JP2006247849A - Laminate, its manufacturing method and flexible printed board using laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate reduced in water absorption and achieving high-degree flame retardancy, and its manufacturing method. <P>SOLUTION: The laminate is constituted by laminating polyimide resin layers on both sides of a film comprising a cycloolefinic polymer and manufactured by performing operation, which subjects the surface of the film comprising the cycloolefinic polymer to oxidation treatment and applies polyamic acid or soluble polyimide to the treated surface of the film to heat the coated film, with respect to both sides of the film comprising the cycloolefinic polymer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a laminate having a low water absorption rate and achieving high flame retardancy, a method for producing the laminate, and a flexible printed board using the laminate.

  Conventionally, the flame retardancy required for optical resin materials used in these devices has increased with the increase in performance, density, and size of electronic devices such as liquid crystal display devices, electroluminescence display devices, and touch panels. It is stricter than However, conventional optical resins have the drawback of being easily combusted, and are difficult to develop in applications where flame retardancy is required.

Conventionally, a method for imparting heat resistance and hard-to-repair burnability by laminating a resin such as polyamic acid on a polyester film has been proposed.
JP 2001-187433 A JP 2002-172747 A Japanese Patent Laid-Open No. 2003-200545

However, the flame retardancy expressed in these techniques is still insufficient. Moreover, the film obtained has a problem of high water absorption.
Then, this invention aims at provision of the laminated body which achieved small flame absorption and high flame retardance.

The laminate of the present invention is characterized in that a layer having a polyimide resin is laminated on both sides of a film having a cyclic olefin polymer.
The method for producing a laminate of the present invention comprises subjecting the surface of a film having a cyclic olefin polymer to oxidation treatment by at least one method selected from the group consisting of corona treatment, flame treatment, plasma treatment and ozone treatment, An operation of applying polyamic acid or soluble polyimide to the surface of the film and heating is performed on both sides of the film.
The flexible printed board of the present invention is characterized by using the laminate of the present invention.
Details of the present invention will be described below.

<Laminate>
Cyclic Olefin Polymer The cyclic olefin polymer used in the present invention is obtained by ring-opening polymerization or addition polymerization of a monomer having a norbornene structure and other polymerizable monomer added as necessary. The resulting polymer is included. In particular, a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (a)”) and a structural unit represented by the following formula (2) (hereinafter also referred to as “structural unit (b)”). A cyclic olefin addition polymer containing at least one selected from the group (A) is preferred, and a polymer containing the structural unit (a) is particularly preferred.

[In Formula (1) and Formula (2), A ^{1 to} A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group, an aryl group, an alkoxyl group, an alkoxy group. A carbonyl group, a carboxyl group, an alkylsilyl group, a hydrolyzable silyl group, or a cycloalkyl group having 4 to 15 carbon atoms. A ¹ and A ² , A ¹ and A ^3, or A ² and A ⁴ may be bonded to each other to form a ring structure, and the bond includes —O—, —OCO—, —COO—, and It may be bonded via a bonding group selected from -N = C = N-. Moreover, p shows the integer of 0-2. ]

In particular, the cyclic olefin polymer is obtained by including a structural unit of a substituted cyclic olefin having an alkyl group (that is, a structural unit in which any one of A ^{1 to} A ⁴ is an alkyl group in the above formula). Molding processability can be improved by controlling the glass transition temperature of the polymer, and flexibility can be imparted to the obtained film substrate.

  Such a structural unit (a) is formed by addition polymerization of a cyclic olefin compound represented by the following general formula (3) (hereinafter also referred to as “specific monomer (1)”). The structural unit (b) is formed by subjecting the specific monomer (1) to ring-opening polymerization and further hydrogenation.

Wherein ^(3), A 1 to A ⁴ and p are as defined in formula (1) and (2). ]

Specific examples of the specific monomer (1) include the following compounds, but the present invention is not limited to these specific examples.
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-pentylbicyclo [2.2.1] hept-2-ene,
5-butyl-6-methylbicyclo [2.2.1] hept-2-ene,
5-chloro-6-butylbicyclo [2.2.1] hept-2-ene,
5-fluoro-6-butylbicyclo [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,
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-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene,
5,6-di (methoxycarbonyl) -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,
8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-ethoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-dimethoxychlorosilyl-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-triethoxysilyl-bicyclo [2.2.1] hept-2-ene,
5-diethoxychlorosilyl-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-triethoxysilyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyldimethoxysilyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

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 ] dodeca- 3-ene,
8- [1′-methyl-2 ′, 6′-dioxa-1′-silacyclohexyl] -tetracyclo [4.4.0.1 ^2,5 1 ^7,10 ] dodec-3-ene,
These may be used, and these may be used alone or in combination of two or more.

