JP2017179168A - Curable composition, cured article thereof, and production method of the cured article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition having low viscosity and excellent adhesive property, a cured article thereof and a production method of the cured article.SOLUTION: The curable composition is provided that contains: (A) an acrylic acid ester compound of polyalcohol or the like; (B) an epoxy compound; (C) an oxetane compound; (D) a polymer having, in structure, a skeleton represented by the following general formula (1), where Rrepresents an alkyl group, Rrepresents hydrogen or a methyl group and * represents a bound; (E) a compound having a hydroxymethylene group in structure, a compound having a hydroxymethane group in structure, or the like; and (F) a polymerization initiator. In the curable composition, the component (B) of 10 to 250 pts.mass, the component (D) of 1 to 80 pts.mass, the component (E) of 1 to 30 pts.mass and the component (F) of 1 to 30 pts.mass are contained based on 100 pts.mass of the component (A).SELECTED DRAWING: None

Description

  The present invention relates to a curable composition, a cured product thereof, and a method for producing the cured product, and more particularly to a curable composition having a low viscosity and excellent adhesiveness, a cured product thereof, and a method for producing the cured product.

  A curable composition curable by light or heat is used as an adhesive. Adhesives are used in a wide range of fields including automobiles, aircraft, and electrical / electronic equipment. In particular, in recent years, the application of adhesive technology in electrical and electronic equipment has become increasingly diverse and sophisticated. In addition, materials used in electrical and electronic equipment have been newly developed and have become diverse and diverse, and conventional adhesives cannot satisfy sufficient requirements. In particular, conventional adhesives are unable to satisfy sufficient requirements for producing fine optical components typified by polarizing plates used in liquid crystal display devices.

  As a conventional adhesive, for example, in Patent Document 1, a poly (meth) acrylate of a polyol having 2 to 15 carbon atoms, a polyglycidyl ether of a polyol having 2 to 10 carbon atoms, in one molecule There has been proposed a photocurable adhesive composition containing a compound having a molecular weight of 500 or less having two or more oxetanyl groups, a polymer having an epoxy group, and a photocationic polymerization initiator in a specific ratio. In Patent Document 2, a poly (meth) acrylate of a polyol having 2 to 15 carbon atoms, a polyglycidyl ether of a polyol having 2 to 10 carbon atoms, an oxetane compound having a specific structure, and a (meth) acrylic compound A photocurable adhesive composition containing a polymer and a cationic photopolymerization initiator in a specific ratio has been proposed.

JP-A-2015-143352 Japanese Patent Laying-Open No. 2015-040283

  However, the conventionally proposed adhesives have high viscosity, so it is difficult to make the adhesive thin, and the adhesive strength may be insufficient. In this regard, there is room for further improvement. Is left behind.

  Accordingly, an object of the present invention is to provide a curable composition having a low viscosity and excellent adhesion, a cured product thereof, and a method for producing the cured product.

  As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by a curable composition having a specific composition, and has completed the present invention.

（式中、Ｒ^１はアルキル基を表し、Ｒ^２は水素またはメチル基を表し、＊は結合手を表す。）で表される骨格を有する重合体と、（Ｅ）構造中にヒドロキシメチレン基を有する化合物、構造中にヒドロキシメチン基を有する化合物および水からなる群から選ばれる少なくとも１種の化合物と、（Ｆ）重合開始剤と、を含有する硬化性組成物において、
前記（Ａ）多価アルコールのアクリル酸エステル化合物および多価アルコールのメタクリル酸エステル化合物からなる群から選ばれる少なくとも１種の化合物１００質量部当たり、前記（Ｂ）エポキシ化合物１〜２００質量部、前記（Ｃ）オキセタン化合物１０〜２５０質量部、前記（Ｄ）構造中に上記一般式（１）で表される骨格を有する重合体１〜８０質量部、前記（Ｅ）構造中にヒドロキシメチレン基を有する化合物、構造中にヒドロキシメチン基を有する化合物および水からなる群から選ばれる少なくとも１種の化合物１〜３０質量部、前記（Ｆ）重合開始剤１〜３０質量部であることを特徴とするものである。 That is, the curable composition of the present invention comprises (A) at least one compound selected from the group consisting of an acrylic acid ester compound of a polyhydric alcohol and a methacrylic acid ester compound of a polyhydric alcohol; (C) an oxetane compound, and (D) the following general formula (1),

(Wherein R ¹ represents an alkyl group, R ² represents hydrogen or a methyl group, and * represents a bond), and (E) a hydroxymethylene group in the structure In a curable composition comprising: a compound having: a compound having a hydroxymethine group in the structure; and at least one compound selected from the group consisting of water and (F) a polymerization initiator,
(B) 1 to 200 parts by mass of the epoxy compound per 100 parts by mass of at least one compound selected from the group consisting of an acrylic acid ester compound of a polyhydric alcohol and a methacrylic acid ester compound of a polyhydric alcohol, (C) 10 to 250 parts by mass of an oxetane compound, 1 to 80 parts by mass of a polymer having a skeleton represented by the general formula (1) in the structure (D), and a hydroxymethylene group in the structure (E). 1 to 30 parts by mass of at least one compound selected from the group consisting of a compound having, a compound having a hydroxymethine group in the structure and water, and 1 to 30 parts by mass of the (F) polymerization initiator Is.

