JP2006328358A - Resin molded product, layered product using the same, and method for producing the layered product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin molded product, which is excellent in transparency, heat resistance, and adhesive property with an adherend and is capable of maintaining for a long time such excellent adhesive property and forming a layered product that is produced through proper adhesion without using any adhesive or forming any adhesive layers. <P>SOLUTION: The resin molded product comprises a polymer having a unit represented by general formula (1) and has a glass transition temperature between 230 and 450°C and has a surface, at least a part of which has been subjected to oxidation treatment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin molded body capable of producing a laminate without using an adhesive or forming an adhesive layer, a laminate using the same, and a method for producing the laminate.

  Resin molded products such as films and lenses obtained from cyclic olefin addition polymers are widely used in various optical applications and electronic material applications because of their excellent heat resistance and optical transparency. The resin molded body is often used by being bonded to other adherends such as a gas barrier layer, an antireflection layer, an easy adhesion layer, and a hard coat layer. However, since a resin molded body obtained from a polymer having an alicyclic structure has poor adhesion to an adherend, an adhesive is generally used between the layers. Usually, since the adhesive is dissolved in an organic solvent, there are problems of environmental pollution and fire hazard due to the volatile solvent generated in the drying process. In order to solve such a problem, an efficient manufacturing method of a laminate without using an adhesive has been studied.

As a method for improving the adhesion between the cyclic olefin-based addition polymer resin and the adherend, Patent Document 1 discloses that a polymer molded product obtained by a reaction injection molding method (RIM molding method) is subjected to steam treatment, Next, a painting method for painting is disclosed.

Further, Patent Document 2 discloses that a cyclic olefin-based addition polymer resin obtained by the RIM molding method or a cyclic olefin-based addition polymer molded product and another adherend are bonded with an adhesive. There has been proposed a method of treating the surface of an addition polymer molded product in advance with an organic solvent containing at least one of a ketone solvent having 4 or more carbon atoms or a carboxylic acid ester solvent having 2 or more carbon atoms. Further, Patent Document 3 proposes a surface treatment method for a cyclic olefin polymer molded product obtained by reaction injection molding.

  However, as a result of the study by the present inventors, when the cyclic olefin-based addition polymer resin molded article and the adherend are bonded, a method using a steam treatment or a method using a solvent treatment with a ketone, an ester or the like is sufficient. Adhesiveness was not expressed. Moreover, in the resin molding obtained by patent document 3, the duration of the process effect was very short.

  For this reason, sufficient adhesive performance can be efficiently expressed over a long period of time on the cyclic olefin addition polymer resin molded article and the adherend without using an adhesive, and without performing steam treatment or organic solvent treatment. Moreover, the appearance of a resin molded product obtained from a cyclic olefin-based addition polymer resin with high productivity and a laminate obtained therefrom is desired.

As a result of intensive studies in view of such circumstances, the present inventor has made a resin molded body comprising a specific cyclic olefin addition polymer resin having a glass transition temperature as high as 230 to 450 ° C. and subjected to oxidation treatment on the surface. However, it has been found that it has excellent adhesiveness, is suitable for films and sheets for optical applications, and can maintain good adhesiveness for a long period of time, and has completed the present invention.
JP-A-8-103723 JP 11-71554 A JP 2004-269742 A

The present invention is obtained from a cyclic olefin-based addition polymer resin, and provides sufficient adhesion performance over a long period of time on a cyclic olefin-based addition polymer resin molded article and an adherend without steam treatment or organic solvent treatment. It is an object of the present invention to provide a resin molded article that is well expressed and excellent in productivity, a laminate of the resin molded article and an adherend, and a method for producing the laminate.

  The resin molded body of the present invention comprises a polymer having a structural unit represented by the following general formula (1), a glass transition temperature in the range of 230 to 450 ° C., and at least a part of the surface is subjected to an oxidation treatment. It is characterized by being given.

(In Formula (1), A < ¹ > -A < ⁴ > is respectively independently a hydrogen atom, a halogen atom, a C1-C10 alkyl group, a C5-C15 cycloalkyl group, and a C6-C20 aryl. Group, C1-C10 alkoxy group, C3-C15 hydrolyzable silyl group, C3-C15 oxetanyl group, C1-C15 N-substituted imide group, Carbon number of alkoxy group Represents an atom or a substituent selected from the group consisting of an alkoxycarbonyl group, a trialkylsiloxycarbonyl group, a dialkylaluminoxycarbonyl group, a carbonate group, and a glycidyl group, wherein these substituents have 1 to 10 carbon atoms. the alkylene group may be bonded to the ring together, bonded to each other a ¹ and a ^2, alicyclic structure, aromatic cyclic structure, the cyclic acid anhydride group, cyclic Lee Alicyclic structure, cyclic aromatic structure of de group or may form an alkylidene group having 1 to 15 carbon atoms, A ¹ and A ³ with 1 to 15 carbon atoms in the carbon atoms bonded thereto, A cyclic acid anhydride group or a cyclic imide group may be formed, and m represents an integer of 0 or 1.)
In the resin molded body of the present invention, the glass transition temperature of the polymer is preferably in the range of 250 to 400 ° C.

  In the resin molded body of the present invention, the oxidation treatment is preferably at least one method selected from the group consisting of corona treatment, beam treatment, flame treatment, plasma treatment and ozone treatment, and the oxidation treatment is corona treatment or plasma treatment. More preferably.

The laminate of the present invention is characterized by having the resin molded body of the present invention in at least one layer.
The manufacturing method of the laminated body of this invention has the process of shape | molding the polymer which has a structural unit represented by the said General formula (1), and has a glass transition temperature in the range of 230-450 degreeC, and the obtained shaping | molding It comprises a step of subjecting at least a part of the surface of the body to an oxidation treatment and a step of adhering at least a part of the part subjected to the oxidation treatment to an adherend.