The monomer composition to be subjected to the polymerization reaction in the present invention is an ester other than the specific monomer (1) for the purpose of imparting adhesiveness to the obtained copolymer and introducing a crosslinking site. A cyclic olefin compound having a functional group such as a group, an acid anhydride group, a carbonimide group, or a hydrolyzable silyl group as a side chain substituent in an amount of 10 mol% or less with respect to 100 mol% of all monomers. May be. Specific examples of such cyclic olefin compounds include:
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]} dodeca-9-ene-4-carboxylic acid methyl 4-methyl-tetracyclo [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]} such as dodeca-9-ene, and the like, but not limited thereto. When the ratio of these cyclic olefin compounds exceeds 10 mol%, the water absorption of the film or sheet formed from the resulting copolymer increases, and transparency and mechanical strength may be impaired. The polymerization activity in the addition polymerization reaction may be greatly reduced.

Furthermore, as a monomer other than the specific monomer (1),
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,
The structural unit (a) or the structural unit (b) is obtained by subjecting a cyclic diolefin compound such as addition polymerization or ring-opening polymerization to hydrogenation of the olefinic unsaturated bond present in the side chain. Can do.

Among these monomers, 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,
Tricyclo [5.2.1.0 ^2,6 ] dec-8-ene,
Tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene,
And tricyclo [6.2.1.0 ^2,7 ] undec-9-ene.
In addition, tricyclo [5.2.1.0 ^2,6 ] dec-8-ene containing at least 80% endo isomer,
Tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene,
Tricyclo [6.2.1.0 ^2,7 ] undec-9-ene,
By containing 10 mol% or more of the structural unit (a) obtained by addition polymerization using a ring or the structural unit (b) obtained by ring-opening polymerization and hydrogenation of the structural unit in all the structural units, high toughness is crosslinked. Film is obtained.

The proportion of the structural unit (a) or structural unit (b) in which A ^{1 to} A ⁴ in the cyclic olefin polymer used in the present invention are hydrogen atoms and / or hydrocarbons is 70 mol% in all structural units. As described above, preferably 90 mol% or more, the water absorption (wet) property of the polymer is lowered, which is particularly preferable.

  In the cyclic olefin addition polymer used in the present invention, a structural unit (c) obtained by addition polymerization or ring-opening polymerization and hydrogenation of an α-olefin compound or a conjugated diene compound can be further introduced.

Specific examples of such an 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 the repeating unit (c) derived from the α-olefin compound into the polymer, the glass transition temperature of the cyclic olefin addition type (co) polymer of the present invention can be controlled. The ratio of the repeating unit (c) contained in the cyclic olefin polymer used in the present invention is usually 0 to 25 mol%, preferably 0 to 20 mol%, in all the structural units of the cyclic olefin polymer. . In addition, when the ratio of the repeating unit (c) exceeds 25 mol%, the glass transition temperature of the polymer is lowered to 130 ° C. or lower, and the heat resistance may be lowered, which is not preferable.

  The molecular weight of the cyclic olefin polymer used in the present invention is, in terms of polystyrene, usually a number average molecular weight of 10,000 to 300,000, a weight average molecular weight of 20,000 to 700,000, preferably a number average molecular weight. The average 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 film or sheet 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 becomes high, the workability of film formation by the solution casting method, the surface smoothness of the obtained film or sheet, etc. May get worse.

  Moreover, the glass transition temperature of the cyclic olefin polymer used for this invention is 130-450 degreeC, Preferably it is 200-400 degreeC. When the glass transition temperature of the polymer is lower than 130 ° C, the heat resistance may be insufficient. On the other hand, when it exceeds 450 ° C, the resulting film or sheet may not be tough and may be easily broken.

Film Production Method A film having a cyclic olefin polymer used in the present invention is produced by a known method such as a melt extrusion method, an inflation method or a solution casting method using the cyclic olefin polymer. Since the surface property is excellent and the optical distortion is small, those produced by a solution casting method are preferred.
As a general process of the solution casting method, first, a cyclic olefin polymer containing a hydrolyzable silyl group and a solvent, and an additive or compounding agent such as an antioxidant or a leveling agent as required, are used. A polymer solution (hereinafter also referred to as “casting composition”) is prepared, and then the casting composition is cast on a support such as a metal belt, metal drum, or plastic film, and then dried. A series of steps of peeling the body and further drying as necessary can be exemplified, but the present 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 is applied using a brush or brush, sprayed by spraying, screen printing, flow coating, DAIKO. A known method such as a coating method using a coater such as a coater, a spin coating method or a dipping method can be applied.