  In the curable composition of the present invention, the compound (E) having a hydroxymethylene group in the structure and the compound having a hydroxymethine group in the structure are preferably compounds having a weight average molecular weight of 50 to 1,000. . Here, the weight average molecular weight is a weight average molecular weight measured by GPC in a tetrahydrofuran (THF) solvent and obtained in terms of styrene.

  The cured product of the present invention is obtained by curing the curable composition of the present invention.

The method for producing a cured product according to the present invention includes a substrate preparation step for preparing a substrate, a coating step for applying the curable composition to the substrate, and an irradiation step for irradiating energy rays.
The curable composition is the curable composition of the present invention.

Another method for producing a cured product of the present invention is a method for producing a cured product comprising a substrate preparation step for preparing a substrate, a coating step for applying the curable composition to the substrate, and a heating step for heating.
The curable composition is the curable composition of the present invention.

  According to the present invention, it is possible to provide a curable composition having a low viscosity and excellent adhesion, a cured product thereof, and a method for producing the cured product.

  The curable composition of this invention can be conveniently used as an adhesive agent from the effect which there exists. More specifically, as an adhesive that can be suitably used for the use of a photocationic curable adhesive or a thermal cation curable adhesive, and is used when manufacturing a fine optical component represented by a polarizing plate. Is preferred. As an adhesive used for the polarizing plate, for example, a triacetyl cellulose (hereinafter sometimes abbreviated as TAC) film is bonded to both surfaces of a polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) polarizer film. Adhesive used at the time, polyester resin, polycarbonate resin, acrylic resin, amorphous polyolefin resin or cycloolefin resin as a protective film or optical compensation film on one side, and TAC film on the other side Adhesives used for combining can be mentioned as suitable applications.

  Hereinafter, the curable composition of the present invention, the cured product thereof, and the method for producing the cured product will be described in detail.

  The curable composition of the present invention comprises (A) at least one compound selected from the group consisting of a polyhydric alcohol acrylic acid ester compound and a polyhydric alcohol methacrylic acid ester compound (hereinafter referred to as “component (A)”). ), (B) epoxy compound (hereinafter also referred to as “component (B)”), (C) oxetane compound (hereinafter also referred to as “component (C)”), and (D) A polymer having a skeleton represented by formula (hereinafter also referred to as “component (D)”), (E) a compound having a hydroxymethylene group in the structure, a compound having a hydroxymethine group in the structure, and water. Curability containing at least one compound selected from the group consisting of (hereinafter also referred to as “(E) component”) and (F) a polymerization initiator (hereinafter also referred to as “(F) component”). It is a composition.

ここで、式（１）中、Ｒ^１はアルキル基を表し、Ｒ^２は水素またはメチル基を表し、＊は結合手を表す。

Here, in Formula (1), R ¹ represents an alkyl group, R ² represents hydrogen or a methyl group, and * represents a bond.

  In the curable composition of the present invention, (B) component 1 to 200 parts by mass, (C) component 10 to 250 parts by mass, (D) component 1 to 80 parts by mass, E) 1-30 parts by mass of component, (F) 1-30 parts by mass of component.

  The acrylic acid ester compound of the polyhydric alcohol in the component (A) is not particularly limited, and a well-known general polyhydric alcohol acrylic acid ester compound can be used, and a monomer can be used. A polymer obtained by polymerizing an acrylic acid moiety can also be used. The polyhydric alcohol used in the polyhydric alcohol acrylate compound is preferably a polyhydric alcohol having 2 to 15 carbon atoms, and more preferably a polyhydric alcohol having 2 to 10 carbon atoms.

  Examples of the compound that can be preferably used as an acrylate ester of a polyhydric alcohol include, for example, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 3-methyl-1,5-pentanediol diacrylate, and cyclohexanedimethylol. Diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 1,9-nonanediol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, tetramethylene glycol diacrylate, diethylene glycol diacrylate, tri Ethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tricyclodecane dimethylol diacrylate , Trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and diacrylate of hydrogenated bisphenol A and the like.

  The methacrylic acid ester compound of the polyhydric alcohol in the component (A) is not particularly limited, and a well-known general polyhydric alcohol methacrylic acid ester compound can be used, a monomer can be used, and methacrylic acid can be used. A polymer obtained by polymerizing the acid moiety can also be used.