Moreover, the manufacturing method of the laminated body of this invention has the process of shape | molding the polymer which has a structural unit represented by the said General formula (1), and has a glass transition temperature in the range of 230-450 degreeC, and obtained. A step of subjecting at least a part of the surface of the molded body to an oxidation treatment, and a step of laminating a layer selected from a metal, a metal oxide, and a metal nitride on at least a portion of the portion subjected to the oxidation treatment. It is a feature.

  The resin molded body of the present invention is excellent in transparency and heat resistance, has excellent adhesion to an adherend, and can maintain excellent adhesion for a long period of time. Use of an adhesive or formation of an adhesive layer A laminated body suitably bonded can be formed without carrying out the process. In addition, the laminate according to the present invention can be manufactured without using an adhesive or the like by using the resin molded body of the present invention, can maintain an excellent adhesive effect for a long period of time, and is unlikely to be peeled off. Excellent. Such a resin molded body and laminate according to the present invention can be suitably used for electronic material applications such as various optical films and circuit boards.

Hereinafter, the present invention will be specifically described.
<Polymer>
The resin molded body according to the present invention comprises a polymer having a cyclic olefin-based structural unit represented by the following general formula (1), a glass transition temperature as high as 230 to 450 ° C., and an oxidation treatment on the surface. Is given.

  The polymer which comprises the resin molding of this invention has a structural unit represented by following General formula (1).

(In Formula (1), A < ¹ > -A < ⁴ > is respectively independently a hydrogen atom, a halogen atom, a C1-C10 alkyl group, a C5-C15 cycloalkyl group, and a C6-C20 aryl. Group, C1-C10 alkoxy group, C3-C15 hydrolyzable silyl group, C3-C15 oxetanyl group, C1-C15 N-substituted imide group, Carbon number of alkoxy group Represents an atom or a substituent selected from the group consisting of an alkoxycarbonyl group, a trialkylsiloxycarbonyl group, a dialkylaluminoxycarbonyl group, a carbonate group, and a glycidyl group, wherein these substituents have 1 to 10 carbon atoms. the alkylene group may be bonded to the ring together, bonded to each other a ¹ and a ^2, alicyclic structure, aromatic cyclic structure, the cyclic acid anhydride group, cyclic Lee Alicyclic structure, cyclic aromatic structure of de group or may form an alkylidene group having 1 to 15 carbon atoms, A ¹ and A ³ with 1 to 15 carbon atoms in the carbon atoms bonded thereto, A cyclic acid anhydride group or a cyclic imide group may be formed, and m represents an integer of 0 or 1.)
The polymer constituting the resin molded body of the present invention requires a cyclic olefin monomer represented by the following general formula (1 ′) (hereinafter also referred to as a specific monomer (1)). Depending on the case, it can be prepared by addition (co) polymerization with other monomers.

(In formula (1 ′), A ^{1 to} A ⁴ and m are the same as in formula (1).)
Although it does not specifically limit as such a specific monomer (1), For example, the following compounds can be mentioned as a specific example.
Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-propylbicyclo [2.2.1] hept-2-ene,
5-butylbicyclo [2.2.1] hept-2-ene,
5-t-butylbicyclo [2.2.1] hept-2-ene,
5-isobutylbicyclo [2.2.1] hept-2-ene,
5-butyl-6-methylbicyclo [2.2.1] hept-2-ene,
5-pentylbicyclo [2.2.1] hept-2-ene,
5-hexylbicyclo [2.2.1] hept-2-ene,
5-heptylbicyclo [2.2.1] hept-2-ene,
5-octylbicyclo [2.2.1] hept-2-ene,
5-decylbicyclo [2.2.1] hept-2-ene,
5-dodecylbicyclo [2.2.1] hept-2-ene,
5,6-dimethyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-ethyl-bicyclo [2.2.1] hept-2-ene,
5-phenyl-bicyclo [2.2.1] hept-2-ene,
5-cyclohexyl-bicyclo [2.2.1] hept-2-ene,
5-cyclooctyl-bicyclo [2.2.1] hept-2-ene,
Tricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
3-methyltricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
4-methyltricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
5-methyltricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
Tricyclo [4.2.1.0 ^2,5 ] non-7-ene,
3-methyltricyclo [4.2.1.0 ^2,5 ] non-7-ene,
Tricyclo [6.2.1.0 ^2,7 ] undec-9-ene,
Tricyclo [8.2.1.0 ^2,9 ] tridec-11-ene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene.

In addition, the polymer constituting the resin molded body according to the present invention is obtained by adding a cyclic diolefin compound capable of forming the structural unit (1) described above by hydrogenating an olefinically unsaturated bond after addition polymerization. It can also be prepared by using as a monomer. Examples of such cyclic diolefin compounds include the following.
5-vinyl-bicyclo [2.2.1] hept-2-ene,
5- (1-butenyl) -bicyclo [2.2.1] hept-2-ene,
5-vinylidene-bicyclo [2.2.1] hept-2-ene,
Tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene,
Tricyclo [6.2.1.0 ^2,7 ] undeca-3,9-diene,
Tricyclo [6.2.1.0 ^2,7 ] undeca-4,9-diene,
Tricyclo [6.2.1.0 ^2,7 ] undeca-4,8-diene,
Tricyclo [8.2.1.0 ^2,9 ] trideca-7,11-diene,
Tricyclo [8.2.1.0 ^2,9 ] trideca-6,11-diene,
Tricyclo [8.2.1.0 ^2,9 ] trideca-5,11-diene.

