JP2017179165A - Curable composition, manufacturing method of cured article, the cured article and adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition excellent in coatability and less in yellow discoloration of a cured article, a manufacturing method of the cured article and the cured article thereof and an adhesive.SOLUTION: There is provided a curable composition containing (A) at least one compound selected from a group consisting of an acrylic acid ester compound of polyalcohol and a methacrylic acid ester compound of polyalcohol, (B) an epoxy compound, (C) an oxetane compound, (D) a polymer having a skeleton represented by the following general formula (1), where Ris an alkyl group or the like, in the structure, and (E) a polymerization initiator, with the (B) component of 1 to 95 pts.mass, the (C) component of 0.5 to 15 pts.mass, the (D) component of 1 to 30 pts.mass and the (E) component of 1 to 30 pts.mass based on 100 pts.mass of the (A) component and a chlorine content in a range of 0.01 to 1500 ppm.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition, a method for producing a cured product, the cured product, and an adhesive, and more specifically, to produce a curable composition and a cured product that are excellent in coating properties and have little yellowing of the cured product. The present invention relates to a method, a cured product thereof, and an adhesive.

  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 A photocurable adhesive composition containing a compound having a weight average 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 has been proposed. 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, these adhesives have a problem that the coated surface is not uniform, a problem that a cured product obtained by curing the adhesive is yellowed, and a problem that the elastic modulus is low. In particular, the coating surface does not become uniform, which is a major problem. Further, as an adhesive used in manufacturing a fine optical component represented by a polarizing plate, a conventionally proposed adhesive is used. In this case, it is a big problem that a cured product obtained by curing the adhesive is yellowed.

  Then, the objective of this invention is providing the curable composition which is excellent in coating property, and has little yellowing of hardened | cured material, the manufacturing method of hardened | cured material, the hardened | cured material, and an adhesive agent.

  As a result of intensive studies to solve the above problems, the present inventor can solve the above-mentioned problems as long as it is a curable composition having a specific composition having a chlorine content in the range of 0.1 to 1500 ppm. The headline and the present invention were completed.

（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）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１〜９５質量部、前記（Ｃ）オキセタン化合物０．５〜１５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１〜３０質量部、前記（Ｅ）重合開始剤１〜３０質量部であり、塩素含有量が０．０１〜１５００ｐｐｍの範囲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 polymerization initiator, In the containing curable composition,
(B) 1 to 95 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) 0.5 to 15 parts by mass of an oxetane compound, 1 to 30 parts by mass of a polymer having a skeleton represented by the above general formula (1) in the above (D) structure, and (E) a polymerization initiator 1 to It is 30 parts by mass, and the chlorine content is in the range of 0.01 to 1500 ppm.

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.

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

  The adhesive of the present invention comprises the curable composition of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition which is excellent in coating property and has little yellowing of hardened | cured material, the manufacturing method of hardened | cured material, the hardened | cured material, and an adhesive agent can be provided.

  The curable composition of the present invention has a uniform coating surface, a cured product obtained by curing the curable composition is hardly yellowed, has a high elastic modulus, and has good insulation. Since the curable composition of the present invention has the above effects, it can be suitably used as an adhesive, and particularly suitably used as an adhesive used in the production of fine optical components represented by polarizing plates. Can do. 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 method for producing a cured product, and 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 (1) (hereinafter also referred to as “component (D)”) and (E) a polymerization initiator (hereinafter also referred to as “component (E)”). It is a curable composition.

ここで、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。

Here, in the formula, 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 1-95 parts by mass, (C) component 0.5-15 parts by mass, and (D) component 1-30 parts by mass per 100 parts by mass of component (A). (E) The component is 1 to 30 parts by mass, and the chlorine content is in the range of 0.01 to 1500 ppm.

  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. 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 compounding quantity of (B) component used for the curable composition of this invention is the range of 1-95 mass parts per 100 mass parts of said (A) component. Of these, the range of 10 to 95 parts by mass is particularly preferable because of high adhesive strength, and the range of 40 to 90 parts by mass is particularly preferable.

  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. 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 compound 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 and the like. 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 0.5-15 mass parts per 100 mass of said (A) component. Among these, the range of 1 to 10 parts by mass is particularly preferable since the adhesive force is high.

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). Alkoxyalkyl group-containing monofunctional oxetane such as methyl) oxetane, aromatic group-containing monofunctional oxetane 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 L) 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-formaldehyde resin modified by etherification with 3-chloromethyl-3-ethyloxetane, 3 (4), 8 (9) -bis [(3-ethyloxetane-3-yl ) Methoxymethyl] -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 -Ethyloxetane-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 oxeta 3-[(3-ethyloxetane-3-yl) methoxy] propyltrialkoxysilane hydrolysis condensate, tetrakis [(3-ethyloxetane-3-yl) methyl] silicate, 3-ethyloxetane-3-yl Examples thereof include a condensation reaction product of methanol and a silanetetraol polycondensate. Here, oxetanylsilsesquioxane 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 weight average 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 1-30 mass parts per 100 mass parts of said (A) component. Among these, the range of 1 to 20 parts by mass is particularly preferable because of high adhesive strength.

  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 the skeleton represented by the above general formula is 50 mol%. The polymer containing above is preferable, and the polymer containing 80 mol% or more is more preferable.

R ¹ in the general formula (1) represents an alkyl group. For example, methyl group, ethyl group, propyl group, n-butyl group, second 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 can be mentioned. Among these, R ¹ is preferably an alkyl group 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 Yutan monomers; amino group-containing monomer; imide group-containing monomers; glycidyl (meth) an epoxy group-containing monomers such as acrylate; (meth) acryloyl morpholine; and 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).

