TWI523906B - Resin composition and adjuvant - Google Patents

Description

Resin composition and adhesive

The present invention is directed to an adhesive.

The cycloolefin polymer can be used for applications such as electronic materials, optical lenses, and medical materials. Since a cycloolefin polymer has a small polarity and does not have many functional groups on the surface, it is known that it is difficult to be a binder. A solvent-based adhesive and a hot-melt adhesive can be given as an adhesive for the cycloolefin-based resin.

As a method of following the olefin-based resin, as disclosed in Patent Document 1, the method of treating with a primer is followed by an instant adhesive. Patent Document 2 discloses an energy ray-curable resin composition characterized by containing (meth) acrylate.

[Previous Technical Literature] [Patent Document]

Patent Document 1 Japanese Patent Publication No. Sho 62-18485

Patent Document 2 Japanese Patent Publication No. 2007-77321

Patent Document 3 Patent Application WO2010/027041

A solvent-based adhesive is a solvent used. The solvent-based adhesive is not only harmful to the human body, but also the solvent is volatilized, and the strength itself is insufficient.

The hot melt adhesive must have procedures and means for melting the adhesive. Moreover, sufficient adhesion strength cannot be obtained in the case of this adhesive. Further, in the case of using a hot-melt adhesive, if the cycloolefin polymer is heated in advance, although the strength is increased, a new problem of deformation of the resin may occur.

According to the following method disclosed in Patent Document 1, in addition to the problem that the primer treatment is time consuming, sufficient bonding strength is not obtained.

Patent Document 2 discloses an energy ray-curable resin composition characterized by containing (meth) acrylate. However, there is no description of the (meth) acrylate having a dicyclopentenyl group.

Patent Document 3 discloses a photocurable secondary composition comprising a (meth) acrylate oligomer having a polyisoprene, a polybutadiene, a polyurethane skeleton, and a softening component. However, there is no description of (meth)acrylic acid.

The cycloolefin polymer is characterized by low water absorption, high transparency, and low specific gravity. Therefore, the cycloolefin polymer is used as a glass substitute material or a transparent plastic substitute material, and is used for applications such as electronic materials, optical lenses, and medical materials.

However, since the cycloolefin polymer has a small polarity and does not have many functional groups on the surface, it is difficult to continue the problem.

The present invention has been made in view of such circumstances. An object of the present invention is to provide, for example, an adhesive for a cycloolefin polymer which exhibits sufficient adhesion strength to a cycloolefin polymer in a short period of time and which is solvent-free and environmentally friendly.

The inventors of the present invention have continually studied in order to solve the above problems, and finally completed the present invention.

That is, one aspect of the present invention is a resin composition comprising the following components (A) to (F): (A) is a (meth) acrylate having a dicyclopentenyl group; (B) The component is a (meth) acrylate having a hydroxyl group; the component (C) is an oligomer having a diene skeleton or a hydrogenated diene skeleton and having no (meth) acrylonitrile group; The component (D) is a decane coupling agent; the component (E) is a photopolymerization initiator; and the component (F) is (meth)acrylic acid.

In one embodiment of the resin composition of the present invention, the component (G) further contains polyvinyl alcohol.

In one embodiment of the resin composition of the present invention, the component (A) is biscyclopentenyl (meth)acrylate.

In an embodiment of the resin composition of the present invention, the component (C) has a number average molecular weight of 500 to 50,000.

In one embodiment of the resin composition of the present invention, when the thickness is 0.03 mm and the film is cured by irradiation for 15 seconds under the conditions of a wavelength of 365 nm and a cumulative light amount of 2000 mJ/cm ² , the storage elastic modulus of the cured product is 0.1. Within the range of ~100000 MPa (23 ° C).

In an embodiment of the resin composition of the present invention, the antioxidant further contains an antioxidant.

Another aspect of the present invention is an adhesive comprising the resin composition of the present invention.

In one embodiment of the adhesive of the present invention, it is an adhesive for a cycloolefin polymer.

In one embodiment of the adhesive of the present invention, it is an adhesive for a cycloolefin polymer having a dicyclopentadiene ring structure.