Furthermore, examples of the specific monomer (1) include cyclic olefin compounds having a functional group such as an ester group, an acid anhydride group, a carbonimide group, and a hydrolyzable silyl group. When such a specific monomer is used, it is possible to improve the solubility of additives and the like or to introduce a cross-linked site in the resulting copolymer. Although the specific monomer (1) which has such a functional group is not specifically limited, It is preferable that it is a ratio of 10 mol% or less with respect to 100 mol% of all the monomers. Specific examples of such a cyclic olefin compound are not particularly limited, and examples thereof include the following compounds.
Methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Methyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Ethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Ethyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
T-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
T-butyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Tetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7} ] methyl dodeca-9-ene-4-carboxylate,
Tetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7]} dodeca-9-ene-4-carboxylic acid ethyl,
4-methyltetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7} ] methyl dodeca-9-ene-4-carboxylate,
4-ethyltetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7} ] methyl dodeca-9-ene-4-carboxylate,
4-methyltetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7]} dodeca-9-ene-4-carboxylic acid ethyl,
Tetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7]} dodeca-9-ene-4-carboxylic acid propyl,
Tetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7]} dodeca-9-ene-4,5-dicarboxylic acid dimethyl,
Tetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7]} dodeca-9-ene-4-carboxylate-5-carboxylic acid t- butyl,
Bicyclo [2.2.1] hept-5-ene-2,3-N-cyclohexylcarbonimide,
Tetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7]} dodeca-9-ene -4,5-N-cyclohexyl carboxylic imide,
Tetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7]} dodeca-9-ene -4,5-N-ethylcarbonimidoyl,
Bicyclo [2.2.1] hept-5-ene-2,2-N-cyclohexylsuccinimide,
Tetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7]} dodeca-9-ene -4,4-N-cyclohexyl-succinimide,
Tetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7]} dodeca-9-ene-4,5-dicarboxylic anhydride,
5-trimethoxysilylbicyclo [2.2.1] hept-2-ene,
5-triethoxysilylbicyclo [2.2.1] hept-2-ene,
5-chlorodiethoxysilylbicyclo [2.2.1] hept-2-ene,
4-trimethoxysilyltetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7} ] dodeca-9-ene,
4-triethoxysilyltetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7} ] dodeca-9-ene,
5-methyldimethoxysilylbicyclo [2.2.1] hept-2-ene,
4-methyldiethoxysilyltetracyclo [6.2.1.1 ^{3, 6} . 0 ^{2, 7} ] dodeca-9-ene,
5-chloro-6-butylbicyclo [2.2.1] hept-2-ene,
5-fluoro-6-butylbicyclo [2.2.1] hept-2-ene 5-fluorobicyclo [2.2.1] hept-2-ene,
5-chloro-bicyclo [2.2.1] hept-2-ene,
5-methoxy-bicyclo [2.2.1] hept-2-ene,
5-ethoxy-bicyclo [2.2.1] hept-2-ene,
N-phenyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,
5,6-di (methoxycarbonyl) -bicyclo [2.2.1] hept-2-ene,
5-methoxychloromethylsilyl-bicyclo [2.2.1] hept-2-ene,
5-dimethoxychlorosilyl-bicyclo [2.2.1] hept-2-ene,
5-methoxyhydridomethylsilyl-bicyclo [2.2.1] hept-2-ene,
5-dimethoxyhydridosilyl-bicyclo [2.2.1] hept-2-ene,
5-methoxydimethylsilyl-bicyclo [2.2.1] hept-2-ene,
5-ethoxychloromethylsilyl-bicyclo [2.2.1] hept-2-ene,
5-diethoxyhydridosilyl-bicyclo [2.2.1] hept-2-ene,
5-ethoxydimethylsilyl-bicyclo [2.2.1] hept-2-ene,
5-ethoxydiethylsilyl-bicyclo [2.2.1] hept-2-ene,
5-propoxydimethylsilyl-bicyclo [2.2.1] hept-2-ene,
5-tripropoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-triphenoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-trimethoxysilylmethyl-bicyclo [2.2.1] hept-2-ene,
5-dimethylchlorosilyl-bicyclo [2.2.1] hept-2-ene,
5-methyldichlorosilyl-bicyclo [2.2.1] hept-2-ene,
5-trichlorosilyl-bicyclo [2.2.1] hept-2-ene,
5-diethylchlorosilyl-bicyclo [2.2.1] hept-2-ene,
5-ethyldichlorosilyl-bicyclo [2.2.1] hept-2-ene,
5- (2-trimethoxysilyl) ethyl-bicyclo [2.2.1] hept-2-ene,
5- (2-dimethoxychlorosilyl) ethyl-bicyclo [2.2.1] hept-2-ene,
5- (1-trimethoxysilyl) ethyl-bicyclo [2.2.1] hept-2-ene,
5- (2-trimethoxysilyl) propyl-bicyclo [2.2.1] hept-2-ene, 5- (1-trimethoxysilyl) propyl-bicyclo [2.2.1] hept-2-ene, 5-triethoxysilylethyl-bicyclo [2.2.1] hept-2-ene,
5-dimethoxymethylsilylmethyl-bicyclo [2.2.1] hept-2-ene,
5-trimethoxypropylsilyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5- (3-triethoxysilyl) propoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
8-methyldimethoxysilyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-En,
5- [1′-methyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-Methyl-3 ′, 3 ′, 4 ′, 4′-tetraphenyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2- En,
5- [1′-Methyl-3 ′, 3 ′, 4 ′, 4′-tetramethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2- En,
5- [1′-phenyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-ethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
5- [1 ′, 3′-dimethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-3 ′, 4′-dimethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-ethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1 ′, 3′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4 ′, 4′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4 ′, 4′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] methyl-bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4 ′, 4′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] ethyl-bicyclo [2.2.1] hept-2-ene,
5- [1′-phenyl-4 ′, 4′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4′-phenyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4′-spiro-cyclohexyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4′-ethyl-4′-butyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-3 ′, 3′-dimethyl-5′methylene-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-phenyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-3′-phenyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4 ′, 4′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -7-oxa-bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -7-oxa-bicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-2 ′, 7′-dioxa-1′-silacycloheptyl] -bicyclo [2.2.1] hept-2-ene,
8- [1′-Methyl-4 ′, 4′-dimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8- [1′-Methyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene.

