JPH09143431A - Uv-curing composition, bonding using the same and bonded product therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make a molding of thermoplastic norbornene-based resin having no polar group adhere firmly even to an epoxy resin molding. SOLUTION: This method comprises making a thermoplastic norbornene-based resin molding adhere to an epoxy resin molding by UV irradiation by using a UV-curing composition comprising 100 pts.wt. of an alicyclic acrylate component (e.g. isobornyl acrylate), 2-100 pts.wt. of an aminoacrylate component (e.g. dimethylaminoethyl methacrylate) and/or an epoxyacrylate component (e.g. glycidyl methacrylate), 5-200 pts.wt. of an elastomer component (e.g. styrene- ethylene-butadiene-styrene block copolymer rubber), and 1-30 pts.wt. of a photopolymerization initiator component (e.g. 1-hydroxycyclohexyl phenyl ketone).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a UV-curable composition excellent in adhesiveness and durability in bonding a thermoplastic norbornene-based resin molded product and an epoxy resin molded product, a thermoplastic norbornene-based resin molded product and an epoxy. The present invention relates to a method for adhering a resin molded product, and an adhesive comprising a thermoplastic norbornene resin molded product and an epoxy resin molded product using the same.

[0002]

2. Description of the Related Art In various fields, the technology of thermoplastic resin has been developed as a molding material, and heat resistance, light resistance, moisture resistance,
Thermoplastic resins with excellent oxidation resistance have been developed, and replacement of other materials with thermoplastic resins is in progress.

However, a thermoplastic norbornene-based resin having no polar group and an epoxy resin have low affinity with each other, and an adhesive having high affinity with both is not known. Therefore, even if the thermoplastic norbornene-based resin molded product and the epoxy resin molded product are bonded with an adhesive, there is a problem that the bonding surface is separated due to a slight difference in expansion due to temperature change.

An ultraviolet curable adhesive composed of an alicyclic acrylate component, an elastomer, and a photopolymerization initiator is proposed as an adhesive for adhering a thermoplastic norbornene resin molded article and an adherend having a different linear expansion coefficient. (Japanese Patent Laid-Open No. 6-340849). When this adhesive is used, good adhesiveness and durability can be obtained to some extent even in a thermoplastic norbornene-based resin molded product having no polar group and an epoxy resin molded product. However, with the progress of technology, the required performance has become higher, the performance of this adhesive has been insufficient in some cases, and an adhesive having excellent adhesiveness and durability has been demanded.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of earnest research, the inventors of the present invention have conducted an intensive research to improve an adhesive used for bonding a thermoplastic norbornene-based resin molded product and an epoxy resin molded product. By using a curable composition as an adhesive, it was found that a thermoplastic norbornene-based resin molded product and an epoxy resin molded product were firmly bonded, and the present invention was completed.

[0006]

Thus, according to the present invention, (a) an alicyclic acrylate component, (b) an amino acrylate component and / or an epoxy acrylate component, (c) an elastomer component, and (d) photopolymerization. An ultraviolet-curable composition comprising an initiator component, a method for adhering a thermoplastic norbornene-based resin molded product and an epoxy resin molded product, wherein the adhesive surface of the thermoplastic norbornene-based resin molded product and / or the adhesive surface of the epoxy resin molded product The ultraviolet curable composition is applied to, and the adhesive surface of the thermoplastic norbornene resin molded product and the adhesive surface of the epoxy resin molded product are brought into close contact with each other, and the adhesive surface is irradiated with ultraviolet rays to cure the ultraviolet curable composition. And an adhesive comprising a thermoplastic norbornene-based resin molded product and an epoxy resin molded product bonded by the method. It is.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION

(Alicyclic Acrylate Component) The alicyclic acrylate component, which is the component (a) used in the present invention, is an acrylate monomer and / or oligomer thereof having an alicyclic structure and an acrylate group directly bonded thereto. The alicyclic structure may have a substituent, but it is preferably composed of only carbon and hydrogen and does not have a substituent containing an element other than carbon and hydrogen (so-called polar group). The alicyclic acrylate monomer is an ester of an alicyclic alcohol and acrylic acid or methacrylic acid, and may be a monofunctional alicyclic acrylate monomer or a bifunctional or trifunctional polyfunctional alicyclic acrylate monomer. In the present invention, one having one acrylate group is a monofunctional acrylate monomer, and two having an acrylate group are bifunctional acrylate monomers.
The three are called trifunctional acrylate monomers. Of the alicyclic acrylate components, the monofunctional alicyclic acrylate monomer is preferable because the ultraviolet-curable composition of the present invention has more flexibility after curing as the number of acrylate groups is smaller. Further, in the present invention, unless otherwise specified, the acrylate group means a broadly defined acrylate group including a methacrylate group, an ethacrylate group, etc. in addition to the narrowly defined acrylate group, and, for example, “(meth) acrylate” is mentioned in the examples of compound names. ”, The two parts are both exemplified as“ acrylate ”and“ methacrylate ”. Note that an alicyclic acrylate monomer having an acrylate group in a narrow sense, particularly an alicyclic acrylate monomer having only an acrylate group in a narrow sense is preferable so that the curing reaction is not hindered by radical oxygen. From the viewpoint of reactivity, those having 30 or less carbon atoms are preferable, those having 20 or less carbon atoms are more preferable, and those having 3 or more carbon atoms are preferable from the viewpoint of flexibility after curing of the composition of the present invention. The alicyclic acrylate oligomer is obtained by prepolymerizing an alicyclic acrylate monomer by a known method, and the alicyclic acrylate monomer is 2 to 1
It is a large amount of about 00.

Examples of the alicyclic acrylate monomer include those disclosed in JP-A-61-136529 and JP-A-2-5.
Examples thereof include those known in Japanese Patent No. 88529, and specifically, cyclohexyl (meth) acrylate, norbonyl (meth) acrylate, dicyclopentanyl (meth).
Acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, hexacyclo [6,6,1,1 ^3.6, 1 ^{1 0.13,} 0 ^2.7, 0 ^9.14] heptadecyl-4-acrylate, 12-methyl hexa cyclo [6 , 6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0 ^9.14] heptadecyl-4-acrylate, octacyclo [8,
8, 0, 1 ^2.9 , 1 ^4.7 , 1 ^11.18 , 1 ^13.16 , 0 ^3.8 , 0
^12,17] docosyl-5-acrylate, 15-methyl-octa cyclo [8,8,0,1 ^2.9, 1 ^4.7, 1 ^11.18, 1
^13.16, 0 ^3.8, 0 ^12,17] docosyl-5-acrylate, tetracyclo [4,4,0,1 ^2.5, 1 ^7,10] dodecyl-3-acrylate, 2,7-dimethyl-tetracyclo [4,4, 0,1 ^2.5, 1 ^7,10] dodecyl-3-acrylate, 9-stearyl - tetracyclo [4,4,
0,1 ^2.5, 1 ^7,10] dodecyl-3-acrylate.

(Amino Acrylate Component) The amino acrylate component which may be used as the component (b) in the present invention is a compound represented by the following general formula 1. General formula 1:

Embedded image (In the formula, k, l and m are integers of 0 or more, preferably R ¹ represents an acrylate group, and R ² and R ³ each represent a hydrogen atom, an alkyl group or an acrylate group)

In the amino acrylate component and the epoxy acrylate component described later, the alkyl group in the acrylate group has 0 or more carbon atoms and preferably 5 or less carbon atoms. If the carbon number is too large, the reactivity decreases.
When the alkyl group has 0 carbon atoms, the acrylate group means the acrylate group itself in a narrow sense.

As the amino acrylate component, monofunctional amino acrylates such as diethylaminoethyl acrylate, dimethylaminoethyl acrylate and methylethylaminoethyl acrylate; bifunctional amino acrylates such as ethylaminodi (ethyl acrylate) and methylaminoethyl acrylate-methyl acrylate Examples: trifunctional amino acrylates such as aminotri (ethyl acrylate) and aminodi (ethyl acrylate) -methyl acrylate; These may be used in combination. Bifunctional or trifunctional amino acrylates are preferable in that the composition of the present invention has high flexibility after curing. If the flexibility after curing is too low, there is a problem that the base material or the like easily peels off due to expansion or contraction due to temperature change.

