JP2005103949A - Laminate and method for producing laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which can control the occurrence of a curl, can obtain high adhesive properties in a heat resistant resin layer and a metal thin layer, and is excellent in heat resistance and mechanical strength and to provide a method for producing the laminate in high productivity. <P>SOLUTION: In the laminate, the heat resistant layer made of a cyclic olefin polymer having specific structural units and the metal thin layer are laminated. The method for producing the laminate has a process in which a polymer solution containing the cyclic olefin polymer having specific structural units is applied on metal foil, and the obtained coating film is dried. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminate and a method for producing the laminate widely used for electronic material applications, and more particularly to a laminate and a method for producing the laminate suitably used as a flexible printed wiring board.

As a substrate for flexible printed wiring, a laminate in which a resin layer made of a resin such as polyimide and a metal thin layer made of a metal such as copper are laminated is used.
As a method for manufacturing a flexible printed wiring board made of such a laminate, a method of laminating a resin film made of polyimide or the like to a metal foil made of copper or the like by a heat laminating process or an adhesive, a metal made of copper or the like A technique is adopted in which a precursor solution of a resin such as polyimide is applied to the foil and dried.

  In the flexible printed wiring board obtained by such a manufacturing method, in the manufacturing process, due to the difference in the thermal behavior of the material constituting the board, curling (warping), resin layer and thin metal layer, In the meantime, peeling or the like occurs, which causes a problem that it is difficult to pattern the wiring circuit.

Conventionally, by using only one kind of resin as the material constituting the resin layer, curling is suppressed during the production process, and high adhesion is obtained between the resin layer and the metal thin layer, and also excellent heat resistance. In addition, it has been difficult to produce a flexible printed wiring board having mechanical strength.
Thus, a technique for smoothing the curled substrate by heat treatment (see, for example, Patent Document 1), a first resin constituent layer made of a high linear expansion resin on a copper foil, and low linear expansion A technique for suppressing the occurrence of curling by forming the second resin component layer made of resin in this order by controlling the thickness of each resin component layer (for example, Patent Document 2) For example).

  However, when a flexible printed wiring board is manufactured using such a technique, a post-treatment for smoothing is required each time in the process of heating the flexible printed wiring board material. Moreover, since the number of processes increases, there is a problem that high productivity cannot be obtained.

  In addition, in a flexible printed wiring board having a resin layer made of polyimide, there is a problem that curling tends to occur because the water absorption of the resin layer is extremely high.

JP-A-56-23791 JP-A-8-250860

The present invention has been made based on the circumstances as described above, and the object thereof is to suppress the occurrence of curling and to obtain high adhesiveness between the heat-resistant resin layer and the metal thin layer. Another object of the present invention is to provide a laminate having excellent heat resistance and mechanical strength.
Another object of the present invention is to suppress the occurrence of curling and to obtain high adhesion to the heat-resistant resin layer and the metal thin layer, and to increase the laminate having excellent heat resistance and strength. It is to provide a method that can be manufactured with productivity.

  The laminate of the present invention is characterized in that a heat resistant resin layer made of a cyclic olefin polymer having a structural unit represented by the following general formula (1) and a metal thin layer are laminated.

[Wherein, A ¹ , A ² , A ³ and A ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, a halogenated hydrocarbon group, and , A hydrolyzable silyl group, or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group or an arylene group, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an acid. A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _P —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ each independently represents a carbon atom having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an oxetanyl group, and p is an integer of 0 to 5. ]

In the laminate of the present invention, the cyclic olefin polymer includes a structural unit in which at least one of A ¹ , A ² , A ³ and A ⁴ is a hydrolyzable silyl group in the general formula (1). ,
The hydrolyzable silyl group is a group represented by the following general formula (2).

[Wherein Y is an alkoxy group having 1 to 10 carbon atoms, an allyloxy group having 1 to 10 carbon atoms, a halogen atom, or an aliphatic diol having 1 to 10 carbon atoms bonded to each other to form a 5- to 7-membered ring. Represents a group derived from an alicyclic diol or an aromatic diol, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. r is an integer of 0 to 5, and s is an integer of 1 to 3. ]

  In such a laminate, the cyclic olefin polymer is such that the content ratio of the structural unit having a hydrolyzable silyl group represented by the general formula (2) is the total content of the cyclic olefin polymer. It is preferable that it is 0.2-30 mol% with respect to a structural unit.

  The laminate of the present invention is characterized in that a heat-resistant resin layer composed of a crosslinked product of a cyclic olefin polymer having a structural unit represented by the following general formula (1) and a metal thin layer are laminated. .

[Wherein, A ¹ , A ² , A ³ and A ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, a halogenated hydrocarbon group, and , A hydrolyzable silyl group, or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group or an arylene group, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an acid. A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _P —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ each independently represents a carbon atom having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an oxetanyl group, and p is an integer of 0 to 5. ]

In the laminate of the present invention, the cyclic olefin polymer includes a structural unit in which at least one of A ¹ , A ² , A ³ and A ⁴ is a hydrolyzable silyl group in the general formula (1). ,
The hydrolyzable silyl group is preferably a group represented by the following general formula (2).

[Wherein Y is an alkoxy group having 1 to 10 carbon atoms, an allyloxy group having 1 to 10 carbon atoms, a halogen atom, or an aliphatic diol having 1 to 10 carbon atoms bonded to each other to form a 5- to 7-membered ring. Represents a group derived from an alicyclic diol or an aromatic diol, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. r is an integer of 0 to 5, and s is an integer of 1 to 3. ]

  In the laminate of the present invention, the cyclic olefin polymer is such that the content ratio of the structural unit having a hydrolyzable silyl group represented by the general formula (2) constitutes the cyclic olefin polymer. It is preferable that it is 0.2-30 mol% with respect to a structural unit.

  In the laminated body of this invention, it is preferable that a metal thin layer consists of copper foil.

  The laminate of the present invention is preferably used as a flexible printed wiring board.

  The manufacturing method of the laminated body of this invention apply | coats the polymer solution containing the cyclic olefin type polymer which has a structural unit represented by following General formula (1) on metal foil, and dries the obtained coating film. It has the process to make it feature.

[Wherein, A ¹ , A ² , A ³ and A ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, a halogenated hydrocarbon group, and , A hydrolyzable silyl group, or a polar group represented by — (CH ₂ ) _p —X. Further, the A ¹ and A ^4, integrated alkylene group may form a cycloalkylene group or an arylene group, further, A ¹ and A ² or A ³ and A ⁴ are bonded to each other acid A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _P —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ each independently represents a carbon atom having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an oxetanyl group, and p is an integer of 0 to 5. ]

  The manufacturing method of the laminated body of this invention has the process of sticking the heat resistant resin sheet which consists of a cyclic olefin polymer which has a structural unit represented by following General formula (1), and metal foil. .

[Wherein, A ¹ , A ² , A ³ and A ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, a halogenated hydrocarbon group, and , A hydrolyzable silyl group, or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group or an arylene group, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an acid. A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _P —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ each independently represents a carbon atom having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an oxetanyl group, and p is an integer of 0 to 5. ]

In the method for producing a laminate according to the present invention, the cyclic olefin polymer has a structure in which at least one of A ¹ , A ² , A ³ and A ⁴ is a hydrolyzable silyl group in the general formula (1). Including units,
The hydrolyzable silyl group is preferably a group represented by the following general formula (2).