  These specific monomers (1) may be used alone or in combination of two or more. Moreover, when the ratio of the specific monomer (1) having a functional group selected from an ester group, an acid anhydride group, a carboximide group, and a hydrolyzable silyl group exceeds 10 mol% in all monomers, it is obtained. The water-absorbing property of the molded resin molded from the copolymer may be increased, the mechanical strength may be impaired, and the polymerization activity in the addition polymerization reaction may be greatly reduced.

Among these specific monomers (1), preferred are
Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-butylbicyclo [2.2.1] hept-2-ene,
5-hexylbicyclo [2.2.1] hept-2-ene,
5-trimethoxysilylbicyclo [2.2.1] hept-2-ene,
5-triethoxysilylbicyclo [2.2.1] hept-2-ene,
Tricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
Tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene,
Such as tricyclo [6.2.1.0 ^2,7 ] undec-9-ene, and more preferably
Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-butylbicyclo [2.2.1] hept-2-ene,
5-hexylbicyclo [2.2.1] hept-2-ene,
Tricyclo [5.2.1.0 ^2,6 ] dec-8-ene.

Further, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene containing at least 80% of endo isomer,
Tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene,
Tricyclo [6.2.1.0 ^2,7 ] undec-9-ene,
It is preferable to use a resin containing 10 mol% or more of the structural units derived from the above in all the structural units because a resin product with high toughness can be obtained.

In the polymer constituting the resin molded body according to the present invention, A ^{1 to} A ⁴ in the general formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 6 to 6 carbon atoms. When the proportion of the structural unit (1) which is an atom or group selected from 20 aryl groups is 70 mol% or more, preferably 90 mol% or more in all the structural units, the water absorption (wet) property is lowered. preferable.

In addition to the structural unit (1), the polymer constituting the resin molded body according to the present invention is a ring-opening polymerization and hydrogenation of a structural unit derived from an α-olefin compound or a conjugated diene compound, or a cyclic olefin compound. It may contain other structural units such as a structural unit obtained in this way.

  Specific examples of the α-olefin compound include ethylene, propylene, 1-butene, 1-hexene, 1-octene, trimethylsilylethylene, triethylsilylethylene, styrene, and the like, preferably ethylene.

  Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, cyclopentadiene, 1,3-cyclohexadiene, and preferably 1,3-cyclohexadiene, cyclohexane. Pentadiene.

These compounds can be used alone or in combination of two or more.
By introducing a structural unit derived from an α-olefin compound, the glass transition temperature of the polymer constituting the resin molded body according to the present invention can be controlled.

  The proportion of other structural units contained in the polymer constituting the resin molded body according to the present invention is usually 0 to 15 mol%, preferably 0 to 10 mol%, in all the structural units of the resin. In addition, when the ratio of other structural units exceeds 15 mol%, the glass transition temperature of the polymer is lowered to 230 ° C. or lower, which is not preferable because the heat resistance may be lowered.

  The molecular weight of the polymer constituting the resin molding according to the present invention is, in terms of polystyrene, usually a number average molecular weight of 10,000 to 300,000 and a weight average molecular weight of 20,000 to 700,000, preferably a number average. The molecular weight is 20,000 to 200,000, the weight average molecular weight is 50,000 to 500,000, more preferably the number average molecular weight is 50,000 to 150,000, and the weight average molecular weight is 100,000 to 300,000. . When the number average molecular weight is less than 10,000 and the weight average molecular weight is less than 20,000, the resin molded article may be inferior in toughness and easily cracked. On the other hand, when the number average molecular weight exceeds 300,000 and the weight average molecular weight exceeds 700,000, the solution viscosity increases, and the workability of molding and the surface smoothness of the molded article may deteriorate.

Moreover, the glass transition temperature of the polymer which comprises the resin molding which concerns on this invention is 230-450 degreeC, Preferably it is 250-400 degreeC. When the glass transition temperature of the polymer is less than 230 ° C., the heat resistance may be insufficient. On the other hand, when it exceeds 450 ° C., the resulting resin molded body may not be tough and may be easily broken.
<Molding>
The shape of the resin molded body of the present invention is not particularly limited, and may be any desired shape, but is preferably a shape that can be used for optical purposes such as a film shape, a sheet shape, a plate shape, and a lens shape. A film shape, a sheet shape and the like are more preferable.

  The method for molding the polymer according to the present invention may be appropriately selected depending on the desired shape, and is not particularly limited, and examples thereof include a solution casting method, a melt extrusion method, and a mold molding method. For example, in the case of forming into a film shape, the cyclic olefin polymer is used and is produced by a known method such as a melt extrusion method, an inflation method, or a solution casting method. The resin used in the present invention has a glass transition temperature. Is very high, and those produced by the solution casting method are preferred.

As a general process of the solution casting method, first, a polymer solution and a solvent, and optionally a resin solution containing additives and compounding agents such as an antioxidant or a leveling agent (hereinafter referred to as “casting composition”) are also used. After that, the casting composition is cast on a support such as a metal belt, metal drum or plastic film and dried, and then the support is peeled off and further dried as necessary. Although a process can be illustrated, this invention is not limited to this illustration. The casting method (coating method for forming a film) of the casting composition is not particularly limited, and application using a brush or brush, spraying by spraying, screen printing method, flow coating method, die coater A known method such as a coating method using a coater such as a spin coat method or a dipping method can be applied. In the course of drying, the surface may be molded with a mold or the like as necessary.
<Oxidation treatment>
The resin molded body of the present invention is subjected to an oxidation treatment on at least a part of the surface, and the method for producing a laminate of the present invention includes a step of performing an oxidation treatment on at least a part of the surface of the molded body.

The surface oxidation treatment method is not particularly limited, and examples thereof include corona treatment, plasma treatment, beam treatment, flame treatment, and ozone treatment. Among these, in order to obtain better adhesion without deteriorating the mechanical properties of the resin in the present invention, corona treatment or plasma treatment is preferably used. Corona treatment is preferred because it is faster, cheaper and easier to apply to in-line industrial processes than to vacuum and vacuum processes. A “corona” discharge is a discharge that occurs at substantially atmospheric pressure and occurs under vacuum characterized by a strong diffuse glow in the space between the anode and cathode, sometimes referred to as a “glow” discharge It is a discharge that should be distinguished from a discharge that does. In a preferred embodiment of the present invention, the intensity of corona discharge is 10 to 1,000 w · min / m ² , more preferably 30 to 500.
The range is w · min / m ² . In the present invention, a corona treatment apparatus manufactured by Kasuga Electric Co., Ltd. was used.

