JP2008231407A - Radiation-curable adhesive composition, composite body, and manufacturing method for composite body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-curable adhesive composition capable of easily adhering a molded body of PVA based resin and the other body to be adhered, and forming a composite body (laminated film or the like) excellent in cutting-resistance, moist/heat-resistance and adhesion strength. <P>SOLUTION: The composition contains (A) an alicyclic epoxy compound, (B) a compound having a molecular weight of 500 or higher and containing at least one hydroxyl group, and (C) an optical acid generating agent. The composite body 1 is formed by laminating an adherend 3 onto one surface of the PVA based molded body 2 through an adhesive layer 4 comprising a cured product of the radiation-curable adhesive composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a radiation curable adhesive composition, a composite formed using the radiation curable adhesive composition, and a method for producing the composite.

Conventionally, a laminated film excellent in gas barrier properties is known.
For example, a transparent primer layer on at least one surface of a substrate made of a transparent plastic material, a thin film layer made of an inorganic oxide having a thickness of 5 to 300 nm, an aqueous polymer, and (a) one or more metal alkoxides and hydrolysates thereof Alternatively, (b) a gas barrier coating layer formed by applying a coating agent mainly composed of an aqueous solution containing at least one of tin chloride or a water / alcohol mixed solution, followed by heating and drying, and then sealing through an adhesive. A strong adhesion transparent laminate for boil and retort characterized by laminating a polyolefin-based thermoplastic resin layer as a layer has been proposed (Patent Document 1).

And a gas barrier film having a ratio (B) / (A) of 2.0 or more between the oxygen transmission rate (A) at 23 ° C. and a relative humidity of 60% and the oxygen transmission rate (B) at 23 ° C. and a relative humidity of 80%; A laminate film bonded with a sealant film, wherein the adhesive used for laminating the gas barrier film and the sealant film is a laminate adhesive mainly composed of an epoxy resin and an epoxy resin curing agent, and There has been proposed a laminate film characterized in that the skeleton structure represented by the formula (1) contained in the cured epoxy resin formed by the laminating adhesive is 40% by weight or more (Patent Document 2). ).
Japanese Patent Laid-Open No. 10-722 JP 2003-251752 A

Generally, when a laminated film (for example, a gas barrier film) is commercialized, it is required to have excellent cutting resistance. That is, the laminated film is usually used after being cut to a size suitable for the purpose of use, but at the time of this cutting, peeling (chip part of the adhesive layer) occurs at the cutting part (end after cutting). There is a problem that there is. This peeling not only hinders the gas barrier performance of the peeled portion, but also promotes moisture absorption of the gas barrier film and may cause deformation under high temperature and high humidity.
In addition, the laminated film is also required to be excellent in heat and humidity resistance, adhesion strength between the adherend and the adhesive layer, and the like.
The present invention has been made in view of the above-mentioned background. For example, a molded body made of a PVA-based resin, and an adherend of the same or different type as the molded body made of the PVA-based resin can be easily manufactured. Radiation curable adhesion that can form composites (laminated films, etc.) that can be bonded in a short time in the process, and that are excellent in cutting resistance, moisture and heat resistance, and adhesion strength between adherend and adhesive layer, etc. An object is to provide a pharmaceutical composition.

  As a result of intensive studies to solve the above problems, the present inventor, for example, uses a radiation-curable adhesive composition containing a specific component, for example, from a molded body made of a PVA resin and the PVA resin. Can be bonded to the same type or different types of adherends in a short time with a simple manufacturing process, and is excellent in cutting resistance, moist heat resistance, adhesion strength between adherend and adhesive layer, etc. The present invention was completed.

（式中、ｎは０〜４の整数である。）
［５］ 下記一般式（１）で表される構造を含むポリビニルアルコール系樹脂からなるＰＶＡ系成形体の表面に、接着剤層を介して、上記ＰＶＡ系成形体と同種又は異種の被着体を接着してなる複合体であって、上記接着剤層が、前記［４］に記載の放射線硬化性接着剤用組成物の硬化物からなる複合体。

（式中、ｎは０〜４の整数である。）
［６］ 上記ＰＶＡ系成形体と同種又は異種の被着体が、ノルボルネン系樹脂フィルムである前記［５］に記載の複合体。
［７］ 前記［５］又は［６］に記載の複合体の製造方法であって、上記ＰＶＡ系成形体の表面に、上記ＰＶＡ系成形体と同種又は異種の被着体を、放射線硬化性接着剤用組成物を介して積層する積層工程と、上記放射線硬化性接着剤用組成物に放射線を照射して硬化させ、上記複合体を得る放射線硬化工程を含む複合体の製造方法。 That is, the present invention provides the following [1] to [6].
[1] (A) an alicyclic epoxy compound, (B) a compound having a polystyrene-equivalent number average molecular weight of 500 or more as measured by gel permeation chromatography, and containing at least one hydroxyl group, and (C) A composition for a radiation curable adhesive, comprising a photoacid generator.
[2] The component (B) is a compound having a polystyrene-equivalent number average molecular weight of 1,000 or more measured by gel permeation chromatography and containing one or more hydroxyl groups. ] The composition for radiation-curable adhesives of description.
[3] In the above [1] or [2], the radiation curable adhesive composition has a light transmittance of 550 nm when the cured product has a thickness of 200 μm. The composition for radiation-curable adhesives described.
[4] A PVA-based molded article comprising a polyvinyl alcohol-based resin having a structure represented by the following general formula (1), wherein the radiation-curable adhesive composition is the same or different from the PVA-based molded article. The composition for a radiation curable adhesive according to any one of the above [1] to [3], which is a composition for use in adhesion to an adherend.

