JP2010031073A - Curable resin composition - Google Patents

Abstract

（式中、Ｒ^aは水素原子又は炭素数１〜７のアルキル基を示し、Ａは単結合又は２価の炭化水素基を示す。Ｒ^b、Ｒ^cは炭素数１〜６のアルキル基等を示し、Ｒ^dは炭素数１〜６のアルキル基を示す。ｘは０又は１であり、ｙは１〜１０の整数である）で表される一種又は複数種のアルコキシシリル基含有ビニル単量体ａのみをモノマー成分とする重合体Ａと、前記式（１）で表されるアルコキシシリル基含有ビニル単量体ａ、３〜５員の環状エーテル基を有するビニル単量体ｂ、及び側鎖にε−カプロラクトン開環重合鎖部を有するヒドロキシル基含有ビニル単量体ｃをモノマー成分として含有してなる共重合体Ｂとを含む。
【選択図】 なしPROBLEM TO BE SOLVED: To obtain a curable resin composition capable of obtaining a cured product having excellent adhesion to a substrate and excellent heat resistance and chemical resistance.
The curable resin composition of the present invention has the following formula (1).
[Chemical 1]

(In the formula, R ^a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, A represents a single bond or a divalent hydrocarbon group. R ^b and R ^c represent an alkyl group having 1 to 6 carbon atoms, etc. R ^d represents an alkyl group having 1 to 6 carbon atoms, x is 0 or 1, and y is an integer of 1 to 10). A polymer A containing only the monomer a as a monomer component, an alkoxysilyl group-containing vinyl monomer a represented by the formula (1), a vinyl monomer b having a 3- to 5-membered cyclic ether group, and And a copolymer B containing a hydroxyl group-containing vinyl monomer c having an ε-caprolactone ring-opening polymer chain moiety in the side chain as a monomer component.
[Selection figure] None

Description

  The present invention relates to a polymer comprising only an alkoxysilyl group-containing vinyl monomer as a monomer component, and a copolymer having an alkoxysilyl group, a cyclic ether group, and a hydroxyl group-containing group containing an ε-caprolactone ring-opening polymerization site. The present invention relates to a curable resin composition containing The curable resin composition of the present invention is useful for paints, coating agents, adhesives, and electronic materials (protective films, sealing materials, nanoimprint materials, etc.).

  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.

  In order to solve this problem, Japanese Patent Application Laid-Open No. 2007-223825 discloses a hydrophilic coating liquid composition containing a polymer compound having a reactive group such as a silane coupling group at its terminal and a hydrolyzable metal alkoxide compound. A heat-resistant glass is disclosed in which a hydrophilic surface layer is formed by coating and drying it on the surface of a glass substrate. This heat-resistant glass is said to have a hydrophilic surface and a surface hydrophilic layer that is excellent in durability, transparency, and storage stability, and has durable antifouling properties and antifogging properties. However, the monomer component is complicated, and it is necessary to use a monomer that is difficult to obtain.

JP 2007-223825 A

  The present inventors have a simple monomer component, an easily available monomer, an excellent solvent resistance, and a polymer that can provide a cured product with excellent adhesion to a substrate. A polymer having only a vinyl monomer as a monomer component is proposed. However, a coating film obtained by curing a composition containing this polymer does not always have sufficient chemical resistance, particularly alkali resistance performance.

  Accordingly, an object of the present invention includes a polymer obtained from an easily available monomer, and has excellent adhesion to a substrate, and also has excellent heat resistance and chemical resistance (particularly alkali resistance and solvent resistance). It is in providing the curable resin composition obtained, and the hardened | cured material obtained by hardening | curing this curable resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that a polymer containing only an alkoxysilyl group-containing vinyl monomer as a monomer component, an alkoxysilyl group-containing vinyl monomer, and a 3- to 5-membered cyclic group. A curable resin composition comprising a mixture of a vinyl monomer having an ether group and a copolymer containing, as a monomer component, a hydroxyl group-containing vinyl monomer obtained by ring-opening polymerization of ε-caprolactone in the side chain. It was found that when applied to a material and cured, a coating film of a cured product having excellent chemical resistance, solvent resistance, and alkali resistance and particularly excellent adhesion to a substrate was found, and the present invention was completed.

