydrogen group equivalent ratio) of about 1.5 to 10.0, preferably 2.0 Examples include a method of reacting with a blocking agent after reacting at about ~ 7.0.

  Each of the above reactions is carried out in a solvent having no active hydrogen group (for example, aromatic solvents such as benzene, toluene and xylene, petroleum solvents such as Solvesso 100 and Solvesso 200, and ester solvents such as ethyl acetate and butyl acetate). , Acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, ether solvents such as tetrahydrofuran, or the like, or in the absence of such a solvent. In the reaction, for example, a known catalyst such as a tertiary amine or an organic metal may be used.

  Among the block polyisocyanate compounds B, commercially available products such as Coronate 2507, Coronate 2513, Coronate AP staple, etc. from Nippon Polyurethane Industry Co., Ltd., Takenate B-882N, Takenate B-830, Takenate B from Mitsui Chemicals Polyurethane Co., Ltd. -815N, Takenate B-842N, Takenate B-846N, Takenate B-870N, Takenate B-874N, etc. Asahi Kasei, such as Burnock D-500, Burnock D-550, Burnock B3-867 made by Dainippon Ink & Chemicals, Inc. DURANATE MF-B60X, DURANATE MF-K60X, etc., manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Elastron BN-P17, Elastron BN-04, Elastron BN-08, Elastron BN-44, Such as Rasutoron BN-45 and the like.

[Curable resin composition]
The curable resin composition of the present invention can be prepared by mixing the copolymer A and the block polyisocyanate compound B. For example, the block polyisocyanate compound B or a solution thereof is added to a polymer solution obtained when the copolymer A is produced or a solution obtained by subjecting the polymer solution to operations such as concentration adjustment, solvent exchange, and filtration treatment. Thus, a curable resin composition can be prepared. Further, the copolymer A produced from the polymerization solution is isolated by precipitation, crystallization, etc., and cured by adding the block polyisocyanate compound B or a solution thereof to a solution obtained by dissolving the purified polymer in an appropriate solvent. A functional resin composition can also be prepared.

  The blending ratio of the copolymer A and the block polyisocyanate compound B can be selected within a wide range. Generally, the former / the latter (weight ratio) = 5/95 to 95/5, preferably the former / the latter (weight ratio). ) = 10/90 to 90/10, more preferably 20/80 to 80/20, and particularly preferably 30/70 to 70/30. When the block polyisocyanate compound B is not blended, the hardness of the cured product is insufficient. Further, depending on the type of the solvent, the adhesion to the substrate when in contact with the solvent becomes insufficient.

  In the curable resin composition of the present invention, a curing catalyst [thermal acid generator (thermosetting catalyst, thermal cationic polymerization initiator), photoacid generator (photocuring catalyst, photocationic polymerization initiator), as necessary. ], Curing agents, curing accelerators, additives (fillers, antifoaming agents, flame retardants, antioxidants, UV absorbers, stress reducing agents, flexibility imparting agents, waxes, resins, crosslinking agents, halogens Trapping agents, leveling agents, wetting improvers, etc.) can also be added.

  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.

  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 A (resin component) in the curable resin composition. A curing catalyst can be used individually or in combination of 2 or more types.

  Furthermore, fine particles of glass, ceramic, inorganic material, metal, metal oxide, and resin can be blended with the curable resin composition of the present invention depending on the application.

  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

Synthesis Example 1 (Preparation of copolymer solution 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. Subsequently, in the flask, 60 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate (trade name “Cyclomer M100”, manufactured by Daicel Chemical Industries, Ltd.), 2- [O- (1′-methylpropylidene methacrylate) Amino) carboxyamino] ethyl (trade name “Karenz MOI-BM”, Showa Denko KK) 40 parts by weight dissolved in 30 parts by weight of propylene glycol monomethyl ether acetate over about 4 hours using a dropping pump It was dripped. 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 (copolymer solution 1) having a solid content of 32.6% by weight. The produced copolymer had a weight average molecular weight Mw of 9000 and a dispersity of 1.80.

Synthesis Example 2 (Preparation of copolymer solution 2)
The monomer composition was 60 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate (trade name “Cyclomer M100”, manufactured by Daicel Chemical Industries, Ltd.), 2- [O- (1′-methylpropylideneamino) methacrylate. ) Carboxyamino] ethyl (trade name “Karenz MOI-BM”, manufactured by Showa Denko KK) 20 parts by weight, operation similar to Synthesis Example 1 except for changing to 20 parts by weight of 2-hydroxyethyl methacrylate (HEMA) And a copolymer solution (copolymer solution 2) having a solid content of 32.6% by weight was obtained. The resulting copolymer had a weight average molecular weight Mw of 9300 and a dispersity of 1.86.

