JP5178165B2 - Adhesive, sheet-like adhesive, and bonding method using these - Google Patents

Description

  The present invention relates to an adhesive containing a reactive polymer and / or oligomer having an allyl ester group, a sheet-like adhesive, and an adhesion method using them.

  Cycloolefin polymer is a polymer synthesized using cycloolefin as a monomer, and it is known that various polymers can be obtained by various polymerization reactions. It has high birefringence, heat resistance and low hygroscopicity. It attracts attention as a material used for reliable plastic optical components. Among these, thermoplastic norbornene resins are thermoplastic transparent resins with excellent heat resistance, light resistance, moisture resistance, and surface smoothness, and their resin molded products include moisture-resistant packaging materials such as containers and films, and electrical insulation. It is known to be useful for materials, artificial marble and the like, and is attracting attention especially in optical applications because of its transparency and low birefringence.

  The resin molded product may be used alone, but in particular when used as an optical application, it is often used by adhering to an adherend made of the same material or another material. However, a resin molded product made of a thermoplastic norbornene-based resin has a problem that it is difficult to adhere when it adheres to an adherend made of the same material or another material. In order to solve such a problem, an adhesive used for bonding a molded article of a thermoplastic norbornene polymer has been proposed (for example, Patent Documents 1 and 2). However, the adhesives disclosed in Patent Documents 1 and 2 cannot be said to have sufficient adhesive strength due to large shrinkage due to curing and low wettability to norbornene-based polymers, and the adhesive layer has There was a problem that blisters (foaming) occurred. Under such circumstances, it is desired to develop an adhesive having excellent adhesive strength and less blistering in bonding of a molded product made of cycloolefin polymer, particularly thermoplastic norbornene resin.

Japanese Patent No. 2805225 JP-A-6-340849

  An object of the present invention is to provide an adhesive, a sheet-like adhesive having excellent adhesive strength in bonding a molded product made of a cycloolefin polymer, particularly a thermoplastic norbornene resin, and generating less blisters, and these. It is to provide a bonding method.

As a result of intensive studies to achieve the above object, the present inventors have found that a molded article in which an adhesive containing a reactive polymer or oligomer having an allyl ester group comprises a cycloolefin polymer, particularly a thermoplastic norbornene resin. It was found that excellent adhesion strength was exhibited in the adhesion. The present invention has been completed based on such findings.
That is, the present invention provides the following adhesives, sheet-like adhesives, and bonding methods using these.
1. (A) Component: 30 to 99% by mass of a reactive polymer and / or oligomer having an allyl ester group represented by the following general formula (1) , (B) component: monomer 0 to copolymerize with (A) component 60% by mass, component (C): thermal polymerization initiator 0-10% by mass, component (D): polyfunctional (meth) acrylic monomer and / or oligomer 0.5-30% by mass, and component (E): light Polymerization initiator 0.1 to 10% by mass
Adhesive for resin molded products mainly containing a cycloolefin polymer containing.

[Wherein, R ¹ represents an alkanediyl group or alkenediyl group having 1 to 4 carbon atoms, and R ² represents a cycloalkanediyl group, a cycloalkenediyl group or an arenediyl group. A plurality of R ¹ and R ² may be the same or different. N is a number of 1 to 30 representing the average number of polymerizations. ]
2. 2. The adhesive according to 1 above, wherein the cycloolefin polymer is a thermoplastic norbornene-based polymer.
3. A sheet-like adhesive obtained by spreading the adhesive described in 1 or 2 above and irradiating it with an energy ray to cause gelation.
4). 4. The sheet-like adhesive according to 3 above, wherein the energy rays are ultraviolet rays.
5. 3. An adhesive method, wherein the adhesive according to 1 or 2 is cured by heat treatment.
6). 5. A bonding method, wherein after the resin molded product and the adherend are brought into close contact with each other using the sheet-like adhesive according to 3 or 4, the adhesive is cured by heat treatment.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive agent which has the outstanding adhesive strength in the adhesion | attachment of the molded article which consists of cycloolefin polymers, especially thermoplastic norbornene-type resin, a sheet-like adhesive agent, and the adhesion | attachment method using these can be obtained.

