JP2001301088A - Laminated film and printed board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film excellent in heat resistance, reduced in its dimensional change caused by water absorption and showing sufficient adhesion between a laminated metal and a resin film, and a printed board using the laminated film. SOLUTION: The laminated film is constituted by forming a metal membrane with a thickness of 0.1-100 μm comprising at least one metal selected from the group consisting of gold, silver, copper, nickel and aluminum on at least the single surface of a film with a thickness of 3-300 μm comprising a cyclic polyolefinic resin containing at least one polar group selected from the group consisting of an ether group, an ester group, a carbonyl group and a hydroxyl group in its structure and the printed board is obtained using this laminated film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film in which a metal thin film is formed on at least one surface of a cyclic polyolefin-based resin film, and more particularly, to a heat-resistant, less dimensional change due to water absorption, and a metal thin film. The present invention relates to a laminated film showing sufficient adhesion to a resin film, and a printed circuit board using the laminated film, particularly a flexible printed circuit board.

[0002]

2. Description of the Related Art In recent years, as electronic devices have become smaller, lighter, and higher in density, a printed circuit board in which a metal layer is laminated on a flexible substrate, particularly a flexible printed circuit board (FPC) using a laminated film has been developed. , Has come to be used frequently.
FPC is a method in which a metal layer is laminated on a plastic film, a specific pattern is etched to form a target circuit, and then the plastic film is laminated or resin-coated to provide a protective coating. Can form a part of a circuit, and a wiring connection between specific circuits can be formed. As described above, the FPC is superior to a rigid printed circuit board conventionally used in that it can be three-dimensionalized and has a high density, and is excellent in that the degree of freedom in wiring such as curved wiring and folding wiring is increased. As a material of the laminated film used for the FPC, a resin film having relatively excellent heat resistance, such as polyester such as PET, aromatic polyamide, and polyimide is generally used. However, since polyester shrinks sharply at temperatures exceeding 200 ° C., it cannot be used in fields requiring heat resistance of 200 ° C. or higher, fields requiring soldering, military applications, and the like. Polyamide, polyimide and the like are used. However,
The aromatic polyamide has high crystallinity and excellent heat resistance, but lacks dimensional stability because it has a large heat shrinkage and expands due to moisture absorption. Polyimides have better heat resistance than aromatic polyamides, but also have the disadvantages of a large heat shrinkage and large dimensional changes due to moisture absorption.

The structure of the flexible printed circuit board includes a three-layer structure in which a metal thin film is bonded to a resin film via an adhesive, and a two-layer structure in which a metal thin film is formed directly on a resin film. Of these, a substrate having a two-layer structure is preferable because the reliability of the bonding surface is high and the thicknesses of the resin film and the metal thin film can be freely selected. In a two-layer structure substrate, the resin film and the metal thin film need to have sufficient adhesion, but conventionally used resin materials can be used even in vacuum deposition or the like that can obtain a coating with high adhesion. Unless a pretreatment is performed before forming a metal thin film, the required adhesion cannot be obtained. In addition, this adhesiveness means what corresponds to the peel strength (peel strength) between the resin film and the metal thin film. As described above, laminated films that are excellent in heat resistance, have little dimensional change due to water absorption, show sufficient adhesion between metal thin films and resin films, and are suitable for flexible printed circuit board materials have not been found so far. It is.

[0004]

The present invention has been made in view of the above-mentioned problems of the prior art, and has excellent heat resistance, little dimensional change due to water absorption, and sufficient adhesion between a metal thin film and a resin film. The present invention is directed to a laminated film exhibiting properties and a printed board using the laminated film, particularly a flexible printed board.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on the types and thicknesses of the resin film and the metal thin film, and as a result, have obtained a laminated film having the following structure.
The present invention has been found to be achieved. The present invention relates to a laminated film, wherein a metal thin film is formed on at least one surface of a film made of a cyclic polyolefin-based resin. It is preferable that the cyclic polyolefin-based resin contains at least one polar group selected from the group consisting of an ether group, an ester group, a carbonyl group, and a hydroxyl group in the structure. The thickness of the film made of the cyclic polyolefin resin is preferably 3 to 300 μm, and the thickness of the metal thin film is preferably 0.1 to 100 μm.
Further, the metal thin film preferably contains at least one selected from the group consisting of gold, silver, copper, nickel, and aluminum. Further, the present invention relates to a printed circuit board (hereinafter, may be described as a flexible printed circuit board as a representative of the printed circuit board) using the laminated film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the laminated film of the present invention, a metal thin film is formed on at least one surface of a film made of a cyclic polyolefin resin. Examples of the cyclic polyolefin resin used in the present invention include the following polymers. A ring-opened polymer of a monomer represented by the following general formula (I) (hereinafter, referred to as “specific monomer”). A ring-opening copolymer of a specific monomer and a copolymerizable monomer. Hydrogenation (co) of the above or ring-opened (co) polymers
Polymer. A hydrogenated (co) polymer obtained by cyclizing the above or the ring-opened (co) polymer by Friedel-Crafts reaction. A saturated copolymer of a specific monomer and an unsaturated double bond-containing compound and a hydrogenated (co) polymer thereof. An addition type (co) polymer of one or more monomers selected from a specific monomer, a vinyl-based cyclic hydrocarbon-based monomer and a cyclopentadiene-based monomer, and a hydrogenated copolymer thereof.