(Epoxy acrylate component) The epoxy acrylate component which may be used as the component (b) in the present invention is a compound represented by the following general formula 2. General formula 2:

Embedded image (In the formula, n is an integer of 0 or more, and R ⁴ represents an acrylate group)

Examples of the epoxy acrylate component include glycidyl acrylate and glycidyl methacrylate.

(Elastomer Component) The elastomer component as the component (c) used in the present invention is not particularly limited as long as it is a polymer having rubber elasticity.

The number average molecular weight of the elastomer component is preferably 10,000 or more, more preferably 20,000.
Or more, particularly preferably 30,000 or more, preferably 4
It is preferably 100,000 or less, more preferably 300,000 or less, and particularly preferably 200,000 or less.
If the number average molecular weight is too small, the mechanical properties will be poor, and if it is too high, production will be difficult. Specifically, for example, polystyrene-based elastomer, polyolefin-based elastomer,
Examples thereof include polyester-based elastomers, polyurethane-based elastomers, diene-based elastomers, acrylic rubbers, modified elastomers obtained by grafting a dicarboxylic acid anhydride, an epoxy compound or a tertiary amine on these, hydrogenated products thereof, and the like. From the viewpoint of heat resistance, polystyrene-based elastomers are preferable, and polystyrene-based block copolymer elastomers are particularly preferable. Examples of the polystyrene block copolymer elastomer include styrene.
Butadiene / styrene block copolymer elastomer,
Styrene / isoprene / styrene / block copolymer elastomers, styrene / ethylene / butadiene / styrene / block copolymer elastomers, styrene / isoprene / pentadiene / styrene / block copolymer elastomers, and dicarboxylic acid anhydrides and epoxy compounds Or a modified elastomer grafted with a tertiary amine, a hydrogenated product of a modified or unmodified elastomer, and the like. Hydrogenated products are preferred from the viewpoint of weather resistance. Further, a thermoplastic elastomer having a Tg of 40 ° C. or lower is preferable because it has excellent impact resistance. Some block copolymers and the like have a Tg of 2 or more, but if one of them has a temperature of 40 ° C. or less, it is preferable as the elastomer used in the present invention.

(Photopolymerization Initiator Component) The photopolymerization initiator component which is the component (d) used in the present invention is not particularly limited and may be a known one. For example, 2,2-dimethoxy-
2-phenylacetophenone, 2,2-diethoxyacetophenone, chlorinated acetophenone, 2-methyl-1-
Acetophenones such as (4-methylthiophenyl) -2-morpholino-propan-1-one; Benzophenones such as benzophenone and benzoylbenzoic acid; Benzoins such as benzyl, methyl orthobenzoylbenzoate, benzoin methyl ether and benzoin ethyl ether; Azo compounds such as α, α′-azobisisobutyronitrile, 2,2′-azobispropane and hydrazone; organic peroxides such as benzoyl peroxide and ditertiary butyl peroxide;
Diphenyl disulfides such as diphenyl disulfide, dibenzyl disulfide, dibenzoyl disulfide; and the like. Further, commercially available photopolymerization initiation such as Irgacure 184 (1-hydroxycyclohexyl phenyl ketone manufactured by Ciba-Geigy) can also be used.

(Ultraviolet curable composition) The ultraviolet curable composition of the present invention comprises (a) an alicyclic acrylate component and (b)
It is composed of an amino acrylate component and / or an epoxy acrylate component, (c) an elastomer component, and (d) a photopolymerization initiator component. 2 parts by weight or more, preferably 6 parts by weight or more, more preferably 10 parts by weight or more and 100 parts by weight or less, preferably 80 parts by weight or less, more preferably 100 parts by weight of the component (a). 60
Parts by weight or less, 5 parts by weight or more of the component (c), preferably 10
Parts by weight or more, more preferably 15 parts by weight or more and 200 parts by weight or less, preferably 150 parts by weight or less, more preferably 100 parts by weight or less, component (d) component 1 part by weight or more, preferably 2 parts by weight or more, more preferably Is 3 parts by weight or more, 30
Add parts by weight or less, preferably 25 parts by weight or less.