（式中、Ｒ^aは水素原子又は炭素数１〜７のアルキル基を示し、Ａは単結合又は２価の炭化水素基を示す。Ｒ^b、Ｒ^cは、同一又は異なって、炭素数１〜６のアルキル基、アリール基又は炭素数１〜６のアルコキシ基を示し、Ｒ^dは炭素数１〜６のアルキル基を示す。ｘは０又は１であり、ｙは１〜１０の整数である。ｙが２〜１０の整数の場合、ｙ個のＲ^b、Ｒ^cは、それぞれ、同一であっても異なっていてもよい）
で表される一種又は複数種のアルコキシシリル基含有ビニル単量体ａのみをモノマー成分とする重合体Ａと、前記式（１）で表される一種又は複数種のアルコキシシリル基含有ビニル単量体ａ、３〜５員の環状エーテル基を有する一種又は複数種のビニル単量体ｂ、及び側鎖にε−カプロラクトン開環重合鎖部を有する一種又は複数種のヒドロキシル基含有ビニル単量体ｃをモノマー成分として含有してなる共重合体Ｂとを含むことを特徴とする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 ^a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, A represents a single bond or a divalent hydrocarbon group. R ^b and R ^c are the same or different and each represents 1 carbon atom. -6 represents an alkyl group, aryl group, or alkoxy group having 1 to 6 carbon atoms, R ^d represents an alkyl group having 1 to 6 carbon atoms, x is 0 or 1, and y is an integer of 1 to 10. When y is an integer of 2 to 10, y R ^b and R ^c may be the same or different)
A polymer A containing only one or a plurality of alkoxysilyl group-containing vinyl monomers a represented by the formula (1), and one or a plurality of alkoxysilyl group-containing vinyl monomers represented by the formula (1) Body a, one or more kinds of vinyl monomers b having 3 to 5 membered cyclic ether groups, and one or more kinds of hydroxyl group-containing vinyl monomers having an ε-caprolactone ring-opening polymer chain moiety in the side chain A curable resin composition comprising a copolymer B containing c as a monomer component is provided.

  In this curable resin composition, the content ratio of the polymer A and the copolymer B is preferably in the range of 25:75 to 75:25 by weight.

  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 is possible to obtain a cured product (cured film or the like) that is excellent in chemical resistance, solvent resistance, and alkali resistance and particularly excellent in adhesion to a substrate. 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 (protective film, sealing material, nanoimprint material, etc.).

  The curable resin composition of the present invention includes a polymer A containing only one or a plurality of alkoxysilyl group-containing vinyl monomers a represented by the formula (1) as a monomer component, and the formula (1). One or more types of alkoxysilyl group-containing vinyl monomers a, one or more types of vinyl monomers b having a 3- to 5-membered cyclic ether group, and ε-caprolactone ring-opening polymer chain in the side chain And a copolymer B formed by containing one or more kinds of hydroxyl group-containing vinyl monomers c having a moiety as monomer components.

[Polymer A]
The polymer A contains only one or a plurality of alkoxysilyl group-containing vinyl monomers a represented by the formula (1) as a monomer component. In the present specification, the term “monomer” or “monomer component” does not include a polymerization initiator, a chain transfer agent, or a decomposition product thereof used for the polymerization reaction.

In the alkoxysilyl group-containing vinyl monomer a represented by the formula (1), ^Ra represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, and A represents a single bond or a divalent hydrocarbon group. R ^b and R ^c are the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an aryl group or an alkoxy group having 1 to 6 carbon atoms, and R ^d represents an alkyl group having 1 to 6 carbon atoms. x is 0 or 1, and y is an integer of 1 to 10. When y is an integer of 2 to 10, y R ^b and R ^c may be the same or different.

Examples of the alkyl group having 1 to 7 carbon atoms in R ^a include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl groups and the like. Can be mentioned. Among these, a methyl group and an ethyl group are preferable. R ^a is particularly preferably a hydrogen atom or a methyl group.

  In the formula (1), examples of the divalent hydrocarbon group for A include linear or branched alkylene groups such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene and the like. An arylene group such as a phenylene group; a cycloalkylene group such as a cyclohexylene group; a group in which two or more of these are bonded. Among these, a linear or branched alkylene group having 1 to 6 carbon atoms is preferable, and in particular, a linear or branched alkylene group having 1 to 3 carbon atoms such as methylene, ethylene, and propylene group. preferable.