  The polyhydric alcohol used for the methacrylic acid ester compound of the polyhydric alcohol is preferably a polyhydric alcohol having 2 to 15 carbon atoms, and more preferably a polyhydric alcohol having 2 to 10 carbon atoms. Examples of the compound that can be preferably used as the methacrylic acid ester of the polyhydric alcohol include neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, and cyclohexanedi. Methylol dimethacrylate, 2-butyl-2-ethyl-1,3-propanediol dimethacrylate, 1,9-nonanediol dimethacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, tetramethylene glycol dimethacrylate, diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tricycle Decane dimethylol dimethacrylate, trimethylol propane trimethacrylate, ditrimethylol propane tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, and dimethacrylate of hydrogenated bisphenol A An acrylate etc. are mentioned.

  The component (A) may have an ester skeleton or an isocyanurate skeleton. Specific examples of the compound having an ester skeleton include an esterification reaction product of neopentyl glycol, hydroxypivalic acid and acrylic acid, an esterification reaction product of neopentyl glycol, hydroxypivalic acid and methacrylic acid, and the like. Examples of the compound having an isocyanurate skeleton include diacrylate of isocyanuric acid alkylene oxide adduct, triacrylate of isocyanuric acid alkylene oxide adduct, dimethacrylate of isocyanuric acid alkylene oxide adduct, trimethacrylate of isocyanuric acid alkylene oxide adduct Etc.

  Of these, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, esterification reaction product of neopentyl glycol, hydroxypivalic acid and acrylic acid, neopentyl glycol, hydroxypivalic acid and methacrylic acid. The esterification reaction product is particularly preferable in terms of low viscosity, excellent adhesion and durability, and low odor.

  When the component (A) is a polymer, the preferred weight average molecular weight is in the range of 500 to 1,000,000, preferably in the range of 500 to 10,000.

  The compounding quantity of (B) component used for the curable composition of this invention is the range of 1-200 mass parts per 100 mass parts of said (A) component. Among these, the case of 50 to 150 parts by mass is particularly preferable because of high adhesive force.

  The epoxy compound is not particularly limited as long as it is a compound having an epoxy group, but an aliphatic epoxy compound can be preferably used, and among them, polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof can be used. It can be preferably used. For example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, cyclohexane dimethylol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4 -Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolpropane diglycidyl ether, 1,9-nonanediol diglycidyl ether, resorcin diglycidyl ether, polyethylene glycol diglycidyl Ether, cyclohexanedimethanol diglycidyl ether, tri Tyrolpropane triglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, diglycidyl ether of isocyanuric acid ethylene oxide adduct, triglycidyl ether of isocyanuric acid ethylene oxide adduct, hydroquinone diglycidyl ether, bisphenol A type epoxy resin Bisphenol F type epoxy resin, phenol bonolac type epoxy resin and the like. A polyglycidyl ether of a polyhydric alcohol having 2 to 10 carbon atoms is preferable because of low viscosity and high adhesive strength, and a diglycidyl ether of an alkanediol having 2 to 10 carbon atoms is particularly preferable.

  Commercially available epoxy compounds include, for example, ADEKA ADEKA glycalol ED-523 (neopentylglycol diglycidyl ether), ADEKA glycilol ED-503 (1,6-hexanediol diglycidyl ether), ADEKA RESIN EP -4085 (cyclohexanedimethanol diglycidyl ether), Adeka Resin EP-4080 (hydrogenated bisphenol A type diglycidyl ether), Adeka Resin EP-4100L, Adeka Resin EP-4901, Epolite 100MF (Trimethylolpropane triglycidyl) manufactured by Kyoeisha Chemical Co., Ltd. Ether), and EX-321L (trimethylolpropane diglycidyl ether) manufactured by Nagase ChemteX Corporation. Among these, when the weight average molecular weight is 500 or less, it is preferable because the effect of uniforming the coating surface is high when the photocationic curable adhesive and the thermal cation curable adhesive are applied. Moreover, it is preferable to use an epoxy compound having a chemical purity of 98% or more. The chemical purity of 98% or more means a case where the impurity organic substances other than the epoxy compound present in the epoxy compound is less than 2%.

  Moreover, an alicyclic epoxy can also be used as said (B) component. For example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9 diepoxy limonene, 3,4-epoxycyclohexenylmethyl-3, '4'-epoxycyclohexene carboxylate, etc. Can be mentioned. These are commercially available from Daicel Chemical Industries, Ltd. under the trade names CEL2000, CEL3000, and CEL2021P. Among these, those having two or more epoxy groups in the structure are preferable.

  The compounding quantity of (C) component used for the curable composition of this invention is the range of 10-250 mass parts per 100 mass parts of (A) component. Among these, the case of 50 to 200 parts by mass is particularly preferable because of high adhesive force, and the case of 100 to 200 parts by mass is particularly preferable.