Another aspect of the present invention is a binder which is formed by adhering the adherends to each other using the adhesive of the present invention.

In one embodiment of the battery of the present invention, one or more selected from the group consisting of a cycloolefin polymer, a polycarbonate, a cellulose triacetate, a polyvinyl alcohol, and a glass are used.

Still another aspect of the present invention is a method for producing a laminate comprising applying an adhesive of the present invention to a surface of a adherend so as to have a thickness of 0.0001 to 5 mm, so that the adherends are attached to each other. Further, the adhesive is cured under the conditions of a wavelength of 200 to 500 nm, a cumulative light amount of 200 to 6000 J/cm ² , and an irradiation time of 1 to 60 seconds.

The resin composition of the present invention is characterized in that, for example, it exhibits high adhesion strength to a cycloolefin polymer and is excellent in moisture resistance.

In the present invention, the component (A) is a (meth) acrylate having a dicyclopentenyl group. More specifically, the component (A) is a (meth) acrylate containing one or more dicyclopentenyl groups at the molecular terminal or in the side. Examples of the (meth) acrylate of the component (A) include dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyloxypropyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. . Among these, dicyclopentenyl (meth)acrylate is preferred.

The component (B) is a hydroxyl group-containing (meth) acrylate. More specifically, the component (B) is a (meth) acrylate having one or more hydroxyl groups at the molecular terminal or in the side. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and (meth)acrylic acid. 2-hydroxy-3-phenoxypropyl ester, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 4-hydroxycyclohexyl (meth)acrylate, and the like. Among these, 2-hydroxy-3-phenoxypropyl (meth)acrylate is preferred from the viewpoint of adhesion.

The component (C) is an oligomer having a diene skeleton or a hydrogenated diene skeleton. The component (C) is preferably free of (meth)acrylonitrile. The component (C) is the following component from the viewpoint of imparting flexibility to the resin.

The main chain skeleton of the oligomer is a diene skeleton or a hydrogenated diene skeleton. The diene skeleton or the hydrogenated diene skeleton can be selected from the group consisting of polybutadiene, polyisoprene, hydride of polybutadiene, and hydride of polyisoprene. One or more skeletons. Among these, one or more selected from the group consisting of polyisoprene and a hydrogenated product of polyisoprene are preferred, and polyisoprene is more preferred.

The number average molecular weight of the oligomer of the component (C) is preferably from 500 to 50,000, more preferably from 5,000 to 45,000, most preferably from 8,000 to 40,000. When the number average molecular weight is 500 or more, the hardness of the hardened body obtained by irradiating the adhesive of the present invention with an energy ray is high, and the adhesive layer is easily formed. When the number average molecular weight is 50,000 or less, since the viscosity of the obtained adhesive is small, the workability in mixing in the production process and the workability in using the adhesive in practical use are good.

Examples of the oligomer of the component (C) include "LIR-50" (isoprene oligomer) manufactured by Kuraray Co., Ltd., "LIR-30" (isoprene oligomer) manufactured by Kuraray Co., Ltd., and Kuraray Co., Ltd. "LBR-307" (butadiene oligomer), "LBR-305" (butadiene oligomer) manufactured by Kuraray Co., Ltd., and "LBR-300" (butadiene oligomer) manufactured by Kuraray Co., Ltd. Among these, from the viewpoint of flexibility and adhesion, one or more kinds of isoprene oligomers and/or butadiene oligomers are preferable.

The component (D) is a decane coupling agent. Examples of the decane coupling agent include γ-chloropropyltrimethoxydecane, vinyltrimethoxydecane, vinyltrichlorodecane, vinyltriethoxydecane, vinylpropyltrimethoxydecane, and vinyl- Reference (β-methoxyethoxy)decane, γ-(meth)acryloxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, Γ-glycidoxypropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, γ- Aminopropyltriethoxydecane, N-β-(aminoethyl)-γ-aminopropyltrimethoxydecane, N-β-(aminoethyl)-γ-aminopropylmethyl Dimethoxy decane, γ-ureidopropyl triethoxy decane, hydroxyethyl (meth) acrylate, acid (meth) propylene oxy oxyethyl phosphate, acid (A) Base) propylene methoxy oxyethyl phosphate monoethylamine half salt and the like. Among these, from the viewpoint of adhesion to glass or the like, γ-glycidoxypropyltrimethoxydecane and γ-(meth)acryloxypropyltrimethoxy group are preferred. One or more selected from the group consisting of decane and vinyl propyl trimethoxy decane.