[Wherein Y is an alkoxy group having 1 to 10 carbon atoms, an allyloxy group having 1 to 10 carbon atoms, a halogen atom, or an aliphatic diol having 1 to 10 carbon atoms bonded to each other to form a 5- to 7-membered ring. Represents a group derived from an alicyclic diol or an aromatic diol, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. r is an integer of 0 to 5, and s is an integer of 1 to 3. ]

  In the manufacturing method of the laminated body of this invention, the said cyclic olefin type polymer has a content rate of the structural unit which has a hydrolyzable silyl group represented by the said General formula (2), The said cyclic olefin type polymer. It is preferable that it is 0.2-30 mol% with respect to all the structural units to comprise.

  In the manufacturing method of the laminated body of this invention, it is preferable that a metal thin layer consists of copper foil.

Since the laminate of the present invention has a heat-resistant resin layer made of a specific cyclic olefin-based polymer or a heat-resistant resin made of a crosslinked product of the specific cyclic olefin-based polymer, in the production process and at the time of use In addition, curling can be suppressed and high adhesiveness can be obtained between the heat-resistant resin layer and the metal thin layer, and excellent heat resistance and mechanical strength can be obtained.
Therefore, the laminate of the present invention can be suitably used as a flexible printed wiring board.

  According to the method for producing a laminate of the present invention, a specific resin material is used as the heat-resistant resin constituting the heat-resistant resin layer, whereby the heat-resistant resin layer in the obtained laminate is constituted by a kind of resin. Even without post-treatment for smoothing, high adhesion is obtained between the heat-resistant resin layer and the metal thin layer, and a laminate having excellent heat resistance and mechanical strength is produced with high productivity. be able to.

Hereinafter, embodiments of the present invention will be described in detail.
The laminate of the present invention (hereinafter also referred to as “specific laminate”) is a laminate in which a heat-resistant resin layer and a thin metal layer are integrally laminated. ) Or (b).

(A) Cyclic olefin polymer having a structural unit represented by the general formula (1) (hereinafter also referred to as “specific structural unit”) (hereinafter also referred to as “specific cyclic olefin polymer”). ) And a thin metal layer (hereinafter, also referred to as “first laminated body”).
(B) A laminate (hereinafter referred to as “second”) in which a heat-resistant resin layer composed of a crosslinked product of a specific cyclic olefin polymer (hereinafter also referred to as “specific crosslinked product”) and a metal thin layer are laminated. Also referred to as a laminate of

<First laminate>
The first laminate is formed by integrally laminating a heat-resistant resin layer made of a first heat-resistant resin made of a specific cyclic olefin-based polymer and a thin metal layer, and has the same configuration. It is preferable that the above specific structural units are continuously arranged.

  In the first laminate, the thickness of the heat resistant resin layer is preferably 5 to 150 μm, and the thickness of the metal thin layer is preferably 2 to 100 μm.

  The specific cyclic olefin polymer constituting the heat-resistant resin layer in the first laminate has at least one specific structural unit. The specific cyclic olefin-based polymer preferably has a portion in which at least two or more specific structural units having the same configuration are continuously arranged.

In general formula (1) representing a specific structural unit, A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or cycloalkyl. Group, a halogenated hydrocarbon group, a hydrolyzable silyl group, or a polar group represented by — (CH ₂ ) _p —X (hereinafter also referred to as “specific polar group”).
Here, in — (CH ₂ ) _P —X representing the specific polar group, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ each independently represents the number of carbon atoms. It represents a substituent containing 1 to 10 hydrocarbon groups, halogenated hydrocarbon groups, or oxetanyl groups, and p is an integer of 0 to 5.

A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group, or an arylene group. Further, A ¹ and A ² or A ¹ and A ⁴ may be bonded to each other to form a group derived from an acid anhydride, lactone or imide.
m is 0 or 1.

When the specific cyclic olefin polymer has two or more specific structural units, all the specific monomers constituting the specific cyclic olefin polymer have the same configuration. However, by using a plurality of types of monomers, A ¹ , A ² , A ³ , A ⁴ and m in each specific structural unit may be partially or entirely different. Good.

The specific cyclic olefin-based polymer preferably contains a specific structural unit in which at least one of A ¹ , A ² , A ³ and A ^{4 in} the general formula (1) is a hydrolyzable silyl group.
Since the specific cyclic olefin-based polymer has a specific structural unit containing a hydrolyzable silyl group, the solubility in hydrocarbon solvents such as toluene and cyclohexane is increased. Preparation of a polymer solution containing a specific cyclic olefin polymer used for forming a heat resistant resin layer in the laminate (hereinafter also referred to as “first polymer solution for forming a heat resistant resin layer”) is easy. It becomes.

The hydrolyzable silyl group is preferably a group represented by the general formula (2) (hereinafter also referred to as “specific hydrolyzable silyl group”).
In the general formula (2), the group Y is an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 1 to 10 carbon atoms, a halogen atom, or a 1 to 10 carbon atoms that are bonded to each other to form a 5- to 7-membered ring. A group derived from an aliphatic diol, alicyclic diol or aromatic diol is shown, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
r is an integer of 0 to 5, and s is an integer of 1 to 3.

In the specific cyclic olefin polymer, the content ratio of the specific structural unit containing the specific hydrolyzable silyl group (hereinafter also referred to as “specific silyl group-containing structural unit”) is determined by the specific cyclic olefin polymer. It is preferable that it is 0.2-30 mol% with respect to all the structural units which comprise this, Especially preferably, it is 0.5-20 mol%.
When the content ratio of the specific silyl group-containing structural unit is less than 0.2 mol%, the solubility of the specific cyclic olefin polymer in the organic solvent is reduced, and the first polymer solution for forming a heat resistant resin layer is obtained. Depending on the manufacturing method used, it may be difficult to form the heat resistant resin layer, and the solvent resistance, chemical resistance and mechanical strength of the heat resistant resin layer in the obtained first laminate are reduced, and the heat resistance is further reduced. There is a possibility that the adhesiveness of the resin layer to the thin metal layer may be reduced.
On the other hand, when the content ratio of the specific silyl group-containing structural unit exceeds 30 mol%, the water resistance of the heat-resistant resin layer in the obtained first laminate is increased, resulting in the first laminate. There is a risk of curling.

  The specific structural unit constituting the specific cyclic olefin polymer is formed by a monomer represented by the following general formula (3) (hereinafter also referred to as “specific monomer”).

[Wherein A ¹ , A ² , A ³ and A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group, or a halogenated hydrocarbon. Group and a hydrolyzable silyl group or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group or an arylene group, and A ¹ and A ² are integrated to form an alkylidene group. Furthermore, A ¹ and A ² or A ¹ and A ⁴ may be bonded to each other to form a group derived from an acid anhydride, lactone, or imide. m is 0 or 1.
Here, in — (CH ₂ ) _P —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ each independently represents a carbon atom having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an oxetanyl group, and p is an integer of 0 to 5. ]

As a specific example of such a specific monomer,
Bicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-propylbicyclobicyclo [2.2.1] hept-2-ene,
5-butylbicyclo [2.2.1] hept-2-ene,
5-hexylbicyclo [2.2.1] hept-2-ene,
5-decylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-ethyl-bicyclo [2.2.1] hept-2-ene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-chlorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,6-dimethylbicyclo [2.2.1] hept-2-ene,
5-phenylbicyclo [2.2.1] hept-2-ene,
5-cyclohexylbicyclo [2.2.1] hept-2-ene,
5-cyclooctylbicyclo [2.2.1] hept-2-ene,
5-indanylbicyclo [2.2.1] hept-2-ene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene,
9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-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,
Tricyclo [6.2.1.0 ^2,7 ] undec-9-ene,
Tricyclo [8.2.1.0 ^2,9 ] tridec-11-ene,
Tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene,
Tricyclo [6.2.1.0 ^2,7 ] undeca-3,9-diene,
Tricyclo [8.2.1.0 ^2,9 ] trideca-5,11-diene,