Plasma treatment is performed using plasma (also referred to as non-equilibrium plasma) generated in a region where the electron temperature is high but the gas temperature is low, and ions such as active species, electrons, radicals, vacuum ultraviolet rays, etc. are generated in the plasma. This is a technology that activates the surface by acting on the surface of the substrate and performing surface modification such as etching, implantation, and radical generation. The plasma treatment according to the present invention is preferably performed under normal pressure or a pressure condition close thereto, for example, under a pressure of 0.1 to 1.1 kg / cm ² , the temperature during the discharge treatment is usually 10 to 80 ° C. , Preferably, it can carry out in the temperature range of about 25-60 degreeC. The gas used for such plasma treatment is not particularly limited, but is inert gas such as He, Ar, Ne, Kr, Xe, Rn, carbon oxide gas such as CO ₂ , CO, O ₂ , etc. An oxidizing gas such as CF _4, a reactive gas such as CF ₄ , a polymerizable unsaturated compound gas such as ethylene and propylene, and air. These are appropriately selected according to the purpose and used alone or in combination. In the present invention, a plasma surface treatment apparatus manufactured by Shinko Seiki Co., Ltd. was used.

  In the plasma treatment, a functional group such as a hydroxyl group, an amino group, a carbonyl group, or a carboxyl group on the surface of a substrate made of a norbornene resin can be introduced. By introducing these groups, preferably a hydroxyl group or an amino group, onto the substrate surface, the wettability of the substrate surface is improved and the adhesion is improved. In particular, the introduction of a hydroxyl group to the surface of a substrate made of norbornene resin significantly improves the adhesion between the substrate surface and the urethane adhesive, and also improves the wettability. Improved.

  In the plasma treatment, in order to introduce a hydroxyl group on the surface of a substrate made of a norbornene-based resin, it is preferable to perform a plasma treatment in an atmosphere containing water vapor or water, oxygen, etc., and in order to introduce an amino group, ammonia or The plasma treatment is preferably performed in an atmosphere containing nitrogen or further water vapor or hydrogen.

The surface oxidation treatment may be performed on the entire surface of the molded body, or may be performed on a part of the molded body, but when the resin molded body and the adherend are bonded, the surface oxidation treatment is performed on the portion that contacts the bonding surface. Is desirable.
<Laminate>
The laminate of the present invention is a laminate of the above-described resin molded body according to the present invention and an adherend. The laminate of the present invention may have only one layer of the resin molded body according to the present invention or may have a plurality of layers. In this invention, the adhesiveness outstanding between both can be provided by giving an oxidation process to the surface of the adhesion | attachment site | part with the to-be-adhered body in the resin molding which comprises a laminated body.

  The adherend may be made of the same resin as the above-described resin molded body according to the present invention, may be made of other materials, and is not limited, but includes various resins. Any of them can be used. For example, urethane resin, acrylic resin, epoxy resin, silicone resin and the like can be suitably used. Further, a layer selected from metals, metal oxides, and metal nitrides may be laminated as the adherend. Specific examples include metal thin films such as aluminum, copper, and gold, metal oxides such as indium / tin oxide, silicon dioxide, titanium oxide, and niobium oxide, and metal nitrides such as silicon nitride. Is not to be done.

  The lamination of the resin molded body and the adherend according to the present invention is preferably performed without interposing an adhesive or an adhesive layer between the resin molded body and the adherend, and usually the laminate of the present invention. The resin molded body and the adherend are directly laminated without using an adhesive or an adhesive layer. Such a laminate according to the present invention has no problem due to solvent evaporation of the adhesive, can be produced economically and efficiently, and has an advantage that optical properties are not deteriorated by the adhesive layer in optical applications.

The method of adhering and laminating the resin molded body and the adherend is not particularly limited depending on the shape of the resin molded body and the adherend and the material of the adherend, but the surface is oxidized. A method for forming an adherend on a resin molded body subjected to oxidization, a method for pressure bonding or thermocompression bonding of a molded resin body with an oxidation treatment on the surface and a molded adherend, and a resin with an oxidation treatment on the surface Examples of the method include a method of laminating on the molded body by a method such as a vacuum deposition method, a sputtering method, an ion plating method, and the like. In the present invention, the step of adhering the resin molded body according to the present invention having an oxidation treatment on the surface and the adherend is formed on the surface portion of the resin molded body subjected to the oxidation treatment. Is preferably performed. Specifically, for example, by casting and drying a solution of a resin as an adherend on the surface portion of the resin molded body that has been subjected to an oxidation treatment, the adherend is molded and the resin molded body and the covered body are covered. A laminated body to which the adherend is bonded can be preferably produced.
<Application>
Since the molded body of the present invention has excellent adhesiveness and ability to retain the adhesiveness, a light diffusion film, an antireflection film, a transparent conductive film, a highly reflective film, a transflective film, an ND filter, a dichroic filter, It can be used in various applications such as electromagnetic shielding films, beam splitters, optical communication filters, optical lens units, protective films, touch panels, and liquid crystal display elements.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