[0007]

Embedded image

(Wherein R ^{1 to} R ⁴ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or another monovalent organic group. R ¹ and R ² or R ³ and R
⁴ may combine to form a divalent hydrocarbon group,
R ¹ or R ² and R ³ or R ⁴ are bonded to each other,
It may form a monocyclic or polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer. )

The cyclic polyolefin resin includes a ring-opened polymer of a specific monomer. <Specific monomer> As a preferable specific monomer, in the above general formula (I), R ¹ and R ^{3 each} represent a hydrogen atom or a carbon atom
To 10, more preferably 1 to 4, particularly preferably 1 to
R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ represents a hydrogen atom and a polar group other than a hydrocarbon group;
m is an integer of 0 to 3, p is an integer of 0 to 3, and m + p is 0 to 4, more preferably 0 to 2, and particularly preferably 1. Examples of the polar group of the specific monomer include an ether group, an ester group such as an alkyl ester group and an aromatic ester group, a carbonyl group, a hydroxyl group,
Examples include an amino group, an amide group, a cyano group, an acyl group, a silyl ether group, a thioether group, and a halogen. Among them, ether groups, ester groups such as alkyl ester groups and aromatic ester groups, carbonyl groups,
A hydroxyl group is preferable, and an ester group such as an alkyl ester group and an aromatic ester group is particularly preferable.

Further, among the specific monomers, in particular, at least one polar group of R ² and R ⁴ has the formula — (CH ₂ ) nC
The monomer represented by OOR ⁵ is preferable in that the resulting cyclic polyolefin resin has a high glass transition temperature (high heat resistance) and a low hygroscopic property. The above formula-(C
H ₂ ) In the polar group represented by nCOOR ⁵ , R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2, and preferably an alkyl group. In addition, n is generally 0 to 5, but a smaller value of n is preferable because the glass transition temperature of the obtained cyclic polyolefin resin becomes higher. Further, a specific monomer in which n is 0 is preferable because its synthesis is easy. Further, in the general formula (I), R ¹ or R ³ is preferably an alkyl group, and the alkyl group preferably has 1 to 4 carbon atoms, and more preferably 1 to 4 carbon atoms.
Two, particularly preferably one methyl group. In particular, the alkyl group is, the above formula - (CH ₂₎ it is preferred that nCOOR polar group represented by ⁵ are attached to the same carbon atom and a carbon atom bonded. Further, the specific monomer in which m is 1 in the general formula (I) is preferable in that a cyclic polyolefin-based resin having a high glass transition temperature can be obtained.