The component (E) is a photopolymerization initiator. The photopolymerization initiator may, for example, be an ultraviolet polymerization initiator, a visible light polymerization initiator, or the like, and may be used without limitation. Examples of the ultraviolet polymerization initiator include a benzoin system, a diphenylketone system, and an acetophenone system. Examples of the visible light polymerization initiator include a fluorenylphosphine oxide system, a 9-thioxanthone system, a metallocene system, an anthraquinone system, and an α-aminoalkylphenone.

The photopolymerization initiator can be exemplified by diphenyl ketone, 4-phenyl diphenyl ketone, benzamidine benzoic acid, 2,2-diethoxy phenethyl hydrazine, bis diethylamine diphenyl ketone, and Phenylenedione, benzoin, benzhydryl isopropyl ether, benzil dimethyl ketal, 1-hydroxycyclohexylphenylacetone, 9-thioxanthone, 2-methyl Base-9-thioxanthone, 2,4-dimethyl 9-thioxanthone, isopropyl 9-thioxanthone, 2,4-diethyl-9-thioxanthone, 2,4-diiso Propyl-9-thioxanthone, 1-(4-isopropylphenyl)2-hydroxy-2-methylpropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl )-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydrazine, oxidized 2,4,6-trimethyl Benzobenzyldiphenylphosphine, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2-methyl-1-(4-(methylthio)phenyl) -2-N-morpholinylpropan-1-one, 2-benzyl-2-dimethylamine-1-(4-N-morpholinylphenyl)-1-butanone-1, 2-di Methylamine-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, bis(2,6-dimethoxybenzoate) Mercapto)-2,4,4-trimethylpentyl Phosphine and the like. Among these, dimethyl benzophenone is preferred.

The component (F) is (meth)acrylic acid (acrylic acid or methacrylic acid). It is used from the viewpoint of durability such as moisture resistance.

The resin composition of the present invention contains the components (A) to (F) as essential components. The resin composition containing the components (A) to (F) described above is cured by irradiating light thereto. The cured product shows good adhesion to the cycloolefin polymer and is highly surface hardenable in the aforementioned hardening. The resin composition of the present invention exhibits high adhesion strength even for a general-purpose plastic resin such as polycarbonate, cellulose triacetate or polyvinyl alcohol, or a glass-attached body.

The resin composition of the present invention may contain a component (G): polyvinyl alcohol. The following components are exemplified from the viewpoint of adhesion to a adherend composed of a polyvinyl alcohol resin.

The polyvinyl alcohol is not particularly limited as long as it is a polyvinyl alcohol derivative obtained by saponifying polyvinyl acetate. The average degree of polymerization of the polyvinyl alcohol is preferably from 100 to 5,000, more preferably from 1,000 to 4,000. The average degree of saponification of the polyvinyl alcohol is preferably from 85 to 100 mol%, more preferably from 90 to 100 mol%.

The amount of the resin composition of the present invention used is as follows from the viewpoint of making the adhesion of the adhesive to the cycloolefin polymer particularly high and also having high adhesion strength to other adherends.

The amount of the component (A), the component (B), and the component (C) is preferably a component (A), a component (B), and a component (C) in a total amount of 100 parts by mass. ) Component: (C) component = 40~90: 1~20: 5~45 (mass ratio), more preferably (A) component: (B) component: (C) component = 55~85: 3~10: 10~40 (mass ratio).

The amount of the component (D) to be used is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 100 parts by mass based on 100 parts by mass of the total of the components (A), (B), (C) and (F). 5 parts by mass, typically 0.5 to 1.0 part by mass.

The amount of the component (E) to be used is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 100 parts by mass based on 100 parts by mass of the total of the components (A), (B), (C) and (F). 20 parts by mass, typically 5 to 10 parts by mass.