The oxetane compound is not particularly limited, and is a compound having a 4-membered ether, that is, an oxetane ring in the molecule. Examples of oxetane compounds used in the curable composition of the present invention include bis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxy). Monofunctional oxetane containing alkoxyalkyl group such as methyl) oxetane, monofunctional oxetane containing aromatic group such as 3-ethyl-3-phenoxymethyloxetane, 1,4-bis [(3-ethyloxetane-3-yl) Methoxymethyl] benzene, 1,4-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-Ethyloxetane-3-yl) methoxy] benzene, 4,4′-bis [(3-ethyloxetane-3-yl) Methoxy] biphenyl, 2,2′-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis [(3-ethyloxetane -3-yl) methoxy] biphenyl, 2,7-bis [(3-ethyloxetane-3-yl) methoxy] naphthalene, bis [4-{(3-ethyloxetane-3-yl) methoxy} phenyl] methane, Bis [2-{(3-ethyloxetane-3-yl) methoxy} phenyl] methane, 2,2-bis [4-{(3-ethyloxetane-3-yl) methoxy} phenyl] propane, novolak type phenol- Etherified modification of formaldehyde resin with 3-chloromethyl-3-ethyloxetane, 3 (4), 8 (9) -bis [(3-ethyloxetane-3-yl) me Toximethyl] -tricyclo [5.2.1.0 ^2,6 ] decane, 2,3-bis [(3-ethyloxetane-3-yl) methoxymethyl] norbornane, 1,1,1-tris [(3- Ethyloxetane-3-yl) methoxymethyl] propane, 1-butoxy-2,2-bis [(3-ethyloxetane-3-yl) methoxymethyl] butane, 1,2-bis [{2- (3-ethyl Oxetane-3-yl) methoxy} ethylthio] ethane, bis [{4- (3-ethyloxetane-3-yl) methylthio} phenyl] sulfide, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane), 3-ethyl-[{(3-triethoxysilylpropoxy) methyl) oxetane, oxetanylsilsesquioxane, phenol novolac oxetane, -[(3-ethyloxetane-3-yl) methoxy] propyltrialkoxysilane hydrolysis condensate, tetrakis [(3-ethyloxetane-3-yl) methyl] silicate, 3-ethyloxetane-3-ylmethanol and Examples include condensation reaction products of silanetetraol polycondensates. Here, the oxetanyl silsesquioxane is obtained by hydrolytic condensation of a silane compound having an oxetanyl group, for example, the aforementioned 3-ethyl-3-[{(3-triethoxysilyl) propoxy} methyl] oxetane. A network-like polysiloxane compound having a plurality of oxetanyl groups. Among these oxetane compounds, oxetane compounds having two or more oxetanyl groups in one molecule are preferable, and among these, oxetane compounds having a molecular weight of 500 or less are particularly preferable.

  Examples of commercially available oxetane compounds include trade names OXT-101 (3-ethyl-3-hydroxymethyloxetane), OXT-121 (xylylenebisoxetane), and OXT-, which are commercially available from Toagosei Co., Ltd. 211 (3-ethyl-3- (phenoxymethyl) oxetane), OXT-221 (3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane), OXT-212 (2-ethylhexyl) That having two or more oxetane rings in its structure, such as OXT-221, is preferable.

  The compounding quantity of (D) component used for the curable composition of this invention is the range of 1-80 mass parts per 100 mass parts of (A) component. Among these, 1-60 mass parts is preferable and the range of 5-60 mass parts is especially preferable.

  The component (D) may be a polymer having a skeleton represented by the general formula (1) in its structure, and is not particularly limited, but is represented by the general formula (1). A polymer containing 50 mol% or more of the skeleton is preferable, and a polymer containing 80 mol% or more is more preferable.

R ¹ in the general formula represents an alkyl group, for example, methyl group, ethyl group, propyl group, n-butyl group, secondary butyl group, tertiary butyl group, isobutyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group. N-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group and the like. Among these, R ¹ is preferably an alkyl having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

  Component (D) may be a copolymer of an ethylenically unsaturated monomer copolymerizable with acrylate or methacrylate, assuming that the polymer has a skeleton represented by general formula (1). Good. Examples of copolymers of ethylenically unsaturated monomers copolymerizable with acrylates and methacrylates include, for example, carboxyl group-containing monomers such as (meth) acrylic acid; acrylamide 2-methylpropanesulfonic acid and styrenesulfone Sulfonic acid group-containing monomers such as acids; phosphoric acid group-containing monomers; cyano group-containing monomers such as (meth) acrylonitrile; vinyl esters; aromatic vinyl compounds such as styrene and α-methylstyrene; Group-containing monomers; hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate; acrylamide, dimethylacrylamide, diethyl Amide groups such as acrylamide Examples of the monomer include: an amino group-containing monomer; an imide group-containing monomer; an epoxy group-containing monomer such as glycidyl (meth) acrylate; a (meth) acryloylmorpholine; and a vinyl ether. As the component (D), it is possible to use a copolymer obtained by combining one or more of these compounds on the premise that the component has a skeleton represented by the general formula (1).