5-trimethoxysilylbicyclo [2.2.1] hept-2-ene,
5-triethoxysilylbicyclo [2.2.1] hept-2-ene,
5-methyldimethoxysilylbicyclo [2.2.1] hept-2-ene,
5-methyldiethoxysilylbicyclo [2.2.1] hept-2-ene,
5-methyldichlorosilylbicyclo [2.2.1] hept-2-ene,
5-dimethylmethoxysilylbicyclo [2.2.1] hept-2-ene,
5-dimethylethoxysilylbicyclo [2.2.1] hept-2-ene,
5-dimethylchlorosilylbicyclo [2.2.1] hept-2-ene,
4-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene,
4-methyldimethoxysilyltetracyclo [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- [1′-methyl-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 ′, 3 ′, 4′-trimethyl-2 ′, 5′-dioxa-1′-silacyclopentyl] bicyclo [2.2.1] hept-2-ene,
5- [1 ′, 3 ′, 3 ′, 4 ′, 4′-pentamethyl-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 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] bicyclo [2.2.1] hept-2-ene,
5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] methylbicyclo [2.2.1] hept-2-ene,
5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] ethylbicyclo [2.2.1] hept-2-ene,
5- [1′-methyl-4′-phenyl-2 ′, 6′-dioxa-1′-silacyclohexyl] bicyclo [2.2.1] hept-2-ene,
5- [3′-methyl-2 ′, 4′-dioxa-3′-silaspiro [5.5] undecyl] 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-2 ′, 7′-dioxa-1′-silacycloheptyl] bicyclo [2.2.1] hept-2-ene,
4- [1′-Methyl-2 ′, 6′-dioxa-1′-silacyclohexyl] tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene,
4- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene,

Methyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Ethyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
T-butyl bicyclo [2.2.1] hept-5-ene-2-carboxylate,
Methyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Ethyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
T-butyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Trifluoromethyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Trifluoroethyl 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylate,
Dimethyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate,
Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylate,
2-methylbicyclo [2.2.1] hept-5-en-2-ethyl acetate,
8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

Bicyclo [2.2.1] hept-5-en-2-yl acrylate,
Bicyclo methacrylate [2.2.1] hept-5-en-2-yl,
Bicyclo [2.2.1] hept-5-en-2-ylmethyl acrylate,
Bicyclo methacrylate [2.2.1] hept-5-en-2-ylmethyl,

2-[(3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene,
2-[(3-ethyl-3-oxetanyl) methoxy] bicyclo [2.2.1] hept-5-ene,
2-[(3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-5-ene,
2-[(3-ethyl-3-oxetanyl) methoxymethyl] bicyclo [2.2.1] hept-5-ene,
4-[(3-Methyl-3-oxetanyl) methoxymethyl] tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene,
Bicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-oxetanyl) methyl,
And cyclic olefins such as 2-methylbicyclo [2.2.1] hept-5-ene-2-carboxylic acid (3-ethyl-3-oxetanyl) methyl.
These can be used alone or in combination of two or more.

Specific monomers for forming a specific structural unit include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and tricyclo [5. 2.1.0 ^2,6 ] dec-8-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . It is preferable to use one or more cyclic olefins selected from 1 ^7,10 ] dodec-3-ene.
By using such a cyclic olefin as the specific monomer, a cyclic olefin polymer having a sufficiently high glass transition temperature and a low linear expansion coefficient can be obtained.

Specific monomers for forming the specific silyl group-containing structural unit include 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene and 5-triethoxysilylbicyclo [2.2. 1] Hept-2-ene, 5-methyldimethoxysilylbicyclo [2.2.1] hept-2-ene, 5-methyldiethoxysilylbicyclo [2.2.1] hept-2-ene, 4-tri Methoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 5- [1′-methyl-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 ′, 4 ′, 4′-trimethyl-2 ′, 6'-dioxa-1'-silacyclohexyl] bicyclo [2.2.1] hept-2-ene is preferably used, and in particular, 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene. 5-triethoxysilylbicyclo [2.2.1] hept-2-ene, 5-methyldimethoxysilylbicyclo [2.2.1] hept-2-ene, 4-trimethoxysilyltetracyclo [6.2 1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 5- [1 ′, 4 ′, 4′-trimethyl-2 ′, 6′-dioxa-1′-silacyclohexyl] bicyclo [2.2.1] hepta-2 It is preferable to use one or more cyclic olefins selected from -enes.

  In the specific cyclic olefin polymer, the glass transition temperature is appropriately selected by appropriately selecting the type of the specific structural unit constituting the specific cyclic olefin polymer and the content ratio of the specific structural unit in all the structural units. In addition, physical properties such as linear expansion coefficient, solubility in organic solvents, and the like can be controlled.

  Specifically, for example, a specific cyclic olefin polymer having a specific structural unit derived from a cyclic olefin having a chain alkyl group such as 5-hexylbicyclo [2.2.1] hept-2-ene, While the solubility with respect to an organic solvent becomes high, the obtained heat-resistant resin layer will have a softness | flexibility, and also control of the glass transition temperature will become easy.

In addition, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, tricyclo [6.2.1.0 ^2,7 ] undec-9-ene, tricyclo [5.2.1.0 ^{2 , 6} ] The specific cyclic olefin-based polymer having a plurality of types of specific structural units derived from cyclic olefins such as deca-3,8-diene has excellent toughness in the heat-resistant resin layer in the specific laminate obtained. It has flexibility.
Furthermore, the specific cyclic olefin polymer having a specific structural unit containing a specific polar group is such that the heat-resistant resin layer has excellent adhesion to the metal thin layer in the specific laminate obtained.

The specific cyclic olefin polymer may contain a structural unit other than the specific structural unit (hereinafter also referred to as “other structural unit”).
Specific examples of other structural units include structural units derived from α-olefins such as ethylene, structural units derived from monocyclic olefins such as cyclohexene, and structural units derived from (meth) acrylic acid esters. .
The content ratio of such other structural units is preferably 20 mol% or less in all the structural units.

The specific cyclic olefin-based polymer has a glass transition temperature in the range of usually 150 to 450 ° C, preferably 300 to 400 ° C.
When the glass transition temperature is less than 150 ° C., there is a possibility that problems such as thermal deformation of the heat-resistant resin layer in the specific laminate obtained may occur. On the other hand, when the glass transition temperature exceeds 450 ° C., the specific cyclic olefin-based polymer becomes rigid, so that the heat-resistant resin layer in the specific laminate obtained is easily broken and has low toughness.
Here, the glass transition temperature of a specific cyclic olefin polymer is the temperature distribution of Tan δ (ratio E ″ / E ′ of storage elastic modulus E ′ and loss elastic modulus E ″) obtained by dynamic viscoelasticity measurement. It is determined as the peak temperature value.

The specific cyclic olefin polymer has a polystyrene-reduced number average molecular weight (Mn) of 30,000 to 500, as measured by gel permeation chromatography (GPC) at a temperature of 120 ° C. using o-dichlorobenzene as a solvent. The weight average molecular weight (Mw) in terms of polystyrene is preferably 50,000 to 1,000,000, and more preferably the number average molecular weight (Mn) is 50,000 to 200,000 and the weight. The average molecular weight (Mw) is preferably 100,000 to 500,000.
When the number average molecular weight is less than 30,000 and the weight average molecular weight is less than 50,000, the specific cyclic olefin-based polymer has a low breaking strength and a low elongation at break. There is a possibility that the heat-resistant resin layer in the specific laminate to be easily cracked. On the other hand, when the number average molecular weight exceeds 500,000 and the weight average molecular weight exceeds 1,000,000, the heat resistant resin layer may be formed by a production method using a polymer solution for forming a heat resistant resin layer described later. May be difficult.