The amount of the component (F) to be used is preferably 0.1 to 30 parts by mass, more preferably 1 to 1 part by mass, based on 100 parts by mass of the total of the component (A), the component (B), the component (C), and the component (F). 20 parts by mass, typically 10 to 15 parts by mass.

The amount of the component (G) to be used is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 100 parts by mass based on 100 parts by mass of the total of the components (A), (B), (C) and (F). 30 parts by mass, typically 0.5 to 1.0 part by mass.

Further, the resin composition of the present invention can use a graft copolymer, a solvent, a filler, a reinforcing material, a plasticizer, a tackifier, a dye, a pigment, a flame retardant, etc., within a range not impairing the object of the present invention. Additives such as antioxidants and surfactants.

The cured product of the resin composition of the present invention preferably has a storage elastic modulus of 0.1 to 100,000 MPa (23 ° C), more preferably a storage elastic modulus of 10 to 10,000 MPa, and is typically 500 to 5000 MPa. When the storage elastic modulus of the cured product of the resin composition is 0.1 MPa or more, the cured product is hardened and no unreacted components remain. When the storage elastic modulus is 100,000 MPa or less, the cured product does not become too rigid and the adhesive force does not decrease.

The resin composition of the present invention can be used as an adhesive. The adhesive agent of the present invention exhibits, for example, one or more selected from the group consisting of a cycloolefin polymer, a polycarbonate, a cellulose triacetate (triacetyl cellulose), a polyvinyl alcohol, and a glass. Then the intensity. That is, when such a resin is used as a adherend, it can be used as a useful adhesive. The adhesive of the present invention exhibits high adhesion strength to the cycloolefin polymer in these adherends.

The cyclic olefin polymer to be used as the binder of the application of the present invention is, for example, a constituent unit derived from a cyclic olefin (cycloolefin) monomer such as a norbornene or a polycyclic norbornene-based monomer. Thermoplastic resin. The cycloolefin polymer may, for example, be a ring-opening polymer of a cyclic olefin, a hydrogenated product of a ring-opening copolymer using two or more kinds of cyclic olefins, an addition copolymer of an aromatic compound having a chain olefin or a vinyl group and a cyclic olefin. Etc., the binder of the present invention is particularly effective as a cycloolefin polymer having a dicyclopentadiene ring configuration. Further, a polar group may be introduced into the cycloolefin polymer.

Examples of the commercially available cycloolefin polymer include "Topas" manufactured by Ticona Co., Ltd., "ARTON" manufactured by JSR Corporation, "ZEONOR" and "ZEONEX" manufactured by Japan ZEON Co., Ltd., and "APEL" manufactured by Mitsui Chemicals Co., Ltd. Wait.

The subsequent method of the adhesive of the present invention is carried out, for example, as follows. Preferably, the adhesive is applied to at least one of the two adherends in a thickness of 0.0001 to 5 mm, typically 0.01 to 0.50 mm, and then the adherends are bonded to each other. Further, the wavelength is 200 to 500 nm, typically 350 to 420 nm, the cumulative light amount is 200 to 6000 mJ/cm ² , typically 300 to 2000 mJ/cm ² , and the irradiation time is 1 to 60 seconds, typically 2 to 30 seconds. The adhesive is hardened to carry out the subsequent method of the adherend.

Antioxidants can also be used as other ingredients in the present invention. A phenol type or a hydroquinone type can be used for an antioxidant, and a phenol type is preferable. Antioxidants can be exemplified by β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methyl hydrogen, hydroquinone, 2,2-methylene-bis(4-methyl-6-tris Butyl phenol), catechol, hydroquinone monomethyl ether, monoterpene butyl hydroquinone, 2,5-di-tertiary butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone , 2,5-di-tertiary butyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tertiary butyl catechol, 2-butyl-4-hydroxyanisole and 2,6-double Butyl-butyl P-cresol and so on. Among these, 2,2-methylene-bis(4-methyl-6-tertiarybutylphenol) is preferred.

The antioxidant is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, per 100 parts by mass of the total of the components (A), (B), (C) and (F). More preferably, it is 2.0 to 8.0 parts by mass.

