JP2003136631A - Flexible copper-clad laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flexible copper-clad laminated sheet which shows a sufficient mechanical strength and at the same time, outstanding heat resistance, workability and adhesive properties, especially a superb solder heat resistance. SOLUTION: The flexible copper-clad laminated sheet has an adhesive layer formed on one side or both sides of a polymer film and a copper foil laminated on one side or both sides of the polymer film through the adhesive layer. In this flexible copper-clad laminated sheet, a resin composition constituted of a polyimide composed of a specific dianhydride esterate and a specific diamine and an epoxy resin is included in the adhesive layer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flexible copper-clad laminate using a bonding sheet having an adhesive layer made of a resin composition containing a polyimide resin and an epoxy resin on one side or both sides, and having sufficient mechanical strength. The present invention relates to a flexible copper clad laminate having excellent heat resistance, workability and adhesiveness, and particularly excellent solder heat resistance.

[0002]

2. Description of the Related Art In recent years, electronic devices have become more sophisticated, have higher performance,
The miniaturization is progressing, and the miniaturization and the weight reduction of the electronic components used in association with them are demanded. Therefore, semiconductor device packaging methods and wiring materials or wiring components for mounting them have been required to have higher density, higher function, and higher performance. In particular, semiconductor packages, COL and LOC packages, MCM (Mu
There is a demand for an insulating adhesive material having good adhesive properties, which can be suitably used as a high-density mounting material such as an lti Chip Module), a printed wiring board material such as a multilayer flexible printed circuit, and an aerospace material. Conventionally,
Acrylic resins, phenol resins, epoxy resins, polyimide resins, etc. are known as resins exhibiting good mechanical properties, heat resistance properties, and insulation properties in semiconductor packages and other mounting materials.

However, phenolic and epoxy resins, which are excellent in adhesiveness, are inferior in flexibility. The acrylic resin, which is excellent in flexibility, has a problem of low heat resistance.

In order to solve these problems, the use of polyimide resin has been studied. Since polyimide resin has excellent heat resistance among various organic polymers, it is widely used in the fields of space and aeronautics to the field of electronic communications, and is also used as an adhesive. However, a polyimide resin adhesive having high heat resistance requires a high temperature of about 300 ° C. and a high pressure for bonding, and the adhesive force is not so high. Also, the PCT required for flexible printed wiring boards
(Pressure cooker test) PCT for resistance
After that, there was also a problem that the adhesive strength was significantly reduced. Further, in a solder bath exposed to a high temperature of 250 ° C. or higher, water contained in the adhesive material evaporates, causing whitening and foaming, which impairs the adhesion between the copper foil and the adhesive layer (this phenomenon in the present specification. Is called a reflow crack).

[0005]

SUMMARY OF THE INVENTION Therefore, the problem to be solved by the present invention is excellent in heat resistance, workability and adhesiveness while having sufficient mechanical strength, and particularly excellent in solder heat resistance. To provide a flexible copper clad laminate.

[0006]

SUMMARY OF THE INVENTION The present invention provides a novel flexible copper clad laminate having the following constitution, which achieves the above object. 1) In a flexible copper clad laminate obtained by providing an adhesive layer on one side or both sides of a polymer film and laminating a copper foil on one side or both sides of the polymer film via the adhesive layer, the adhesive layer is It is a resin composition containing a polyimide resin and a thermosetting resin obtained by reacting an acid dianhydride component containing an acid dianhydride represented by the following general formula (1) with a diamine component. Flexible copper clad laminate.

[0007]

[Chemical 7] (In the formula, V is —O— or —O—T—O—
Represents a divalent organic group) 2) The diamine component is a diamine component containing a diamine represented by the following general formula (2) 1)
The flexible copper clad laminate described.

[0008]

[Chemical 8] (Wherein, Y is, -C (= O) -, - SO 2 -, - O-,
_{-S -, - (CH 2)} m -, - NHCO -, - C (C
_{H 3) 2 -, - C} (CF 3) 2 -, - C (= O) O-, or indicate binding. m and n are integers of 1 or more and 5 or less. 3) The flexible copper-clad laminate according to 1), wherein the diamine component is a diamine component containing a diamine having a hydroxyl group and / or a carboxyl group. 4) The flexible copper-clad laminate according to 1), wherein the diamine component is a diamine component represented by the general formula (2) and a diamine having a hydroxyl group and / or a carboxyl group. 5) The flexible copper clad laminate according to 3) or 4), wherein the diamine having a hydroxyl group is 3,3′-dihydroxy-4,4′-diaminobiphenyl represented by the following formula (3). .