The specific monomer represented by the above general formula (I)
The following compounds may be mentioned as specific examples. Bi
Cyclo [2.2.1] hept-2-ene, tricyclo
[5.2.1.0^2,6] -8-decene, tetracyclo
[4.4.0.1^2,5. 1^7,10] -3-Dodecene, pen
Tacyclo [6.5.1.1^3,6. 0^2,7. 0^9,13] -4
-Pentadecene, pentacyclo [7.4.0.1^2,5.
1^9,12. 0^8,13] -3-pentadecene, tricyclo
[4.4.0.1^2,5] -3-undecene, 5-methyl
Bicyclo [2.2.1] hept-2-ene, 5-ethyl
Bicyclo [2.2.1] hept-2-ene, 5-methoxy
Cycarbonylbicyclo [2.2.1] hept-2-e
5-methyl-5-methoxycarbonylbicyclo
[2.2.1] Hept-2-ene, 5-cyanobicyclo
[2.2.1] Hept-2-ene, 8-methoxycarbo
Nyltetracyclo [4.4.0.1^2,5. 1^7,10] -3
-Dodecene, 8-ethoxycarbonyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
n-propoxycarbonyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8-isopropoxy
Carbonyltetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8-n-butoxycarbonyl
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 8-methyl-8-methoxycarbonyltetracy
Black [4.4.0.1^2,5. 1 ^7,10-3-dodecene,
8-methyl-8-ethoxycarbonyltetracyclo
[4.4.0.1^2,5. 1 ^7,10] -3-dodecene, 8-
Methyl-8-n-propoxycarbonyltetracyclo
[4.4.0.1^{2, Five}. 1^7,10] -3-dodecene, 8-
Methyl-8-isopropoxycarbonyltetracyclo
[4.4.0.1^{2, Five}. 1^7,10] -3-dodecene, 8-
Methyl-8-n-butoxycarbonyltetracyclo
[4.4.0.1^2,5. 1^{7,, 10}] -3-dodecene, di
Methanooctahydronaphthalene, ethyl tetracyclod
Decene, 6-ethylidene-2-tetracyclododecene,
Trimethanooctahydronaphthalene, pentacyclo
[8.4.0.1^2,5. 1^9,12. 0^8,13] -3-Hexa
Decene, heptacyclo [8.7.0.1^3,6.
1^10,17. 1^12,15. 0^2,7. 0^11,16] -4-eiko
Sen, heptacyclo [8.8.0.1^4,7. 1^11,18.
1^13,16. 0^3,8. 0^12,17-5-heneikosen,
5-ethylidenebicyclo [2.2.1] hept-2-e
, 8-ethylidenetetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 5-phenylbisic
B [2.2.1] hept-2-ene, 8-phenyltet
Lacyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
5-fluorobicyclo [2.2.1] hept-2-
Ene, 5-fluoromethylbicyclo [2.2.1] hep
To-2-ene, 5-trifluoromethylbicyclo [2.
2.1] Hept-2-ene, 5-pentafluoroethyl
Bicyclo [2.2.1] hept-2-ene, 5,5-di
Fluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2
-Ene, 5,5-bis (trifluoromethyl) bicyclo
[2.2.1] Hept-2-ene, 5,6-bis (tri
Fluoromethyl) bicyclo [2.2.1] hept-2-
Ene, 5-methyl-5-trifluoromethylbicyclo
[2.2.1] Hept-2-ene, 5,5,6-triff
Fluorobicyclo [2.2.1] hept-2-ene, 5,
5,6-tris (fluoromethyl) bicyclo [2.2.
1] Hept-2-ene, 5,5,6,6-tetrafluoro
Lobicyclo [2.2.1] hept-2-ene, 5,5
6,6-tetrakis (trifluoromethyl) bicyclo
[2.2.1] Hept-2-ene, 5,5-difluoro
-6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5,
6-bis (trifluoromethyl) bicyclo [2.2.
1] Hept-2-ene, 5,5,6-trifluoro-5
-Trifluoromethylbicyclo [2.2.1] hept-
2-ene, 5-fluoro-5-pentafluoroethyl-
6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5-
Heptafluoro-iso-propyl-6-trifluoro
Methylbicyclo [2.2.1] hept-2-ene, 5-
Chloro-5,6,6-trifluorobicyclo [2.2.
1] Hept-2-ene, 5,6-dichloro-5,6-bi
(Trifluoromethyl) bicyclo [2.2.1] hep
To-2-ene, 5,5,6-trifluoro-6-trif
Fluoromethoxybicyclo [2.2.1] hept-2-e
, 5,5,6-trifluoro-6-heptafluorop
Lopoxybicyclo [2.2.1] hept-2-ene, 8
-Fluorotetracyclo [4.4.0.1^2,5.
1^7,10] -3-Dodecene, 8-fluoromethyltetracy
Black [4.4.0.1^2,5. 1^7,10-3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-Dodecene, 8-trifluoromethyl
Letetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, 8-pentafluoroethyltetracyclo
[4.4.0.1^2,5. 1^7,10-3-dodecene, 8,
8-difluorotetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8,9-difluorotetracycline
B [4.4.0.1^2,5. 1^7,10-3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo
[4.4.0.1^2,5. 1 ^7,10-3-dodecene, 8,
9-bis (trifluoromethyl) tetracyclo [4.
4.0.1.^2,5. 1 ^7,10] -3-dodecene, 8-methyl
-8-trifluoromethyltetracyclo [4.4.0.
1^2,5. 1 ^7,10] -3-dodecene, 8,8,9-triff
Fluorotetracyclo [4.4.0.1^2,5. 1^7,10]-
3-dodecene, 8,8,9-tris (trifluoromethyl
Le) tetracyclo [4.4.0.1^{2, Five}. 1^7,10] -3
-Dodecene, 8,8,9,9-tetrafluorotetracy
Black [4.4.0.1^2,5. 1^7,10-3-dodecene,
8,8,9,9-tetrakis (trifluoromethyl) te
Toracyclo [4.4.0.1^{twenty five}. 1^7,10] -3-do
Decene, 8,8-difluoro-9,9-bis (trifur
(Oromethyl) tetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8,9-difluoro-8,9-
Bis (trifluoromethyl) tetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8,8,9-
Trifluoro-9-trifluoromethyltetracyclo
[4.4.0.1^{twenty five}. 1^7,10-3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxy
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 8,8,9-trifluoro-9-pentafluoro
Lopropoxytetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-fluoro-8-pentaful
Oroethyl-9,9-bis (trifluoromethyl) tet
Lacyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
, 8,9-difluoro-8-heptafluoroiso-
Propyl-9-trifluoromethyltetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8-chloro
-8,9,9-trifluorotetracyclo [4.4.
0.1^2,5. 1^7,10-3-Dodecene, 8,9-dichlone
B-8,9-Bis (trifluoromethyl) tetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
(2,2,2-trifluoroethoxycarbonyl) tetra
Lacyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
8-methyl-8- (2,2,2-trifluoroethene
Xycarbonyl) tetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene and the like. This
These can be used alone or in combination of two or more.
it can.

Among these specific monomers, 8-methyl-
8-methoxycarbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, 8-ethyl-tetracyclododecene [4.4.0.1 ^2, 5.
1 ^7,10 ] -3-dodecene, pentacyclo [7.4.0.
^12.5 . ^19,12 . [0 ^8,13 ] -3-pentadecene is preferred in that the finally obtained cyclic polyolefin resin has excellent heat resistance, and in particular, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0]. .1 ^2,5 . 1
^7,10 ] -3-dodecene is most preferable in terms of adhesion to the cladding material.

In the ring-opening polymerization step, the above-mentioned specific monomer may be subjected to ring-opening polymerization alone, or the above-mentioned specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization. . <Copolymerizable monomer> Specific examples of the copolymerizable monomer used in this case include cyclobutene, cyclopentene,
Cycloheptene, cyclooctene, tricyclo [5.
2.1.0 ^{2, 6} ] -3-decene, 5-ethylidene-2-
Examples thereof include cycloolefins such as norbornene and dicyclopentadiene. The carbon number of the cycloolefin is preferably 4 to 20, more preferably 5 to 20.
~ 12. These can be used alone or in combination of two or more.