Polyimide resin In the present invention, the polyimide resin layer formed on both sides of the cyclic olefin polymer film is usually formed by applying a polyamic acid, which is a polyimide precursor, or a solvent-soluble polyimide solution to the film and drying. The

  A polyamic acid is obtained by reacting a diamine with tetracarboxylic dianhydride. The polyimide is obtained by dehydrating and ring-closing the polyamic acid. Here, examples of the diamine and tetracarboxylic dianhydride used are as follows.

(Diamine)
4,4'-diaminodiphenylpropane, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, benzidine, 4,4 ' -Diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4, 4′-diaminobenzanilide, 3,3′-diaminobenzanilide, 4,4′-diamino-2,2′-trifluoromethylbiphenyl, 3,3′-diamino-2,2′-trifluoromethylbiphenyl, 1,1-metaxylylenediamine, 2,2-bis (4-aminophen L) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 1,3-bis (3-aminophenoxy) benzene, 3,5-diamino-1-[(4-trifluoromethyl) phenoxyphenyl] benzamide, 1- [2,2-bis (trifluoromethyl)- 3,3,4,4,5,5,5-heptafluoropentyl] -3,5-diaminobenzene, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,5-diaminonaphthalene, bis ( 4-aminophenoxy) biphenyl, 9,9-bis (4-aminophenoxy) fluorene, 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 9,9-bis [4 (4-aminophenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (3-aminophenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-aminophenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (4-amino-3-trifluoromethylphenoxy) -3-phenylphenyl] fluorene,
9,9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (3-amino-4-trifluoromethylphenoxy) -3 -Phenylphenyl] fluorene, 9,9-bis [4- (3-amino-5-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (3-amino-6-tri) Fluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-amino-3-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2 -Amino-4-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-amino-5-trifluoromethyl) Enoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-amino-6-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, and the like, and lower alkyls, aryls of these aromatic rings, Aromatic diamines such as aralkyl, halogen, halogenated alkyl, or substituted aryl halide groups;

1,3-bis (4-aminophenyl) adamantane, 1,3-bis [4- (4-aminophenoxy) phenyl] adamantane, 1,6-bis (4-aminophenyl) diamantane, 1,6-bis [ 4- (4-aminophenoxy) phenyl] diamantane, 4,9-bis (4-aminophenyl) diamantane, 4,9-bis [4- (4-aminophenoxy) phenyl] diamantane, tetrahydrodicyclopentadienylene Amine, hexahydro-4,7-methanoin danylene dimethylenediamine, 5-amino-1,3,3, -trimethylcyclohexanemethylamine (also known as isophoronediamine), 1,4-cyclohexanediamine, 4,4′-methylenebis (Cyclohexylamine) and its 3,3′-dimethyl substituted bis (aminomethyl) bicyclo [2.2 1] Heptane, 1,3-diaminoadamantane, 3,3′-diamino-1,1′-biadamantyl, 4,4′-hexafluoroisopropylidenebis (cyclohexylamine) 4,4′-hexafluoroisopropylidene Bis (cyclohexylamine))
1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, tetrahydrodicyclopentadienylenediamine, hexahydro Aliphatic and cycloaliphatic diamines such as -4,7-methanoin danylene dimethylene diamine and tricyclo [6,2,1,0 ^2.7 ] -undecylenedimethyl diamine.
These diamine compounds can be used alone or in combination of two or more.

(Tetracarboxylic dianhydride)
Examples of the tetracarboxylic dianhydride include the following compounds.
Pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis ( 2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 2,2-bis (3 , 4-Dicarbo Cyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane dianhydride,

3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetra Carboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride P-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether Anhydride, bis (triphenyl phthalic acid) -4,4'-diphenylmethane dianhydride,
9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) phenyl] fluorene dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 9,9- Bis [4- (3,4-dicarboxyphenoxy) -3-phenylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -3-phenylphenyl] fluorene dianhydride 9,9-bis [4- (3,4-dicarboxyphenoxy) -2-phenylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -2- Enylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -3-methylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-di Carboxyphenoxy) -3-methylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -2-methylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -2-methylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -3-ethylphenyl] fluorene dianhydride, 9-bis [4- (2,3-dicarboxyphenoxy) -3-ethylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -2-ethyl Enyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -2-ethylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxy) Phenoxy) -3-propylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -3-propylphenyl] fluorene dianhydride, 9,9-bis [4- ( 3,4-dicarboxyphenoxy) -2-propylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -2-propylphenyl] fluorene dianhydride, 9,9 -Bis [4- (3,4-dicarboxyphenoxy) -3-butylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -3-butylphenol Enyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -2-butylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxy) Phenoxy) -2-butylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -3-t-butylphenyl] fluorene dianhydride, 9,9-bis [4 -(2,3-dicarboxyphenoxy) -3-t-butylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -2-t-butylphenyl] fluorene di Anhydrides, aromatic tetracarboxylic dianhydrides such as 9,9-bis [4- (2,3-dicarboxyphenoxy) -2-t-butylphenyl] fluorene dianhydride;

  Butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2 , 3,4,5-Tetrahydrofurantetracar Boronic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3- Dione, 1,3,3a, 4,5,9b-Hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3- Dione, 1,3,3a, 4,5,9b-Hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3- Dione, 1,3,3a, 4,5,9b-Hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3- Dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl)- Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl)- Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, Bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, represented by the following formula (I) And (II) an aliphatic, such as a compound represented by and cycloaliphatic tetracarboxylic dianhydride;

(Wherein R ¹ and R ⁴ represent a divalent organic group having an aromatic ring, R ² and R ³ represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ³ are the same. But it may be different.)

Ethylene glycol-bis (anhydro trimellitate), propylene glycol-bis (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (am Hydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), the following formulas (1) to Aromatic tetracarboxylic dianhydrides such as compounds represented by (4) can be mentioned. These may be used alone or in combination of two or more.

(Synthesis of polyamic acid)
The proportion of the diamine and tetracarboxylic dianhydride used in the polyamic acid synthesis reaction is 0.2 eq. Of tetracarboxylic dianhydride acid anhydride group with respect to 1 equivalent of amino group contained in the diamine. The ratio which becomes -2 equivalent is preferable, More preferably, it is the ratio which becomes 0.3-1.2 equivalent.
The synthetic reaction of polyamic acid is usually carried out in an organic solvent under a temperature condition of -20 to 150 ° C, preferably 0 to 100 ° C. The organic solvent used for the synthesis of polyamic acid is not particularly limited as long as it can dissolve tetracarboxylic dianhydride, diamine, and polyamic acid produced by the reaction. For example, γ-butyrolactone, N-methyl- Aprotic polar solvents such as 2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoryltriamide, 1,3-dimethyl-2-imidazolidinone; Mention may be made of phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol.
The amount (A) of the organic solvent used is such that the total amount (B) of the tetracarboxylic dianhydride as the reaction raw material and the diamine compound is 0.1 to 30% by weight based on the total amount (A + B) of the reaction solution. It is preferable that the amount is small.

  In addition, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for polyamic acid, are used in combination with the organic solvent as long as the resulting polyamic acid does not precipitate. be able to. Specific examples of such poor solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetic acid. Methyl, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monomethyl ester Ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol dimethyl ether , Dipropylene glycol diethyl ether, ethylene glycol ethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, ethyl lactate, methyl lactate, butyl lactate, ethyl ethoxy acetate, ethyl hydroxy acetate, 2 -Methyl hydroxy-3-methylbutanoate, 3-metho Methyl cypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-methyl-3-methoxybutanol, 3-ethyl-3-methoxybutanol, 2-methyl-2-methoxybutanol, 2-ethyl- 2-methoxybutanol, 3-methyl-3-ethoxybutanol, 3-ethyl-3-ethoxybutanol, 2-methyl-2-ethoxybutanol, 2-ethyl-2-ethoxybutanol, tetrahydrofuran, dichloromethane, 1,2-dichloroethane Examples thereof include 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like. These can be used alone or in combination of two or more.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. The polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent once or several times.

(Additive)
The polyamic acid is likely to proceed with imidization due to the coexistence of a basic compound. Such a basic compound is a compound whose pKa (25 ° C. in water) which is the acid dissociation constant of the conjugate acid is more than 8, preferably 9 to 11.5, more preferably 9.5 to 11.5. Yes, it is a compound capable of acid-base interaction with the carboxyl group of polyamic acid.