If the amount of the component (b) is too small, the adhesiveness to the epoxy resin molded product after curing becomes insufficient, and if it is too large, the adhesiveness to the thermoplastic norbornene resin molded product after curing becomes insufficient. When the amount of the component (c) is too small, the flexibility of the composition after curing becomes low and the composition tends to peel off from the substrate, and when it is too large, the viscosity becomes high and the coating workability becomes poor. If the amount of component (d) is too small, it will take a long time to cure, and if it is too large, the number average molecular weight after curing will decrease and the adhesive strength will decrease.

In addition to the above, the ultraviolet curable composition of the present invention may further contain usual elastomers, acrylate monomers, acrylate oligomers, antioxidants, and thermal polymerization inhibitors, as long as the effects of the present invention can be exhibited. Additives such as agents, curing accelerators, ultraviolet absorbers, antistatic agents, colorants, and inorganic fillers such as talc and silica may be blended.

The ultraviolet-curable composition of the present invention is effective as an adhesive for bonding thermoplastic norbornene resin molded products and epoxy resin molded products, thermoplastic norbornene resin molded products, epoxy resin molded products and the like. is there.

(Thermoplastic Norbornene Resin Molded Product) The thermoplastic norbornene resin is disclosed in JP-A-1-168725.
Japanese Patent Laid-Open No. 1-190726, Japanese Patent Laid-Open No. 3-1
Resins known in JP-A-4882, JP-A-3-122137, JP-A-4-63807, and the like, and specifically, ring-opening polymers of norbornene-based monomers, hydrogenated products thereof, norbornene-based Examples thereof include addition-type polymers of monomers, addition-type polymers of norbornene-based monomers and olefins, and the like.

The thermoplastic norbornene-based resin molded article to be bonded in the present invention is preferably one in which at least the bonding surface does not have a polar group, that is, a thermoplastic norbornene-based resin composed only of carbon and hydrogen is highly effective. . The thermoplastic norbornene-based resin having no polar group is
A polymer obtained by using a norbornene-based monomer composed only of carbon and hydrogen, or a hydrogenated product thereof.

Norbornene-based monomers composed of only carbon and hydrogen are also known monomers in the above-mentioned publications, JP-A-2-227424 and JP-A-2-276842, and examples thereof include norbornene. , Its alkyl, alkylidene, aromatic substituted derivatives such as 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5-ethyl-2-norbornene,
5-butyl-2-norbornene, 5-ethylidene-2-
Norbornene, 5-phenyl-2-norbornene, 5-
Phenyl-5-methyl-2-norbornene, 5-hexyl-2-norboernene, 5-octyl-2-norbornene, 5-octadecyl-2-norbornene, etc .; a monomer in which one or more cyclopentadiene is added to norbornene, Derivatives and substitutes similar to the above, for example,
1,4: 5,8-Dimethano-2,3-cyclopentadieno-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 6-methyl-1,4: 5,8 -Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-
2,3-cyclopentadieno-1,2,3,4,4a,
5,5a, 6,9,9a, 10,10a-dodecahydroanthracene, etc .; cyclopentadiene monomer having a polycyclic structure which is polymerized by Diels-Alder reaction
Derivatives and substituents similar to the above, for example, dicyclopentadiene, 2,3-dihydrodicyclopentadiene and the like; Addition products of cyclopentadiene and tetrahydroindene, derivatives and substituents similar to the above, for example, 1 , 4-methano-1,4,4a, 4b, 5,8,8
a, 9a-octahydrofluorene, 5,8-methano-
2,3-cyclopentadieno-1,2,3,4,4a,
5,8,8a-octahydronaphthalene and the like; and the like.