[0009]

[Chemical 9] 6) T in the general formula (1) of the acid dianhydride component is

[0010]

[Chemical 10] Groups represented by and

[0011]

[Chemical 11] (Wherein, Z _{is, -C Q H 2Q -, -} C (= O) -, - SO 2
It is a divalent group selected from the group consisting of-, -O- and -S-, and Q is an integer of 1 to 5. ) A group consisting of groups represented by the formula (1), wherein the acid dianhydride represented by the general formula (1) is at least one acid dianhydride selected from the group 1) to The flexible copper-clad laminate according to any one of 5). 7) The said polyimide resin makes the diamine component represented by General formula (2) 60-99 mol% of all diamine components,
Flexible according to 5) or 6), which is a polyimide obtained by reacting a diamine component containing 3,3′-dihydroxy-4,4′-diaminobiphenyl in an amount of 40 to 1 mol% of all diamine components. Copper clad laminate. 8) The diamine represented by the general formula (2) is a diamine represented by the following formula (4) and having an amino group at the meta position, 2), 4), 5), 6), The flexible copper clad laminate according to any one of 7).

[0012]

[Chemical 12] (Wherein, Y is, -C (= O) -, - SO 2 -, - O-,
_{-S -, - (CH 2)} m -, - NHCO -, - C (C
_{H 3) 2 -, - C} (CF 3) 2 -, - C (= O) O-, or indicate binding. m and n are integers of 1 or more and 5 or less. ) 9) The flexible copper-clad laminate according to any one of 1) to 8), wherein the copper foil has a thickness of 5 μm or less. 10) The flexible copper-clad laminate according to any one of 1) to 9), wherein the polymer film is a polyimide film.

According to the present invention, a flexible copper clad laminate having sufficient mechanical strength, excellent heat resistance, workability and adhesiveness, and particularly excellent in solder heat resistance is provided.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The flexible copper clad laminate of the present invention comprises an adhesive layer, a polymer film and a copper foil. The adhesive layer, polymer film and copper foil will be described below. The adhesive used in the present invention is a resin composition containing a polyimide resin having a specific composition and a thermosetting resin.

(Polyimide Resin) The polyimide resin used in the present invention is preferably a soluble polyimide resin. In the present invention, “soluble” of the soluble polyimide resin means that it dissolves in dioxolane in an amount of 1% by weight or more in the temperature range of room temperature to 100 ° C.

Such a polyimide resin comprises an acid dianhydride component containing an acid dianhydride represented by the following general formula (1):
It is obtained by reacting with a diamine component. The polyimide resin is obtained by reacting an acid dianhydride component and a diamine component, and the acid dianhydride component contains the acid dianhydride represented by the general formula (1).

[0017]

[Chemical 13] (In the formula, V is -O- or -OT-O-, and T is 2
Represents a valent organic group) Among these, T in the general formula (1) is

[0018]

[Chemical 14] Groups represented by and

[0019]

[Chemical 15] (Wherein, Z _{is, -C Q H 2Q -, -} C (= O) -, - SO 2
It is a divalent group selected from the group consisting of-, -O- and -S-, and Q is an integer of 1 to 5. ) In the group consisting of groups represented by the formula (1), using at least one kind of acid dianhydride selected from the group as the acid dianhydride represented by the general formula (1) is solder heat resistance and PCT resistance. It is preferable from the viewpoint that a resin composition having excellent properties can be obtained. Also, the following

[0020]

[Chemical 16] It is also possible to use the acid dianhydride represented by
It is preferable because a resin composition having excellent T resistance can be obtained.

Among these acid dianhydrides, T in the general formula (1) is

[0022]

[Chemical 17] When the 4,4 '-(4,4'-isopropylidenediphenoxy) bisphthalic anhydride represented by is used, the solubility of the polyimide obtained in a solvent and the processing characteristics and heat resistance of the adhesive obtained using the polyimide obtained Is particularly preferable in terms of improving the balance.

The acid dianhydride is 50% of the total acid dianhydride component.
It is preferable to use mol% or more.