The glass transition temperature, contact angle (with purified water), and adhesion (cross-cut test) of the sample used in this example were measured by the following methods.
(1) Glass transition temperature Using Leo Vibron DDV-01FP (Orientec), with a measurement frequency of 10 Hz, a heating rate of 4 ° C./min, an excitation mode of a single waveform, and an excitation amplitude of 2.5 μm The peak temperature of Tan δ (= E ″ / E ′) derived from the storage elastic modulus (E ′) and loss elastic modulus (E ″) determined was defined as the glass transition temperature of the copolymer.
(2) Contact angle The contact angle between the sample and purified water was measured using an automatic contact angle meter CA-V type (manufactured by Kyowa Interface Science Co., Ltd., attached to ZR-21 for dynamic contact angle system). In this case, the contact angle is an angle within the purified water at a position where the free surface of the purified water is in contact with the sample surface, and the angle formed by these contact points. An improvement in the contact angle with purified water over time means that the sample surface is hydrophobized, indicating that the adhesion to other materials is reduced. The measurement was performed under conditions of a temperature of 23 ° C. and a relative humidity (50 ± 5)%. Purified water was used that complies with the 13th revised Japanese Pharmacopoeia standards.
(3) Adhesiveness (cross-cut test)
In the adhesion test in the present invention, the adhesion with a 25 μm-thick urethane resin (Yokohama Rubber JKS-100) layer was examined. 1 cross section of 1 mm ^{2 on} the urethane resin laminate surface
After putting 00 pieces, applying scotch tape and press-bonding, it peeled in the direction of 90 degrees, and the number of remaining urethane resin layers was measured.

Reference Example 1 (Synthesis of cyclic olefin addition polymer)
A 100 ml glass pressure-resistant reaction vessel was charged with 22 g of dehydrated toluene and 22 g of cyclohexane, and then 50 mmol (7.5 g) of 5-butylbicyclo [2.2.1] hept-2-ene obtained in the synthesis example, 5.48 ml of a dry toluene solution of 7.66 mol / l bicyclo [2.2.1] hept-2-ene (42 mmol) was added. The reaction vessel was sealed with a rubber seal, ethylene pressure was added as a molecular weight regulator to 0.1 MPa, and then the temperature was raised to 75 ° C. Then, 0.405 ml of 0.0005 mol / l palladium acetate in toluene, 0.10 ml of 0.002 mol / l tricyclohexylphosphine / triethylaluminum complex in toluene, 0.0005 mol / l triphenylcarbenium tetrakis Polymerization was started by adding 0.40 ml of a toluene solution of (pentafluorophenyl) borate. When 45 minutes and 90 minutes had elapsed after the start of polymerization, 0.52 ml of each of the above bicyclo [2.2.1] hept-2-ene in toluene was added, and the polymerization was continued for a total of 3 hours. The conversion ratio of all monomers to the polymer was 99.5%. The obtained copolymer solution is poured into about 1 L of isopropyl alcohol to be solidified and dried under vacuum at 80 ° C. for 17 hours to obtain a cyclic olefin addition copolymer A (hereinafter also referred to as “copolymer A”). It was. The content of 5-butylbicyclo [2.2.1] hept-2-ene in copolymer A was 50 mol%, the number average molecular weight was 48,000, and the weight average molecular weight was 199,000.

  As an antioxidant, 0.5 part by weight of pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate and tris (2,4- 0.5 parts by weight of di-t-butylphenyl phosphite was dissolved in a mixed solvent consisting of 280 parts by weight of cyclohexane and 70 parts by weight of toluene, and this solution was cast at 25 ° C. until the residual solvent was about 12%. The solvent was gradually evaporated and then kept at 200 ° C. for 90 minutes to obtain a film A having a thickness of 100 μm, and the glass transition temperature of the copolymer A measured using the film A was 260 ° C.

Reference Example 2 (Synthesis 2 of cyclic olefin addition polymer)
In a 100 ml glass pressure bottle under nitrogen atmosphere, 20 ml of toluene with 20 ppm water, 30 ml of cyclohexane, and as a monomer, bicyclo [2.2.1] hept-2-ene, 55 mmol, 4-methyltetracyclo [6. 2.1.1 ^3,6 . ^0,7 ] methyl dodec-9-ene-4-carboxylate 20 mmol, catalyst component (a) 0.002 mmol tricyclohexyl palladium bis (2-ethylhexanoate), catalyst component (b) Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate and 0.002 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were charged and sealed with a rubber cap with a crown. Furthermore, 20 ml of gaseous 0.1 MPa ethylene was charged through a rubber cap of a pressure bottle. Polymerization is started by heating the pressure bottle to 60 ° C., and 5 mmol of bicyclo [2.2.1] hept-2-ene is added 5 times every 30 minutes, and the addition polymerization reaction is carried out for 3 hours. And copolymer B was obtained. In the copolymer B thus obtained, 4-methyltetracyclo [6.2.1.1 ^3,6 . The proportion of structural units derived from methyl 0 ^2,7 ] dodeca-9-ene-4-carboxylate was 15 mol%.

  As an antioxidant, 0.5 part by weight of pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate and tris (2,4- 0.5 part by weight of di-t-butylphenyl phosphite was dissolved in a mixed solvent consisting of 350 parts by weight of toluene, this solution was cast at 25 ° C., and the solvent was gradually evaporated until the residual solvent was about 10%. Subsequently, the film was held at 200 ° C. for 90 minutes to obtain a film B having a thickness of 100 μm, and the glass transition temperature of the copolymer B measured using the film B was 285 ° C.

Reference Example 3 (Synthesis of cyclic olefin ring-opening polymer)
In a 300 ml glass pressure-resistant bottle, in a nitrogen atmosphere, 80 ml of toluene as a solvent, 4-methyltetracyclo [6.2.1.1 ^3,6 . ^0,7 ] methyl dodeca-9-ene-4-carboxylate, 165 mmol, bicyclo [2.2.1] hept-2-ene, 5 mmol, molecular weight regulator 12.5-hexene, 42.5 mmol, Further, 0.119 mmol of triethylaluminum as a catalyst component and methanol-modified tungsten hexachloride [methanol / tungsten = 3 (mol / mol)] were added in the order of 0.017 mmol. Polymerization was performed at 80 ° C. for 2 hours, and the polymerization was stopped with methanol. The conversion rate of the monomer to the ring-opening polymer was 97%. To the polymerization reaction solution, 660 ml of water and 47.5 mmol of lactic acid were added and stirred, and then allowed to stand and separate. The aqueous phase containing the reaction product of the catalyst component is removed, and the unreacted monomer is removed by adding the polymerization reaction solution to 3 liters of isopropanol to solidify the ring-opened polymer. It dried and the ring-opening polymer C was obtained. From the 270 MHz ¹ H-NMR spectrum of ring-opening polymer C in benzene-d ₆ , 4-methyltetracyclo [6.2.1.
1 ^3,6 . The content of structural units derived from methyl 0 ^2,7 ] dodec-9-ene-4-carboxylate was determined to be 98 mol% (3.2 to 3.6 ppm absorption based on the methoxycarbonyl group; (Calculated from the ratio of 5.4 to 5.8 ppm absorption based on hydrogen adjacent to the heavy bond).