Examples of the alkyl group having 1 to 6 carbon atoms in R ^b , R ^c and R ^d include linear or branched chains such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl and hexyl groups. An alkyl group. Among these, a linear or branched alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and isopropyl groups is preferable.

Examples of the aryl group in R ^b and R ^c include phenyl and naphthyl groups.

Examples of the alkoxyl group having 1 to 6 carbon atoms in R ^b and R ^c include linear or branched chain such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, pentoxy, hexyloxy group, etc. An alkoxyl group is mentioned.

  As typical examples of the alkoxysilyl group-containing vinyl monomer a represented by the formula (1), for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ- ( (Meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ- (meth) ) Acryloyloxypropyltriethoxysilane, β- (meth) acryloyloxyethyltrimethoxysilane, β- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) acryloyloxybutylphenyldimethoxysilane, γ- ( Data) acryloyloxy-butylphenyl diethoxy silane alkoxysilyl group-containing polymerizable unsaturated compounds such as and the like, can be used singly or in combination of two or more kinds selected from these.

  The polymer A can be obtained by subjecting a monomer component consisting only of one or plural kinds of alkoxysilyl group-containing vinyl monomers represented by the formula (1) to polymerization. Details of the polymerization method will be described later.

  The weight average molecular weight of the polymer A is generally about 500 to 20000, preferably 700 to 5000, and more preferably 2000 to 5000. The weight average molecular weight of the polymer A can be adjusted by the kind and amount of the polymerization initiator, the kind and amount of the chain transfer agent, and the like. The degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the polymer A is about 1 to 3, and preferably 1 to 2.6.

  For example, the amount of the polymerization initiator used is, for example, about 7 to 30 parts by weight, preferably about 10 to 25 parts by weight, and more preferably about 10 to 20 parts by weight with respect to 100 parts by weight of the total monomer components. Thus, a low molecular weight polymer having a weight average molecular weight of 700 to 5,000 can be produced with good reproducibility. When the amount of the polymerization initiator used is less than 7 parts by weight with respect to 100 parts by weight of the total monomer components, the weight average molecular weight of the obtained polymer A often exceeds 5000, and the resulting weight When the dispersion degree of the combined A exceeds 2.6 and the high molecular weight component tends to increase, when the curable resin composition containing this polymer is cured, the adhesion with the base material tends to deteriorate. On the other hand, when the amount of the polymerization initiator used is more than 30 parts by weight with respect to 100 parts by weight of the total monomer components, the amount of residual initiator in the system after the reaction is increased, When the curable resin composition containing is applied to a substrate and cured, the solvent resistance of the coating film tends to be lowered. Further, when the polymerization initiator is decomposed by heating, a high molecular weight resin is generated by the heating. As a result, when the curable resin composition comprising this polymer is applied to the substrate and cured, Adhesion tends to be poor.

[Copolymer B]
The copolymer B is a monomer unit corresponding to one or more kinds of alkoxysilyl group-containing vinyl monomers a represented by the formula (1), and one or more kinds having a 3- to 5-membered cyclic ether group. It contains at least a monomer unit corresponding to the vinyl monomer b and a monomer unit corresponding to one or plural kinds of hydroxyl group-containing vinyl monomers c having an ε-caprolactone ring-opening polymerization chain portion in the side chain.

  As the one or plural alkoxysilyl group-containing vinyl monomers a represented by the formula (1), those described above can be used.

  In the copolymer B, 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, An oxolane ring (oxolanyl group) -containing polymerizable unsaturated compound is included.

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 B, 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.).

  As the vinyl monomer b, an oxirane ring (epoxy group) -containing polymerizable unsaturated compound is preferable, and in particular, an alicyclic ring in which an epoxy group is formed on an alicyclic carbocycle (monocyclic or polycyclic). Vinyl monomers containing a formula epoxy group are preferred.

  In the copolymer B, examples of the hydroxyl group-containing vinyl monomer c having an ε-caprolactone ring-opening polymerization chain moiety in the side chain include monoesterified products of polyhydric alcohol and acrylic acid or methacrylic acid [for example, 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, etc.] Examples thereof include ring-opened polymerization compounds (6-hexanolide addition polymer, degree of polymerization of ε-caprolactone of about 1 to 6).