(In the formula, n is an integer of 0 to 4.)
[5] An adherend of the same or different type as that of the PVA-based molded body is provided on the surface of a PVA-based molded body made of a polyvinyl alcohol-based resin having a structure represented by the following general formula (1) via an adhesive layer. Wherein the adhesive layer is made of a cured product of the radiation-curable adhesive composition according to [4].

(In the formula, n is an integer of 0 to 4.)
[6] The composite according to [5], wherein the adherend of the same or different type as the PVA-based molded body is a norbornene-based resin film.
[7] The method for producing a composite according to [5] or [6], wherein an adherend of the same or different type as the PVA-based molded body is applied to the surface of the PVA-based molded body. A method for producing a composite comprising a laminating step of laminating via an adhesive composition and a radiation curing step of irradiating and curing the radiation curable adhesive composition to obtain the composite.

Since the composition for radiation-curable adhesives of the present invention contains a specific component, for example, it is suitable for adhesion between a PVA-based molded body and an adherend of the same or different type from the PVA-based molded body. In particular, even when a norbornene resin film is used as the adherend, good adhesive strength can be obtained. In this case, both excellent gas barrier properties and low moisture permeability (low moisture permeability) are achieved. can do.
Moreover, since the composite of the present invention is made of a cured product of a radiation-curable adhesive composition having a specific component in the adhesive layer, it has excellent cutting resistance (the adhesive layer does not peel off during cutting). ), Heat and humidity resistance, adhesion between the adherend and the adhesive layer, and the like.
Furthermore, according to the method for producing a composite of the present invention, for example, an adherend is laminated on the surface of a PVA-based molded body via a radiation curable adhesive composition, and the radiation curable adhesive composition is laminated. A composite (for example, a gas barrier film that is a laminated film) can be formed simply by irradiating and curing the light, and the production efficiency of the composite can be improved.

First, the radiation curable adhesive composition of the present invention will be described in detail.
The composition for radiation-curable adhesive of the present invention comprises the following components (A) to (C) and other optional components.
[Component (A)]
Component (A) constituting the radiation curable adhesive composition is an alicyclic epoxy compound, preferably an alicyclic epoxy compound having two or more alicyclic epoxy groups in one molecule. When an alicyclic epoxy compound having two or more alicyclic epoxy groups in one molecule is contained in an amount of 50% by mass or more in the total amount of the component (A), a better curing speed and mechanical strength can be obtained. .
Specific examples of the alicyclic epoxy compound used as the component (A) include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5 -Spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6 -Methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4- Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), diethylene glycol (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxycyclohexahydrophthalate, di-2-ethylhexyl epoxycyclohexahydrophthalate, and the like.

  Among these alicyclic epoxy compounds, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, ε-caprolactone modified 3,4-epoxy Cyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxy More preferred is cyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexane Cyclohexylmethyl) adipate is more preferable.

  These commercially available products include Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-400, Epolide 401, Epolide 403 (or more, Daicel Chemical Industries, Ltd.).

  The content of the (A) alicyclic epoxy compound in the radiation curable adhesive composition is 20 to 80% by mass, preferably 25 to 70% by mass, and more preferably 30 to 60% by mass. When the content is less than 20% by mass, the mechanical strength and heat and humidity resistance of the adhesive layer tend to be insufficient. When the said content rate exceeds 80 mass%, there exists a tendency for deformation | transformation, such as curvature of the adhesive bond layer formed by hardening | curing the composition for radiation-curable adhesives to become large.

[Component (B)]
The component (B) constituting the radiation curable adhesive composition is a compound having a molecular weight of 500 or more and containing one or more hydroxyl groups.
The number average molecular weight of the component (B) (polystyrene conversion value by gel permeation chromatography (GPC)) is 500 or more, preferably 1,000 or more. Although the upper limit of this molecular weight is not specifically limited, From a viewpoint of preventing the excessive increase in the viscosity of the composition for adhesive agents, Preferably it is 20,000, More preferably, it is 10,000. When the molecular weight is less than 500, the cutting resistance cannot be sufficiently improved, which is not preferable.
The molecular weight of the component (B) was converted to polystyrene using HPC-8220GPC (manufactured by Tosoh Corporation), two columns TFKgel G4000HXL, G3000HXL, and G2000HXL, using tetrahydrofuran as a developing solvent, and a flow rate of 1 cc / min at 40 ° C. The number average molecular weight of
The compound suitably used as component (B) is preferably a compound having 1 or more hydroxyl groups in one molecule, more preferably 1 to 4 hydroxyl groups in one molecule. Of these, diols and polyols are preferred, and polyols are more preferred. By using the component (B), a laminated film having excellent cutting resistance can be obtained.

Examples of the compound suitably used as the component (B) include polycarbonate diol, polycaptolactone diol, polyether diol, and polyester diol.
Examples of the polycarbonate diol include polytetrahydrofuran polycarbonate and 1,6-hexanediol polycarbonate. Examples of commercially available products of these polycarbonate diols include DN-980, 981, 982, 983 (manufactured by Nippon Polyurethane), PC-8000 (manufactured by PPG), PC-THF-CD (manufactured by BASF), C-2050. C-2090 (manufactured by Kuraray Co., Ltd.), Plaxel CD CD210PL, Plaxel CD CD220PL (manufactured by Daicel Chemical Industries, Ltd.), and the like.

  Examples of the polycaprolactone diol include polycaprolactone diol obtained by reacting ε-caprolactone and diol. Examples of the diol used here include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, Examples include 1,4-cyclohexanedimethanol and 1,4-butanediol. Examples of commercially available products of these polycaprolactone diols include Plaxel 205, 205H, 205AL, 212, 212AL, 220, and 220AL (manufactured by Daicel Chemical Industries, Ltd.).