Specific examples include n-butylamine (pKa 10.77 / bp. 78 ° C), n-amylamine (pKa 10.63 / bp. 104 ° C), tert-butylamine (pKa 10.83 / bp. 46 ° C), ethylenediamine (pKa10 .81 / bp.118 ° C.), aliphatic amines such as benzylamine (pKa 9.33 / bp.184 ° C.) and alkyl-substituted products thereof and derivatives thereof;
Pyrrolidine (pKa 11.27 / bp. 88 ° C.), 1,2-dimethylpyrrolidine (pKa 10.20 / bp. 106 ° C.), n-methylpyrrolidine (pKa 10.32 / bp. 81 ° C.), cyclohexylamine (pKa 10.66) /Bp.134° C.), n-butylcyclohexylamine (pKa 11.23 / bp.173 ° C.), piperazine (pKa 9.83 / bp. 109 ° C.), 2,5-dimethylpiperazine (pKa 9.66 / mp.115 ° C.) ), Piperidine (pKa 11.12 / bp. 106 ° C.), 1,2-dimethylpiperidine (pKa 10.20 / bp. 144 ° C.), 2,5-diazabicyclo [2,2,1] heptane (pKa about 11), 1,5-diazabicyclo [4,3,0] non-5-ene (pKa about 11 / bp. 95 ° C.-7.5 mmHg), 1,4-diazabicyclo [2,2,2] octane (pKa about 11 / mp.158 ° C.), 1,8-diazabicyclo [5,4,0] -7-undecene (pKa about 11 / bp.80 ° C.− 0.6 mmHg) and other alicyclic amines and their alkyl substituents and derivatives thereof;
Nitrogen-containing heterocyclic compounds such as 4-aminopyridine (pKa 9.11 / bp. 273 ° C.), 4-methylaminopyridine (pKa 9.65 / bp. 100 ° C.-0.1 mmHg), alkyl substitution products thereof and derivatives thereof, etc. Is mentioned.

  Among these basic compounds, those having a normal pressure boiling point of 100 to 250 ° C. are preferable, and the weight loss rate of thermogravimetric measurement in an air atmosphere is from room temperature to 200 ° C. (heating rate 5 ° C./min). A compound containing a nitrogen atom that is 90% or more in the measurement is preferred. In this invention, a compound can be used individually or in combination of 2 or more types. A basic compound is 0.5 equivalent or less with respect to the carboxyl group of a polyamic acid, Preferably it is 0.3-0.01 equivalent.

(Imidation reaction)
The polyimide resin used in the present invention is obtained by dehydrating and ring-closing (imidizing) a polyamic acid. The polyamic acid is dehydrated and closed by (i) a method in which the polyamic acid is heated, or (ii) the polyamic acid is dissolved in an organic solvent, and a dehydrating agent and a dehydrating ring-closing catalyst are added to this solution and heated as necessary. By the method. In the present invention, the method (i) is carried out by applying a polyamic acid solution to a cyclic olefin polymer film and heating it. In addition, when using the method (ii), a soluble polyimide is prepared in advance by the method (ii), and the resulting soluble polyimide is applied to a cyclic olefin polymer film and dried to form a polyimide resin layer. To do.

The reaction temperature in the method (i) of heating the polyamic acid depends on the glass transition temperature of the resulting polyimide, but is usually 80 to 250 ° C, preferably 100 to 220 ° C. If it is less than 80 degreeC, a solvent and a catalyst may remain. The heating time is usually 5 to 360 minutes, preferably 10 to 240 minutes. If it is less than 5 minutes, a solvent and a catalyst may remain.
On the other hand, in the above method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used. Can do. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the polyamic acid repeating unit. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And the reaction temperature of dehydration ring closure reaction is 0-180 degreeC normally, Preferably it is 10-150 degreeC. Moreover, a polyimide can be refine | purified by performing operation similar to the purification method of a polyamic acid with respect to the reaction solution obtained in this way.

(Formation of polyimide resin layer)
As a method for forming a polyimide resin layer in the present invention, for example, a method in which a polyimide resin film is bonded to a cyclic olefin polymer film, a polyamic acid or a solution containing a soluble polyimide is applied to a cyclic olefin polymer film, and a coating film is formed. And a method of heating the coating film. Among these, a method of applying and heating a solution of polyamic acid or soluble polyimide is preferably used.
The solution can be applied to the substrate by a usual method such as a casting method, a spray method, or a dipping method.

When using a polyamic acid solution, the imidation ratio of the polyamic acid in the polyamic acid solution is not particularly limited, but is preferably 40% or less in terms of solubility. When the imidation ratio is within such a preferable range, it can be easily dissolved in a solvent. The imidation ratio of the polyamic acid in this solution is more preferably 20% or less, and further preferably 10% or less.
Moreover, it is preferable that the imidation ratio of the polyimide in the polyimide resin layer used by this invention is 70% or more, and it is especially preferable that it is 80% or more. By using a polyimide resin layer having an imidization rate of 70% or more, a low water absorption laminate can be obtained.
Here, the “imidization rate” is the percentage of the number of repeating units formed with an imide ring with respect to the total number of repeating units in the polymer.