  As a representative example of the hydroxyl group-containing vinyl monomer c having an ε-caprolactone ring-opening polymerization chain portion in the side chain, a 6-hexanolide addition polymer of 2-hydroxyethyl (meth) acrylate (degree of polymerization 1 to 6) (Plaxel FA series, Plaxel FM series, etc. manufactured by Daicel Chemical Industries, Ltd.).

  In the copolymer B, the monomer unit corresponding to the hydroxyl group-containing vinyl monomer c having an ε-caprolactone ring-opening polymerization chain portion in the side chain mainly includes tack-free flexibility and solubility in a solvent. This contributes to improving the compatibility with other raw materials.

  In the copolymer B, 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 vinyl monomer c may each be one kind, Two or more kinds may be present.

  The proportion of the monomer unit corresponding to the vinyl monomer a in the copolymer B is, for example, 1 to 95% by weight, preferably 10 to 90% by weight, based on all the monomer units constituting the copolymer B. Preferably, it is 20 to 85% by weight.

  The proportion of the monomer unit corresponding to the vinyl monomer b in the copolymer B is, for example, 1 to 95% by weight, preferably 5 to 80% by weight, based on all monomer units constituting the copolymer B. Preferably it is 12 to 70% by weight.

  The proportion of the monomer unit corresponding to the vinyl monomer c in the copolymer B is, for example, 0.1 to 95% by weight, preferably 0.2 to 50%, based on all monomer units constituting the copolymer B. % By weight, more preferably 0.2 to 30% by weight.

  The proportion 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 vinyl monomer c to the copolymer B constitutes the copolymer B For example, it is 40 to 100% by weight, preferably 50 to 100% by weight, more preferably 60 to 100% by weight, and particularly preferably 80 to 100% by weight, based on the total monomer units.

  The copolymer B 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 vinyl monomer c. In addition to the monomer unit corresponding to the monomer a, the monomer unit corresponding to the vinyl monomer b, and the monomer unit corresponding to the vinyl monomer c, other monomer units 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 vinyl monomer c, and has adhesion and resistance to a substrate. It is not particularly limited as long as it is a structural unit that does not impair the chemical properties.

  As monomers that can form other monomer units that may be contained in such a copolymer B, (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester (Meth) acrylic acid aralkyl ester, aromatic vinyl compound, hydroxyl group-containing monomer [(meth) acrylic acid hydroxyalkyl ester], carboxyl group or acid anhydride group-containing monomer. These monomers can be used alone or in combination of two or more.

  The weight average molecular weight of the copolymer B 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 B is about 1 to 3.

[Polymerization method]
As described above, the polymer A can be produced by subjecting a monomer component consisting only of one or plural kinds of alkoxysilyl group-containing vinyl monomers represented by the formula (1) to polymerization. The copolymer B is composed of an alkoxysilyl group-containing vinyl monomer a represented by the formula (1), a vinyl monomer b having a 3- to 5-membered cyclic ether group, and ε-caprolactone in the side chain. It can be produced by subjecting a monomer mixture containing a hydroxyl group-containing vinyl monomer c having a ring-opening polymer chain portion and another copolymerizable monomer as necessary 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 polymerization, 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, 2-ethylhexyl mercaptoacetate), 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 diacetate, glycerol mono-, di- or triacetate, glycerin mono- or di-C _1-4 alkyl ethers di- or mono-acetate, tripropylene glycol monoalkyl ether acetates, glycol acetates or glycol ether acetates, such as 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.

  Polymer A and copolymer B are produced by the above method.

  The polymer solution containing the polymer A obtained by the above method and the polymer solution containing the copolymer B are each adjusted for solids concentration as necessary, solvent exchange, or after filtration treatment, Mix at an appropriate ratio, and if necessary, curing catalyst [thermal acid generator (thermal curing catalyst, thermal cationic polymerization initiator), photoacid generator (photocuring catalyst, photocationic polymerization initiator)], curing Agent, curing accelerator, additive (filler, antifoaming agent, flame retardant, antioxidant, UV absorber, stress reducing agent, flexibility imparting agent, wax, resin, crosslinking agent, halogen trapping agent, A curable resin composition can be obtained by blending a leveling agent, a wetting improver, and the like. Moreover, the polymer produced | generated by superposition | polymerization can be refine | purified by precipitation or reprecipitation etc., and the solution which melt | dissolved this refined polymer in a suitable solvent can also be used for preparation of curable resin composition.