[Adhesive: Component (A)]
The adhesive of the present invention comprises (A) component: the following general formula (1):

It is the adhesive agent containing the reactive polymer and / or oligomer which have the allyl ester group represented by these.
Here, R ¹ represents an alkanediyl group or alkenediyl group having 1 to 4 carbon atoms, and R ² represents a cycloalkanediyl group, a cycloalkenediyl group or an arenediyl group. A plurality of R ¹ and R ² may be the same or different. R ¹ and R ² may have a substituent and may be linear or branched. There is no restriction | limiting in particular as a substituent, For example, a halogen atom, a hydroxy group, an amino group, an imino group, an amide group, a carboxy group etc. are mentioned. R ¹ is preferably a methylene group, an ethylene group or a propylene group in order to obtain good adhesive strength, and R ² is preferably a cyclohexanediyl group or a phenylene group. n represents the average number of polymerizations, and is a number of 1 to 30, preferably 1 to 10.

The weight average molecular weight of the reactive oligomer is 300 to 10000, preferably 500 to 9000, and more preferably 800 to 8000. If the weight average molecular weight of the reactive oligomer is within the above range, it is preferable because excellent adhesive strength can be obtained and processability when obtaining a sheet-like adhesive is improved. The weight average molecular weight is a value measured by gel permeation chromatography and converted to polystyrene.
Moreover, the weight average molecular weight of a reactive polymer is 10,000 or more, Preferably it is 10000-50000. If the weight average molecular weight of the reactive polymer is within the above range, excellent adhesive strength can be obtained, and a sheet-like adhesive described later can be easily produced.

  Component (A): The reactive polymer or oligomer having an allyl ester group represented by the general formula (1) can be synthesized by a known method, for example, di (meta) of a divalent carboxylic acid or its anhydride. ) Method of synthesizing allyl ester and polyhydric alcohol by transesterification in the presence of a catalyst (see, for example, JP-A-6-73145), lower ester of allyl alcohol and saturated polycarboxylic acid, and polyhydric alcohol And a method of synthesizing from the above (for example, see JP-A-2-251509). In addition, although low molecular weight raw material monomers remain in the synthesized reactive polymer and / or oligomer, in the present invention, these monomers may be used as they are without being separated. In addition, (A) component may use what was synthesize | combined as mentioned above, and may use a commercially available thing. As a commercial item, "PP201 (brand name)", "DA101 (brand name) And “BA901 (trade name)” (both manufactured by Showa Denko KK).

[Adhesive: Component (B)]
The adhesive of the present invention can further contain (B) component: a monomer copolymerizable with component (A), and (C) component: thermal polymerization initiator.
The component (B) is used as a diluent and can be used without particular limitation as long as it is a monomer copolymerizable with the component (A). Of these, allyl ester monomers are preferred, and examples of allyl ester monomers include cyclohexanedicarboxylic acid diallyl ester, cyclohexanetricarboxylic acid triallyl ester, cyclohexanetetracarboxylic acid tetraallyl ester, diallyl phthalate monomer, diallyl isophthalate monomer, and diallyl terephthalate. Monomers, diallyl adipate monomers, triallyl isocyanurate monomers, triallyl trimellitate monomers, diethylene glycol diallyl carbonate and the like. Among them, using at least one selected from diallyl adipate monomer, diallyl cyclohexanedicarboxylate, diethylene glycol diallyl carbonate, diallyl phthalate monomer, diallyl isophthalate monomer, and diallyl terephthalate monomer, the heat resistance of the adhesive, solvent resistance, And preferable in terms of impact resistance.

[Adhesive: Component (C)]
The component (C) is used for promoting the curing of the adhesive, and a commonly used thermal polymerization initiator can be used without limitation.
Examples of the component (C) include hydrogen peroxide; peroxodisulfates such as ammonium peroxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate; 2,2′-azobis (2-amidinopropane) dihydrochloride, 4 Azo compounds such as 2,4′-azobis (4-cyanovaleric acid), 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); Examples thereof include organic peroxides such as mill peroxide, benzoyl peroxide, lauroyl peroxide, peracetic acid, persuccinic acid, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, and the like. These thermal polymerization initiators may be used alone or in combination of two or more.

[Adhesive: Component (D)]
The adhesive of this invention can contain (D) component which has curability by an energy ray: A polyfunctional (meth) acryl monomer and / or an oligomer.
Preferred examples of the polyfunctional (meth) acrylic monomer include (meth) acrylates having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified diphosphate ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( (Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, Examples include ethylene oxide-modified bisphenol A diacrylate. These polyfunctional (meth) acrylic monomers may be used alone or in combination of two or more.