  The polyether diol is preferably an aliphatic polyether diol, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, and polydecamethylene glycol. Commercial products of these polyether diols include PEG # 600, # 1000, # 1500, # 1540, # 4000 (above, manufactured by Lion), Exenol 720, 1020, 2020, 3020, 510, Preminol PPG4000 (above, Asahi Glass Co., Ltd.).

  The polyester diol is preferably a copolymer of an aliphatic diol compound and an aliphatic dicarboxylic acid compound. Examples of the aliphatic diol compound include 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl- 1,5-pentanediol and the like, and examples of the aliphatic dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and the like. One or more aliphatic diols can be used, and one or more aliphatic dicarboxylic acids can be used. Commercially available products of these polyester diols include Kuraray polyol N-2010, O-2010, P-510, P-1010, P-1050, P-2010, P-2050, P-3010, P-3050 (or more, Kuraray Co., Ltd.).

Examples of the polyol include trihydric or higher polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose, and quadrol, and cyclic compounds such as ethylene oxide (EO), propylene oxide (PO), butylene oxide, and tetrahydrofuran. A polyether polyol obtained by modifying with an ether compound can be mentioned. Specific examples of such compounds include EO-modified trimethylolpropane, PO-modified trimethylolpropane, tetrahydrofuran-modified trimethylolpropane, EO-modified glycerol, PO-modified glycerol, tetrahydrofuran-modified glycerol, EO-modified pentaerythritol, PO-modified pentaerythritol, Tetrahydrofuran-modified pentaerythritol, EO-modified sorbitol, PO-modified sorbitol, EO-modified sucrose, PO-modified sucrose, EO-modified sucrose, EO-modified quadrole, etc. can be exemplified, and among these, EO-modified trimethylolpropane, PO-modified trimethylol Propane, PO-modified glycerin and PO-modified sorbitol are preferred.
Examples of commercially available polyols include Sannix TP-700, Sannix GP-1000, Sannix SP-750, Sannix GP-600 (manufactured by Sanyo Chemical Co., Ltd.), and the like.

  Moreover, as a polyol used suitably as a component (B), the polymer of a hydroxyl-containing unsaturated compound can be mentioned. Examples of the hydroxyl group-containing unsaturated compound include a hydroxyl group-containing (meth) acrylate. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6- Hexanediol mono (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol penta (meth) acrylate. Furthermore, the compound obtained by addition reaction of glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid is mentioned.

  In the composition for radiation curable adhesive, the content of component (B) is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, and particularly preferably 7 to 15% by mass. When the content is less than 3% by mass, the cutting resistance of the adhesive layer is inferior, which is not preferable. On the other hand, if the content exceeds 30% by mass, the viscosity of the radiation-curable adhesive composition becomes too high, resulting in poor coating properties, and poor adhesive strength between the adhesive layer and the adherend. Therefore, it is not preferable.

[Component (C)]
Component (C) constituting the composition for radiation curable adhesive is a photoacid generator.
The photoacid generator is a photocationic polymerization initiator that releases Lewis acid upon receiving light.
Examples of the photoacid generator include an onium salt having a structure represented by the following general formula (2). This onium salt has a substantial light absorption wavelength below 400 nm.
_{^{[R 11 a R 12 b R}} 13 c R 14 d Z] s + [MX s + t] s- (2)
(Wherein the cation is an onium ion, Z represents S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or N≡N, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ represents an organic group which is the same or different from each other, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of Z + s. MX _{s + t} ] represents a metal or metalloid constituting the central atom of, for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is a halogen atom such as F, Cl, Br, etc., s is the net charge of the halide complex ion, and t is the valence of M.)

In the general formula (2), specific examples of the onium ion include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl). Diaryliodonium such as iodonium, triarylsulfonium such as triphenylsulfonium and diphenyl-4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- ( 2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, η ⁵ -2,4- (cyclopentadienyl) [1,2,3,4,5,6-η]-(methylethyl) -benzene] -Iron (1+) etc. are mentioned.
In the general formula (2), specific examples of the anion [MX _{s + t} ] include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarce. Nate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ) and the like.
In addition, an onium salt having an anion represented by the general formula [MX _e (OH) ⁻ ] can be used. Further, perchlorate ion (ClO ₄ ⁻ ), trifluoromethane sulfonate ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluene sulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene sulfonate Onium salts having other anions such as anions can also be used.

  Examples of onium salts used as the component (C) include aromatic halonium salts described in, for example, JP-A-50-151996 and JP-A-50-158680, JP-A-50-151997, VIA group aromatic onium salts described in JP-A-52-30899, JP-A-56-55420, JP-A-55-125105, etc., VA described in JP-A-50-158698, etc. Aromatic aromatic onium salts, oxosulfoxonium salts described in JP-A-56-8428, JP-A-56-149402, JP-A-57-192429, etc., JP-A-49-17040 And aromatic thiobililium salts described in US Pat. No. 4,139,655. Moreover, an iron / allene complex, an aluminum complex / photolytic silicon compound-based initiator, and the like can also be mentioned. The photoacid generator preferably used as the component (C) is an aromatic onium salt such as a diaryl iodonium salt or a triarylsulfonium salt, and more preferably a triarylsulfonium salt.