The specific cyclic olefin-based polymer has a linear expansion coefficient in the range of 70 ppm / ° C. or less, and preferably 60 ppm / ° C. or less.
When the linear expansion coefficient exceeds 70 ppm / ° C., the heat resistant resin layer in the obtained specific laminate may be deformed due to a dimensional change in a use environment having a large temperature change.

A known antioxidant can be added to the specific cyclic olefin polymer, whereby the oxidation stability of the specific cyclic olefin polymer can be improved.
Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 4,4′-thiobis- (6-t-butyl-3-methylphenol), 1,1′-bis (4 -Hydroxyphenyl) cyclohexane, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,5-di-t-butylhydroquinone, pentaerythrityltetrakis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like phenol compounds or hydroquinone compounds, tris (4-methoxy-3, 5-diphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite Phosphorus compounds such as bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite are used. Of these, compounds having a decomposition temperature (5% weight loss) of 250 ° C. or higher can be preferably used. Such an antioxidant is preferably added at a ratio of 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the specific cyclic olefin polymer.

  The specific cyclic olefin polymer as described above can be produced by addition polymerization of a monomer and hydrogenation as necessary.

In the addition polymerization treatment, a monomer, a solvent having a mass ratio of 1 to 20 with respect to the monomer, and a molecular weight regulator as necessary are charged in a reaction vessel in a nitrogen or argon atmosphere. After the system is set to a temperature range of -20 to 100 ° C, a polymerization catalyst is further added to carry out the polymerization reaction of the monomer at a polymerization temperature of -20 to 100 ° C.
The molecular weight of the specific cyclic olefin polymer to be obtained can be adjusted by controlling the amount of polymerization catalyst and molecular weight regulator used for the polymerization reaction, the conversion rate of the monomer to the polymer and the polymerization temperature. it can.

Solvents include cycloaliphatic hydrocarbon solvents such as cyclohexane, cyclopentane and methylcyclopentane, aliphatic hydrocarbon solvents such as hexane, heptane and octane, aromatic hydrocarbon solvents such as toluene, benzene, xylene and mesitylene, chloro Halogenated hydrocarbon solvents such as methane, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chloroform, carbon tetrachloride, chlorocyclopentane, chlorocyclohexane, chlorobenzene, dichlorobenzene, ethyl acetate, nitromethane, N -Polar solvents such as methylpyrrolidone, pyridine, dimethylformamide, and acetamide can be used.
These can be used alone or in combination of two or more.

  Examples of molecular weight regulators include α-olefins such as ethylene, 1-hexene and 1-octene, styrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 3,5-dimethylstyrene, and 1-vinylnaltalene. , Aromatic vinyl compounds such as divinylbenzene, cyclic non-conjugated polyenes such as cyclooctadiene and cyclododecatriene, diphenyldisydrosilane, hydrogen and the like, and α-olefins or aromatic vinyl compounds are preferably used.

  As the polymerization catalyst, for example, the following catalysts (1) to (3) can be used.

(1) A nickel-based multicomponent catalyst comprising a nickel compound, a compound selected from super strong acids, Lewis acids and ionic boron compounds, and an organoaluminum compound. (2) Sigma bond connecting at least one nickel-carbon. A nickel-based single-component catalyst comprising a nickel complex having a super strong acid anion as a counter anion (3) a palladium compound, a phosphine compound and / or a phosphonium compound, an ionic boron compound, and, if necessary, an organoaluminum compound Alternatively, a palladium-based multicomponent catalyst containing an organolithium compound

  As a polymerization terminator for the polymerization reaction, water, alcohol, organic acid, carbon dioxide gas or the like can be used.

  The polymer contained in the reaction solution obtained by the above addition polymerization treatment is poured into a poor solvent such as methanol, ethanol, isopropanol, acetone after removing the catalyst residue by a known method. As a result, unreacted monomers remaining in the solution can be removed, the polymer can be solidified, and the obtained solidified product can be recovered by drying under reduced pressure. Moreover, if the reaction solution obtained by the addition polymerization treatment does not impair the performance of the first sealing material to be obtained, the heat treatment such as a film forming process can be performed without removing the catalyst residue or coagulating. It can be used in a process for forming a resin layer.

  As a method for removing the catalyst residue, for example, a water / alcohol mixture of an organic acid such as maleic acid, fumaric acid, oxalic acid, malic acid or the like is added to the reaction solution, and this mixed solution is added to the polymer solution phase and the catalyst residue. For example, a method of removing the aqueous phase by separating it from an aqueous phase containing the above, an adsorption removal method using an adsorbent such as diatomaceous earth, alumina, or silica, a filtration separation method using a filter, or the like can be used.

As a specific monomer for obtaining a specific cyclic olefin-based polymer, tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene or 5-ethylidenebicyclo [2.2.1] hepta When a specific monomer having an unsaturated bond that does not participate in polymerization, such as 2-ene (hereinafter also referred to as “specific unsaturated bond-containing monomer”), is used. The polymer obtained by subjecting the monomer to addition polymerization treatment needs to be further subjected to hydrogenation treatment, whereby specific structural units derived from the specific unsaturated bond-containing monomer are formed.
In addition, when the polymer obtained by the addition polymerization treatment contains an unsaturated bond, the polymer is likely to be oxidized under high temperature conditions and easily deteriorated by heat. It is preferable to perform a hydrogenation treatment so as to hydrogenate 90 mol% or more, preferably 95 mol% or more, more preferably 99 mol% or more of the unsaturated bonds in the polymer.

  In particular, when a specific olefin polymer having a specific structural unit having an acryloyl group or a methacryloyl group is to be obtained, a monomer containing a specific unsaturated bond is provided for the addition polymerization treatment. Preferably not.

  As the hydrogenation catalyst, a compound such as nickel, rhodium, palladium, platinum, etc., a heterogeneous catalyst supported on a solid such as silica, diatomaceous earth, alumina, activated carbon, etc., a compound such as titanium, nickel, palladium, cobalt, etc. A homogeneous catalyst obtained by combining an organometallic compound, a catalyst comprising a complex of ruthenium, osmium, rhodium, iridium, or the like can be preferably used.

  As the solvent, aromatic hydrocarbons such as toluene, xylene, ethylbenzene and tetralin, alicyclic hydrocarbons such as cyclohexane, methylpentane, methylcyclohexane and decalin can be used, and if necessary, hexane, Aliphatic hydrocarbons such as heptane, ethers such as tetrahydrofuran, dimethoxyethane, and butyl ether can also be used.

  The hydrogenation treatment is preferably performed at a hydrogen pressure of 0.5 to 15 MPa and a temperature of 20 to 200 ° C.

  The hydrogenated polymer in the state of being contained in the reaction solution obtained by the hydrogenation treatment as described above is a catalyst residue obtained by a known method in the same manner as the polymer obtained directly by the addition polymerization treatment. After removing the catalyst, the hydrogenated polymer is coagulated by pouring the solution from which the catalyst residue is removed into a poor solvent, and the resulting coagulated product is recovered by drying under reduced pressure.