  Examples of the multifunctional (meth) acrylic oligomer include epoxy (meth) acrylate-based, urethane (meth) acrylate-based, polyester (meth) acrylate-based, and polyether (meth) acrylate-based oligomers. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used.

  Furthermore, polyfunctional (meth) acrylic oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity having (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicones (meth) having polysiloxane bonds in the main chain. Acrylate oligomer, aminoplast resin (meth) acrylate oligomer modified by aminoplast resin with many reactive groups in a small molecule, or novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. And an oligomer having a cationic polymerizable functional group in the molecule.

[Adhesive: Component (E)]
The adhesive of the present invention preferably contains (E) component: photopolymerization initiator in order to promote curing of the polyfunctional (meth) acrylic monomer and / or oligomer of component (D).
Examples of the photopolymerization initiator include phenone photopolymerization initiators such as acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-diethoxy-2-phenylacetophenone; 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxy Ketone-based photopolymerization initiators such as ethoxy) phenyl-2 (hydroxy-2-propyl) ketone; benzoin, benzoin alkyl ether, benzoin hydroxyalkyl ether, diacetyl and derivatives thereof; anthraquinone and derivatives thereof; diphenyl disulfide and derivatives thereof Benzophenone and derivatives thereof; benzyl and derivatives thereof; 2,2′-azobis (2-amidinopropane), 2,2′-azobis (N, N′-dimethyleneisobutylamidine), 2,2′-azobis [ 2- (5-methyl-2-imidazolin-2-yl) propane], 1,1′-azobis (1-amidino-1-cyclopropylethane), 2,2′-azobis (2-amidino-4-methyl) Pentane), 2,2′-azobis (2-N-phenylaminoamidinopropane), 2,2′-azobis (1-imino-1-ethylamino-2-methylpropane), 2,2′-azobis (1 -Allylamino-1-imino-2-methylbutane), 2,2′-azobis (2-N-cyclohexylamidinopropane), 2,2′-azobis (2-N-benzylamidinopro) Bread) and its hydrochloric acid, sulfuric acid, acetate; 4,4′-azobis (4-cyanovaleric acid) and its alkali metal, ammonium and amine salts; 2- (carbamoylazo) isobutyronitrile, 2,2 '-Azobis (isobutylamide), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis [2-methyl-N- (1,1'- Bis (hydroxymethyl) ethyl) propionamide], 2,2′-azobis [2-methyl-N- (1,1′-bis (hydroxyethyl) propionamide]] and the like; -Hydroxy-2-methyl-1-phenylpropan-1-one, etc. These photopolymerization initiators can be used alone or in combination. You can also.

[Adhesive: Various additives]
In the adhesive of the present invention, various kinds of fillers, thixotropic agents, plasticizers, adhesiveness imparting agents, curing catalysts, stabilizers, polyfunctional thiol compounds, etc., as long as they do not reduce the adhesive strength. You may mix | blend an additive.
Examples of the filler include calcium carbonate, surface-hydrophobized calcium carbonate, carbon black, talc, titanium oxide, and rubber powder.
Examples of the thixotropic agent include colloidal silica, hydrogenated castor oil, and organic bentonite. Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate, dioctyl adipate, diisodecyl adipate, tributyl phosphate (TBP), trioctyl phosphate, propylene glycol adipate polyester, and epoxidized soybean oil.
Examples of the adhesiveness imparting agent include various titanate coupling agents, silane coupling agents, and reaction products of these coupling agents and isocyanate compounds. Examples of the curing catalyst include tertiary amines such as triethylamine, organometallic compounds such as dibutyltin dilaurate, tin octenoate, and lead naphthenate.
Examples of the stabilizer include trade name “Tinubin 327” (manufactured by Ciba Geigy), trade name “Irganox 1010” (manufactured by Ciba Geigy), trade name “Tomithorpe 800” (manufactured by Yoshitomi Pharmaceutical), and the like. Examples of the polyfunctional thiol compound include dipentaerythritol hexakis (3-mercaptopropionate).