  (D) When using a polymer having a skeleton represented by the general formula (1) and being a copolymer with an acidic group-containing monomer (hereinafter also referred to as (D-1)) as the component (D) Is preferable because the curable composition of the present invention is excellent in solubility in an organic solvent and further has an excellent effect of adhesion. Examples of the acidic group-containing monomer include a carboxyl group-containing monomer, a sulfone group-containing monomer, an acid anhydride group-containing monomer, and a phosphate group-containing monomer. The body is preferred. As the component (D-1), when the acid value is 20 mgKOH / g or less, it is preferable because of high storage stability, and those having an acid value of 15 mgKOH / g or less are particularly preferable.

  As molecular weight of (D) component, 500-500,000 are preferable at a weight average molecular weight, More preferably, it is 1,000-200,000.

  (D) As a component, although various polymers can be used from an above-described polymer, it contains the alkyl (meth) acrylate containing a C1-C10 alkyl group as a structural monomer unit, and is a weight average. A polymer having a molecular weight of 1,000 to 500,000 is particularly preferred.

  The compounding quantity of (E) component used for the curable composition of this invention is the range of 1-30 mass parts per 100 mass parts of (A) component. Among these, 1-20 mass parts is preferable.

  The compound which has a hydroxymethylene group in the said structure is not specifically limited, What is necessary is just a compound which has a hydroxymethylene group in the structure. Examples of the compound that can be preferably used in the curable composition of the present invention include alcohols such as methanol, ethanol, 2-propanol, and n-butanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2, 4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6 -Hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl Low molecular glycol compounds such as lu-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, trimethylolpropane and tripropylene glycol; high molecular glycol compounds such as polyethylene glycol and polypropylene glycol (Molecular weight of about 200 to 2000); ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether Propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and 3-methyl-3- Low molecular glycol ether compounds such as methoxy-3-methoxybutanol; polymer glycol ether compounds (molecular weight: about 200 to 2,000) such as polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, and polyethylene glycol monobutyl ether; Among these, among these, low molecular weight glycol compounds and high molecular glycosyl In particular, the case where the molecular weight is in the range of 50 to 1,000 is preferred.

  The compound which has a hydroxymethine group in the said structure is not specifically limited, What is necessary is just a compound which has a hydroxymethine group in the structure. Examples of the compound that can be preferably used in the curable composition of the present invention include cyclohexanol and 1,4-cyclohexanediol.

  As the at least one compound selected from the group consisting of a compound having a hydroxymethylene group in the structure, a compound having a hydroxymethine group in the structure and water used in the curable composition of the present invention, the viscosity is low, In order to obtain a curable composition having excellent adhesive strength, it is preferable to use at least one compound having a hydroxymethylene group or water in the structure, and the molecular weight is in the range of 50 to 1,000. It is particularly preferable to use at least one kind of a compound having a hydroxymethylene group or water.

  The compounding quantity of (F) component used for the curable composition of this invention is the range of 1-30 mass parts per 100 mass parts of (A) component. Among these, 1-20 mass parts is preferable.

  It does not specifically limit as a polymerization initiator used for the curable composition of this invention, Although a well-known general polymerization initiator can be used, For example, a photoinitiator and a thermal-polymerization initiator are mentioned. be able to.

  When using polyester resin, polycarbonate resin, acrylic resin, amorphous polyolefin resin, cycloolefin resin, etc. as an adhesive for bonding to other resins, such as PVA resin, use a photopolymerization initiator. Photocationic curing is convenient and advantageous. Examples of the photopolymerization initiator include a photocationic polymerization initiator and a photoradical polymerization initiator.

  The cationic photopolymerization initiator is a compound that generates cationic species or Lewis acid upon irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates polymerization of epoxy groups. Examples of the photopolymerization initiator include sulfonium salts and iodonium salts.

  Examples of sulfonium compounds include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluoro Phosphate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide, bishexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide, bishexa Fluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p-toluyl) Honio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4′-diphenylsulfonio-diphenylsulfide hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4′-diphenylsulfone Nio-diphenyl sulfide hexafluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4'-di (p-toluyl) sulfonio-diphenyl sulfide, tetrakis (pentafluorophenyl) borate and the like.

  Examples of the iodonium salt type include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.

  A radical photopolymerization initiator is a compound that can release a substance that initiates radical polymerization by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams. Can do. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- ( 4'-methylmercapto) benzoylpropane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, -Butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2'-morpholinoisobutyroyl) carbazole 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6 -Bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O -Benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl -, 1- (O-acetyl oxime), and the like. It is preferable to use a radical photopolymerization initiator in combination with the curable composition of the present invention because the curing speed becomes very fast. The concentration of the photo radical polymerization initiator is preferably 0.1 to 10% by mass.

  These photopolymerization initiators may be used alone or in combination of two or more. In the curable composition of the present invention, it is preferable to use a mixture of one or more photocationic polymerization initiators and photoradical polymerization initiators, since the viscosity is low and the effect of increasing the adhesive force is improved. Especially, it is preferable to make photocationic polymerization initiator and radical photopolymerization initiator into the range of 50: 50-95: 5 by weight ratio, and it is especially preferable to set it in the range of 60: 40-80: 20. Commercially available products of these photopolymerization initiators include, for example, trade names PI-2074 commercially available from Rhodia, trade names Irg184 and Irg369 commercially available from BASF.