(C) Examples of commercially available photoacid generators include UVI-6950, UVI-6970, UVI-6974, UVI-6990 (manufactured by Union Carbide), Adekaoptomer SP-150, SP-151, SP-170, SP-172 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (above, made by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-2638, CI-2064 (above , Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, manufactured by Sartomer), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS- 103, MPI-103, BBI-103 (above, manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, manufactured by Nippon Kayaku Co., Ltd.), CPI-110A, CPI-101A (above, San Apro Co., Ltd.) and the like can be mentioned. Among these, UVI-6970, UVI-6974, Adeka optomer SP-170, SP-172, CD-1012, MPI-103, CPI-110A, CPI-101A are compositions for adhesives containing these. It is particularly preferable because a high photocuring sensitivity can be expressed in the product. Said photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
A sensitizer may be used in combination in order to promote the generation of acid by the photoacid generator. Examples of the sensitizer include dihydroxybenzene, trihydroxybenzene, hydroxyacetophenone, dihydroxydiphenylmethane, and the like.

  In the composition for radiation curable adhesive of the present invention, the content of (C) photoacid generator is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, particularly preferably 0. .3 to 3% by weight. When the content is less than 0.1% by mass, the radiation curability of the radiation curable adhesive composition is lowered, and an adhesive layer having sufficient mechanical strength cannot be formed. On the other hand, if the content exceeds 10% by mass, the photoacid generator may adversely affect the long-term characteristics of the adhesive layer, which is not preferable.

[Component (D)]
The composition for radiation curable adhesives can further contain an aliphatic epoxy compound as component (D). The aliphatic epoxy compound of component (D) is an optional component added to control the mechanical strength and the like of the adhesive layer.
Specific examples of the aliphatic epoxy compound include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl. Ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ethers; polyether polyol obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, etc. Diglycidyl esters of aliphatic long-chain dibasic acids; Monoglycidyl ethers of higher aliphatic alcohols; Glycidyl esters of higher fatty acids Le acids; epoxidized soybean oil; butyl epoxy stearate, epoxy stearic octyl, epoxidized linseed oil, epoxy polybutadiene, and the like.

  In the composition for radiation curable adhesive, the content of the (D) aliphatic epoxy compound is preferably 0 to 50% by mass, more preferably 15 to 45% by mass, and particularly preferably 30 to 40% by mass. When the content exceeds 50% by mass, the content of the essential component (A) alicyclic epoxy compound and the like is decreased, and the effect of the present invention cannot be obtained, which is not preferable.

Moreover, various additives can be mix | blended with the composition for radiation-curable adhesives of this invention as another arbitrary component in the range which does not impair the objective and effect of this invention. Such additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone oligomers and polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; Plasticizers; UV absorbers; silane coupling agents; inorganic fillers; pigments; dyes and the like.
The composition for radiation curable adhesives can be prepared by uniformly mixing the components (A) to (C) and, if necessary, the above optional components. The viscosity of the radiation-curable adhesive composition thus obtained is usually 2,000 mPa · s or less, preferably 500 mPa · s or less, more preferably 300 mPa · s or less, at the temperature at the time of coating.
In addition, a solvent such as an organic solvent can be added to the radiation curable adhesive composition as necessary. However, in the present invention, since the composition for a radiation curable adhesive can be prepared even without a solvent, it is preferable not to contain a solvent from the viewpoint of maintaining the working environment and environmental burden.
When the radiation-curable adhesive composition is a cured product having a thickness of 200 μm, the light transmittance at a wavelength of 550 nm is preferably 70% or more, more preferably 80% or more.

Next, the composite of the present invention and the production method thereof will be described with reference to the drawings as appropriate.
FIG. 1 is a cross-sectional view schematically showing an example of the composite of the present invention. FIG. 2 is a flowchart showing an example of the method for producing the composite of the present invention.
In FIG. 1, a composite 1 includes a PVA-based molded body 2, an adhesive layer 4 formed on the upper surface of the PVA-based molded body 2, and an adherend 3 formed by laminating on the upper surface of the adhesive layer 4. It consists of.

（式中、ｎは０〜４の整数である。）
一般式（１）中、ｎは０〜４の整数であり、好ましくは０である。
このようなポリビニルアルコール系樹脂としては、ポリビニルアルコール、エチレン・ビニルアルコール共重合体などが挙げられるが、耐水性の点から、エチレン・ビニルアルコール共重合体が好ましい。 [PVA molded product]
As a PVA type molded object, the molded object which consists of polyvinyl alcohol-type resin containing the structure represented by following General formula (1) is mentioned.

(In the formula, n is an integer of 0 to 4.)
In general formula (1), n is an integer of 0 to 4, preferably 0.
Examples of such polyvinyl alcohol resins include polyvinyl alcohol and ethylene / vinyl alcohol copolymers, and ethylene / vinyl alcohol copolymers are preferred from the viewpoint of water resistance.

Examples of polyvinyl alcohol include partially saponified polyvinyl alcohol in which several tens of percent of acetate groups remain, fully saponified polyvinyl alcohol in which acetate groups do not remain, and modified polyvinyl alcohol in which hydroxyl groups have been modified. Is not to be done. Specific examples of the polyvinyl alcohol include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (degree of saponification) manufactured by the same company. = 40%, polymerization degree = 2,000), Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization degree = 1,400), and the like.
Polyvinyl alcohol is obtained, for example, by saponifying a polymer of a fatty acid vinyl ester such as vinyl acetate, vinyl propionate or vinyl pivalate using an alkali catalyst or the like.

The ethylene-vinyl alcohol copolymer is obtained by saponifying a copolymer of ethylene and vinyl acetate, that is, an ethylene-vinyl acetate random copolymer, and has an acetate group of several tens mol%. The remaining saponified product is not particularly limited, and includes a partially saponified product in which only a few mol% of acetic acid groups remain or no acetic acid group remains.
The saponification degree of the ethylene / vinyl alcohol copolymer is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%.
As a commercial item of the said ethylene vinyl alcohol copolymer, Kuraray Co., Ltd. product, Eval EP-F101 (ethylene content; 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908, D2935 (ethylene content; 29 mol%), D2630 (ethylene amount; 26%), A4412 (ethylene amount 44%), and the like.