  Examples of the first heat-resistant resin for forming the heat-resistant resin layer constituting the first laminate include hydrogen of a known cyclic olefin-based ring-opening (co) polymer in addition to a specific cyclic olefin-based polymer. And an addition polymer of cyclic olefin and ethylene may be contained, and the specific heat-resistant resin layer in the obtained heat-resistant resin layer does not impair the toughness derived from the specific cyclic olefin-based polymer. The glass transition temperature of the olefin polymer can be adjusted.

The metal thin layer in the first laminate is preferably made of a metal foil, and examples of the material constituting the metal foil include copper, stainless steel, nickel, aluminum, beryllium-copper alloy, and nickel-copper alloy. And a copper-aluminum composite material.
In the first laminate, the thin metal layer is preferably made of a copper foil.

The first laminate is preferably produced by a method having a step of applying a polymer solution containing a specific cyclic olefin polymer onto a metal foil and drying the obtained coating film.
According to such a technique, specifically, a first heat-resistant resin layer-forming polymer solution in which a specific cyclic olefin-based polymer is dissolved in a solvent is prepared, and the first heat-resistant resin layer-forming polymer is prepared. A polymer solution is applied onto a metal foil, and the resulting coating film is dried, whereby a metal thin layer and a heat-resistant resin layer made of a specific cyclic olefin polymer are integrally laminated. A 1st laminated body can be manufactured easily.

  Solvents for preparing the polymer solution include cycloaliphatic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane, aliphatic hydrocarbon solvents such as hexane, heptane, and octane, toluene, benzene, xylene, mesitylene, etc. Aromatic hydrocarbon solvents, halogenated hydrocarbons such as chloromethane, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chloroform, carbon tetrachloride, chlorocyclopentane, chlorocyclohexane, chlorobenzene, dichlorobenzene, etc. A solvent or the like can be used. These can be used alone or in combination of two or more.

  As a method for applying the polymer solution, for example, a method using a coating device such as a T die, a roll coater, a knife coater, a bar coater, or a spin coater, or a method using a printing method such as screen printing can be used.

  The conditions for the drying treatment of the coating film are appropriately selected depending on the type of solvent used, but when it is carried out under normal pressure, the drying temperature is usually 50 to 280 ° C., and the drying time is usually 10 minutes to 24 hours. is there. The drying treatment may be performed under reduced pressure, or multistage drying such as two-stage drying may be applied by changing the temperature and pressure. For example, it is preferable to pre-dry for several hours under the boiling point of the solvent under normal pressure, and then to perform a drying process under reduced pressure at a drying temperature of 80 to 150 ° C. and a drying time of 1 to 12 hours. Can be reduced.

  In addition, the first laminate is made of, for example, a heat-resistant resin sheet made of a specific cyclic olefin polymer formed by a technique such as a solution casting method or a melt extrusion method, and a metal foil. It can also be manufactured by a method having a step of attaching using a sticker, and can also be manufactured by other methods.

<Second laminate>
The second laminate is formed by integrally laminating a heat resistant resin layer made of a second heat resistant resin made of a crosslinked product of a specific cyclic olefin polymer and a metal thin layer.

  In the second laminate, the thickness of the heat-resistant resin layer is preferably 5 to 200 μm, and the thickness of the metal thin layer is preferably 2 to 100 μm.

The specific crosslinked body constituting the heat-resistant resin layer in the second laminate is formed by obtaining a crosslinkable composition containing a specific cyclic olefin-based polymer and crosslinking the crosslinkable composition. is there.
This specific cross-linked product has excellent characteristics of the specific cyclic olefin polymer constituting the cross-linkable composition for forming the specific cross-linked product, and has a cross-linked structure formed. Therefore, the coefficient of linear expansion is further reduced, and the breaking strength and breaking elongation are increased. Therefore, the heat-resistant resin layer in the obtained second laminate has more excellent heat resistance, machine Strength, solvent resistance, and chemical resistance can be obtained.

  As a crosslinkable composition for obtaining a cross-linked product, a specific cross-linked product can be obtained in a short time under a relatively mild temperature condition in the range of 10 to 280 ° C. Therefore, radical reaction, hydrolysis / condensation reaction Or the composition which can form a crosslinked body by a cation reaction is used suitably.

  Examples of the crosslinkable composition for obtaining a crosslinked product by radical reaction (hereinafter also referred to as “radical crosslinkable composition”) include the following compositions (1) to (2).

(1) A composition obtained by blending a specific cyclic olefin polymer with a peroxide or an azo compound.
Such a composition is crosslinked by radicals generated by the action of heat, actinic rays, and the like.

(2) A composition obtained by blending a specific cyclic olefin polymer with a peroxide and a reducing metal compound.
Such a composition is crosslinked by radicals generated by a redox reaction.

  The radical crosslinkable composition as described above is used when a cyclic olefin polymer having a specific structural unit having a methacryloyl group or an acryloyl group as a side chain substituent is used as the specific cyclic olefin polymer. Can obtain a crosslinked body more easily.

  A crosslinkable composition for obtaining a crosslinked product by hydrolysis / condensation reaction (hereinafter, also referred to as “hydrolyzed crosslinkable composition”), and a crosslinkable composition for obtaining a crosslinked product by cationic reaction (hereinafter, “cation”). As the specific cyclic olefin polymer, the cyclic olefin polymer having a specific silyl group-containing structural unit, or the cyclic olefin system having a specific unit structure having an oxetanyl group, respectively. Examples of the composition include the following (1) to (4) using a polymer (hereinafter also referred to as “specific group-containing cyclic olefin polymer”).

(1) Specific group-containing cyclic olefin-based polymer, metal oxide such as tin, aluminum, zinc, titanium, antimony, alkoxide of the metal, phenoxide of the metal, β-diketonate of the metal, alkyl of the metal A composition comprising a metal compound such as a halide, a halide of the metal, or an organic acid salt of the metal.
(2) An aromatic sulfonium salt having a counter anion selected from BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , B (C ₆ F ₅ ) _4, etc., in the specific group-containing cyclic olefin polymer, the counter anion Having an aromatic ammonium salt having the counter anion, an aromatic phosphonium salt having the counter anion, an aromatic iodonium salt having the counter anion, a hydradium salt having the counter anion, and the counter anion A composition comprising a compound that acts as an acid when heated, such as a ferrocenium salt.
(3) To a specific group-containing cyclic olefin polymer, trialkyl phosphite ester, triaryl phosphite ester, dialkyl phosphite ester, monoalkyl phosphite ester, hypophosphite ester, organic carboxylic acid and Esters with secondary or tertiary alcohols, hemiacetal esters of organic carboxylic acids, trialkylsilyl esters of organic carboxylic acids, monocyclic or polycyclic cycloalkyl esters of alkylsulfonic acids, monocyclic or alkylarylsulfonic acids A composition comprising an ester compound that acts as an acid when heated in the presence of water or water vapor, such as a polycyclic cycloalkyl ester.
(4) Bronsted by irradiating a specific group-containing cyclic olefin polymer with light rays such as g- and h-rays in the visible region, i-rays in the ultraviolet region, ultraviolet rays, far ultraviolet rays, X-rays and electron beams. Diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphonium salts, arsenium salts, oxonium salts and other onium salts that generate acids or Lewis acids, halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogens Halogen-containing organic compounds such as benzophenone compounds, quinonediazide compounds, α, α-bis (sulfonyl) diazomethane compounds, α-carbonyl-α-sulfonyl-diazomethane compounds, sulfonyl compounds, organic acid ester compounds, organic acid amide compounds, organic acids Imide compound Composition obtained by blending a photoacid generator such as.