  As the component (D), 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 the component (D-1)) was used. In this case, the curable composition of the present invention is preferable because it 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 addition amount 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, the range of 5 to 20 parts by mass is preferable because optical properties such as transparency are high and durability is improved.

  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.

  These photopolymerization initiators may be used alone or in combination of two or more. In the present invention, it is preferable to use a mixture of one or more photocationic polymerization initiators and radical photopolymerization 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^３およびＲ^４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^５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 ³ and R ⁴ 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 ⁵ 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^６およびＲ^７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 ⁶ and R ⁷ 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 benzoin methyl ether, benzoin isopropyl ether, benzoin derivatives such as α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate Benzophenone derivatives such as 4,4′-bis (diethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone; N-methyl Acridone derivatives such as acridone and N-butylacridone; others, α, α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, halogen compounds, photoreducible dyes However, it is not limited to these. Moreover, these may be used independently or may use 2 or more types. 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 per 100 parts by mass of the component (A).

  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.

  The curable composition of the present invention has a chlorine content in the range of 0.1 to 1500 ppm. When the chlorine content is less than 0.01 ppm, the time required for curing increases. Further, when the chlorine content is 1500 ppm, the uniformity of the coated surface is deteriorated, and further, the cured product obtained by curing the adhesive is yellowed, the elastic modulus is low, and the insulating property is deteriorated. Preferably, it is within the range of 0.01 ppm to 1000 ppm, more preferably within the range of 0.1 ppm to 500 ppm, and particularly preferably within the range of 10 to 500 ppm. Examples of the chlorine supply method include a method of directly adding chlorine, a method using a raw material containing chlorine, a method of adding an additive containing chlorine, and the like. Among these, it is preferable to adjust the amount of chlorine in the entire curable composition by the component (B) containing chlorine.

  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.

  Commercially available antioxidants include, for example, AO-20, AO-30, AO-50 and AO-80 (above, manufactured by ADEKA Corporation), dibutylhydroxytoluene (BHT), Irganox 1010, Irganox. 1035FF, Irganox 565, and the like. As for the usage-amount of antioxidant, 0.0001-10 mass parts is preferable per 100 mass parts of said (A) component.

  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 parts is preferable per 100 mass parts of said (A) component.

  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.

  Moreover, the other manufacturing method of the hardened | cured material of this invention includes the base | substrate preparation process which prepares a base | substrate, the application | coating process which apply | coats the curable composition of this invention to a base | substrate, and the heating process of heating.

  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; Examples include oxyethylene and norbornene resins; resins containing colored pigments, colored dyes, and carbon black; polyimide films. Prior to the 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 hot cation curable adhesive satisfactorily without reducing the optical performance of the polarizer is used, but there is no particular limitation on the type thereof. 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 known general method can be used, and for example, a heater or the like can be used. What is necessary is just to adjust a heating condition suitably within the range of 50-200 degreeC according to the catalyst to be used. 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, it is known that when a protective film or an optical compensation film is attached to a polarizing plate, the polarizing plate has a good appearance, but the viscosity is 200 mPa · s or less (25 ° C.). Furthermore, when the chlorine content of the curable composition is in the range of 0.01 to 1500 ppm, there is a particularly excellent effect that the coated surface of the adhesive becomes uniform.

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

[Examples 1-7 and Comparative Examples 1-6]
Using the compounds shown in Table 1, the curable compositions of Examples 1 to 7 and Comparative Examples 1 to 6 were produced with the formulations shown in Tables 2 and 3. In addition, the unit of the compounding quantity in a table | surface is a mass part.

化合物Ｎｏ．１

Compound No. 1

化合物Ｎｏ．２

Compound No. 2

COP (cycloolefin polymer) which applied corona discharge treatment using a laminator after apply | coating the curable composition of Examples 1-7 and Comparative Examples 1-6 to one TAC film which carried out the corona discharge treatment respectively. The test pieces of Examples 1 to 7 and Comparative Examples 1 to 6 were obtained by bonding to a film and irradiating and adhering energy of 1000 mJ / cm ² using an electrodeless ultraviolet lamp.

[Evaluation of coatability and yellowing]
The coated surface in the application | coating process of the curable composition of Examples 1-7 and Comparative Examples 1-6 was observed visually. The case where the coated surface was uniform was defined as +, and the case where the coated surface was non-uniform was denoted as-. Moreover, the color of the test piece of the curable composition of Examples 1-7 and Comparative Examples 1-6 was observed visually, and the case where it was not yellowing was set to ++, and the case where it was yellowing was set to-. . The results are also shown in Tables 2 and 3.

From the results of Tables 2 and 3, Examples 1 to 7 have a uniform coating surface, while Comparative Examples 1 to 6 have a non-uniform coating surface. Moreover, all the hardened | cured materials were yellowing in Comparative Examples 1-6, and yellowing was not confirmed in all of Examples 1-7.

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 polymerization initiator, In the containing curable composition,
(B) 1 to 95 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) 0.5 to 15 parts by mass of an oxetane compound, 1 to 30 parts by mass of a polymer having a skeleton represented by the above general formula (1) in the above (D) structure, and (E) a polymerization initiator 1 to It is 30 mass parts, Chlorine content is the range of 0.01-1500 ppm, The curable composition 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 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, 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, The manufacturing method of the hardened | cured material characterized by the above-mentioned.   A cured product obtained by curing the curable composition according to claim 1.   An adhesive comprising the curable composition according to claim 1.