  In the curable resin composition of the present invention, the content ratio of the polymer A and the copolymer B (the former: the latter) can be selected in a wide range, but in general, the weight ratio is 5:95 to 95: 5, Preferably it is 25: 75-75: 25, More preferably, it is 30: 70-70: 30. By satisfying such conditions, the cured product obtained by curing the curable resin composition has excellent chemical resistance, solvent resistance, and alkali resistance, and particularly excellent adhesion to the substrate. Can be.

  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, based on the total amount (resin content) of the polymer and copolymer in the curable resin composition. is there. A curing catalyst can be used individually or in combination of 2 or more types.

  As a hardening | curing agent, an epoxy resin, a phenol resin, an acid anhydride etc. are mentioned, for example.

  The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule (polyfunctional epoxy resin). For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type Examples thereof include epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl ether type epoxy resins such as brominated bisphenol A, dimer acid diglycidyl esters, and phthalic acid diglycidyl esters. In addition, as an epoxy resin, a polyfunctional alicyclic epoxy resin [for example, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate (trade name “Celoxide 2021” manufactured by Daicel Chemical Industries, Ltd.) Etc.] can also be used. An epoxy resin can be used individually or in combination of 2 or more types. The compounding quantity of an epoxy resin can be suitably selected in the range of 0-50 weight part (for example, about 5-50 weight part) with respect to 100 weight part of copolymers of this invention, for example.

  As the phenol resin, for example, a resin obtained by polymerizing phenol or cresol using formaldehyde can be used. This resin may be a copolymer of an alicyclic compound or aromatic compound such as dicyclopentadiene, naphthalene, or biphenyl. The addition amount of a phenol resin can be suitably selected, for example in the range of 0-200 weight part (for example, about 5-200 weight part) with respect to 100 weight part of resin total amount in curable resin composition.

Examples of the acid anhydride include polybasic acid anhydrides. Specifically, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, Δ ⁴ -tetrahydrophthalic anhydride, 4 -Methyl-Δ ⁴ -tetrahydrophthalic anhydride, 3-methyl-Δ ⁴ -tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, 4- (4-methyl-3-pentenyl) ) Tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, maleic anhydride, sebacic anhydride, dodecanedioic anhydride, methylcyclohexene tetracarboxylic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, 4-methylhexahydro Phthalic anhydride, 3-methylhexahydrophthalic anhydride, vinyl ether-maleic anhydride Acid copolymers, alkyl styrene-maleic anhydride copolymer and the like. The compounding quantity of an acid anhydride can be suitably selected, for example in the range of 0-160 weight part (for example, about 20-160 weight part) with respect to 100 weight part of resin total amount in curable resin composition.

  When a phenol resin or acid anhydride is used as the curing agent, it is preferable to use a curing accelerator together. The curing accelerator is not particularly limited as long as it is generally used. However, phosphorus curing accelerators such as diazabicycloundecene curing accelerators (diazabicycloalkenes), phosphate esters, phosphines, Examples include amine-based curing accelerators such as tertiary amines and quaternary ammonium salts. Examples of the diazabicycloundecene-based curing accelerator include 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and salts thereof. In particular, 1,8-diazabicyclo [ 5.4.0] Organic salts of undecene-7 such as octylate, sulfonate, orthophthalate, and coalate are preferred. Specific examples of the other curing accelerator include tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol, 2-ethyl-4-methylimidazole, 1 -Phosphorus compounds (phosphonium salts, etc.) that do not contain aromatics, such as imidazoles such as cyanoethyl-2-ethyl-4-methylimidazole, tetra-n-butylphosphonium-O, O-diethyl phosphorodithioate, and tertiary amines Known compounds such as salts, metal salts such as quaternary ammonium salts and tin octylate can be exemplified. Furthermore, a metal organic acid salt can be used in combination with the organic acid salt of the diazabicycloalkenes. Examples of the metal organic acid salt include tin octylate, zinc octylate, tin naphthenate, and zinc naphthenate. The usage-amount of a hardening accelerator can be suitably selected, for example in the range of 0-3 weight part (for example, about 0.05-3 weight part) with respect to 100 weight part of resin total amount in curable resin composition.

  The curable resin composition may contain fine particles such as glass fine particles, metal oxide fine particles, rubber fine particles, and ceramic fine particles. These can 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 (protective film, sealing material, nanoimprint material, etc.).