The melt flow index of the polyvinyl alcohol-based resin is 1 to 50 g / 10 minutes, preferably 5 to 45 g / 10 minutes, under the conditions of 210 ° C. and a load of 21.168 N. If the melt flow index is less than 1 g / 10 minutes, the gas barrier properties may deteriorate. On the other hand, if it exceeds 50 g / 10 minutes, the water resistance and the solvent resistance may decrease, which is not preferable.
A polyvinyl alcohol-type resin can be used individually by 1 type, or can also use 2 or more types together.

A PVA-type molded object is obtained by shape | molding the above-mentioned polyvinyl alcohol-type resin by methods, such as casting molding method. The PVA-based molded body may be crosslinked or stretched with boric acid or the like.
Although it does not specifically limit as a shape of a PVA type molded object, For example, a film etc. are mentioned. In this specification, the term “film” includes not only a sheet having a small thickness (thickness of less than 1 mm) but also a thick sheet (for example, having a thickness of 1 to 5 mm).
Although the thickness of a PVA-type molded object is not specifically limited, For example, in the case of a polarizing film, it is normally determined so that it may be 10-40 micrometers.
[Adhesive layer]
An adhesive bond layer is a hardened | cured material layer formed by carrying out radiation hardening of the above-mentioned composition for radiation-curable adhesives.
By forming an adhesive layer using the above-described radiation-curable adhesive composition, excellent cutting resistance can be obtained, and even if the adherend is COP-based, the adherend- A composite having excellent adhesive strength between adhesive layers can be obtained.
The thickness of the adhesive layer is not particularly limited, but is determined to be, for example, 0.5 to 3 μm.

[Adherent]
As the adherend to be bonded to the PVA-based molded body, either the same type of adherend as the PVA-based molded body or a different type of adherend can be used.
Examples of the same kind of adherend as the PVA-based molded body include those made of the polyvinyl alcohol-based resin represented by the general formula (1) as described above. In this case, the adherend need not have the same composition as the PVA-based molded body. For example, the PVA-based molded body can be a film made of polyvinyl alcohol, and the adherend can be a film made of an ethylene / vinyl alcohol copolymer.
Examples of the adherend different from the PVA-based molded body include, for example, norbornene-based resins, acetate-based resins (for example, triacetyl cellulose), polyester-based resins (for example, polyethylene terephthalate resin), polyethersulfone-based resins, A film made of a resin such as a polycarbonate resin, a polyamide resin, a polyimide resin, a polyolefin resin, or an acrylic resin is used. Among these, norbornene-based resin films are preferable.
When a norbornene resin film is used as the adherend to be bonded to the PVA-based molded body, both excellent gas barrier properties and low moisture permeability can be achieved.
Although the thickness of a to-be-adhered body is not specifically limited, For example, it determines so that it may be 15-100 micrometers.

(Norbornene resin film)
In addition, as the above-mentioned norbornene-based resin film, a film made of a resin obtained by polymerizing a monomer composition containing at least one norbornene-based compound and further hydrogenating as necessary is preferable.
As said norbornene-type compound, the norbornene-type compound represented by following General formula (3) can be mentioned, for example.

(In Formula (3), R ^{1 to} R ⁴ are each independently a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom which may have a linking group containing oxygen, nitrogen, sulfur or silicon. It represents a 1-15 hydrocarbon group or other monovalent organic group. Alternatively R ¹ and R ² or R ³ and R ⁴ are bonded to each other may form an alkylidene group, R ¹ and R ² , R ³ and R ⁴ or R ² and R ³ are bonded to each other to form a carbocyclic or heterocyclic ring (these carbocyclic or heterocyclic rings may have a monocyclic structure, or other rings may be condensed to form a polycyclic ring). The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring, and x is 0 or an integer of 1 to 3, y is Represents 0 or 1, but when x is 0, y is also 0.)

Specific examples of the norbornene-based compound represented by the general formula (3) include the compounds shown below, but are not limited to these examples.
Bicyclo [2.2.1] hept-2-ene (norbornene)
5-methyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept 2-ene-5-phenyl-bicyclo [2.2.1] hept-2-ene-5- (4-biphenyl) -bicyclo [2.2.1] hept-2-ene-5-methoxycarbonyl- Bicyclo [2.2.1] hept-2-ene · 5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene · 5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2 -Ene, 5-phenylcarbonyloxy-bicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-methyl- 5-phenoxycarboni -Bicyclo [2.2.1] hept-2-ene.5-methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene.5-vinyl-bicyclo [2.2.1] ] Hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5,6-dimethyl -Bicyclo [2.2.1] hept-2-ene, 5-fluoro-bicyclo [2.2.1] hept-2-ene, 5-chloro-bicyclo [2.2.1] hept-2-ene 5-bromo-bicyclo [2.2.1] hept-2-ene5,6-difluoro-bicyclo [2.2.1] hept-2-ene5,6-dichloro-bicyclo [2.2 .1] Hept-2-ene-5,6-dibromo-bicyclo [2.2.1 Hept-2-ene, 5-hydroxy-bicyclo [2.2.1] hept-2-ene, 5-hydroxyethyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2 2.1] hept-2-ene, 5-amino-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, tricyclo [ 4.4.0.1 ^2,5 ] Undec-3-ene.7-methyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene.7-ethyl-tricyclo [4.3. 0.1 ^2,5] dec-3-ene-7-cyclohexyl - tricyclo [4.3.0.1 ^2,5] dec-3-ene-7-phenyl - tricyclo [4.3.0.1 ^{2 , 5]} dec-3-ene-7- (4-biphenyl) - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-7,8 Methyl - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-7,8,9- trimethyl - tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene-8- Methyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene · 8-phenyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene · 7-fluoro-tricyclo [ 4.3.0.1 ^2,5 ] dec-3-ene.7-chloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene.7-bromo-tricyclo [4.3. 0.1 ^2,5] dec-3-ene-7,8-dichloro - tricyclo [4.3.0.1 ^2,5] dec-3-ene-7,8,9- trichloro - tricyclo [4. 3.0.1 ^2,5 ] dec-3-ene · 7-chloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene · 7-dichloromethyl-tricycl B [4.3.0.1 ^2,5 ] dec-3-ene · 7-trichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene · 7-hydroxy-tricyclo [4 .3.0.1 ^2,5 ] dec-3-ene · 7-cyano-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene · 7-amino-tricyclo [4.3.0 .1 ^2,5] deca-3-ene-tetracyclo [4.4.0.1 ^2,5. 1 ^7,10 ] dodec-3-ene pentacyclo [7.4.0.1 ^2,5 . 1 ^8,11 . 0 ^7,12] pentadeca-3-ene-hexacyclo [8.4.0.1 ^2,5. 1 ^7,14 . 1 ^9,12 . 0 ^8,13] heptadec-3-en-8-methyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8-ethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8-cyclohexyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8- (4-biphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-methoxycarbonyloxy - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-phenoxyethyl carbonyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-ethylidene - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8,8-dimethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10] dodeca-3-ene-8,9-dimethyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-fluoro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-chloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-bromo - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene.8,8-dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene.8,9-dichloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene. 8,8,9,9-tetrachloro-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-hydroxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene-8-methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene-8-cyano - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene-8-amino-tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] dodec-3-ene These norbornene compounds may be used alone or in combination of two or more.