Example

Hereinafter, the present invention will be described in further detail by way of Experimental Examples, but the present invention is not limited thereto. Further, each component in the adhesive described in the experimental examples was selected from the following compounds.

(A) component: (meth) acrylate containing dicyclopentenyl, dicyclopentenyl acrylate ("FA-511AS" by Hitachi Chemical Co., Ltd.)

(A) component: (meth) acrylate containing dicyclopentenyl, A: dicyclopentenyloxyethyl methacrylate ("FA-512MT" by Hitachi Chemical Co., Ltd.)

(B) component: (meth) acrylate containing a hydroxyl group, 2-hydroxy-3 phenoxypropyl acrylate ("M-5700" manufactured by Toagosei Co., Ltd.)

(B) component: (meth) acrylate containing a hydroxyl group, 2-hydroxyethyl methacrylate ("Light Ester HO" by Kyoeisha Chemical Co., Ltd.)

(C) component: oligomer, isoprene oligomer ("LIR-30" manufactured by Kuraray Co., Ltd.) (quantitative molecular weight of 28,000 in terms of GPC to polystyrene)

(C) component: oligomer, butadiene oligomer ("LBR-307" manufactured by Kuraray Co., Ltd.) (the average molecular weight of 8,000 in terms of GPC converted to polystyrene)

(D) component: decane coupling agent, γ-glycidoxypropyltrimethoxy decane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.)

(D) component: decane coupling agent, (vinyl propyl) trimethoxy decane ("KBM-1003" manufactured by Shin-Etsu Chemical Co., Ltd.)

(D) component: decane coupling agent, γ-methacryloxypropyltrimethoxydecane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd.)

(E) component: photoinitiator, dimethylene diphenylethanedione ("IRGACURE651" by Ciba Specialty Chemicals Co., Ltd.)

(E) component: photoinitiator, bis(2,4,6-trimethylbenzylidene)phenylphosphine ("IRGACURE 819" by Ciba Specialty Chemicals Co., Ltd.)

(F) component: methacrylic acid ("AM" by Mitsubishi Rayon Co., Ltd.)

(F) component: Acrylic ("Methyl acrylate AM" manufactured by Nippon Shokubai Co., Ltd.)

(G) component: polyvinyl alcohol ("Denka POVOL H-17" by Electric Chemical Industry Co., Ltd.) (average polymerization degree 1200, average saponification degree: 97 mol%)

(G) component: polyvinyl alcohol (Denka POVOL F-12, manufactured by Denki Kagaku Kogyo Co., Ltd.) (average polymerization degree 1200, average saponification degree: 99 mol%)

Antioxidant (D-1) 2,2-methylene-bis(4-methyl-6-tertiary butyl phenol) (Sumitomo Chemical Co., Ltd. "SUMILIZER MDP-S")

Various physical properties were measured as follows.

[Photohardenability]

Measured at a temperature of 23 °C. In the photocurability, the adhesive was applied to a surface of a test piece (width: 25 mm × length 25 mm × thickness: 2.0 mm) of a ZEONEX 480R (manufactured by Nippon Zeon Co., Ltd.) so that the thickness of the adhesive was 0.03 mm. The thickness is controlled by 0.03mm glass beads. Then, it was irradiated by irradiation with a curing device manufactured by Fusion Co., Ltd. using an electrodeless discharge lamp at a wavelength of 365 nm and a cumulative light amount of 2000 mJ/cm ² for 15 seconds, and hardened. The curing rate is described as photocurability. The hardening rate was calculated by the following formula using FT-IR.