In a 500 milliliter stainless steel pressure-resistant reactor, a solution obtained by dissolving 15 grams of the ring-opened polymer C obtained above in 200 grams of toluene, carbonylchlorohydridotris (triphenylphosphine) ruthenium [RuHCl (CO) (PPh ₃ ) ₃ ] was added in an amount of 70 ppm in terms of ruthenium atoms, and a hydrogenation reaction was performed at 140 ° C. for 4 hours at a hydrogen pressure of 10 MPa. The resulting hydrogenated ring-opening polymer solution was detouched with an aqueous lactic acid solution and then coagulated with isopropyl alcohol to obtain hydrogenated ring-opening polymer CH. ^The hydrogenation rate determined from ¹ H-NMR measurement was 99.7%. (The hydrogenation rate is 3.2 to 3.6 ppm based on the methoxycarbonyl group and 5.4 to 5.8 ppm based on hydrogen adjacent to the double bond of the ring-opened polymer remaining unhydrogenated. The number average molecular weight (Mn) in terms of polystyrene of the ring-opening polymer CH is 19,000, the weight average molecular weight (Mw) is 75,000, and Mw / Mn is 3.7. Met.

As an antioxidant, 0.5 part by weight of pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate and tris (2,4- 0.5 part by weight of di-t-butylphenyl phosphite was dissolved in a mixed solvent consisting of 380 parts by weight of toluene, this solution was cast at 25 ° C., and the solvent was gradually evaporated until the residual solvent was about 10%. Subsequently, the film was held at 120 ° C. for 120 minutes to obtain a film C having a thickness of 103 μm, and the glass transition temperature of the copolymer CH measured using the film C was 165 ° C.

Reference Example 4 (Synthesis of cyclic olefin addition polymer)
To a 100 ml glass pressure-resistant reaction vessel, 57 g of dehydrated toluene was charged, and then 73 mmol (11.0 g), 0.0069 mol of 5-butylbicyclo [2.2.1] hept-2-ene obtained in the synthesis example was obtained. 11.6 ml of a dry toluene solution of / l bicyclo [2.2.1] hept-2-ene (80.3 mmol) was added. The reaction vessel was sealed with a rubber seal, ethylene pressure was added as a molecular weight regulator to 0.23 MPa, and the temperature was raised to 60 ° C. Subsequently, 0.072 ml of a toluene solution of 0.0047 mol / l palladium acetate, 0.037 ml of a toluene solution of 0.0092 mol / l tricyclohexylphosphine, and 0.002 mol / l triphenylcarbenium tetrakis (pentafluorophenyl) ) 0.17 ml of a borate solution in toluene was added to initiate polymerization. When 45 minutes and 90 minutes had passed after the start of polymerization, 1.1 ml of the above bicyclo [2.2.1] hept-2-ene in toluene was added, and the polymerization was continued for a total of 3 hours. The conversion ratio of all monomers to the polymer was 99.5%. The obtained copolymer solution is poured into about 1 L of isopropyl alcohol to be solidified and dried under vacuum at 80 ° C. for 17 hours to obtain a cyclic olefin addition copolymer D (hereinafter also referred to as “copolymer D”). It was. The content of 5-butylbicyclo [2.2.1] hept-2-ene in copolymer D was 56.6 mol%, the number average molecular weight was 37,000, and the weight average molecular weight was 167,000.

  As an antioxidant, 0.5 part by weight of pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)] propionate and tris (2,4- 0.5 part by weight of di-t-butylphenyl phosphite was dissolved in a mixed solvent consisting of 280 parts by weight of cyclohexane and 70 parts by weight of toluene, and this solution was cast at 25 ° C. until the residual solvent was about 12%. The solvent was gradually evaporated and then kept at 200 ° C. for 90 minutes to obtain a film D having a thickness of 100 μm, and the glass transition temperature of the copolymer D measured using the film D was 260 ° C.

Film A was subjected to a corona treatment having a strength of 50 W · min / m ² . The change with time of the contact angle of the film 1 was examined. In addition, a urethane resin (JKS-100, manufactured by Yokohama Rubber Co., Ltd.) was applied to a part of the film 1 after the corona treatment to a thickness of 25 μm and cured, and then adhesion was confirmed by a cross-cut test. These results are shown in Table 1. Film 1 showed a small increase in contact angle even after 50 days, and showed good adhesion even in a cross-cut test.

Measurement was performed in the same manner as in Example 1 except that the film 2 was subjected to a corona treatment having an intensity of 300 W · min / m ² to produce the film 2. The results are shown in Table 1. Film 2 showed a small increase in contact angle even after 50 days, and showed good adhesion even in a cross-cut test.

Measurement was performed in the same manner as in Example 1 except that the film B was subjected to corona treatment with an intensity of 30 W · min / m ² to produce the film 3. The results are shown in Table 1. In the film 3, the increase in the contact angle was small even after 50 days, and good adhesion was shown in the cross cut test.

The measurement was performed in the same manner as in Example 3 except that the film 4 was subjected to corona treatment having an intensity of 500 W · min / m ² to prepare the film 4. The results are shown in Table 1. Film 4 showed a small increase in contact angle even after 50 days, and showed good adhesion even in a cross-cut test.