Examples of the acid dianhydride other than the acid dianhydride represented by the general formula (1) include the followings.

Pyromellitic dianhydride, 3,3 ', 4
4'-benzophenone tetracarboxylic dianhydride, 3,
3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 4 4'-oxydiphthalic anhydride,
3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) ) Diphenylpropanoic acid dianhydride, 4,
4'-hexafluoroisopropylidene diphthalic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, p -Phenylene diphthalic anhydride and the like, but not limited to.

The polyimide resin has the general formula (2)

[0027]

[Chemical 18] What was obtained using the diamine compound represented by is preferable. (Wherein, Y is, -C (= O) -, - SO 2 -, - O-,
_{-S -, - (CH 2)} m -, - NHCO -, - C (C
_{H 3) 2 -, - C} (CF 3) 2 -, - C (= O) O-, or indicate binding. m and n are integers of 1 or more and 5 or less. ) The diamine compounds may be used alone or in combination of two or more kinds. Here, in equation (2),
A plurality of Y's may be the same or different in each repeating unit, and a hydrocarbon group such as a methyl group or an ethyl group or a halogen group such as Br or Cl is introduced into each benzene ring. Is also good.

Examples of the diamine compound represented by the general formula (2) include bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1, 1-bis [4- (3
-Aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2- Bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4-
(3-Aminophenoxy) phenyl] propane, 2,
2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl ] -1, 1, 1, 3, 3,
3-hexafluoropropane, 2,2-bis [4-
(4-Aminophenoxy) phenyl] -1,1,1,
3,3,3-Hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4'-bis (4-aminophenoxy) ) Benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4-
(3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone,
Bis [4- (3-aminophenoxy) phenyl] sulfide, Bis [4- (4-aminophenoxy) phenyl] sulfide, Bis [4- (3-aminophenoxy) phenyl] sulfone, Bis [4- (4-amino) Phenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4-
(4-Aminophenoxy) phenyl] ether, 1,
4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3
-(4-Aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-
Bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis
[4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4- {4- (4
-Aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy)-
Examples include α, α-dimethylbenzyl] benzene and 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene.

Further, in the diamine compound represented by the general formula (2), a diamine compound having an amino group at the meta position,
That is, the diamine compound represented by the general formula (4) is preferable because it gives a thermoplastic polyimide resin having higher solubility than the diamine compound having an amino group at the para position.

[0030]

[Chemical 19] (Wherein, Y is, -C (= O) -, - SO 2 -, - O-,
_{-S -, - (CH 2)} m -, - NHCO -, - C (C
_{H 3) 2 -, - C} (CF 3) 2 -, - C (= O) O-, or indicate binding. m and n are integers of 1 or more and 5 or less. ) The diamine compound represented by the general formula (3) is 1,1
-Bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy)
Phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4-
(3-Aminophenoxy) phenyl] butane, 2,2
-Bis [3- (3-aminophenoxy) phenyl]-
1,1,1,3,3,3-hexafluoropropane,
1,3-bis (3-aminophenoxy) benzene, 1,
4-bis (3-aminophenoxy) benzene, bis [4- (3-aminophenoxy) phenyl] ketone,
Bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis [4 -(3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4'-bis [3- (3-aminophenoxy)
Examples thereof include benzoyl] diphenyl ether.

Of the above diamine compounds, 1,3-
By using bis (3-aminophenoxy) benzene, solubility in various organic solvents, solder heat resistance, PCT
It is particularly preferable because it gives a resin composition having excellent resistance.

The diamine component is also preferably a polyimide resin obtained by using a diamine having a hydroxyl group and / or a carboxyl group. Since a hydroxyl group and / or a carboxyl group is introduced into a polyimide resin using a diamine having a hydroxyl group and / or a carboxyl group, it can be reacted with a compound having a group capable of reacting with the hydroxyl group and / or the carboxyl group. Therefore, if a resin having a group capable of reacting with a hydroxyl group and / or a carboxyl group is used as a thermosetting resin component described below, crosslinking proceeds, and further heat resistance, solder heat resistance and P
It is possible to provide a resin composition having excellent CT resistance.