<Ring-Opening Polymerization Catalyst> In the present invention, the ring-opening polymerization reaction is carried out in the presence of a metathesis catalyst. This metathesis catalyst comprises (a) at least one selected from compounds of W, Mo, and Re; (b) a group IA element (eg, Li, Na, K, etc.) of the Deming periodic table; For example, Mg, Ca, etc.), group IIB element (eg,
n, Cd, Hg, etc.), Group IIIA elements (eg, B, A
l), a compound of a group IVA element (eg, Si, Sn, Pb, etc.) or a group IVB element (eg, Ti, Zr), wherein at least one of the element-carbon bond or the element-hydrogen bond is formed. It is a catalyst comprising a combination with at least one member selected from those having. In this case, an additive (c) described below may be added to enhance the activity of the catalyst.

[0015] W, Mo or suitable as component (a)
As a typical example of the compound of Re, WCl₆, MoC
l_Five, ReOCl_ThreeJP-A-1-240517
Can be mentioned. (B) ingredients
For example, n-C_Four H₉ Li, (C_Two H_Five )_Three A
l, (C _Two H_Five )_Two AlCl, (C_TwoH_Five )_1.5 AlC
l_1.5 , (C_Two H_Five ) AlCl_Two, Methylalumoxa
And LiH described in JP-A-1-240517.
Can be mentioned.

As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used.
The compounds shown in JP-A-240517 can be used.

With respect to the amount of the metathesis catalyst used, the molar ratio of the component (a) to the specific monomer is "component (a): specific monomer", usually from 1: 500 to 1: 50,000. , Preferably 1: 1,000 to 1: 10,000
The range is 0. The ratio of the component (a) to the component (b) is such that “(a) :( b)” is 1: 1 to 1:
50, preferably in the range of 1: 2 to 1:30.
The molar ratio of the component (a) to the component (c) is "(c) :( a)" in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. It is said.

<Molecular weight regulator> The molecular weight of the ring-opened (co) polymer obtained can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent.
It is preferable to adjust the molecular weight by coexisting a molecular weight modifier in the reaction system. Here, suitable molecular weight regulators include, for example, ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,
Examples thereof include α-olefins such as -nonene and 1-decene and styrene, among which 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used alone or in combination of two or more. The amount of the molecular weight modifier used is 0.005 to 0.5 to 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.
6 mol, preferably 0.02 to 0.5 mol.

<Solvent for Ring-Opening Polymerization Reaction> Examples of the solvent (solvent for dissolving the specific monomer, the metathesis catalyst and the molecular weight modifier) used in the ring-opening polymerization reaction include pentane, hexane, heptane, octane, nonane, and the like. Alkanes such as decane; cyclohexane, cycloheptane,
Cycloalkanes such as cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; chlorobutane;
Halogenated alkanes such as bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, and tetrachloroethylene;
Compounds such as aryl halides; ethyl acetate, acetic acid n
-Butyl, iso-butyl acetate, methyl propionate,
Saturated carboxylic esters such as dimethoxyethane; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane can be used, and these can be used alone or in combination. Of these, aromatic hydrocarbons are preferred. The amount of the solvent used is such that “solvent: specific monomer (weight ratio)” is usually 1: 1 to 1
The amount is 10: 1, preferably 1: 1 to 5: 1.

The ring-opened (co) polymer obtained as described above may contain a known antioxidant such as 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-
3,3'-di-tert-butyl-5,5'-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane; UV absorber, for example, It can be stabilized by adding 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and the like. In addition, additives such as a lubricant can be added for the purpose of improving workability.

The ring-opened (co) polymer obtained as described above can be used as a film as it is, but it is further subjected to hydrogenation to use a hydrogenated product of the ring-opened (co) polymer. Is preferred. <Hydrogenation catalyst> The hydrogenation reaction is carried out in a usual manner, that is, by adding a hydrogenation catalyst to a solution of a ring-opening (co) polymer,
This is performed by applying hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm at 0 to 200 ° C, preferably 20 to 180 ° C. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. As the hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are known.

Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst such as palladium, platinum, nickel, rhodium and ruthenium is supported on a carrier such as carbon, silica, alumina and titania. Examples of the homogeneous catalyst include nickel / triethylaluminum naphthenate, nickel acetylacetonate / triethylaluminum, cobalt octoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, and chlorotris (triphenylphosphine) rhodium. , Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of the catalyst may be powdery or granular. These hydrogenation catalysts have a “ring-opening (co) polymer: hydrogenation catalyst (weight ratio)” of 1: 1 ×
It is used at a ratio of 10 ⁻⁶ to 1: 2. in this way,
The hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its properties are not deteriorated by heating during molding or use as a product. Here, the hydrogenation rate is 60 MHz, ¹
The value measured by 1 H-NMR is usually at least 50%, preferably at least 70%, more preferably at least 90%. The higher the hydrogenation rate, the better the stability to heat and light. The hydrogenated (co) polymer used as the cyclic polyolefin-based resin of the present invention preferably has a gel content of 5% by weight or less in the hydrogenated (co) polymer. It is particularly preferred that the content is not more than weight%. If the gel content exceeds 5% by weight, molding defects such as fish eyes and die lines are likely to occur in film molding. The above-mentioned gel content means that at a temperature of 25 ° C., 50 g of a hydrogenated (co) polymer is dissolved in tetrahydrofuran so as to have a concentration of 1%, and this solution is weighed in advance to a membrane having a pore size of 0.5 μm. It is obtained by filtering using a filter, drying the filter after filtration, and calculating the gel content from the increase in weight.