The kind and amount of the norbornene-based compound are appropriately selected depending on the properties required for the obtained resin.
Of these, when a compound having a structure containing at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom in the molecule (hereinafter referred to as “polar structure”) is used. It is preferable because of excellent adhesion and adhesion to other materials. In particular, in the formula (3), R ¹ and R ³ are a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and any one of R ^{2 and} R ⁴ is A compound having a polar structure and the other being a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable because the water absorption (wet) property of the resin is low. Furthermore, a norbornene compound in which a group having a polar structure is a group represented by the following general formula (4) is easy to balance the heat resistance and water absorption (wet) property of the resulting resin, and can be preferably used.

_{- (CH 2) z COOR (} 4)
(In formula (4), R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and z represents 0 or an integer of 1 to 10).
In general formula (4), the smaller the value of z, the higher the glass transition temperature of the resulting hydrogenated product and the better the heat resistance. Therefore, z is preferably an integer of 0 or 1 to 3, and z A monomer in which is 0 is preferred in that its synthesis is easy. Further, R in the general formula (4) tends to decrease the water absorption (wetness) of the resulting hydrogenated polymer as the carbon number increases, but also tends to decrease the glass transition temperature. From the viewpoint of maintaining heat resistance, a hydrocarbon group having 1 to 10 carbon atoms is preferable, and a hydrocarbon group having 1 to 6 carbon atoms is particularly preferable.

  In the general formula (3), when an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, is bonded to the carbon atom to which the group represented by the general formula (4) is bonded, It is preferable in terms of the balance of water absorption (wet). Furthermore, in the general formula (3), a compound in which x is 0 or 1 and y is 0 is highly reactive, a polymer can be obtained in a high yield, and a polymer having high heat resistance. It is preferably used because a hydrogenated product is obtained and it is easily industrially available.

In the norbornene-based resin, the monomer composition can be polymerized with another monomer copolymerizable with the norbornene-based compound.
Examples of other copolymerizable monomers include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and cyclododecene, and non-conjugated cyclic polyenes such as 1,4-cyclooctadiene, dicyclopentadiene, and cyclododecatriene. Can be mentioned.
These other copolymerizable monomers may be used alone or in combination of two or more.

As for the polymerization method of the monomer composition containing the norbornene compound, for example, a known method by metathesis ring-opening polymerization or addition polymerization described in JP-A-2006-201736, JP-A-2005-164632, etc. Can be used.
Moreover, the known method described in said literature can also be used also about the method of hydrogenation of the obtained (co) polymer.
The hydrogenation rate of the hydrogenated polymer is preferably 50% or more, more preferably 70% or more, further preferably 90% or more, and most preferably 98% or more as a value measured by 500 MHz and ¹ H-NMR. . The higher the hydrogenation rate, the better the stability to heat and light, and stable characteristics can be obtained over a long period of time.

The intrinsic viscosity [η] _inh of the norbornene resin is preferably 0.2 to 2.0 dl / g, more preferably 0.35 to 1.0 dl / g, and particularly preferably 0.4 to 0.85 dl / g. is there.
The number average molecular weight (Mn) in terms of polystyrene of the norbornene resin measured by gel permeation chromatography (GPC) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and particularly preferably 1. 50,000 to 250,000. The weight average molecular weight (Mw) is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,000,000, and particularly preferably 30,000 to 500,000.
The glass transition temperature (Tg) of the norbornene resin is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and particularly preferably 150 ° C. or higher.
The saturated water absorption of the norbornene resin is preferably 1% by mass or less, more preferably 0.1 to 0.8% by mass. When the saturated water absorption exceeds 1% by mass, the protective film obtained from the resin may have a problem in durability such as water absorption (wet) deformation with time depending on the environment used. On the other hand, if it is less than 0.1% by weight, there may be a problem in adhesion. The saturated water absorption is a value obtained by immersing in water at 23 ° C. for 1 week and measuring an increased mass according to ASTM D570.