[adhesive]
The adhesive of the present invention essentially comprises the component (A) and further contains components (B) to (E) as necessary.
When the adhesive of this invention contains (A)-(C) component, content in the adhesive of each component is (A) component 30-99 mass%, (B) component 0-60 mass%. And (C) component 0.1 to 10% by mass is preferred, more preferably (A) component 40 to 90% by mass, (B) component 8 to 55% by mass, and (C) component 1 to 5% by mass. is there. If the content of each component is within the above range, it is preferable because excellent adhesive strength can be obtained.
The adhesive of the present invention comprises (A) to (D) components, (A) to (E) components, (A) and (D) components, or (A), (D) and (E) components. When contained, the content of each component in the adhesive is (A) component 30 to 99% by mass, (B) component 0 to 60% by mass, (C) component 0 to 10% by mass, (D) component. 0.5-30 mass% and (E) component 0.1-10 mass% are preferable, More preferably, (A) component 40-85 mass%, (B) component 8-50 mass%, (C) component It is 1-5 mass%, (D) component 3-20 mass%, and (E) component 1-5 mass%. If the content of each component is within the above range, it is preferable because excellent adhesive strength can be obtained.

The adhesive of the present invention has excellent adhesive strength in the adhesion of a resin molded product containing a cycloolefin polymer as a main component, particularly a resin molded product containing a thermoplastic norbornene-based polymer as a main component.
Thermoplastic norbornene resins include ring-opening (co) polymers of norbornene monomers, addition polymers of norbornene monomers, copolymers of norbornene monomers and α-olefins such as ethylene and propylene, and non-polymers thereof. Examples thereof include graft modified products modified with saturated carboxylic acid or an oil conductor thereof, and hydrides thereof. In addition, the adhesive of the present invention has an excellent adhesive strength even in the adhesion of a resin molded product whose main component is a cyclopentene polymer, a cyclobutene polymer or the like as a cycloolefin polymer.

[Sheet adhesive]
The sheet-like adhesive of the present invention comprises (A) to (D) components, (A) to (E) components, (A) and (D) components, and (A), (D) and (E) components. The adhesive contained is spread on a substrate, and irradiated with energy rays so that the adhesive is gelled (semi-cured).
As the degree of gelation, the gel fraction of the sheet adhesive is usually in the range of 1 to 50%, preferably 3 to 30%. If the gel fraction of the sheet adhesive is within the above range, good adhesive strength can be obtained. Here, the gel fraction is an index indicating the degree of curing of the sheet-like adhesive, and the mass A and the mass B are measured as described below, and calculated by the following formula (I) using this. This is the value obtained. The mass of the produced sheet-like adhesive is defined as mass A, and the measured sheet-like adhesive is refluxed with acetone for 3 hours, and then extracted for 24 hours in an environment of 23 ° C. (relative humidity 50%), then 80. The ratio of the mass B to the mass A when the mass after drying at ° C. for 12 hours is defined as the mass fraction is the gel fraction. The mass is measured with a precision balance.

The substrate is not particularly limited as long as it does not deteriorate even when irradiated with energy rays. For example, a sheet made of polyethylene resin, polypropylene resin, polyethylene terephthalate resin, or the like can be used. There is no restriction | limiting in particular in the thickness of a base material, Usually, about 10-100 micrometers, 20-75 micrometers is preferable, More preferably, it is 25-50 micrometers.
As the substrate, for the purpose of improving the usability of the sheet-like adhesive, a release sheet provided with a release layer formed by applying a release agent can be used, and the release sheet is made of the sheet-like adhesive. It can be provided on one or both sides. For example, a sheet-like adhesive provided with release sheets on both sides is spread (applied) to a predetermined thickness after curing the adhesive on the release sheet and irradiated with energy rays from the applied adhesive side. Thus, the adhesive is gelled (semi-cured) to form a sheet-like adhesive, and further obtained by stacking release sheets.
As the release agent, a release agent containing an alkyd resin, a silicone resin, or the like can be used, and the release layer is provided by applying the release agent on the surface of the substrate. There is no restriction | limiting in particular in the thickness of this peeling layer, Usually, it is about 0.05-30 micrometers, Preferably it is 0.1-10 micrometers.

Examples of the energy rays include ionizing radiation, that is, ultraviolet rays or electron beams. When ultraviolet rays are used as the ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be used. What is necessary is just to select suitably according to the thickness of resin to be used or a sheet-like adhesive agent, and it is about 50-500 mJ / cm < ² > normally, 100-450 mJ / cm < ² > is preferable and 200-400 mJ / cm < ² > is preferable. More preferred. Moreover, ultraviolet illuminance is about 50-500 mW / cm < ² > normally, 100-450 mW / cm < ² > is preferable and 200-400 mW / cm < ² > is more preferable. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

  When an electron beam is used as the ionizing radiation, the acceleration voltage may be appropriately selected according to the thickness of the resin or sheet adhesive used, and is preferably about 70 to 300 kV. Further, the irradiation dose is preferably such an amount that the adhesive gels, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.