  Furthermore, a photosensitizer can be used in combination with the curable composition of the present invention as necessary. By using a photosensitizer, the reactivity is improved, and the mechanical strength and adhesive strength of the cured product can be improved. Examples of the photosensitizer include anthracene compounds, naphthalene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes.

  Examples of the anthracene compound include those represented by the following formula (2).

ここで、式（２）中、Ｒ^１およびＲ^２は、各々独立に水素原子、炭素原子数１〜６のアルキル基または炭素原子数２〜１２のアルコキシアルキル基を表し、Ｒ^３は水素原子または炭素原子数１〜６のアルキル基を表す。

Here, in Formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 12 carbon atoms, and R ³ represents a hydrogen atom. Alternatively, it represents an alkyl group having 1 to 6 carbon atoms.

  Specific examples of the anthracene compound represented by the above formula (2) include the following compounds.

  9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 9, 10-dihexyloxyanthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-ethoxyethoxy) anthracene, 9,10-bis (2-butoxyethoxy) anthracene, 9,10-bis (3-butoxypropoxy) anthracene, 2-methyl- or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl- or 2-ethyl-9,10-diethoxyanthracene, 2-methyl- or 2-ethyl- 9,10-dipropoxyanthracene, 2- Til- or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl- or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipentyloxyanthracene, 2-methyl- or 2-ethyl-9,10-dihexyloxyanthracene and the like.

  As a naphthalene-type compound, what is represented by following formula (3) is mentioned, for example.

ここで、式（３）中、Ｒ^４およびＲ^５は各々独立に炭素原子数１〜６のアルキル基を表す。

Here, in formula (3), R ⁴ and R ⁵ each independently represents an alkyl group having 1 to 6 carbon atoms.

  Specific examples of the naphthalene compound represented by the above formula (3) include the following compounds.

  4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1- Ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene and the like.

  Examples of other photosensitizers include, for example, benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, o-benzoylbenzoate Benzophenone derivatives such as methyl acid, 4,4′-bis (diethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N -Acridone derivatives such as methylacridone and N-butylacridone; others, α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, halogen compounds, photoreduction Examples thereof include, but are not limited to, intrinsic dyes. Moreover, these may be used independently or may use 2 or more types together. Examples of commercially available photosensitizers include Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.). The photosensitizer is preferably blended in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the epoxy compound.

  Examples of the thermal polymerization initiator include benzylsulfonium salt, thiophenium salt, thioranium salt, benzylammonium, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, and amine imide. These initiators can be obtained commercially, for example, trade names Adeka Opton CP77 (above, manufactured by ADEKA Corporation), CI-2639, CI-2624 (above, manufactured by Nippon Soda Co., Ltd.) , Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.

  As long as the effects of the present invention are not impaired, other additives such as an antioxidant and a silane coupling agent can be added to the curable composition.

  Examples of commercially available antioxidants include AO-20, AO-30, AO-50, and AO-80 (manufactured by ADEKA Corporation), such as dibutylhydroxytoluene (BHT), Irganox 1010, and Irga. Knox 1035FF, Irganox 565, etc. are mentioned. As for the usage-amount of antioxidant, 0.0001-10 mass% is preferable.

  Commercially available silane coupling agents include, for example, epoxy (KBM403, KBM303), vinyl (KBM1003), acrylic silane coupling agent (KBM503), 3-ethyl (triethoxysilylpropoxymethyl) oxetane (TESOX (Toho) Synthetic Co., Ltd.)) and the like. As for the usage-amount of a silane coupling agent, 0.0001-10 mass% is preferable.

  The curable composition of the present invention can be obtained by stirring the above-described components in a container and stirring until a uniform liquid is obtained.

  A method for producing a cured product from the curable composition of the present invention includes a substrate preparation step for preparing a substrate, a coating step for applying the curable composition of the present invention to the substrate, an irradiation step of irradiating energy rays, including.

  Examples of the material of the base used in the base preparation step include silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, ruthenium oxide, zirconium oxide, hafnium oxide, and lanthanum oxide; glass such as soda glass and quartz glass. Metal such as ruthenium metal; cellulose ester such as diacetylcellulose, triacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose; polyamide; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1 , 4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, polybutylene terephthalate Polyester such as rate; Polyvinyl alcohol; Polystyrene; Polyolefin such as polyethylene, polypropylene and polymethylpentene; Acrylic resin such as polymethyl methacrylate; Cycloolefin resin; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Oxyethylene, norbornene resin, etc. can be mentioned, but at least one side of the substrate is a resin film that transmits visible light. Among these, when using PVA, TAC, polyester resin, polycarbonate resin, acrylic resin, amorphous polyolefin resin, and chloroolefin resin, the adhesive strength between the cured product and the substrate is good. To preferred. The amorphous polyolefin-based resin usually has a polymerization unit of a cyclic polyolefin such as norbornene or a polycyclic norbornene-based monomer, and may be a copolymer of a cyclic olefin and a chain cyclic olefin.