In the present invention, additives such as an antioxidant and an ultraviolet absorber can be further added as long as the effects of the present invention are not impaired.
Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [ And methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.
Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.

(Manufacturing method of norbornene resin film)
As a method for producing the norbornene-based resin film, known methods described in JP 2006-201736 A, JP 2005-164632 A, and the like can be used. That is, the norbornene-based resin film can be suitably formed by directly melt-molding the norbornene-based resin or by a method of dissolving in a solvent and casting (cast molding).

Next, the manufacturing method of a composite_body | complex is demonstrated.
The method for producing a composite according to the present invention includes a step of laminating an adherend of the same or different type as a PVA-based molded body on the surface of a PVA-based molded body via a radiation-curable adhesive composition, It includes a radiation curing step in which the radiation curable adhesive composition is cured by irradiation (light irradiation).
In FIG. 2, the manufacturing method of the composite 1 includes the step (a) of preparing the PVA-based molded body 2 and the radiation curable adhesive composition on the surface (one side) of the adherend 3 that is the main body of the protective film. Step (b) to obtain a protective film 3 ′ having a composition layer 4 ′ for adhesive, and a protective film 3 ′ on the upper surface of the PVA-based molded body 2, and a composition layer 4 ′ for adhesive. Includes a step (c) of laminating so as to face each other and a step (d) of curing the adhesive composition layer 4 ′ by light irradiation.
Hereinafter, it demonstrates for every process.

[Step (a)]
Step (a) is a step of preparing a PVA-based molded body 2 (see (a) in FIG. 2).
[Step (b)]
Step (b) is a step of applying a radiation-curable adhesive composition to one surface of the adherend 3 to obtain a protective film 3 ′ having an adhesive composition layer 4 ′ (in FIG. 2). (See (b)).
Specifically, the radiation curable adhesive composition is applied to one surface of the adherend 3 and, if necessary, dried to form a layer 3 ′ composed of the adhesive composition. At this time, when a non-PVA film is adhered, it is preferable to perform corona treatment on the surface on which the adhesive composition is applied in order to increase the adhesive strength.
Although it does not specifically limit as a coating method of the said composition for radiation curable adhesives, For example, the die-coating method, the roll-coating method, the gravure coating method, and a spin coat method are mentioned.

[Step (c)]
Step (c) is a step of laminating a protective film 3 ′ on the upper surface of the PVA-based molded body 2 so that the adhesive composition layer 4 ′ faces (see (c) in FIG. 2).

[Step (d)]
The step (d) is a step of curing the adhesive composition layer 4 ′ by irradiating the radiation 5 (see (d) in FIG. 2).
Specifically, the light 5 is irradiated from the PVA-based molded body 2 and / or the adherend 3 side. As a result, the adhesive composition layer 4 ′ is cured to become the adhesive layer 4. As a result, the PVA-based molded body 2 and the adherend 3 are bonded via the adhesive layer 4 to obtain the composite 1 (see (e) in FIG. 2).
The dose of light is not particularly limited, wavelength 200 to 450 nm, the light intensity 1 to 500 mW / cm ^2, irradiation amount by irradiation so that 10~10,000mJ / cm ² exposure It is preferable to do.
Here, the radiation irradiation is not limited to the adherend 3 side, and the radiation 5 may be irradiated from the PVA-based molded body 2 side, or may be performed from both.
Visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, and the like can be used as the type of radiation to be irradiated, and ultraviolet rays are particularly preferable. For example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp is preferably used as the radiation irradiation apparatus.
The obtained composite is usually subjected to processing such as cutting, and used for applications such as polarizing plates, packaging materials such as foods, beverages, pharmaceuticals, and cosmetics, or containers.

Hereinafter, the present invention will be specifically described by way of examples.
[Examples 1 to 5, Comparative Examples 1 and 2]
[1. Preparation of composition for radiation curable adhesive]
Components (A) to (C) and optional components were added to a container equipped with a stirrer at the blending ratio shown in Table 1, and stirred for 4 hours to uniformly mix. Stirring was stopped and the mixture was allowed to stand for 24 hours to obtain radiation curable compositions used in Examples 1 to 5. Similarly, the radiation curable composition used for Comparative Examples 1 and 2 was obtained.
In addition, the compound name of each component in Table 1 is as follows.
(A) component:
(A-1) Celoxide 2021P: 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (manufactured by Daicel)
(A-2) KRM2199: Bis (3,4-epoxycyclohexylmethyl) adipate (manufactured by Adeka)
(B) component:
(B-1) Kuraray polyol P-510: Poly [(3-methyl-1,5-pentanediol) -alt- (adipic acid)] (manufactured by Kuraray Co., Ltd .; number average molecular weight 700)
(B-2) Kuraray polyol P-1010: Poly [(3-methyl-1,5-pentanediol) -alt- (adipic acid)] (manufactured by Kuraray Co., Ltd .; number average molecular weight 1,200)
(B-3) Preminol PPG4000: Polypropylene glycol (manufactured by Asahi Glass; number average molecular weight 4,100)
(B-4) Kuraray polyol C-2090: poly ((3-methyl-1,5-pentanediol; 1,6-hexanediol) carbonate) (manufactured by Kuraray Co., Ltd .; number average molecular weight 2,000)
(C) component:
CPI-110A: Diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (manufactured by San Apro)
Other ingredients:
SR-NPG: Neopentyl glycol diglycidyl ether (manufactured by Sakamoto Pharmaceutical Co., Ltd.)
Sanniks GP-400: Polyoxypropylene glyceryl ether (manufactured by Sanyo Chemical Industries, Ltd .; number average molecular weight 420)