In the present invention, the number average molecular weight of the thermoplastic norbornene-based resin is GPC with a toluene solvent.
The polystyrene conversion value measured by the (gel permeation chromatography) method is 10,000 or more, preferably 15,000 or more, more preferably 20,000.
Or more and 200,000 or less, preferably 100,000
The following are more preferable, and those of 50,000 or less are more preferable.
If the molecular weight is too small, the mechanical strength will be low, and if it is too large, molding will be difficult. When the main chain structure has an unsaturated bond like a ring-opening polymer of a norbornene-based monomer,
It is preferable to saturate the main chain structure by hydrogenation. When hydrogenated, the hydrogenation rate of the main chain structure is preferably 90% or more, more preferably 95% or more, and particularly preferably 99% or more. When the hydrogenation rate is low and the number of unsaturated bonds in the main chain structure is large, the heat deterioration resistance may be poor and stable use for a long period of time may be difficult.

The glass transition temperature (hereinafter referred to as Tg) of the thermoplastic norbornene-based resin is preferably 110 ° C. or higher, more preferably 120 ° C. or higher, 1
Those having a temperature of 30 ° C. or higher are particularly preferable. If the Tg is too low, the heat resistance will decrease.

Various additives may be added to the thermoplastic norbornene-based resin of the present invention depending on the application. For example,
Anti-aging agents such as phenol and phosphorus; Heat deterioration inhibitors such as phenol; UV stabilizers such as benzophenone; Antistatic agents such as amine; Esters of aliphatic alcohols, partial esters and moieties of polyhydric alcohols Various additives such as a lubricant such as ether; may be added. In addition, a resin such as an ethylene polymer or a rubbery polymer may be added, or a filler may be blended and used, as long as the characteristics of the composition of the present invention are not lost depending on the application.

The method for producing the thermoplastic norbornene-based resin molded product is not particularly limited. General molding methods for thermoplastic resins such as injection molding, melt extrusion, hot pressing, solvent casting, inflation, vacuum molding and blow molding can be used. In the present invention, any molding method may be used as long as the adhesive surface is made of a thermoplastic norbornene-based resin having no polar group, for example,
It may be formed by inserting a metal or the like and integrally molded, or may be polished after molding or laminated with various films on the surface. The shape is also not particularly limited.

In the present invention, in order to improve the adhesiveness of the thermoplastic norbornene resin molded product, the adhesive surface of the molded product may be subjected to surface modification treatment and / or primer treatment. Examples of the surface modification treatment include energy ray irradiation treatment such as corona discharge treatment, plasma treatment, electron beam irradiation treatment and ultraviolet ray irradiation treatment, and chemical treatment brought into contact with an oxidizing agent aqueous solution such as potassium dichromate solution.

(Epoxy Resin Molded Product) The epoxy resin molded product used in the present invention has an adhesive surface formed of an epoxy resin and has a shape capable of bonding to the adhesive surface of a thermoplastic norbornene resin molded product. It is not particularly limited. The type of epoxy resin is not particularly limited, and examples thereof include novolac type epoxy resin, alicyclic epoxy resin, and brominated epoxy resin, and the epoxy monomer is 25% by weight or more, preferably 50% by weight or more, more preferably Is 7
It is obtained by epoxy-curing a monomer mixture containing 5% by weight or more and curing it. Epoxy resin has a filler,
A curing agent, a catalyst, a release agent, a coupling agent, a flame retardant, a coloring agent and the like may be added.

(Adhesion Method) In the present invention, the ultraviolet-curable composition of the present invention is applied to the adhesive surface of the thermoplastic norbornene-based resin molded article and / or the adhesive surface of the epoxy resin molded article to form a thermoplastic norbornene-based resin. The adhesive surface of the molded product and the adhesive surface of the epoxy resin molded product are brought into close contact with each other, and the adhesive surface is irradiated with ultraviolet rays to cure the ultraviolet curable composition and adhere.

The coating method is not particularly limited, and for example, spraying, dipping, brush coating, spin coating, a method using a roll coater, a method using a micro dispenser and the like are possible.