The cyclic polyolefin resin of the present invention
The above ring-opened (co) polymer is
After cyclization, a hydrogenated (co) polymer is also used.
Can be used. <Cyclization by Friedel Craft reaction>
How to cyclize a polymer by the Friedel-Crafts reaction
Although not particularly limited, JP-A-50-1543
A known method using an acidic compound described in JP-A-99-99 is adopted.
Can be used. As the acidic compound, specifically, AlCl
_Three, BF_Three, FeCl_Three, Al_TwoO_Three, HCl, CH_Three
Lewis such as ClCOOH, zeolite, activated clay, etc.
Acids and Bronsted acids are used. Cyclized ring opening
The (co) polymer is hydrogenated similarly to the above ring-opened (co) polymer.
Can be added.

Further, as the cyclic polyolefin resin, a saturated copolymer of a specific monomer and an unsaturated double bond-containing compound may be mentioned. <Unsaturated double bond-containing compound constituting a saturated copolymer>
Examples of the unsaturated double bond-containing compound to be copolymerized with the specific monomer include olefin compounds having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, such as ethylene, propylene, and butene. The preferred use range of the specific monomer / unsaturated double bond-containing compound is 90/1 by weight.
0 to 40/60, more preferably 85/15 to
50/50.

<Catalyst Used for Obtaining Saturated Copolymer>
Copolymerization reaction between specific monomer and unsaturated double bond-containing compound
The catalysts used for vanadium compounds and organic
A catalyst comprising a luminium compound is used. Vanaji
The compound represented by the general formula VO (OR)_aX_bOr
V (OR)_cX _d[Where R is a hydrocarbon group, X is halo
A gen atom, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a +
b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ (c + d) ≦
Vanadium compound represented by formula [4]
Child-donating appendages are used. Al donors
Coal, phenols, ketones, aldehydes, carvone
Acids, esters of organic or inorganic acids, ethers, acids
Donation of oxygen-containing electrons such as oxides, acid anhydrides and alkoxysilanes
Body, ammonia, amine, nitrile, isocyanate
Any nitrogen-containing electron donor can be used. Organic aluminum
At least one aluminum compound catalyst component
Has a hydrogen-carbon or aluminum-hydrogen bond
At least one member selected from the following is used. Touch
The ratio of the medium component is aluminum source to vanadium atom.
2 or more, preferably 2 to 50,
It is preferably in the range of 3 to 20.

<Solvent used for obtaining saturated copolymer>
As the solvent used in the copolymerization reaction between the specific monomer and the unsaturated double bond-containing compound, the same solvents as those used in the ring-opening polymerization reaction can be used, for example, pentane, hexane, heptane Alkane such as octane, nonane and decane; cycloalkane such as cyclohexane and methylcyclohexane; aromatic hydrocarbon such as benzene, toluene and xylene and halogen derivatives thereof, among which cyclohexane is preferable. Adjustment of the molecular weight of the obtained saturated copolymer is usually performed using hydrogen.

Further, as the cyclic polyolefin-based resin, an addition type (co) of one or more monomers selected from the above-mentioned specific monomers, vinyl-based cyclic hydrocarbon-based monomers and cyclopentadiene-based monomers is used. Polymers and their hydrogenated (co) polymers can also be used. <Vinyl cyclic hydrocarbon monomer> Examples of the vinyl cyclic hydrocarbon monomer include vinyl cyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene, and 4-vinyl. 5-membered ring hydrocarbon monomer such as vinylcyclopentane monomer such as cyclopentane and 4-isopropenylcyclopentane, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-iso Vinylcyclohexene-based monomers such as propenylcyclohexene, 2-methyl-4-vinylcyclohexene and 2-methyl-4-isopropenylcyclohexene; vinylcyclohexane-based monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane Monomer, styrene, α-methyls Ren, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenyl styrene,
styrene monomers such as p-methoxystyrene, d-terpene, 1-terpene, diterpene, d-limonene, 1
-Terpene monomers such as limonene and dipentene;
Examples include vinylcycloheptene-based monomers such as vinylcycloheptene and 4-isopropenylcycloheptene, and vinylcycloheptane-based monomers such as 4-vinylcycloheptane and 4-isopropenylcycloheptane.
Preferred are styrene and α-methylstyrene. These can be used alone or in combination of two or more.

<Cyclopentadiene-based monomer> Examples of the cyclopentadiene-based monomer used for the addition-type (co) polymer monomer of the present invention include cyclopentadiene and
Examples thereof include 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, and 5,5-methylcyclopentadiene. Preferred is cyclopentadiene. These can be used alone or in combination of two or more.

The addition type (co) polymer of at least one kind of monomer selected from the above-mentioned specific monomer, vinyl-based cyclic hydrocarbon-based monomer and cyclopentadiene-based monomer can be used as the above-mentioned specific monomer. And an unsaturated double bond-containing compound. The hydrogenated (co) polymer of the addition type (co) polymer can be obtained by the same hydrogenation method as the hydrogenated (co) polymer of the ring-opened (co) polymer. The resin for a laminated film of the present invention is preferably a norbornene-based resin among the cyclic polyolefin-based resins, and specifically, Arton (trade name, manufactured by JSR Corporation) is exemplified.