(hardening rate) = [100 - ((absorption spectrum intensity of carbon-carbon double bond after hardening) / (absorption spectrum intensity of carbon-carbon double bond before hardening))] × 100 (%)

[Evaluation of cyclic olefin polymer adhesion (stretching strength between cyclic olefin polymer (ZEONEX) test pieces)]

In order to control the thickness of the adhesive, a Teflon (registered trademark) tape 10 (thickness 80 μm × width 25 mm × length 25 mm) of a hole 11 having a size of 0.5 cm ² is affixed to the center, and is attached to the ZEONEX 480R (manufactured by Japan ZEON Co., Ltd.). The front end portion of the test piece 12a (width 25 mm × length 100 mm × thickness 2.0 mm) in the longitudinal direction. After the adhesive 13 was supplied to the hole 11 so that the thickness of the adhesive was 80 μm, another piece of ZEONEX 480R (manufactured by ZEON CORPORATION, Japan) test piece 12b (width 25 mm × length 100 mm × thickness) was applied so as to cover the hole 11 The front end portion of 2.0 mm is attached to the Teflon (registered trademark) tape 10. The appearance at this time is shown in Fig. 1. After the hardening, the test piece is passed through the adhesive, and the arrow is stretched left and right according to the arrow of Fig. 1. The tensile strength was measured, and the curing conditions were as described in [Photocurability].

[moisture resistance]

The test piece for the evaluation of the adhesion of the above cyclic olefin polymer was exposed to 85 ° C × 85% RH for 24 hours, and the tensile strength was measured using the test piece.

[Evaluation of general-purpose polymer adhesion (strength and strength between test pieces of polycarbonate (manufactured by Teijin Co., Ltd.)]

A Teflon (registered trademark) tape having a thickness of 80 μm × a width of 11.5 mm × a length of 25 mm was used as a spacer, and PANLITE (manufactured by Teijin Co., Ltd.) test pieces (width 25 mm × length 25 mm × thickness 2.0 mm) were adhered to each other (following) The area is 3.125cm ² ). After the hardening, the tensile strength was measured using the test piece followed by the adhesive. The curing conditions are based on the method described in [Photocurability].

[Evaluation of general-purpose polymer adhesion (polyvinyl alcohol (Kuraray) Stretch between test pieces and strength)

A Teflon (registered trademark) tape having a thickness of 80 μm × a width of 11.5 mm × a length of 25 mm was used as a spacer, and test pieces (width 25 mm × length 25 mm × thickness 0.03 mm) were adhered to each other with an adhesive (the area was 3.125 cm ² ). After the hardening, the tensile strength was measured using the test piece followed by the adhesive. The curing conditions are based on the method described in [Photocurability].

[Evaluation of general-purpose polymer adhesion (stretching strength between test pieces of triethylene cellulose (manufactured by Konica Minolta Co., Ltd.)]

A Teflon (registered trademark) tape having a thickness of 80 μm × a width of 11.5 mm × a length of 25 mm was used as a spacer, and test pieces (width 25 mm × length 25 mm × thickness 0.03 mm) were adhered to each other with an adhesive (the area was 3.125 cm ² ). After the hardening, the tensile strength was measured using the test piece followed by the adhesive. The curing conditions are based on the method described in [Photocurability].

[Evaluation of glass adhesion (stretching strength between heat-resistant glass test pieces)]

A Teflon (registered trademark) tape having a thickness of 80 μm × a width of 11.5 mm × a length of 25 mm was used as a spacer, and a heat-resistant glass test piece (25 mm × 25 mm × 2.0 mm) was adhered to each other with an adhesive (the area was 3.125 cm ² ). The curing conditions are based on the method described in [Photocurability]. After the adhesive was cured under the above conditions, a galvanized steel sheet (100 mm × 25 mm × 2.0 mm, manufactured by Engineering Test Service Co., Ltd.) was further placed on the inside of the test piece, using an adhesive "G-55" manufactured by Denki Kogyo Co., Ltd. After curing at 23 ° C × 50% RH × 24 hours, the tensile strength was measured using the test piece followed by the adhesive. The tensile shear strength (unit: MPa) was measured at a tensile speed of 10 mm/min under an environment of a temperature of 23 ° C and a humidity of 50%.

[Evaluation of storage elastic modulus]

The adhesive was cured to prepare a cured sample having a length of 20 mm, a width of 5 mm, and a thickness of 1 mm. The curing conditions are based on the method described in [Photocurability]. This hardened sample was evaluated. The temperature was changed at a frequency of 1 Hz and a distortion of 0.05% using a Tension Module DMS 210 manufactured by Seiko Instruments Inc., and the dynamic viscoelastic spectrum in the tensile mode was measured to obtain a storage elastic modulus E' at 23 °C. value.