The thickness of the sheet-like adhesive thus obtained may be appropriately selected depending on the application, and is usually about 10 to 300 μm, preferably 10 to 100 μm, and more preferably 20 to 75 μm.
The sheet-like adhesive of the present invention is less likely to cause protrusion or blistering when a liquid adhesive is used, and can form an adhesive layer with a uniform thickness, so that even if the adhesive area increases, the adhesive part It is an adhesive excellent in that uniform adhesive strength can be obtained over the entire surface. The sheet-like adhesive of the present invention has an excellent adhesive strength in the adhesion of a resin molded product mainly composed of the above-mentioned cycloolefin polymer, especially a resin molded product mainly composed of a thermoplastic norbornene polymer. It is.

[Adhesive bonding method]
The bonding method of the present invention is characterized in that the adhesive of the present invention is cured by heat treatment. Specifically, the adhesive of the present invention is applied to one or both of the resin molded product and the adherend, and the adhesive surfaces of the resin molded product and the adherend are brought into close contact with each other and fixed so as not to move. Then, the adhesive is cured by curing the adhesive.
The application of the adhesive can be performed by various coating methods without particular limitation, and can be performed by, for example, a roll coater, spray, spin coating, or a manual applicator (such as an applicator). As for the application amount of the adhesive, the thickness after curing of the adhesive is preferably about 10 to 100 μm, and more preferably 25 to 75 μm.
The heat treatment may be performed using a hot air dryer or the like, and the heat treatment conditions may be appropriately selected depending on the amount of adhesive applied, the shape of the adhesive surface, etc., but usually heat deformation of the adherend occurs. The temperature is 100 to 150 ° C., preferably 100 to 135 ° C., for 1 to 5 hours, preferably 1 to 3 hours.
The adherend is not particularly limited as long as it has an adhesive surface that is in close contact with the adhesive surface of the resin molded body, and may be the same resin molded body or made of another material different from the resin molded body. An adherend may be used. Examples of the adherend made of another material different from the resin molded body include glass, ceramics, and metal in optical applications.

[Adhesion method of sheet adhesive]
The method for adhering the sheet-like adhesive of the present invention is to adhere the sheet-shaped adhesive of the present invention by closely bonding the resin molded product and the adherend and then curing the sheet-like adhesive by heat treatment. is there. More specifically, the sheet-shaped adhesive of the present invention is sandwiched and adhered between the adhesive surfaces of the resin molded product and the adherend, and the heat treatment is performed to cure the sheet-shaped adhesive. It adheres the body.
About heat processing and a to-be-adhered body, it is the same as that of the adhesion | attachment method of said adhesive agent.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by this example.
(Evaluation method)
The adhesives obtained in each Example and Comparative Example were evaluated by the following methods.
(1) Measurement of adhesive strength The test pieces obtained in each Example and Comparative Example were measured for peel strength at a peel angle of 180 ° and a peel speed of 100 mm / mm according to JIS K6854-2.
(2) Measurement of gel fraction The mass of the measurement sample collected from the sheet-like adhesives obtained in Examples 4 to 7 is defined as mass A, and the sample after measurement is refluxed with acetone and extracted for 3 hours. Then, the gel fraction was calculated according to the following formula (I), with mass B after drying for 24 hours under an environment of 23 ° C. (50% relative humidity) and then for 12 hours at 80 ° C. The mass is measured with a precision balance.

(3) Evaluation of blister (foaming) In the test pieces used for the measurement of the adhesive strength of each Example and Comparative Example, the state of blister (foaming) was visually confirmed for the cured state of the adhesive, and the following criteria It was evaluated with. The evaluation results are shown in Table 2.
○: Blister was not generated at all △: Blister was generated slightly, but there was no problem in practical use except for optical use.