The cyclic polyolefin resin used in the present invention preferably has an intrinsic viscosity [η] measured in chlorobenzene at 30 ° C. of preferably 0.2 to 1.5 dl /.
g, more preferably 0.3 to 1 dl / g. When the intrinsic viscosity [η] is less than 0.2 dl / g, mechanical properties are poor and impact resistance is low. On the other hand, when it exceeds 1.5 dl / g, moldability is poor. When the weight average molecular weight is in the above range, the molding processability, heat resistance, water resistance, chemical resistance, mechanical properties, and the like of the cyclic polyolefin resin are improved. The flexural modulus of the cyclic polyolefin-based resin is preferably from 1.0 × 10 ^{4 to} 4.0 × 10 ⁴ kgf when measured in accordance with the ASTM D790 test method.
/ Cm ² , more preferably 2.5 × 10 ^{4 to} 3.5 ×
10 ⁴ kgf / cm ² , the thermal conductivity is preferably 0.1 at room temperature, as measured by the unsteady cooling method / hot wire probe method.
05 to 10 W / mK, more preferably 0.1 to 0.5
W / mK.

The ring-opened (co) polymer, hydrogenated (co) polymer, saturated copolymer, or addition-type (co) polymer and the ring-opened (co) polymer as described above are used in the present invention. It is composed of a hydrogenated (co) polymer,
To this, a known antioxidant, an ultraviolet absorber or the like can be added for further stabilization. In addition, additives used in conventional resin processing, such as a lubricant, can be added to improve processability.

In the present invention, a film made of a cyclic polyolefin resin is formed into a sheet by a solution casting method or a melt molding method, and the film is made to have a uniform thickness by stretching, surface pressing, passing through a die, or the like. Can be obtained. As the solvent for the solution casting method, any of the solvents mentioned as the above-mentioned solvent for polymerization reaction, such as toluene, can be used as appropriate. As the melt molding method, T
A method such as extrusion molding from a die or an inflation method is used. In the case of the melt molding method, the melting temperature is preferably 200 to 350 ° C, more preferably 2 to 350 ° C.
It is 50-330 ° C, particularly preferably 280-320 ° C. The thickness of the obtained resin film is preferably 3 to 3
The thickness is 00 μm, more preferably 5 to 150 μm, and particularly preferably 7 to 75 μm. When the thickness is less than 3 μm, the film is weak and the mechanical strength is reduced, and the electric insulation is undesirably reduced. On the other hand, if it exceeds 300 μm, the flexibility is reduced and it is difficult to obtain a flexible printed board.

In the present invention, the metal thin film is formed on at least one surface of a film made of a cyclic polyolefin resin. There is no particular limitation on the material of the metal thin film, as long as it shows conductivity as the substrate wiring. For example, Be, Mg, Al, Si, Ca, Sc, Ti,
V, Cr, Mn, Fe, Co, Ni, Cu, Zn, G
a, Ge, As, Se, Sr, Y, Zr, Nb, Mo,
Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, S
b, Te, Ba, lanthanoid metal, Hf, Ta,
W, Re, Os, Ir, Pt, Au, Tl, Pb, Bi
And solid metals at room temperature, and alloys thereof. Examples of the alloy include binary alloys such as Fe-Co alloys, Fe-Ni alloys, Fe-Si alloys, Fe-C alloys, Cu-Zn alloys, Cu-Sn alloys, and Ni-Cr alloys. Also, ternary alloys such as Fe-Ni-Cr alloys, and other quaternary or more alloys can be used. Further, conductive metal oxides such as tin oxide, indium oxide, vanadium oxide, and ruthenium oxide can also be used. Preferred are gold, silver, copper, nickel and aluminum.

The method for forming the metal thin film is not particularly limited, and may be physical vapor deposition (PVD) or chemical vapor deposition (CV).
It can be formed by dry plating such as D), electroless plating, electroplating, impact plating, or wet plating such as spraying. A particularly preferred forming method is dry plating such as physical vapor deposition (PVD) and chemical vapor deposition (CVD). As the physical vapor deposition method (PVD), a vacuum vapor deposition method, a sputtering method, an ion plating method, or the like can be used. As the vacuum evaporation method, any of known methods such as a heating evaporation method, a laser physical evaporation method, and an induction heating evaporation method can be used. As the vacuum deposition method, a continuous winding type is usually employed industrially, but it is needless to say that a single-plate type may be used. Chemical vapor deposition (CVD) is a method in which energy such as heat or light is applied to a gaseous raw material introduced into a reaction chamber to induce various chemical reactions to deposit and coat a substance on a substrate. For example, a plasma polymerization method or a photopolymerization method using ultraviolet rays can be used. The above-mentioned PVD and CVD have excellent adhesion between the resin film and the metal thin film, but have a low metal deposition rate and a long time to form a metal thin film of 1 μm or more.