(Experimental examples 1 to 14)

The raw materials of the types shown in Table 1 were mixed in the composition shown in Table 1 to prepare an adhesive. Various physical properties were measured for the obtained adhesive. The results are shown in Table 1.

The invention of the present invention exhibits sufficient bond strength to the cyclic olefin polymer, polycarbonate, polyvinyl alcohol, cellulose triacetate, and glass. Moreover, the invention of the present invention has moisture resistance.

[Industry Utilization]

The cycloolefin polymer has a small polarity and does not have many functional groups on the surface, and has a problem that it is difficult to proceed. In order to follow the cycloolefin polymer, it is necessary to further combine the primer treatment with the surface corona treatment after the use of the adhesive. The implementation of primer treatment and surface corona treatment may increase the number of processes.

The invention of the present invention exhibits high adhesion only to the cyclic olefin polymer by the adhesive agent. In the present invention, since the primer treatment and the surface corona treatment are not combined, the cyclic olefin polymer exhibits high adhesion, so that labor can be saved. Therefore, the invention of the present invention is a useful technique.

10‧‧‧ Tape

11‧‧‧ hole

12a, 12b‧‧‧ test strips

13‧‧‧Binder

Fig. 1 is a schematic view showing the order of measuring the tensile strength in the examples.

Claims (14)

A resin composition containing the following (A) to (F) components: (A) is a (meth) acrylate having a dicyclopentenyl group; and (B) is a (meth) acrylate having a hydroxyl group The (C) component is an oligomer having a diene skeleton or a hydrogenated diene skeleton and having no (meth) acrylonitrile group; (D) is a decane coupling agent; and (E) is light. The polymerization initiator; and the component (F) is (meth)acrylic acid. The resin composition of claim 1 further comprising (G) a component: polyvinyl alcohol. In the resin composition of the first aspect of the patent application, the amount of the component (A), the component (B), and the component (C) is 100 parts by mass of the component (A), the component (B), and (C). In the component, (A) component: (B) component: (C) component = 40 to 90: 1 to 20: 5 to 45 (mass ratio); (D) component usage amount, relative to (A) component, ( The total amount of the component B, the component (C), and the component (F) is 0.01 to 10 parts by mass, and the amount of the component (E) is relative to the component (A), the component (B), and (C). The total amount of the component and the component (F) is 100 parts by mass, and is 0.01 to 30 parts by mass. The resin composition according to any one of claims 1 to 3, wherein the component (A) is dicyclopentenyl (meth)acrylate. The resin composition according to any one of claims 1 to 3, wherein the component (C) is an isoprene oligomer and/or a butadiene oligomer. The resin composition according to any one of claims 1 to 3, wherein the component (C) has a number average molecular weight of 500 to 50,000. The resin composition of any one of claims 1 to 3, which has a thickness of 0.03 mm and is cured by irradiation for 15 seconds at a wavelength of 365 nm and a cumulative light amount of 2000 mJ/cm ² , and the storage elasticity of the cured product. The modulus is in the range of 0.1 to 100,000 MPa (23 ° C). The resin composition according to any one of claims 1 to 3, which further contains an antioxidant. An adhesive composition comprising the resin composition according to any one of claims 1 to 8. An adhesive for a cyclic olefin polymer, as in the adhesive of claim 9. An adhesive for a cyclic olefin polymer having a dicyclopentadiene ring structure, as disclosed in claim 9 or 10. An adhesive body obtained by adhering the adherends to each other using an adhesive according to any one of claims 9 to 11. The binder of the 12th aspect of the patent application, wherein the binder system is one or more selected from the group consisting of a cycloolefin polymer, a polycarbonate, a cellulose triacetate, a polyvinyl alcohol, and a glass. A method for producing a laminate comprising the adhesive according to any one of claims 9 to 11 which is applied to the surface of the adherend by coating to a thickness of 0.0001 to 5 mm to form a adherend. The adhesive is cured by bonding to each other at a wavelength of 200 to 500 nm, a cumulative light amount of 200 to 6000 J/cm ² , and an irradiation time of 1 to 60 seconds.