Example 1
Two norbornene-based resin films (“Zeonor ZF-16 (trade name)” manufactured by Optes Corporation, size: 150 mm × 300 mm, thickness: 100 μm) were prepared. The adhesive prepared with the composition and blending ratio in Table 1 was applied on one norbornene-based resin film using an applicator so that the thickness of the adhesive layer after curing of the adhesive was 50 μm. Gently attach one film so that air does not enter, and cure the adhesive at 130 ° C. for 2 hours using a hot air dryer (“LC-234 (model number)”, manufactured by Espec Corporation). Thus, a sample in which two norbornene resin films were bonded was obtained. Thereafter, the sample was cut to obtain a test piece so that the measurement width was 25 mm. The results of measurement and evaluation of the obtained test pieces are shown in Table 2.

Examples 2 and 3
In Example 1, a test piece was prepared in the same manner as in Example 1 except that an adhesive prepared with the composition and blending ratio shown in Table 1 was used. The results of measurement and evaluation of the obtained test pieces are shown in Table 2.

Example 4
Two norbornene-based resin films (“Zeonor ZF-16 (trade name)” manufactured by Optes Corporation, size: 150 mm × 300 mm, thickness: 100 μm) were prepared. The adhesive prepared with the composition and blending ratio in Table 1 was applied on one norbornene-based resin film using an applicator so that the thickness of the adhesive layer after curing of the adhesive was 50 μm. One film was brought into close contact so that air did not enter. This was irradiated with light under the conditions of 300 mW / cm ² and 300 mJ / cm ² using an ultraviolet irradiation device (using Fusion H lamp, manufactured by Fusion), and the adhesive was gelled (semi-cured). A sheet adhesive was obtained. Then, using a hot air dryer, the adhesive was cured at 130 ° C. for 2 hours to obtain a sample in which two norbornene resin films were bonded. Thereafter, the sample was cut to obtain a test piece so that the measurement width was 25 mm. Table 2 shows the results of measurement and evaluation of the obtained sheet-like adhesive and the test piece.

Example 5
In Example 4, a test piece was prepared in the same manner as in Example 4 except that an adhesive prepared with the composition and blending ratio shown in Table 1 was used. Table 2 shows the results of measurement and evaluation of the obtained sheet-like adhesive and the test piece.

Example 6
A polyethylene terephthalate film ("") prepared by applying a release agent made of an alkyd-based resin so that the thickness of the adhesive layer after curing of the adhesive is 50 μm. It applied to the release agent application | coating surface of SP-PET38X (brand name): the Lintec Co., Ltd. thickness, 38 micrometers) using the applicator. This was irradiated with light under the conditions of 300 mW / cm ² and 300 mJ / cm ² using an ultraviolet irradiation device (using Fusion H lamp, manufactured by Fusion), and the adhesive was gelled (semi-cured). Thereafter, a polyethylene terephthalate film (“SP-PET 381031 (trade name)” manufactured by Lintec Corporation, thickness: 38 μm) formed by applying a release agent comprising a silicone resin, and the release agent application surface is in contact with the adhesive. Thus, a sheet-like adhesive having a thickness of 50 μm was produced.
Next, two norbornene-based resin films (“Zeonor ZF-16 (trade name)” manufactured by Optes Corporation) were prepared. Remove the release film on one side of the sheet-like adhesive, apply it to one norbornene resin film using a rubber roller weighing 2 kg, and then peel off the release film on the other side. Another norbornene-based resin film was attached using a rubber roller. Thereafter, the sample was cut to obtain a test piece so that the measurement width was 25 mm. Table 2 shows the results of measurement and evaluation of the obtained sheet-like adhesive and the test piece.

Example 7
In Example 6, a test piece was prepared in the same manner as in Example 6 except that an adhesive prepared with the composition and blending ratio shown in Table 1 was used. Table 2 shows the results of measurement and evaluation of the obtained sheet-like adhesive and the test piece.

Comparative Examples 1 and 2
In Example 1, a test piece was prepared in the same manner as in Example 1 except that an adhesive prepared with the composition and blending ratio shown in Table 1 was used. The results of measurement and evaluation of the obtained test pieces are shown in Table 2.