Synthesis Example 3 (Preparation of copolymer solution 3)
The monomer composition was 60 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate (trade name “Cyclomer M100”, manufactured by Daicel Chemical Industries, Ltd.), 2- [O- (1′-methylpropylideneamino) methacrylate. ) Carboxyamino] ethyl (trade name “Karenz MOI-BM”, Showa Denko KK) 20 parts by weight and methyl methacrylate 20 parts by weight. A 6 wt% copolymer solution (copolymer solution 3) was obtained. The resulting copolymer had a weight average molecular weight Mw of 9300 and a dispersity of 1.86.

Example 1
To 50 parts by weight of the copolymer solution 1 (solid content: 32.6% by weight) obtained in Synthesis Example 1, 20 parts by weight of coronate 2507 (block polyisocyanate compound, content: 80% by weight, manufactured by Nippon Polyurethane Industry Co., Ltd.) A solution dissolved in 30 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was blended to obtain a curable resin composition.

Example 2
To 50 parts by weight of the copolymer solution 2 (solid content 32.6% by weight) obtained in Synthesis Example 2, 20 parts by weight of Coronate 2507 (block polyisocyanate compound, content 80% by weight, manufactured by Nippon Polyurethane Industry Co., Ltd.) A solution dissolved in 30 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was blended to obtain a curable resin composition.

Example 3
To 50 parts by weight of the copolymer solution 3 (solid content 32.6% by weight) obtained in Synthesis Example 3, 20 parts by weight of coronate 2507 (block polyisocyanate compound, content 80% by weight, manufactured by Nippon Polyurethane Industry Co., Ltd.) A solution dissolved in 30 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was blended to obtain a curable resin composition.

Example 4
To 50 parts by weight of the copolymer solution 1 (solid content 32.6% by weight) obtained in Synthesis Example 1, Takenate B-882N (block polyisocyanate compound, content 70% by weight, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 23% by weight A solution in which a part was dissolved in 27 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was blended to obtain a curable resin composition.

Example 5
To 50 parts by weight of the copolymer solution 2 (solid content 32.6% by weight) obtained in Synthesis Example 2, Takenate B-882N (block polyisocyanate compound, content 70% by weight, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 23% by weight A solution in which a part was dissolved in 27 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was blended to obtain a curable resin composition.

Comparative Example 1
The copolymer solution 1 obtained in Synthesis Example 1 was used as it was as a curable resin composition.

Comparative Example 2
The copolymer solution 2 obtained in Synthesis Example 2 was used as it was as a curable resin composition.

Comparative Example 3
The copolymer solution 3 obtained in Synthesis Example 3 was used as it was as a curable resin composition.

Evaluation test (1) Preparation of test piece for evaluation After applying the curable resin composition obtained in each Example and Comparative Example to a base material with a spin coater, it was heated on a hot plate at 100 ° C. for 3 minutes, and then 80 Each test piece for evaluation was produced by heating in an oven at ° C for 30 minutes and further heating in an oven at 220 ° C for 30 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) Coating film hardness About the test specimens for evaluation of the respective Examples and Comparative Examples (those not subjected to other tests), coating was performed in accordance with the scratch hardness (pencil method) of JIS K 5600-5-4. The pencil hardness was measured by scratching the film (cured product) to determine the surface hardness.

  The results of the evaluation test are shown in Table 1.

  As is clear from the table, the cured coating films obtained from the curable resin compositions of the examples have solvent resistance, adhesion to substrates (glass and stainless steel) (adhesion after solvent contact), and coating film hardness. It was excellent in any point. On the other hand, the cured coating film obtained from the curable resin composition of the comparative example was inferior particularly in terms of coating film hardness.

Claims (4)

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 copolymer A comprising at least a monomer unit corresponding to a vinyl monomer a having a blocked isocyanate group and a monomer unit corresponding to a vinyl monomer b having a 3- to 5-membered cyclic ether group And a curable resin composition containing the block polyisocyanate compound B. In addition to the monomer unit corresponding to the vinyl monomer a and the monomer unit corresponding to the vinyl monomer b, the copolymer A has the following formula (2):

(Wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydrocarbon group having 1 to 15 carbon atoms which may have a hydrocarbon group-substituted oxy group)
Corresponding to at least one monomer selected from the group consisting of (meth) acrylic acid ester c, aromatic vinyl compound d, hydroxyl group-containing monomer e, and carboxyl group-containing monomer f The curable resin composition according to claim 1, which is a polymer containing monomer units.   Block polyisocyanate compound B is a block product of organic polyisocyanate, a block product of prepolymer having an isocyanate group at the terminal obtained by reaction of organic polyisocyanate with a compound having two or more active hydrogens, and a large amount of organic polyisocyanate The curable resin composition according to claim 1, wherein the curable resin composition is at least one compound selected from blocked bodies.   Hardened | cured material obtained by hardening | curing the curable resin composition in any one of Claims 1-3.