When a resin film is directly plated by an electroless plating method, the resin film must be subjected to a chemical etching treatment in advance because the adhesion between the resin film and the metal thin film is poor. Further, the electroplating method has a high deposition rate and is effective for obtaining a thick film, but cannot directly electroplate a resin film. When performing electroplating directly on a resin film, it is necessary to apply a conductive paste, a conductive coating agent, or a conductive polymer material on the resin film in advance to impart conductivity. As a usual method of forming a metal thin film of 1 μm or more, a metal thin film having a thickness of less than 1 μm is formed by PVD or CVD, and the thickness of the metal thin film is adjusted by electroplating or electroless plating. There is a method of increasing the thickness. The metals used in the two methods may be the same or different. Before forming the metal thin film, coating with an anchor coat agent and pretreatment such as chemical etching, corona treatment, and plasma treatment may be performed in advance.

In the present invention, the thickness of the metal thin film is preferably 0.1 to 100 μm, more preferably 0.5 to 100 μm.
It is 50 μm, particularly preferably 1 to 25 μm. When the thickness is less than 0.1 μm, the physical properties such as the strength of the metal thin film are remarkably reduced, and there is a problem that it is difficult to process. On the other hand, 100
If it exceeds μm, it will be difficult to maintain sufficient flexibility of the substrate.

The laminated film of the present invention is etched by a known method to form a circuit pattern.
It can be a flexible printed circuit board (FPC). A single-sided FPC is obtained from a resin film having a metal thin film formed only on one side, and a double-sided FPC is obtained from a resin film having a metal thin film formed on both sides.
In a double-sided FPC, a double-sided through-hole circuit can be formed by conducting between both sides. Further, an FPC having a complicated three-dimensional structure circuit can be formed by a known method such as a multi-layer structure by a build-up method. As described above, with the laminated film of the present invention and the flexible printed circuit board using the laminated film, it is easy to reduce the size, weight, and density of electric and electronic devices.

[0038]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, parts and%
Are by weight unless otherwise indicated. Various measurements in the examples are as follows.

Intrinsic viscosity [η] A sample was dissolved in chlorobenzene, five samples having different concentrations were prepared, and the reduced viscosity at each concentration was measured at 30 ° C using an Ubbelohde viscosity tube. I asked. Glass transition temperature (Tg) Scanning calorimeter (DS) manufactured by Seiko Instruments Inc.
C) Measurement was performed by DSC-6200 in a nitrogen atmosphere at a heating rate of 10 ° C./min. Hydrogenation rate In case of hydrogenated homopolymer, 60 MHz, ¹ H-N
The MR was measured, and the hydrogenation rate was measured from the ratio of the respective absorption intensities of methyl hydrogen and olefinic hydrogen of the ester group or the ratio of the respective absorption intensities of paraffinic hydrogen and olefinic hydrogen. In the case of a hydrogenated copolymer, it was calculated by comparing ¹ H-NMR absorption of the copolymer after polymerization with that of the hydrogenated copolymer after hydrogenation. The thickness of the film was measured with a dial type thickness gauge.

Peel Strength Using a tensile tester manufactured by Instron, one end of the chuck was attached to a copper film having a width of 10 mm, the other end was attached to a resin film, and the crosshead was moved at a speed of 10 mm / min in the vertical direction. Then, a tensile test was performed on the laminated film to determine the peel strength. The peel strength was measured at 25 ° C. without heat treatment of the laminated film (before heating), and measured after heating at 170 ° C. for 60 minutes (after heating). A sample (5.0 cm long) of a resin film (a film on which no metal thin film is laminated) under the conditions of a water absorption expansion coefficient, a water absorption rate of 23 ° C., and 50% RH.
X 5.0 cm) was left to measure the dimensional change and weight change of the sample over time. The coefficient of hygroscopic expansion [cm / cm / (% RH)] was calculated from the change in sample size, and the water absorption rate (%) was calculated from the amount of water absorbed at the time when the sample weight no longer changed.

Reference Example 1 (Production of cyclic polyolefin resin)
) 8-methyl-8-methoxycarbonyltetracyclo
[4.4.0.1^2,5. 1 ^7,10] Dodeca-3-ene 10
0 g, 1,2-dimethoxyethane 60 g, cyclohexa
240 g, 1-hexene 9 g, and diethylaluminum
0.96mol / l toluene chloride dissolved in toluene
3.4 ml of the liquid in an autoclave with an internal volume of 1 liter
added. Meanwhile, in another flask,
0.05 mol / l 1,2-dimethoxyethane solution
20 ml of liquid and 0.1 mol / l of paraaldehyde
10 ml of a 1,2-dimethoxyethane solution was mixed. This
Of 4.9 ml of the mixed solution in the above autoclave.
Was added to the material. After sealing, heat the mixture to 80 ° C.
Stirring was performed for 5 hours. In the obtained polymer solution, 1,2-
2/8 of dimethoxyethane and cyclohexane (weight ratio)
1/10 (weight ratio) by adding a mixed solvent of
And then add 20 g of triethanolamine to add 10 g
Stirred for minutes.

To this polymerization solution, 500 g of methanol was added, and the mixture was stirred for 30 minutes and allowed to stand. The upper layer separated into two layers was removed, methanol was added again, and the mixture was stirred and allowed to stand, and then the upper layer was removed. The same operation was further repeated twice, and the obtained lower layer was appropriately diluted with cyclohexane and 1,2-dimethoxyethane to obtain a cyclohexane-1,2-dimethoxyethane solution having a polymer concentration of 10%. 20 g of palladium / silica magnesia (manufactured by Nikki Chemical Co., Ltd., palladium amount = 5%) was added to this solution, and hydrogen pressure was set to 40 in an autoclave.
After reacting at 165 ° C for 4 hours as kg / cm ² ,
The hydrogenation catalyst was removed by filtration to obtain a hydrogenated copolymer solution.