  Among these hydrolyzable crosslinkable compositions or cationic crosslinkable compositions, the composition (3), specifically, a composition in which an ester compound is blended with a specific cyclic olefin polymer is used as a pot life. Is long and has excellent storage stability, and the formed heat-resistant resin layer made of a crosslinked product is preferably used because it has excellent properties such as dimensional stability, solvent resistance and chemical resistance. In addition, the composition (4), specifically a composition containing a photoacid generator, can be crosslinked under relatively mild conditions, and is excellent in the productivity of a crosslinked product. Therefore, it is preferably used.

In the hydrolyzable crosslinkable composition of the above (1) to (4), the content ratio of the specific silyl group-containing structural unit in the specific cyclic olefin-based polymer having the specific silyl group-containing structural unit is the specific cyclic The content is preferably 0.2 to 30 mol%, particularly preferably 0.5 to 20 mol%, based on all structural units constituting the olefin polymer.
When the content ratio of the specific silyl group-containing structural unit is less than 0.2 mol%, the hydrolyzable crosslinkable composition is not sufficiently crosslinked, and the formed crosslinked product has a large linear expansion coefficient. There is a possibility that the second laminate is likely to curl due to an increase in water absorption of the resulting heat resistant resin layer, and the solvent resistance and chemical resistance of the heat resistant resin layer in the obtained second laminate. There is a risk that the heat resistance resin layer may have low adhesion and mechanical strength, and the adhesiveness of the heat-resistant resin layer to the metal thin layer may be small. Further, it may be difficult to form the heat resistant resin layer by a technique using the second polymer solution for forming a heat resistant resin layer.
On the other hand, when the content ratio of the specific silyl group-containing structural unit exceeds 30 mol%, the formed crosslinked product has a large linear expansion coefficient, and the water absorption of the heat-resistant resin layer in the obtained second laminate is Due to the increase, the second laminated body may be easily curled.

Moreover, in the cationic crosslinkable composition of the above (1) to (4), the content ratio of the specific structural unit having the oxetanyl group in the specific cyclic olefin polymer having the specific structural unit having the oxetanyl group is The content is preferably 0.2 to 30 mol%, particularly preferably 0.5 to 20 mol%, based on all structural units constituting the specific cyclic olefin polymer.
When the content ratio of the specific structural unit having an oxetanyl group is less than 0.2 mol%, the cationic crosslinkable composition is not sufficiently crosslinked, and the formed crosslinked product has a large linear expansion coefficient. There is a possibility that the second laminate is likely to curl due to an increase in water absorption of the resulting heat resistant resin layer, and the solvent resistance and chemical resistance of the heat resistant resin layer in the obtained second laminate. There is a risk that the heat resistance resin layer may have low adhesion and mechanical strength, and the adhesiveness of the heat-resistant resin layer to the metal thin layer may be small. Further, it may be difficult to form the heat resistant resin layer by a technique using the second polymer solution for forming a heat resistant resin layer.
On the other hand, when the content ratio of the specific structural unit having an oxetanyl group exceeds 30 mol%, the formed crosslinked product has a large coefficient of linear expansion, and the water absorption of the heat-resistant resin layer in the obtained second laminate is obtained. There is a risk that curling is likely to occur in the second laminate due to the increase in the thickness.

  In the crosslinkable composition (radical crosslinkable composition and hydrolytic crosslinkable composition) for obtaining a crosslinked product, the content ratio of the composition-forming compound blended in the cyclic olefin polymer is a specific cyclic olefin. It is preferable that it is 0.0001-5.0 mass parts with respect to 100 mass parts of polymer.

  The crosslinkable composition for obtaining a specific crosslinked product includes a alkoxide of a metal selected from titanium, aluminum, and zirconium, or a condensation degree of the metal alkoxide and the alkoxide compound of the metal of 3 to 30. , A silane compound having an alkoxyl group, a silane compound having an allyloxyl group, or a condensate having a condensation degree of 3 to 30 (hereinafter, these are also referred to as “addition compounds”). Accordingly, the heat-resistant resin layer formed of the crosslinked body can be made excellent in dimensional stability, solvent resistance and chemical resistance.

  Specific examples of the additive compound include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, Dicyclohexyldimethoxysilane, cyclopentyltrimethoxysilane, bicyclo [2.2.1] hept-2-yltrimethoxysilane, bicyclo [2.2.1] hept-2-en-5-yltrimethoxysilane, aluminum trimethoxy , Aluminum triethoxide, titanium tetraethoxide, zirconium tetraethoxide, and condensates having a degree of condensation of 3 to 30 thereof.

  The addition ratio of the additive compound in the crosslinkable composition is preferably 5 to 60 parts by mass with respect to 100 parts by mass of the specific cyclic olefin polymer.

  In the crosslinkable composition, oxide particles or colloidal particles such as silica, alumina, zirconia, titania and the like having an average particle size of 100 nm or less (hereinafter also referred to as “added particles”) together with additive compounds. Can be added.

The addition ratio of the additive particles (in terms of solid content in colloidal particles) is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the specific cyclic olefin polymer.
When the addition ratio of the additive particles is less than 1 part by mass, the effect of the additive particles is not sufficiently exerted on the hardness, elastic modulus, and linear expansion coefficient of the formed crosslinked product, while the addition ratio of the additive particles When the amount exceeds 40 parts by mass, the formed heat-resistant resin layer may be brittle.

  Moreover, as a crosslinkable composition for obtaining a crosslinked product, a specific cyclic olefin polymer is blended with a silane compound having a radical polymerizable substituent such as a methacryloyl group or an acryloyl group, and a radical generator. Can be used, and such a composition can be crosslinked by the action of light or heat.

The thin metal layer in the second laminate is preferably made of a metal foil. Examples of the material constituting the metal foil include copper, stainless steel, nickel, aluminum, beryllium-copper alloy, and nickel-copper alloy. And a copper-aluminum composite material.
In the second laminate, the metal thin layer is preferably made of a copper foil.

The second laminate is preferably produced by a technique having a step of applying a polymer solution containing a specific cyclic olefin polymer onto a metal foil and drying the obtained coating film.
According to such a technique, specifically, for forming a second heat-resistant resin layer in which a crosslinkable composition obtained by mixing a composition for forming a composition with a specific cyclic olefin polymer is dissolved in a solvent. A polymer solution was prepared, the second polymer solution for forming a heat-resistant resin layer was applied onto a metal foil, and the resulting coating film was dried. By performing the above, it is possible to easily manufacture a second laminated body having a configuration in which a metal thin layer and a heat-resistant resin layer made of a specific crosslinked body are integrally laminated.

  Solvents for preparing the polymer solution include cycloaliphatic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclopentane, aliphatic hydrocarbon solvents such as hexane, heptane, and octane, toluene, benzene, xylene, mesitylene, etc. Aromatic hydrocarbon solvents, halogenated hydrocarbons such as chloromethane, dichloromethane, 1,2-dichloroethane, 1,1-dichloroethane, tetrachloroethane, chloroform, carbon tetrachloride, chlorocyclopentane, chlorocyclohexane, chlorobenzene, dichlorobenzene, etc. A solvent or the like can be used. These can be used alone or in combination of two or more.

  As a method for applying the polymer solution, for example, a method using a coating device such as a T die, a roll coater, a knife coater, a bar coater, or a spin coater, or a method using a printing method such as screen printing can be used.