The change with time of the contact angle of the film 5 prepared by subjecting the film D to plasma treatment was examined. For the plasma treatment, oxygen gas was used, the pressure was set to 20 Pa, the gas flow rate was set to 100 mL / min in a reduced pressure atmosphere, and the treatment was performed at an intensity of 200 W for 30 seconds. Further, urethane resin (Yokohama Rubber JKS-100) was applied to a part of the film 5 after the plasma treatment to a thickness of 25 μm and cured, and then the adhesion was confirmed by a cross-cut test. These results are shown in Table 1. In the film 5, the contact angle with pure water was greatly reduced, and good adhesiveness was shown in the cross-cut test.

  Measurement was performed in the same manner as in Example 5 except that argon was used as the gas used in the plasma treatment. The results are shown in Table 1. This film 6 had a significantly reduced pure water contact angle and showed good adhesion in a cross-cut test.

Comparative Example 1
The film 7 obtained in the same manner as in Example 1 except that the corona and the plasma treatment were not performed was measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
Measurement was performed in the same manner as in Example 1 except that the film C was subjected to corona treatment with an intensity of 30 W · min / m ² to produce the film 8. The results are shown in Table 1. Film 8 showed good adhesion in a cross-cut test immediately after corona treatment, but the contact angle after 50 days had greatly increased.

Comparative Example 3
The measurement was performed in the same manner as in Example 1 except that the film C was subjected to corona treatment with an intensity of 200 W · min / m ² to produce the film 9. The results are shown in Table 1. As in Comparative Example 2, film 9 also showed good adhesion in the cross cut test immediately after the corona treatment, but the contact angle after 50 days had greatly increased.

Comparative Example 4
Measurement was carried out in the same manner as in Example 1 except that a film 10 was prepared by applying a corona treatment having a strength of 200 W · min / m ² using a triacetyl cellulose film (Fujitack manufactured by Fuji Photo Film Co., Ltd.). . The results are shown in Table 1. Similarly to Comparative Example 2, film 10 also showed good adhesion in the cross-cut test immediately after the corona treatment, but the contact angle after 50 days had returned to the same as before the treatment.

Claims (8)

It has a structural unit represented by the following general formula (1), consists of a polymer having a glass transition temperature in the range of 230 to 450 ° C., and is characterized in that at least a part of the surface is subjected to an oxidation treatment. Resin moldings to be

(In Formula (1), A < ¹ > -A < ⁴ > is respectively independently a hydrogen atom, a halogen atom, a C1-C10 alkyl group, a C5-C15 cycloalkyl group, and a C6-C20 aryl. Group, C1-C10 alkoxy group, C3-C15 hydrolyzable silyl group, C3-C15 oxetanyl group, C1-C15 N-substituted imide group, Carbon number of alkoxy group Represents an atom or a substituent selected from the group consisting of an alkoxycarbonyl group, a trialkylsiloxycarbonyl group, a dialkylaluminoxycarbonyl group, a carbonate group, and a glycidyl group, wherein these substituents have 1 to 10 carbon atoms. the alkylene group may be bonded to the ring together, bonded to each other a ¹ and a ^2, alicyclic structure, aromatic cyclic structure, the cyclic acid anhydride group, cyclic Lee Alicyclic structure, cyclic aromatic structure of de group or may form an alkylidene group having 1 to 15 carbon atoms, A ¹ and A ³ with 1 to 15 carbon atoms in the carbon atoms bonded thereto, A cyclic acid anhydride group or a cyclic imide group may be formed, and m represents an integer of 0 or 1.) 2. The resin molded product according to claim 1, wherein the polymer has a glass transition temperature in the range of 250 to 400 ° C.   The resin molding according to claim 1 or 2, wherein the oxidation treatment is at least one method selected from the group consisting of corona treatment, beam treatment, flame treatment, plasma treatment and ozone treatment.   The resin molding according to any one of claims 1 to 3, wherein the oxidation treatment is corona treatment.   The resin molding according to claim 1, wherein the oxidation treatment is a plasma treatment.   A laminate comprising at least one layer of the resin molded body according to claim 1. A step of molding a polymer having a structural unit represented by the following general formula (1) and having a glass transition temperature in the range of 230 to 450 ° C., and at least part of the surface of the obtained molded body is oxidized And a method for producing a laminate, comprising: a step of applying an oxidation treatment; and a step of adhering at least a part of the site subjected to the oxidation treatment to an adherend;

(In Formula (1), A < ¹ > -A < ⁴ > is respectively independently a hydrogen atom, a halogen atom, a C1-C10 alkyl group, a C5-C15 cycloalkyl group, and a C6-C20 aryl. Group, C1-C10 alkoxy group, C3-C15 hydrolyzable silyl group, C3-C15 oxetanyl group, C1-C15 N-substituted imide group, Carbon number of alkoxy group Represents an atom or a substituent selected from the group consisting of an alkoxycarbonyl group, a trialkylsiloxycarbonyl group, a dialkylaluminoxycarbonyl group, a carbonate group, and a glycidyl group, wherein these substituents have 1 to 10 carbon atoms. the alkylene group may be bonded to the ring together, bonded to each other a ¹ and a ^2, alicyclic structure, aromatic cyclic structure, the cyclic acid anhydride group, cyclic Lee Alicyclic structure, cyclic aromatic structure of de group or may form an alkylidene group having 1 to 15 carbon atoms, A ¹ and A ³ with 1 to 15 carbon atoms in the carbon atoms bonded thereto, A cyclic acid anhydride group or a cyclic imide group may be formed, and m represents an integer of 0 or 1.)   A step of molding a polymer having the structural unit represented by the general formula (1) and having a glass transition temperature in the range of 230 to 450 ° C., and at least part of the surface of the obtained molded body is oxidized And a step of laminating a layer selected from a metal, a metal oxide, and a metal nitride on at least a part of the site subjected to the oxidation treatment.