  Examples of commercially available non-crystalline polyolefin-based resins include Arton from JSR Corporation, ZEONEX and ZEONOR from Nippon Zeon Co., Ltd., and APO and Appel from Mitsui Chemicals. In order to form the amorphous polyolefin-based resin into a film, a known method such as a solvent casting method or a melt extrusion method is appropriately used. Prior to bonding to the substrate, the bonding surface of the resin film may be subjected to corona treatment, plasma treatment, excimer treatment, and UV treatment. By performing such treatment, adhesion becomes easier. Examples of the shape of the substrate include a plate shape, a spherical shape, a fiber shape, and a scale shape, and the surface of the substrate may be a flat surface or a three-dimensional structure such as a trench structure. The substrate used in the method for forming a cured product of the present invention preferably has a plate shape, and the surface thereof is preferably a flat surface.

  The coating method used in the coating process is not particularly limited. For example, a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and dipping may be used. it can. Since each coating method has an optimum viscosity range, the viscosity may be adjusted using a solvent. As the solvent for this purpose, a solvent that dissolves the photocationically curable adhesive satisfactorily without degrading the optical performance of the polarizer is used, but the type is not particularly limited. For example, organic solvents such as hydrocarbons typified by toluene and esters typified by ethyl acetate can be used.

  The light source of the energy beam used in the irradiation process for irradiating the energy beam is not particularly limited. For example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, Xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT light sources, etc. High energy rays such as radiation can be used. Preferably, an ultrahigh pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, and the like that emit light having a wavelength of 300 to 450 nm are used.

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser. Further, lasers that emit light in the visible to infrared region such as various semiconductor lasers and YAG lasers are also used. When these lasers are used, a sensitizing dye that absorbs the visible to infrared region is added. Moreover, it can also be used using a halftone mask. After the step of irradiating with energy rays, it is preferable to cure by heating at room temperature overnight or at 40 to 100 ° C. for 1 to 10 minutes.

  Further, another method for producing a cured product from the curable composition of the present invention includes a substrate preparation step for preparing a substrate, a coating step for applying the curable composition to the substrate, and a heating step for heating. .

  Examples of the material of the substrate include silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, ruthenium oxide, zirconium oxide, hafnium oxide, and lanthanum oxide; glass such as soda glass and quartz glass; metal ruthenium and the like. Metal: cellulose ester such as diacetylcellulose, triacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose; polyamide; polycarbonate; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedi Polyethylene such as methylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate Polyvinyl alcohol; polystyrene; polyolefins such as polyethylene, polypropylene and polymethylpentene; acrylic resins such as polymethyl methacrylate; cycloolefin resins; polysulfones; polyether sulfones; polyether ketones; polyether imides; Norbornene resins and the like; resins containing colored pigments, colored dyes, and carbon black; polyimide films. Prior to bonding to the substrate, the bonding surface of the resin film may be subjected to corona treatment, plasma treatment, excimer treatment, and UV treatment. By performing such treatment, adhesion becomes easier. Examples of the shape of the substrate include a plate shape, a spherical shape, a fiber shape, and a scale shape, and the surface of the substrate may be a flat surface or a three-dimensional structure such as a trench structure. The substrate used in the method for forming a cured product of the present invention preferably has a plate shape, and the surface thereof is preferably a flat surface.

  The coating method used in the coating step is not particularly limited. For example, a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and immersion is used. Can do. Since each coating method has an optimum viscosity range, the viscosity may be adjusted using a solvent. As the solvent for this purpose, a solvent that dissolves the photocationically curable adhesive satisfactorily without degrading the optical performance of the polarizer is used, but the type is not particularly limited. For example, organic solvents such as hydrocarbons typified by toluene and esters typified by ethyl acetate can be used.

  As a heating method used in the heating step, a well-known general method can be used. For example, a heater or the like can be used. The heating conditions may be appropriately set according to the catalyst to be used, but it is preferably within the range of 50 to 200 ° C. The heating time is preferably 1 to 60 minutes. After the heating step, it is preferable to heat cure at room temperature overnight or at 40-100 ° C. for 1-10 minutes to ensure curing.

  The curable composition of the present invention preferably has a viscosity of 200 mPa · s or less (25 ° C.), preferably 120 mPa · s or less (25 ° C.). The lower the viscosity, the easier the application and the thinner the adhesive layer can be applied. When the viscosity is within these ranges, the curable composition of the present invention can be suitably used as an adhesive. For example, when used to attach a protective film or an optical compensation film to a polarizing plate, the viscosity is known to be good appearance of the polarizing plate is 200 mPa · s or less (25 ° C.), When the chlorine content, which is a feature of the present invention, is in the range of 0.01 to 1500 ppm, a particularly excellent effect that the coated surface of the adhesive becomes uniform can be achieved.