  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 polymer and a 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 <Polymer Solution A-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 90 ° C. with stirring. Next, a solution prepared by dissolving 100 parts by weight of γ-methacryloxypropyltrimethoxysilane (manufactured by Toray Dow Corning) in 30 parts by weight of propylene glycol monomethyl ether acetate was dropped into the flask over about 4 hours using a dropping pump. did. On the other hand, a solution obtained by dissolving 15 parts by weight of a polymerization initiator 2,2′-azobis (isobutyric acid) dimethyl in 80 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over about 4 hours using another dropping pump. After completion of 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 polymer solution A-1 having a solid content of 33.5% by weight. The produced polymer had a weight average molecular weight Mw of 4000 and a dispersity of 1.85.

Synthesis Example 2 <Polymer solution A-2>
The same procedure as in Synthesis Example 1 was performed except that the monomer composition was changed to 100 parts by weight of γ-methacryloxypropyltriethoxysilane (manufactured by Dow Corning Toray), and a solid content of 33.6% by weight was obtained. A combined solution A-2 was obtained. The produced polymer had a weight average molecular weight Mw of 4300 and a dispersity of 1.86.

Synthesis Example 3 <Polymer solution B-1>
The monomer composition was 75 parts by weight of γ-methacryloxypropyltrimethoxysilane (manufactured by Dow Corning Toray), 23 parts by weight of glycidyl methacrylate (GMA), 6-hexanolide addition polymer of 2-hydroxyethyl acrylate (average) Degree of polymerization 3) (trade name “Placcel FA-3”, manufactured by Daicel Chemical Industries, Ltd.) A polymer having a solid content of 34.0% by weight was subjected to the same operation as in Synthesis Example 1 except that the amount was changed to 2 parts by weight. Solution B-1 was obtained. The produced polymer had a weight average molecular weight Mw of 3900 and a dispersity of 1.82.

Synthesis Example 4 <Polymer solution B-2>
The monomer composition was composed of 50 parts by weight of γ-methacryloxypropyltrimethoxysilane (Toray Dow Corning), 46 parts by weight of glycidyl methacrylate (GMA), 6-hexanolide addition polymer of 2-hydroxyethyl acrylate (average) Degree of polymerization 3) (trade name “Placcel FA-3”, manufactured by Daicel Chemical Industries, Ltd.) A combined solution B-2 was obtained. The produced copolymer had a weight average molecular weight Mw of 4000 and a dispersity of 1.75.

Synthesis Example 5 <Polymer solution B-3>
The monomer composition is 70 parts by weight of γ-methacryloxypropyltrimethoxysilane (manufactured by Dow Corning Toray), 3,4-epoxycyclohexylmethyl methacrylate (trade name “Cyclomer M100”, manufactured by Daicel Chemical Industries, Ltd.) ) 25 parts by weight, 6-hexanolide addition polymer of 2-hydroxyethyl acrylate (average polymerization degree 3) (trade name “Placcel FA-3”, manufactured by Daicel Chemical Industries, Ltd.) The same operation as in Example 1 was performed to obtain a copolymer solution B-3 having a solid content of 33.0% by weight. The produced copolymer had a weight average molecular weight Mw of 4000 and a dispersity of 1.75.

Synthesis Example 6 <Polymer solution C-1>
The monomer composition is 95 parts by weight of glycidyl methacrylate (GMA), 6-hexanolide addition polymer of 2-hydroxyethyl acrylate (average polymerization degree 3) (trade name “Placcel FA-3”, manufactured by Daicel Chemical Industries, Ltd. ) The same operation as Example 1 was performed except changing to 5 weight, and the copolymer solution C-1 of 33.5 weight% of solid content was obtained. The produced copolymer had a weight average molecular weight Mw of 3800 and a dispersity of 1.65.

Synthesis Example 7 <Polymer solution C-2>
The monomer composition is 95 parts by weight of γ-methacryloxypropyltrimethoxysilane (manufactured by Dow Corning Toray), 6-hexanolide addition polymer of 2-hydroxyethyl acrylate (average polymerization degree 3) (trade name “Placcel FA” -3 ", manufactured by Daicel Chemical Industries, Ltd.) Except for changing to 5 parts by weight, the same operation as in Example 1 was performed to obtain a copolymer solution C-2 having a solid content of 33.8% by weight. The resulting copolymer had a weight average molecular weight Mw of 3900 and a dispersity of 1.85.