The coating amount of the ultraviolet curable composition is generally 50 μm or more, preferably 80 μm or more and 200 μm or less, preferably 150 μm after the ultraviolet curing agent composition layer is cured.
The following thickness is preferable. If the layer is too thin, good adhesion cannot be obtained, and if the layer is too thick, the curing reaction will take time and productivity will be poor.In addition, curing will be insufficient and hardness will be low, or flexibility will be insufficient. It is.

The ultraviolet irradiation is performed by irradiating the ultraviolet rays from a light source such as a high pressure mercury lamp that efficiently generates the ultraviolet rays.
Curing occurs in a short time and the adhesive surfaces are adhered to each other. The irradiation dose of ultraviolet rays varies depending on the reactivity with the acrylate component and the photopolymerization initiator, but is 1000 to 3000 mJ / cm.
The energy of about ² is irradiated to cure. For example,
In the case of 80 W / cm high pressure mercury lamp, 90 to 10 from the light source
If UV rays are radiated at a distance of about 0 mm, 5 to 3
It can be cured in a short time of about 0 seconds.

(Adhesive) As the adhesive obtained in the present invention, for example, a lens made of a thermoplastic norbornene resin,
Examples thereof include an optical component in which a prism or the like is adhesively fixed to a frame made of epoxy resin, and a sealed body in which an electronic component such as an image sensor is sealed in a case.

(Aspect) As an aspect of the present invention, (1)
(A) alicyclic acrylate component, (b) amino acrylate component and / or epoxy acrylate component,
An ultraviolet curable composition comprising (c) an elastomer component and (d) a photopolymerization initiator component, (2) an alicyclic acrylate component, an acrylate monomer comprising an alicyclic structure and an acrylate group directly bonded thereto and / or The ultraviolet-curable composition according to (1), which is an oligomer thereof,
(3) The ultraviolet-curable composition according to (1) or (2), wherein the alicyclic acrylate component has an alicyclic structure consisting of only carbon and hydrogen, and (4) the alicyclic acrylate component is
The ultraviolet-curable composition according to (3), which has a carbon-hydrogen substituent in the alicyclic structure, (5) the alicyclic acrylate component is a monofunctional alicyclic acrylate monomer (1) to (4). (6) The ultraviolet curable composition described in (1) to (5), wherein the alicyclic acrylate component is a compound having 30 or less carbon atoms.
Oligomer is 2-10 alicyclic acrylate monomer
UV curable composition according to any one of (1) to (6), wherein the amino acrylate component is a compound represented by the general formula (1) to (7). Curable composition, (9) The amino acrylate component is a bifunctional or trifunctional amino acrylate (1)
To (8), the ultraviolet curable composition, (10) the ultraviolet curable composition according to (1) to (9), wherein the epoxy acrylate component is a compound represented by the general formula 2.
1) Elastomer component has a number average molecular weight of 10,000
The ultraviolet-curable composition according to any one of (1) to (6), wherein the thermoplastic elastomer has at least one Tg of 40 ° C. or less (1) to
The ultraviolet-curable composition according to (11), (13) the thermoplastic elastomer is hydrogenated (1) to
The ultraviolet curable composition according to (12), (14) (a)
2 to 100 parts by weight of the component (b), 5 to 200 parts by weight of the component (c), and 1 to 30 of the component (d) with respect to 100 parts by weight of the component.
An ultraviolet-curable composition according to any one of (1) to (13), which comprises 10 parts by weight, and (15) a method for adhering a thermoplastic norbornene-based resin molded product and an epoxy resin molded product, which comprises bonding a thermoplastic norbornene-based resin molded product. Surface and / or the adhesive surface of the epoxy resin molded product is coated with the ultraviolet-curable composition according to (1) to (14), and the adhesive surface of the thermoplastic norbornene-based resin molded product and the adhesive surface of the epoxy resin molded product are adhered to each other. Let
An adhesive method comprising irradiating an ultraviolet ray to the adhesive surface to cure the ultraviolet curable composition, and comprising a thermoplastic norbornene-based resin molded product and an epoxy resin molded product bonded by the method according to (16) or (15). Adhesives and the like are exemplified.