  The conditions for the drying treatment of the coating film are appropriately selected depending on the type of solvent used, but when it is carried out under normal pressure, the drying temperature is usually 50 to 280 ° C., and the drying time is usually 10 minutes to 24 hours. is there. The drying treatment may be performed under reduced pressure, or multistage drying such as two-stage drying may be applied by changing the temperature and pressure. For example, it is preferable to pre-dry for several hours under the boiling point of the solvent under normal pressure, and then to perform a drying process under reduced pressure at a drying temperature of 80 to 150 ° C. and a drying time of 1 to 12 hours. Can be reduced.

  In addition, the second laminate is a specific crosslinked body obtained by appropriately performing a crosslinking treatment on a resin sheet made of a crosslinkable composition formed by a technique such as a solution casting method or a melt extrusion method. The heat-resistant resin sheet and the metal foil can be manufactured by a method having a process of attaching using a heat laminating process or an adhesive, for example, and can also be manufactured by other methods.

〔Example〕
Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

  In the following, molecular weight, glass transition temperature, and linear expansion coefficient were measured by the following methods.

(1) Weight average molecular weight and number average molecular weight In a 150C-type gel permeation chromatography (GPC) apparatus manufactured by WATERS, an H-type column manufactured by Tosoh Corporation was used, and the temperature was determined using o-dichlorobenzene as a solvent. The measurement was performed at 120 ° C. The obtained molecular weight is a standard polystyrene equivalent value.
(2) Tan δ peak temperature (glass transition temperature)
The peak temperature of Tan δ of dynamic viscoelasticity (ratio E ″ / E ′ of storage elastic modulus E ′ and loss elastic modulus E ″) was measured as the glass transition temperature of the polymer.
The measurement of dynamic viscoelasticity uses "DDV-01FP" manufactured by Orientec Co., Ltd., the measurement frequency is 10 Hz, the heating rate is 4 ° C./min, the excitation mode is a single waveform, and the excitation amplitude is 2.5 μm. The temperature dispersion peak temperature of the obtained Tan δ was determined as the peak temperature related to the glass transition temperature.
(3) Linear expansion coefficient:
Using a TMA (Thermal Mechanical Analysis) device “SS6100” manufactured by Seiko Instruments Inc., a sample having a thickness of 55 μm, a width of 3 mm, and a length of 10 cm or more is fixed at a distance between chucks of 10 mm. After raising the temperature from room temperature to about 200 ° C. to remove residual strain, the temperature was raised from room temperature at 3 ° C./min, and the linear expansion coefficient was obtained from the elongation of the distance between chucks.

Under a nitrogen atmosphere, a stainless steel reactor having a volume of 2 liters was charged with 700 mmol of bicyclo [2.2.1] hept-2-ene and tricyclo [5.2.1.0 ^2,6 ] deca as specific monomers. 570 mmol of -8-ene (endo isomer / exo isomer = 94/4), 30 mmol of 5-triethoxysilylbicyclo [2.2.1] hept-2-ene, and 5 mmol of 1-hexene as a molecular weight regulator. As a solvent, 400 g of cyclohexane and 100 g of methylene chloride were charged. The system was then charged with 8.0 mmol of methyltriethoxysilane, 0.4 mmol of 1,5-cyclooctadiene, 8.0 mmol of methylalumoxane, and 1.2 mmol of boron trifluoride ethyl etherate. Then, a hexafluoroantimonic acid modified product of nickel octoate was charged in this order, and the polymerization reaction was started.
Here, the hexafluoroantimonic acid modified form of nickel octoate is by-produced by reacting a hexane solution of nickel octoate with hexafluoroantimonic acid at a molar ratio of 1: 1 at a temperature of -10 ° C. The precipitate was obtained by removing the precipitate of bis (hexafluoroantimonate) nickel [Ni (SbF ₆ ) ₂ ] by filtration and diluting with toluene, and the amount added was 0.40 mmol as nickel atoms. Was added as follows.

  Then, an addition polymerization treatment was performed for 3 hours under the condition of a temperature of 30 ° C., and this addition polymerization treatment was stopped by adding methanol. The conversion rate of the monomer subjected to the addition polymerization treatment into a polymer was 92%.

The reaction solution obtained by the addition polymerization treatment was diluted by adding 480 g of cyclohexane, 660 ml of water and 48 mmol of lactic acid were added to the diluted solution, and the mixture was sufficiently stirred. The copolymer solution phase containing the coal and the aqueous phase are allowed to stand still to remove the aqueous phase containing residues such as reactants related to the catalyst, and then the copolymer solution is poured into 4 liters of isopropyl alcohol. The copolymer was coagulated with to remove unreacted monomers and residues.
The obtained solidified product was dried to obtain 75 g of a cyclic olefin polymer (hereinafter also referred to as “copolymer (A)”).
The composition of the copolymer (A) was determined by analyzing the unreacted monomer remaining in the obtained copolymer reaction solution by gas chromatography. As a result, bicyclo [2.2 .1] The content ratio of the specific structural unit derived from hept-2-ene is 63 mol%, and the specific structural unit derived from 5-triethoxysilylbicyclo [2.2.1] hept-2-ene Was 2.1 mol%, and the content of the specific structural unit derived from endo-tricyclo [5.2.1.0 ^2,6 ] dec-8-ene was 35 mol%.
The copolymer (A) had a polystyrene-equivalent number average molecular weight of 89,000, a weight average molecular weight of 187,000, and Mw / Mn was 2.1.

Next, 10 g of the copolymer (A) is dissolved in 35.5 g of cyclohexane, and 0.5 part of tributyl phosphite is added to this system as a crosslinking catalyst with respect to 100 parts of the copolymer (A). As a result, a polymer solution for forming a heat resistant resin layer (hereinafter also referred to as “polymer solution for forming a heat resistant resin layer (A)”) was obtained.
A coating film having a thickness of 0.3 mm is formed by coating the polymer solution (A) for forming a heat resistant resin layer on a glass plate, and the coating film is dried for 2 hours at a temperature of 150 ° C. The polymer film was obtained by further processing and drying under vacuum at a temperature of 200 ° C. for 1 hour. Further, the obtained polymer film was heat-treated under steam at 150 ° C. for 4 hours, and then dried under vacuum at a temperature of 200 ° C. for 1 hour, whereby a crosslinked product having a thickness of 55 μm was formed on the glass plate. A film (hereinafter also referred to as “heat-resistant resin film (A)”) was produced. Thereafter, the heat-resistant resin film (A) was peeled off from the glass plate, and the heat-resistant resin film (A) was observed. As a result, no curling (warping) occurred in the heat-resistant resin film (A).
Moreover, when the characteristic about the obtained heat resistant resin film (A) was confirmed, a moisture absorption is 0.02%, the glass transition temperature of the material which comprises the said heat resistant resin film (A) is 375 degreeC, and linear expansion The coefficient was 50 ppm / ° C.

Further, a heat-resistant resin film (cross-linked 55 μm thick) was formed on the copper foil in the same manner as described above except that the polymer solution (A) for heat-resistant resin layer formation was coated on a copper foil having a thickness of 12 μm. By forming a body film), a laminated body in which a thin metal layer made of copper foil and a heat resistant resin layer made of a heat resistant resin film were laminated was produced.
This laminate does not cause curling or peeling between the heat-resistant resin layer and the metal thin layer in the manufacturing process, does not cause curling even in a high humidity environment, and has excellent heat resistance and mechanical properties. It was confirmed that it has a sufficient strength.