＊１，ＤＡ１０１：アリルエステル樹脂８５％，共重合可能なモノマーとして、１，４−シクロヘキサンジカルボン酸ジアリル１５％からなる組成物（昭和電工株式会社製）
＊２，ＢＡ９０１：アリルエステルオリゴマー６０％，共重合可能なモノマーとして、ジアリルイソフタレート４０％から成る組成物（昭和電工株式会社製）
＊３，ＰＰ２０１：アリルエステル樹脂５５％，共重合可能なモノマーとして、１，４−シクロヘキサンジカルボン酸ジアリル４５％からなる組成物（昭和電工株式会社製）
＊４，Ａ−ＤＰＨ：ジペンタエリスリトールヘキサアクリレート（「ＮＫエステルＡ−ＤＰＨ（商品名）」：新中村化学株式会社製）
＊５，Ａ−ＴＭＰ：トリメチロールプロパントリアクリレート（「ＮＫエステルＡ−ＴＭＰＴ（商品名）」：新中村化学株式会社製）
＊６，Ｉｒｇ５００：光重合開始剤（「イルガキュア５００（商品名）」：チバスペシャリティケミカルズ株式会社製）
＊７，Ｉｒｇ１８４：光重合開始剤（「イルガキュア１８４（商品名）」：チバスペシャリティケミカルズ株式会社製）
＊８，ジクミル：熱重合開始剤（ジクミルパーオキサイド：Ａｌｄｒｉｃｈ社製）

* 1, DA101: Composition comprising 85% allyl ester resin and 15% diallyl 1,4-cyclohexanedicarboxylate as a copolymerizable monomer (manufactured by Showa Denko KK)
* 2, BA901: Composition comprising 60% allyl ester oligomer and 40% diallyl isophthalate as a copolymerizable monomer (manufactured by Showa Denko KK)
* 3, PP201: A composition comprising 55% allyl ester resin and 45% diallyl 1,4-cyclohexanedicarboxylate as a copolymerizable monomer (manufactured by Showa Denko KK)
* 4, A-DPH: Dipentaerythritol hexaacrylate ("NK ester A-DPH (trade name)": Shin-Nakamura Chemical Co., Ltd.)
* 5, A-TMP: Trimethylolpropane triacrylate ("NK ester A-TMPT (trade name)": Shin-Nakamura Chemical Co., Ltd.)
* 6, Irg500: Photopolymerization initiator ("Irgacure 500 (trade name)" manufactured by Ciba Specialty Chemicals Co., Ltd.)
* 7, Irg184: Photopolymerization initiator ("Irgacure 184 (trade name)" manufactured by Ciba Specialty Chemicals Co., Ltd.)
* 8, Dicumyl: Thermal polymerization initiator (Dicumyl peroxide: Aldrich)

  It was shown that the adhesives produced in Examples 1 to 7 were excellent in adhesive strength. In addition, it was shown that the adhesives of Examples 5 and 7 did not generate blisters (foaming) at all and were particularly suitable for optical applications using a transparent resin or the like. On the other hand, the adhesive containing the polyfunctional (meth) acrylate and the thermal polymerization initiator of Comparative Example 1 has insufficient adhesive strength, and the adhesive containing the polyfunctional (meth) acrylate and the photopolymerization initiator of Comparative Example 2 Did not adhere.

Claims (6)

(A) Component: 30 to 99% by mass of a reactive polymer and / or oligomer having an allyl ester group represented by the following general formula (1)
(B) component: 0-60 mass% of monomer copolymerizable with (A) component,
(C) component: 0-10 mass% of thermal polymerization initiators,
(D) component: 0.5-30 mass% of polyfunctional (meth) acryl monomer and / or oligomer, and
(E) component: 0.1-10 mass% of photoinitiators
Adhesive for resin molded products mainly containing a cycloolefin polymer containing.

[Wherein, R ¹ represents an alkanediyl group or alkenediyl group having 1 to 4 carbon atoms, and R ² represents a cycloalkanediyl group, a cycloalkenediyl group or an arenediyl group. A plurality of R ¹ and R ² may be the same or different. N is a number of 1 to 30 representing the average number of polymerizations. ] The adhesive according to claim 1 , wherein the cycloolefin polymer is a thermoplastic norbornene-based polymer. A sheet-like adhesive obtained by spreading the adhesive according to claim 1 or 2 and irradiating it with an energy ray to cause gelation. The sheet adhesive according to claim 3 , wherein the energy rays are ultraviolet rays. An adhesive method according to claim 1, wherein the adhesive according to claim 1 or 2 is cured by heat treatment. An adhesive method comprising: bonding a resin molded article and an adherend using the sheet-like adhesive according to claim 3 or 4 ; and curing the adhesive by heat treatment.