[0036]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples.

Example 1 (a) Isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., IB-
XA) 100 parts by weight, (b) dimethylaminoethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester DM) 10
Parts by weight, (c) styrene-ethylene-butadiene-styrene-block copolymer rubber (Kuraray, Septon 2
043, at least one of the glass transition temperatures is 30 ° C or lower, 30 parts by weight of a number average molecular weight of about 50,000, and a photopolymerization initiator (manufactured by Ciba-Geigy, Irgacure 184) 10
By mixing parts by weight, an ultraviolet curable composition was obtained.

A norbornene-based ring-opening polymer hydrogenated product (ZEONEX 280 manufactured by Nippon Zeon, Tg about 140)
℃, number average molecular weight of about 28,000, hydrogenation rate 99% or more) 3 mm thick, 100 mm × 25 mm of the test piece was applied to the adhesion site (12.5 mm × 25 mm), epoxy resin (Sumitomo Bakelite, "Sumikon" EM)
The test piece having a thickness of 1.6 mm and a size of 100 mm × 25 mm was brought into close contact with the bonding site, and was irradiated with ultraviolet rays for 20 seconds at a light source distance of 90 mm using a high-pressure mercury lamp of 80 W / cm to cure. I observed the adhesive surface between the test pieces,
No peeling was observed.

Further, no peeling was observed even after the heat cycle test (a temperature change of 100 cycles was performed by setting 40 minutes at -40 ° C. for 20 minutes and 85 ° C. for 20 minutes as a total of 40 minutes).

Example 2 As component (b), dimethylaminoacrylate (light ester DE, manufactured by Kyoeisha Chemical Co., Ltd.) was used in place of dimethylaminoethylmethacrylate, and as component (c), styrene / ethylene / butadiene / styrene-block copolymer rubber. Was treated in the same manner as in Example 1 except that a maleated styrene / ethylene / butadiene / styrene-block copolymer Tom (KRATON FG1901X manufactured by Shell Chemical Co., Ltd.) was used instead of. As a result of the peeling test, no peeling was observed and no peeling was observed even after the heat cycle test.

Example 3 As component (b), glycidyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., instead of dimethylaminoethyl methacrylate) was used.
The same treatment as in Example 1 was carried out except that light ester GMA) was used. As a result of the peel test, no peel was observed,
No peeling was observed even after the heat cycle test.

Comparative Example 1 Isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., IB-XA)
100 parts by weight, styrene / ethylene / butadiene / styrene-block copolymer rubber (Asahi Kasei, Tuftec)
30 parts by weight and 10 parts by weight of a polymerization initiator (manufactured by Ciba Geigy, Irgacure 184) were mixed to obtain an ultraviolet curable composition. Using this UV curable composition, Example 1
When a peeling test was carried out in the same manner as above, no peeling was observed, but after the heat cycle test, when the adhesive surface was observed, partial peeling was observed, and the peeled area was about 15%.

[0043]

When the thermoplastic norbornene-based resin and the epoxy resin are adhered using the ultraviolet-curable composition of the present invention, the adhesiveness is excellent and the exfoliation does not occur even if expansion and contraction due to temperature changes are repeated.

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Claims (3)

[Claims] 1. (a) an alicyclic acrylate component, (b)
An ultraviolet curable composition comprising an amino acrylate component and / or an epoxy acrylate component, (c) an elastomer component, and (d) a photopolymerization initiator component. 2. A method for adhering a thermoplastic norbornene-based resin molded product and an epoxy resin molded product, wherein the adhesive surface of the thermoplastic norbornene-based resin molded product and / or the adhesive surface of the epoxy resin molded product is according to claim 1. Characterized by applying an ultraviolet curable composition, bringing the adhesive surface of the thermoplastic norbornene resin molded product and the adhesive surface of the epoxy resin molded product into close contact, and irradiating the adhesive surface with ultraviolet light to cure the ultraviolet curable composition And the bonding method. 3. An adhesive product comprising a thermoplastic norbornene-based resin molded product and an epoxy resin molded product bonded by the method according to claim 2.