  In the present invention, in order to improve the adhesion between the cyclic olefin polymer film and the polyimide resin layer, the surface of the cyclic olefin polymer film is selected from the group consisting of corona treatment, flame treatment, plasma treatment and ozone treatment. It is preferable to oxidize by at least one method. Alternatively, a primer layer may be provided between the cyclic olefin polymer film and the polyimide resin layer. When the adhesiveness between the cyclic olefin polymer film and the polyimide resin layer is lowered, there may be a problem when processing the laminate of the present invention, or the flame retardancy effect may be lowered.

As a method for oxidizing the surface of the cyclic olefin polymer film, corona treatment, flame treatment, plasma treatment, ozone treatment and the like are arbitrary.
The method for laminating the primer layer is not particularly limited, and may be any method such as a method in which a solution in which a primer layer forming component is dissolved in a cyclic olefin-based (co) polymer film and / or a resin layer is applied and then dried.

In the present invention, the cyclic olefin polymer film, the polyimide resin layer, and the primer layer may contain various additives, resin compositions, cross-linking materials, and the like as long as the effects of the present invention are not impaired.
In the laminate of the present invention, the film thickness relationship between the cyclic olefin polymer film and the polyimide resin layer is such that the polyimide resin layer is 0.5 to 30% of the film thickness of the cyclic olefin polymer film. It is preferable to have a thickness.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which achieved the high flame retardance with a small water absorption rate can be provided.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited at all by these Examples. The molecular weight, glass transition temperature, and residual solvent amount of the cyclic olefin polymer were measured by the following methods.
(1) Number average molecular weight, weight average molecular weight A 120C type gel permeation chromatography apparatus (GPC) manufactured by WATERS, Inc., using an H-type column manufactured by Tosoh Corporation, and o-dichlorobenzene as a solvent, 120 Measured at ° C. The obtained molecular weight is a standard polystyrene equivalent value.
(2) Glass transition temperature (Tg)
Storage elasticity using Leo Vibron DDV-01FP (manufactured by 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 modulus (E ′) and the loss elastic modulus (E ″) was taken as the glass transition temperature of the copolymer.
(3) Residual solvent amount analysis When measuring the residual solvent amount other than toluene, 1 g of film is dissolved or swollen in 20 ml of toluene, and the residual solvent in the film is extracted, and gas chromatography device HP-5890 (Hewlett-Packard) Poraplot Q (manufactured by Hewlett-Packard) was attached as a column to Packard), and the amount of residual solvent was measured. When measuring the amount of residual toluene in the film, 1 g of film was dissolved or swollen in 20 ml of cyclohexane, and measured and quantified by the same method. When measuring the amount of residual toluene, 1 g of a film was dissolved or swollen in 20 ml of acetone, the residual toluene in the film was extracted, and the amount of residual toluene was measured using the same apparatus.
(4) Copolymer composition The monomer remaining in the polymer solution after completion of the polymerization was determined by measuring with gas chromatography (GC).

Moreover, the evaluation method of a laminated body is as follows.
(1) Water absorption rate After the laminate was immersed in water at 23 ° C for 24 hours, the water absorption rate was measured by a change in weight before and after the immersion. (◯: 0 to 0.5%, Δ: 0.5 to 1.0%, ×: exceeding 1.0%). ○ is accepted.
(2) Film thickness of each layer The thickness (T1) of the polyimide resin layer on one surface of the cyclic olefin polymer film, the thickness (T2) of the polyimide resin layer on the other surface, and the total thickness of the cyclic olefin polymer film ( T3) was measured, and (R) was determined from the following formula.
R = {(T1 + T2) / T3} × 100
(3) Imidation rate of polyimide resin layer The polyimide resin layer in the laminate is scraped off and dissolved in deuterated dimethyl sulfoxide, and 1H-NMR is measured at room temperature using tetramethylsilane as a reference substance, and is represented by the following formula: Obtained by the formula.
Imidation rate (%) = (1-A ¹ / A ² × α) × 100 (ii)
A ¹ : Peak area derived from NH group protons (10 ppm)
A ² : Peak area derived from other protons α: Number ratio of other protons to one proton of NH group in polymer precursor (polyamic acid)