  The curable composition of the present invention can be obtained by stirring the above-described components in a container and stirring until a uniform liquid is obtained. Moreover, a photoinitiator and a thermal polymerization initiator can also be mixed and used as a polymerization initiator in this invention. Such a curable composition can also be suitably used as an adhesive.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited by these Examples.

[Examples 1-8 and Comparative Examples 1-6]
Using the compounds shown in Table 1, curable compositions of Examples 1 to 8 and Comparative Examples 1 to 6 were produced with the formulations shown in Tables 2 to 4. In addition, the unit of the compounding quantity in a table | surface is a mass part.

※１ 構造中にヒドロキシメチレン基を有する化合物
※２ 構造中にヒドロキシメチレン基もヒドロキシメチン基も有さない化合物

* 1 Compound having a hydroxymethylene group in its structure * 2 Compound having neither a hydroxymethylene group nor a hydroxymethine group in its structure

化合物Ｎｏ．１

Compound No. 1

化合物Ｎｏ．２

Compound No. 2

[Viscosity evaluation]
The viscosities of the curable compositions of Examples 1 to 8 and Comparative Examples 1 to 6 were evaluated by measuring using an E-type viscometer TVE-25L manufactured by Toki Sangyo Co., Ltd. The case where the viscosity was less than 120 mPa · s at 25 ° C. was evaluated as ++, and the case where the viscosity was 120 mPa · s or more was evaluated as −. A curable composition having a viscosity of less than 120 mPa · s is a curable composition useful as an adhesive used in the production of fine optical components typified by polarizing plates used in liquid crystal display devices. The results are also shown in Tables 2-4.

[Adhesion evaluation]
After apply | coating the curable composition of Examples 1-8 and Comparative Examples 1-6 to the acrylic film (Sumitomo Chemical Co., Ltd .: Technoloy 123S001) which carried out the corona discharge treatment of each sheet, it was corona discharge-treated using the laminator. And a cycloolefin polymer (manufactured by ZEON Corporation: ZEONOR ZEF014-050) film subjected to the above, and irradiated with an energy of 100 mJ / cm ² using an electrodeless ultraviolet lamp and adhered to Examples 1 to 8 and Test pieces of Comparative Examples 1 to 6 were obtained.

[Evaluation Example 2]
The adhesive strength of the test pieces of Examples 1 to 8 and Comparative Examples 1 to 6 was evaluated by a 90-degree peel test using FTN-13A / 500 manufactured by AIKOH. The case where the adhesive force was 1.0 N / mm or more was evaluated as ++, and the case where the adhesive force was less than 1.0 N / mm was evaluated as-. The results are also shown in Tables 2-4.

From the results of Tables 2 to 4, it can be seen that Examples 1 to 8 all exhibited excellent adhesive strength. On the other hand, it can be seen that Comparative Examples 1 to 6 all have poor adhesion.

Claims (5)

(A) at least one compound selected from the group consisting of polyhydric alcohol acrylate compounds and polyhydric alcohol methacrylate compounds, (B) epoxy compounds, (C) oxetane compounds, and (D) In the structure, the following general formula (1),

(Wherein R ¹ represents an alkyl group, R ² represents hydrogen or a methyl group, and * represents a bond), and (E) a hydroxymethylene group in the structure In a curable composition comprising: a compound having: a compound having a hydroxymethine group in the structure; and at least one compound selected from the group consisting of water and (F) a polymerization initiator,
(B) 1 to 200 parts by mass of the epoxy compound per 100 parts by mass of at least one compound selected from the group consisting of an acrylic acid ester compound of a polyhydric alcohol and a methacrylic acid ester compound of a polyhydric alcohol, (C) 10 to 250 parts by mass of an oxetane compound, 1 to 80 parts by mass of a polymer having a skeleton represented by the general formula (1) in the structure (D), and a hydroxymethylene group in the structure (E). 1 to 30 parts by mass of at least one compound selected from the group consisting of a compound having, a compound having a hydroxymethine group in the structure and water, and 1 to 30 parts by mass of the (F) polymerization initiator Curable composition.   The curable composition according to claim 1, wherein the compound (E) having a hydroxymethylene group in the structure and the compound having a hydroxymethine group in the structure are compounds having a weight average molecular weight of 50 to 1,000.   A cured product obtained by curing the curable composition according to claim 1. In a method for producing a cured product comprising a substrate preparation step for preparing a substrate, a coating step for applying a curable composition to the substrate, and an irradiation step for irradiating energy rays.
The said curable composition is the curable composition of Claim 1 or 2, The manufacturing method of the hardened | cured material characterized by the above-mentioned. In a method for producing a cured product comprising a substrate preparation step for preparing a substrate, a coating step for applying the curable composition to the substrate, and a heating step for heating.
The said curable composition is the curable composition of Claim 1 or 2, The manufacturing method of the hardened | cured material characterized by the above-mentioned.