[Comparative Example 1]
A flask equipped with a stirrer, a nitrogen inlet tube and a thermometer was charged with 26.1 g (0.133 mol) of 4,4′-diaminodiphenylmethane and 150.7 g of N, N-dimethylacetamide as a solvent at a temperature of 40 ° C. Under the conditions of 4,4′-diaminodiphenylmethane was completely dissolved in the solvent. Thereafter, this system was once cooled to around room temperature, and 28.6 g (0.131 mol) of pyrometic dianhydride was added while confirming the temperature of the system. At this time, the temperature of the system rose from around room temperature to 55 ° C. Subsequently, after pyrometic acid dianhydride was completely dissolved in this system, the reaction treatment was performed for 6 hours under the condition of a temperature of 60 ° C. After completion of the reaction, the obtained polyamic acid solution was filtered with a filter having a pore size of 5 μm. And filtered under pressure.
The polyamic acid constituting this polyamic acid solution has a ηinh (intrinsic viscosity) of 0.52 dl / g and an E-type mechanical viscosity of 11000 Pa.s. s.
A coating film having a thickness of 0.40 mm is formed by coating this polyamic acid solution on a glass plate, and this coating film is heated from room temperature to 350 in a nitrogen-substituted inert oven at a temperature rising time of 45 minutes. Drying and imidization treatment was performed by heating to ° C. Thereafter, the imidized membrane was cooled to room temperature, and then the polyimide film was peeled off from the glass plate.
The polyimide film peeled off from the glass plate was observed, and the polyimide film was curled remarkably in the direction of the adhesive surface with the glass plate.
Moreover, the characteristic of the obtained polyimide film was confirmed. The results are shown in Table 1.

  The laminate of the present invention is widely used for electronic materials, and can be particularly suitably used as a flexible printed wiring board.

Claims (13)

A laminate comprising a heat resistant resin layer made of a cyclic olefin polymer having a structural unit represented by the following general formula (1) and a metal thin layer.

[Wherein, A ¹ , A ² , A ³ and A ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, a halogenated hydrocarbon group, and , A hydrolyzable silyl group, or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group or an arylene group, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an acid. A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _P —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ each independently represents a carbon atom having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an axetanyl group, and p is an integer of 0 to 5. ] The cyclic olefin-based polymer includes a structural unit in which at least one of A ¹ , A ² , A ³ and A ⁴ is a hydrolyzable silyl group in the general formula (1),
The laminate according to claim 1, wherein the hydrolyzable silyl group is a group represented by the following general formula (2).

[Wherein Y is an alkoxy group having 1 to 10 carbon atoms, an allyloxy group having 1 to 10 carbon atoms, a halogen atom, or an aliphatic diol having 1 to 10 carbon atoms bonded to each other to form a 5- to 7-membered ring. Represents a group derived from an alicyclic diol or an aromatic diol, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. r is an integer of 0 to 5, and s is an integer of 1 to 3. ]   In the cyclic olefin polymer, the content ratio of the structural unit having a hydrolyzable silyl group represented by the general formula (2) is 0.2 relative to the total structural units constituting the cyclic olefin polymer. The laminate according to claim 2, wherein the laminate is ˜30 mol%. A laminate comprising a heat-resistant resin layer made of a crosslinked product of a cyclic olefin polymer having a structural unit represented by the following general formula (1) and a metal thin layer integrally laminated.

[Wherein, A ¹ , A ² , A ³ and A ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, a halogenated hydrocarbon group, and , A hydrolyzable silyl group, or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group or an arylene group, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an acid. A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _P —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ each independently represents a carbon atom having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an axetanyl group, and p is an integer of 0 to 5. ] The cyclic olefin-based polymer includes a structural unit in which at least one of A ¹ , A ² , A ³ and A ⁴ is a hydrolyzable silyl group in the general formula (1),
The laminate according to claim 4, wherein the hydrolyzable silyl group is a group represented by the following general formula (2).

[Wherein Y is an alkoxy group having 1 to 10 carbon atoms, an allyloxy group having 1 to 10 carbon atoms, a halogen atom, or an aliphatic diol having 1 to 10 carbon atoms bonded to each other to form a 5- to 7-membered ring. Represents a group derived from an alicyclic diol or an aromatic diol, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. r is an integer of 0 to 5, and s is an integer of 1 to 3. ]   In the cyclic olefin polymer, the content ratio of the structural unit having a hydrolyzable silyl group represented by the general formula (2) is 0.2 relative to the total structural units constituting the cyclic olefin polymer. It is -30 mol%, The laminated body of Claim 5 characterized by the above-mentioned.   The laminate according to any one of claims 1 to 6, wherein the metal thin layer is made of a copper foil.   It is used as a flexible printed wiring board, The laminated body in any one of Claims 1-7 characterized by the above-mentioned. A laminate comprising a step of applying a polymer solution containing a cyclic olefin polymer having a structural unit represented by the following general formula (1) on a metal foil and drying the resulting coating film Body manufacturing method.

[Wherein, A ¹ , A ² , A ³ and A ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, a halogenated hydrocarbon group, and , A hydrolyzable silyl group, or a polar group represented by — (CH ₂ ) _p —X. Further, the A ¹ and A ^4, integrated alkylene group may form a cycloalkylene group or an arylene group, further, A ¹ and A ² or A ³ and A ⁴ are bonded to each other acid A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _P —X, X represents —COOR ¹ , —OCOR ^2, or —OR ³ , and R ¹ , R ^2, and R ³ are each independently a group having 1 to 10 carbon atoms. It represents a substituent containing a hydrocarbon group, a halogenated hydrocarbon group, or an axetanyl group, and p is an integer of 0 to 5. ] The manufacturing method of the laminated body which has the process of sticking the heat resistant resin sheet which consists of a cyclic olefin type polymer which has a structural unit represented by following General formula (1), and metal foil.

[Wherein, A ¹ , A ² , A ³ and A ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a cycloalkyl group, a halogenated hydrocarbon group, and , A hydrolyzable silyl group, or a polar group represented by — (CH ₂ ) _p —X. A ¹ and A ⁴ may be integrated to form an alkylene group, a cycloalkylene group or an arylene group, and A ¹ and A ² or A ¹ and A ⁴ are bonded to each other to form an acid. A group derived from an anhydride, lactone or imide may be formed. m is 0 or 1.
Here, in — (CH ₂ ) _P —X, X represents —COOR ¹ , —OCOR ² or —OR ³ , and R ¹ , R ² and R ³ each independently represents a carbon atom having 1 to 10 carbon atoms. This represents a substituent containing a hydrogen group, a halogenated hydrocarbon group, or an axetanyl group, and p is an integer of 0 to 5. ] The cyclic olefin-based polymer includes a structural unit in which at least one of A ¹ , A ² , A ³ and A ⁴ is a hydrolyzable silyl group in the general formula (1),
The method for producing a laminate according to claim 9 or 10, wherein the hydrolyzable silyl group is a group represented by the following general formula (2).

[Wherein Y is an alkoxy group having 1 to 10 carbon atoms, an allyloxy group having 1 to 10 carbon atoms, a halogen atom, or an aliphatic diol having 1 to 10 carbon atoms bonded to each other to form a 5- to 7-membered ring. Represents a group derived from an alicyclic diol or an aromatic diol, and R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. r is an integer of 0 to 5, and s is an integer of 1 to 3. ]   In the cyclic olefin polymer, the content ratio of the structural unit having a hydrolyzable silyl group represented by the general formula (2) is 0.2 relative to the total structural units constituting the cyclic olefin polymer. It is -30 mol%, The manufacturing method of the laminated body of Claim 11 characterized by the above-mentioned.   The method for producing a laminate according to any one of claims 10 to 12, wherein the metal thin layer is made of a copper foil.