(4) Adhesiveness (cross cut test)
After putting 100 pieces of 1 mm ² crosscuts on the surface of the laminate, applying scotch tape and press-bonding, it was peeled off in the 90-degree direction, and was evaluated in three stages according to the number of remaining polyimide resin layers (◎: 90 to 100, ○: 60-89, x: 0-59). ◎, ○ is passed.
(5) Flame resistance 1
The laminate was cut into 5 cm × 20 cm, rounded so as to have a cylindrical shape with a diameter of 12.7 mm and a length of 200 mm, and one end in the longitudinal direction of the film was held so that the longitudinal direction was perpendicular to the ground. Next, the other end was exposed to a flame of about 2 cm for 3 seconds and then released. At this time, the combustion state of the laminated body after the flame release was observed and evaluated in four stages (◎: self-extinguishes within 5 seconds, ○: self-extinguishes within 7 seconds, Δ: self-extinguishes within 10 seconds, × : Did not self-extinguish or burned out within 10 seconds). ◎, ○, and Δ were considered good.
(5) Flame resistance 2
After the evaluation of flame retardancy 1, a flame of about 2 cm was again exposed to the end for 3 seconds immediately after extinguishing the fire, and then the flame was released. This operation is repeated twice, and the total time from flame release to fire extinguishing is evaluated in three stages (◎: self-extinguishes within 7 seconds, ○: self-extinguishes within 10 seconds, x: self within 10 seconds) I did not extinguish the fire.

[Synthesis Example 1 (Synthesis of Cyclic Olefin 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) and 0.42 g of styrene were added. The reaction vessel was sealed with a rubber seal and heated 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 98%. 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 47,000, and the weight average molecular weight was 198,000.

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 A having a thickness of 100 μm, which had a glass transition temperature of 355 ° C. and a residual solvent amount of 250 ppm. A corona treatment with an intensity of 50 W / m ² / min was applied to both sides of A.

[Synthesis Example 2 (Synthesis of Cyclic Olefin Polymer)]
In a 300 ml glass pressure bottle, under a nitrogen atmosphere, 80 ml of toluene as a solvent, 17 mmol of tricyclo [5.2.1.0 ^2,6 ] deca-3,8-diene, 8-methyl-8-methoxycarbonyl -Tetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodec-3-ene 153 mmol, molecular weight regulator 1-hexene 42.5 mmol was charged, triethylaluminum 0.119 mmol as the catalyst component, tungsten hexachloride methanol modified product [methanol / Tungsten = 3 (mol / mol)] was added in the order of 0.017 mmol. Polymerization was performed at 80 ° C. for 2 hours, and the polymerization was stopped with methanol. Conversion of the monomer to a ring-opening (co) 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-opening (co) polymer. For 15 hours to obtain a ring-opening (co) polymer B.

In a 500 ml stainless steel pressure-resistant reactor, a solution obtained by dissolving 15 grams of the ring-opened (co) 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 obtained hydrogenated ring-opening (co) polymer solution was decontacted with an aqueous lactic acid solution and then solidified with isopropyl alcohol to obtain a hydrogenated ring-opening (co) polymer BH. ^The hydrogenation rate determined from ¹ H-NMR measurement was 99.7%. (Hydrogenation rate is 3.2 to 3.6 ppm based on methoxycarbonyl group and 5.4 to 5 based on hydrogen adjacent to double bond of ring-opening (co) polymer remaining unhydrogenated) The ratio of the structural unit derived from 5-triethoxysilyl-bicyclo [2.2.1] hept-2-ene was 2.0 mol%. Further, the ring-opening (co) polymer CH had a polystyrene-equivalent number average molecular weight (Mn) of 19,000, a weight average molecular weight (Mw) of 75,000, and Mw / Mn of 3.7. The glass transition temperature was 168 ° C.

  10 grams of hydrogenated ring-opening (co) polymer BH is dissolved in 35.5 grams of toluene and pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxy is used as an antioxidant. Phenyl) propionate] and tris (2,4-di-t-butylphenyl) phosphite were added in an amount of 0.5 parts by weight per 100 parts by weight of the polymer. Furthermore, 0.05 part by weight of tributyl phosphite was added to 100 parts by weight of the (co) polymer. This (co) polymer solution was cast to produce a film B having a thickness of 100 μm. Film B had a glass transition temperature of 178 ° C. and a residual solvent content of 750 ppm.

[Synthesis composition 3 (synthesis of polyamic acid)]
Nitrogen gas is allowed to flow through a vessel equipped with a stirrer and a nitrogen gas introduction tube, and the inside of the vessel is sufficiently replaced with nitrogen gas. After 119 g of N, N-dimethylacetamide (DMAc) is added, 4,4′-diaminodiphenyl ether 10 0.012 g (50 mmol) was added and dissolved sufficiently at room temperature. Then, 10.906 g (50 mmol) of pyromellitic dianhydride was added. The monomer concentration was 15% by weight. The polymerization reaction was stirred at room temperature for 20 hours to obtain a polyamic acid solution A. The intrinsic viscosity ηinh of the obtained polyamic acid was 0.74 dL / g.