Synthesis Example 8 <Polymer solution C-3>
The same procedure as in Example 1 was performed except that the monomer composition was changed to 70 parts by weight of γ-methacryloxypropyltrimethoxysilane (manufactured by Dow Corning Toray) and 30 parts by weight of glycidyl methacrylate (GMA). A copolymer solution C-3 having a content of 32.8% by weight was obtained. The produced copolymer had a weight average molecular weight Mw of 3800 and a dispersity of 1.82.

  Table 1 summarizes the types of materials used for the synthesis of the polymers in Synthesis Examples 1 to 8 (preparation of polymer solutions) and the amounts used (compositions of the polymers synthesized in Synthesis Examples 1 to 8). In the table, GMA represents glycidyl methacrylate, Cyclomer M100 represents 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Chemical Industries), and Plaxel FA-3 represents 2-hydroxyethyl acrylate. It shows 6-hexanolide addition polymer (average degree of polymerization 3) (manufactured by Daicel Chemical Industries).

<Preparation of curable resin composition>
Example 1
A curable resin composition was obtained by adding 50 parts by weight of polymer solution A-1 to 50 parts by weight of polymer solution B-1 and mixing.

Examples 2-6
A curable resin composition was prepared in the same manner as in Example 1 except that the type and amount of the polymer solution were changed.

Comparative Examples 1-5
A curable resin composition was prepared in the same manner as in Example 1 except that the type and amount of the polymer solution were changed.

  Table 2 summarizes the amounts of materials used to prepare the curable resin compositions of Examples and Comparative Examples and the configuration of each curable resin composition.

Evaluation test (1) Preparation of test piece for evaluation The curable resin composition obtained in each Example and Comparative Example was applied to a substrate with a spin coater, and then heated on an 80 ° C. hot plate for 10 minutes, and then 230 Each evaluation test piece was produced by heating in an oven at 0 ° C. for 1 hour. A glass plate and a stainless steel plate were used as the base material.

(2) Solvent resistance In the examples and comparative examples, the test specimens prepared with glass plates were immersed in isopropyl alcohol (IPA), γ-butyrolactone (γ-BL), N-methylpyrrolidone (NMP), Left for 10 minutes. After washing with water, ◎ if the coating film has not changed at all, ◯ if it is only slightly discolored, △ if the coating film is completely discolored, completely discolored, one If the part was dissolved, it was marked as x. Similar results were obtained when using test specimens made of stainless steel.

(3) Adhesiveness In the examples and comparative examples, the adhesiveness of the test pieces for evaluation after the solvent resistance test was measured by peeling from the base material in accordance with JIS K-5600-5-6. 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.

(4) Alkali resistance In Examples and Comparative Examples, a 1 wt% NaOH aqueous solution was dropped dropwise onto an evaluation test piece made of a glass plate and allowed to stand for 10 minutes. After washing with water, if the location where the 1 wt% NaOH aqueous solution was dripped was not changed at all, ◎, a trace of dripping remains, but if it disappears if wiped off, ○, the trace of dripping remains and disappears even if wiped off If it was not, Δ, and if it was completely discolored, x.

  The results of the evaluation test are shown in Table 3.

Claims (3)

Following formula (1)

(In the formula, R ^a represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, A represents a single bond or a divalent hydrocarbon group. R ^b and R ^c are the same or different and each represents 1 carbon atom. -6 represents an alkyl group, aryl group, or alkoxy group having 1 to 6 carbon atoms, R ^d represents an alkyl group having 1 to 6 carbon atoms, x is 0 or 1, and y is an integer of 1 to 10. When y is an integer of 2 to 10, y R ^b and R ^c may be the same or different)
A polymer A containing only one or a plurality of alkoxysilyl group-containing vinyl monomers a represented by the formula (1), and one or a plurality of alkoxysilyl group-containing vinyl monomers represented by the formula (1) Body a, one or more kinds of vinyl monomers b having 3 to 5 membered cyclic ether groups, and one or more kinds of hydroxyl group-containing vinyl monomers having an ε-caprolactone ring-opening polymer chain moiety in the side chain A curable resin composition comprising a copolymer B containing c as a monomer component.   The curable resin composition according to claim 1, wherein the content ratio of the polymer A and the copolymer B is 25:75 to 75:25 by weight.   A cured product obtained by curing the curable resin composition according to claim 1.