Also, pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] with respect to the hydrogenated copolymer
%, And the solvent was removed at 380 ° C. under reduced pressure. Next, the molten resin is pelletized by an extruder under a nitrogen atmosphere, and an intrinsic viscosity [η] of 0.4 dl / g (3
A thermoplastic resin A having a degree of hydrogenation of 99.5% and a glass transition temperature of 168 ° C. was obtained.

Reference Example 2 (Production of Cyclic Polyolefin Film by Casting Method) 20% of Cyclic Polyolefin Resin A Obtained in Reference Example 1
The toluene solution was passed through a die to form a layer having a uniform thickness, which was dried at 120 ° C. to obtain a cast film (film A) having a thickness of 50 μm. Reference Example 3 (Production of Cyclic Polyolefin Film by Extrusion Method) The cyclic polyolefin resin A obtained in Reference Example 1 was heated and melted at 300 ° C. using a melt extruder, extruded from a T-type die, and extruded to a thickness of 50 μm. An extruded film (film B) was obtained.

Example 1 (Preparation of Laminated Film and Flexible Printed Board) A copper thin film having a thickness of 0.2 μm was formed on one surface of the cast film (film A) by a sputtering method.
Further, the thickness of the copper thin film is reduced to 10 μm using an electrolytic copper plating method.
To form a single-layer film. After applying a resist on the copper thin film of the one-layer film, patterning is performed using a mask having a predetermined shape, and then, etching is performed to process a printed circuit board into a pattern having a line width of 90 μm. A printed circuit board was obtained. The peel strength at room temperature (25 ° C.) of the laminated film after patterning of the obtained flexible printed circuit board was 1,400 g / cm. The peel strength after heating at 170 ° C. for 60 minutes was 1,350 g / cm. Further, when the change in water absorption of the resin substrate was measured under an environment of 23 ° C. and 50% RH, the water absorption was 0.2%,
The coefficient of hygroscopic expansion was 4 × 10 ⁻⁶ cm / cm / (% RH).

Example 2 A flexible printed circuit board was prepared for an extruded film (film B) in exactly the same manner as in Example 1, and the peel strength was measured. The result was at room temperature (25 ° C)
The peel strength after heating at 1,400 g / cm at 170 ° C. for 60 minutes was 1,350 g / cm. 23 ° C, 50
% RH environment, the water absorption of the resin substrate is 0.2%,
The coefficient of hygroscopic expansion was 4 × 10 ⁻⁶ cm / cm / (% RH).

Comparative Example 1 A polyimide film (50 μm thick) manufactured by Kanegafuchi Chemical Industry Co., Ltd.
m) A flexible printed circuit board was produced in the same manner as in Example 1 except that (Film C) was used for NPI-50. The peel strength, the coefficient of hygroscopic expansion and the water absorption of this substrate were measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 A flexible printed board was produced in the same manner as in Example 1 except that Lumirror # 50 (film D), a polyester film (thickness: 50 μm) manufactured by Toray Industries, Inc. was used. The peel strength, the coefficient of hygroscopic expansion and the water absorption of this substrate were measured in the same manner as in Example 1. Table 1 shows the results.

[0049]

[Table 1]

[0050]

The laminated film of the present invention has a metal thin film formed on at least one surface of a cyclic polyolefin resin film, is excellent in heat resistance, has little dimensional change due to water absorption, and has a metal thin film and a resin film. Indicate sufficient adhesion. Furthermore, the flexible printed circuit board obtained by using the laminated film of the present invention has high reliability and can be used as a wiring board for applications in which a large number of fine electrodes need to be manufactured with high precision. As described above, with the laminated film of the present invention and the flexible printed circuit board using the laminated film, it is easy to reduce the size, weight, and density of electric and electronic devices.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 1/03 670 H05K 1/03 670A // C08L 23:00 C08L 23:00 45:00 45: 00F Terms (reference) 4F071 AA04 AA21 AF19 AF45 AF54 AF58 AH13 BA02 BB02 BC02 BC12 4F100 AB01B AB01C AB10B AB10C AB16B AB16C AB17B AB17C AB24B AB24C AB25B AB25C AB33B AB33C AK02A BA02 BA03 BA02 BA25B02B02B00A CA35 CA36 CA38 CA43 CA45 CA46 CB01 CB03 CB04 CD01 CD02 CD03 CD04 CD05 CE03 CG08

Claims (5)

[Claims] 1. A laminated film, wherein a metal thin film is formed on at least one surface of a film made of a cyclic polyolefin-based resin. 2. The laminated film according to claim 1, wherein the cyclic polyolefin resin contains at least one polar group selected from the group consisting of an ether group, an ester group, a carbonyl group, and a hydroxyl group in the structure. 3. The laminated film according to claim 1, wherein the thickness of the film made of the cyclic polyolefin resin is 3 to 300 μm, and the thickness of the thin metal film is 0.1 to 100 μm. 4. The metal thin film has at least one selected from the group consisting of gold, silver, copper, nickel, and aluminum.
The laminated film according to any one of claims 1 to 3, comprising a seed. 5. A printed circuit board using the laminated film according to claim 1.