[2. Production or preparation of adhesive substrate]
[Production Example 1]
“Apel APL6013T” (trade name) manufactured by Mitsui Chemicals was dissolved in cyclopentane to obtain a resin solution having a resin concentration of 30% by weight. This resin solution was applied onto a polyethylene terephthalate film with a bar coater, allowed to stand for 1 hour, and then dried at 80 ° C. for 12 hours to obtain an appel film having a thickness of 72 μm.
[Production Example 2]
A 75 μm topas film was obtained in the same manner as in Production Example except that “TOPAS5013” (trade name) manufactured by Polyplastics was dissolved in methylene chloride.
In addition, the following films were used in the table.
PVA film: Kuraray "Claria S" (trade name)
Eval film: “Eval EF-F” (trade name) manufactured by Kuraray
TAC film: “Fujitac 80D” (trade name) manufactured by Fujifilm
Arton Film: “Arton R5000” (trade name) manufactured by JSR
ZEONOR film: "ZEONOR ZF14-100" (trade name) manufactured by ZEON CORPORATION
Among these, films other than PVA film and Eval film are subjected to corona discharge treatment on the film surface with a discharge amount of 320 W · min / m ² using a corona surface treatment apparatus (“AGF-012” manufactured by Kasuga Denki Co., Ltd.). Adhesion was carried out within 1 hour after the surface treatment.
[3. Preparation of composite (bonding film)]
Each radiation-curable composition of Examples 1 to 5 and Comparative Examples 1 and 2 was applied to a PVA film serving as an adherend using a wire bar coater # 3. The PVA film of the adherend was bonded to another PVA film so that no defects such as bubbles would enter. Four sides of the film were fixed with a tape on a glass plate, and irradiated and adhered with a metal halide lamp (illuminance 220 mW / cm ² , irradiation light quantity 1,000 mJ / cm ² ) to obtain a PVA film / PVA film. In addition, light irradiation was performed from the PVA-type molded object side.
The same operation was performed on other films to prepare various bonded films shown in Table 1. In addition, the light irradiation of the arton film / PVA film / arton film was performed from the side of the film bonded later. After light irradiation, the film was allowed to stand at 23 ° C. and 50% RH for 24 hours to obtain a film for evaluation.

[3. Evaluation of complex]
[Cutting resistance]
The pasted film was punched with “Punch PN-2” (trade name) manufactured by KOKUYO, and the presence or absence and degree of peeling of the circular film piece were confirmed, and judged according to the following criteria. The results are shown in Table 1.
A: No peeling
○: Linear peeling around the section ×: Clear peeling

[Transmissivity at 550 nm]
A PET film (film thickness: 188 μm, surface untreated product) was fixed on a glass plate with an adhesive, and the adhesive compositions of Examples and Comparative Examples were applied on the PET film using a gap 15 mil applicator. This coating film was irradiated with light with a metal halide lamp (illuminance 220 mW / cm ² , irradiation light quantity 1,000 mJ / cm ² ) to cure the composition, and allowed to stand at 23 ° C. and 50% RH for 24 hours. The cured product was peeled from the PET film, and after confirming that the film thickness was 200 ± 5 μm, the transmittance at 550 nm was measured with a U-3410 self-recording spectrophotometer (manufactured by Hitachi, Ltd.) using air as a reference.

  From Table 1, it turns out that the composite_body | complex (lamination film) produced using the radiation-curable composition of Examples 1-5 as an adhesive is excellent in cutting resistance. On the other hand, the composites of Comparative Examples 1 and 2 are inferior in cutting resistance.

It is sectional drawing which shows an example of the composite_body | complex of this invention typically. It is a flowchart which shows an example of the manufacturing method of the composite_body | complex of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Composite 2 PVA-type molded object 3 Adhering body 3 'Protective film 4 Adhesive layer 4' Adhesive composition layer 5 Radiation (ultraviolet rays)

Claims (7)

(A) an alicyclic epoxy compound,
(B) a compound having a polystyrene-equivalent number average molecular weight of 500 or more measured by gel permeation chromatography and containing at least one hydroxyl group, and (C) a photoacid generator,
A composition for radiation curable adhesives, comprising:   The component (B) is a compound having a molecular weight of 1,000 or more in terms of polystyrene measured by gel permeation chromatography and containing one or more hydroxyl groups. Radiation curable adhesive composition.   The radiation curable adhesive according to claim 1 or 2, wherein the radiation curable adhesive composition has a light transmittance of 70% or more when a cured product having a thickness of 200 µm is used. Pharmaceutical composition. The radiation curable adhesive composition is a PVA-based molded body made of a polyvinyl alcohol-based resin having a structure represented by the following general formula (1), and an adherend of the same or different type as the PVA-based molded body. The composition for radiation-curable adhesives according to any one of claims 1 to 3, which is a composition for use in adhesion of a material.

(In the formula, n is an integer of 0 to 4.) An adherend of the same or different type as the PVA-based molded body is bonded to the surface of a PVA-based molded body made of a polyvinyl alcohol-based resin including the structure represented by the following general formula (1) through an adhesive layer. It is a composite_body | complex comprised, Comprising: The said adhesive bond layer consists of hardened | cured material of the composition for radiation-curable adhesives of Claim 4.

(In the formula, n is an integer of 0 to 4.)   The composite according to claim 5, wherein the adherend of the same kind or different kind from the PVA-based molded body is a norbornene-based resin film.   It is a manufacturing method of the composite_body | complex of Claim 5 or 6, Comprising: On the surface of the said PVA-type molded object, the same kind or different kind | species adherend of the said PVA-type molded object, The composition for radiation-curable adhesives A method for producing a composite comprising a laminating step of laminating through and a radiation curing step of irradiating and curing the radiation curable adhesive composition to obtain the composite.

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