[Synthesis Example 4 (Synthesis of polyamic acid)]
A polyamic acid solution B was obtained in the same manner as in Synthesis Example 3, except that 11.209 g (50 mmol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride was used as the tetracarboxylic dianhydride. The obtained polyamic acid had an intrinsic viscosity ηinh of 0.82 dL / g.

Example 1
A polyamic acid solution A is applied to one side of the cyclic olefin polymer film A with a wet thickness of 100 μm and then dried at 100 ° C. for 10 minutes, and the other side of the film A is also wet with a polyamic acid solution A of 100 μm. It was applied in thickness and dried at 100 ° C. for 10 minutes. Thereafter, heat treatment was performed for 30 minutes in heating zones of 150 ° C., 200 ° C., and 240 ° C. to obtain a laminate having polyimide resin layers on both sides of the cyclic olefin polymer film, and evaluation was performed. The resulting laminate had an overall thickness of 110 μm, a polyimide resin layer thickness of 5 μm per side, and an imidization rate of 99%. The results are summarized in Table 1.

Example 2
After applying the polyamic acid solution A wet to a thickness of 20 μm on one side of the cyclic olefin-based polymer film A and drying at 100 ° C. for 10 minutes, the other side of the film A is also wet with the polyamic acid solution A thickness of 20 μm. Then, it was applied and dried at 100 ° C. for 10 minutes. Thereafter, heat treatment was performed for 30 minutes in heating zones of 150 ° C., 200 ° C., and 240 ° C. to obtain a laminate having polyimide resin layers on both sides of the cyclic olefin polymer film, and evaluation was performed. The resulting laminate had an overall thickness of 102 μm, a polyimide resin layer thickness of 1 μm per side, and an imidization rate of 99%. The results are summarized in Table 1.

Example 3
A laminate was obtained and evaluated in the same manner as in Example 2 except that the polyamic acid solution B was used instead of the polyamic acid solution A. The results are summarized in Table 1.
Example 4
A laminate was obtained and evaluated in the same manner as in Example 1 except that the film B was used instead of the film A. The results are summarized in Table 1.
Example 5
A laminate was obtained and evaluated in the same manner as in Example 2 except that the film B was used instead of the film A. The results are summarized in Table 1.
Example 6
A laminate was obtained and evaluated in the same manner as in Example 2 except that the film B was used instead of the film A and the polyamic acid solution B was used instead of the polyamic acid solution A. The results are summarized in Table 1.
Example 7
A laminate was obtained and evaluated in the same manner as in Example 2 except that the heat treatment was performed at 180 ° C. for 60 minutes. The polyimide resin layer in this laminate had an imidization rate of 65%. The results are summarized in Table 1.

Comparative Example 1
A laminate was obtained and evaluated in the same manner as in Example 1 except that the polyamic acid solution A was applied only to one side of the film A. The results are summarized in Table 1.
Comparative Example 2
A laminate was obtained and evaluated in the same manner as in Example 2 except that the polyamic acid solution A was applied only to one side of the film A. The results are summarized in Table 1.
Comparative Example 3
A laminate was obtained and evaluated in the same manner as in Example 2 except that a PET film was used in place of the film A. This film was brittle and inferior in water absorption.

Claims (5)

A laminate having a polyimide resin layer laminated on both surfaces of a film having a cyclic olefin polymer. The laminated body of Claim 1 whose imidation ratio of a polyimide resin is 70% or more. The cyclic olefin polymer has at least one selected from a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and has a number average molecular weight in terms of polystyrene of 10,000. The laminate according to claim 1, which is a polymer of ˜300,000.

[In Formula (1) and Formula (2), A ^{1 to} A ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group, an aryl group, an alkoxyl group, an alkoxy group. A carbonyl group, a carboxyl group, an alkylsilyl group, a hydrolyzable silyl group, or a cycloalkyl group having 4 to 15 carbon atoms. A ¹ and A ² , A ¹ and A ^3, or A ² and A ⁴ may be bonded to each other to form a ring structure, and the bond includes —O—, —OCO—, —COO—, and It may be bonded via a bonding group selected from -N = C = N-. Moreover, p shows the integer of 0-2. ] After oxidizing the surface of the film having a cyclic olefin polymer by at least one method selected from the group consisting of corona treatment, flame treatment, plasma treatment and ozone treatment, polyamic acid or soluble polyimide is applied to the surface of the film. The manufacturing method of a laminated body characterized by performing operation which apply | coats and heats with respect to both surfaces of a film. A flexible printed circuit board comprising the laminate according to claim 1.