The diamine having a hydroxyl group and / or a carboxyl group is not particularly limited as long as it has a hydroxyl group and / or a carboxyl group. For example, diaminophenols such as 2,4-diaminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'- Diamino-2,2 ',
Hydroxybiphenyl compounds such as 5,5′-tetrahydroxybiphenyl, 3,3′-diamino-4,4′-
Dihydroxydiphenylmethane, 4,4'-diamino-
3,3'-dihydroxydiphenylmethane, 4,4 '
-Diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydroxyphenyl] propane, 2,2- Bis [3-amino-4-
Hydroxyphenyl] hexafluoropropane, 4,
Hydroxydiphenylalkanes such as hydroxydiphenylmethane such as 4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylmethane, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 4,
4'-diamino-3,3'-dihydroxydiphenyl ether, 4,4'-diamino-2,2'-dihydroxydiphenyl ether, 4,4'-diamino-2,2 ',
Hydroxydiphenyl ether compounds such as 5,5′-tetrahydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone,
4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, 4,4'-diamino-2,2'-dihydroxydiphenyl sulfone, 4,4'-diamino-
Diphenyl sulfone compounds such as 2,2 ′, 5,5′-tetrahydroxydiphenyl sulfone, 2,2-bis
Bis [(hydroxyphenyl) phenyl] alkane compounds such as [4- (4-amino-3-hydroxyphenoxy) phenyl] propane, 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, etc. Bis (hydroxyphenoxy) biphenyl compounds, 2,2-bis
Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone, diaminobenzoic acids such as 3,5-diaminobenzoic acid, 3,3′-diamino-4 ，
4'-dicarboxybiphenyl, 4,4'-diamino-
Carboxybiphenyl compounds such as 3,3′-dicarboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl and 4,4′-diamino-2,2 ′, 5,5′-tetracarboxybiphenyl , 3,3'-diamino-4,4'-dicarboxydiphenylmethane,
4,4'-diamino-3,3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-dihydroxydiphenylmethane, 2,2-bis [3-amino-
4-carboxyphenyl] propane, 2,2-bis [4-
Amino-3-carboxyphenyl] propane, 2,2-
Bis [3-amino-4-carboxyphenyl] hexafluoropropane, 4,4′-diamino-2,2 ′, 5
Carboxydiphenylalkanes such as carboxydiphenylmethane such as 5′-tetracarboxydiphenylmethane, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino-3,3′-dicarboxydiphenyl ether, 4 , 4'-diamino-
2,2'-dicarboxydiphenyl ether, 4,4 '
-Carboxydiphenyl ether compounds such as diamino-2,2 ', 5,5'-tetracarboxydiphenyl ether, 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, 4,4'-diamino-3,3' −
Dicarboxydiphenyl sulfone, 4,4′-diamino-2,2′-dicarboxydiphenyl sulfone,
Diphenyl sulfone compounds such as 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenyl sulfone, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane, etc. Bis [(carboxyphenyl) phenyl] alkane compounds, 4,
Bis (hydroxyphenoxy) biphenyl compounds such as 4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, etc. And a bis [(carboxyphenoxy) phenyl] sulfone compound.

Among the above diamines having a hydroxyl group and / or a carboxyl group, 3,3 'represented by the following formula (3)
It is particularly preferred to use -dihydroxy-4,4'-diaminobiphenyl.

[0035]

[Chemical 20] The polyimide resin is preferably a combination of a diamine compound represented by the general formula (2) and a diamine having a hydroxyl group, and particularly, as the diamine having a hydroxyl group, 3,3 ′
The combined use of -dihydroxy-4,4'-diaminobiphenyl is preferable from the viewpoint of solder heat resistance and PCT resistance. 60 to 99 mol% of the diamine represented by the formula (2) and a diamine having a hydroxyl group, particularly 40 to 1 mol of the 3,3′-dihydroxy-4,4′-diaminobiphenyl represented by the formula (3). % Is preferable. When the content of 3,3′-dihydroxy-4,4′-diaminobiphenyl exceeds 40 mol%, the solubility of the obtained polyimide resin is lowered.

Other usable diamine components are m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) sulfide, (3 -Aminophenyl) (4
-Aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, ( 3-aminophenyl) (4-aminophenyl) sulfone, bis (4aminophenyl) sulfone,
3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
Examples thereof include, but are not limited to, bis [4- (3-aminophenoxy) phenyl] sulfoxide and bis [4- (aminophenoxy) phenyl] sulfoxide.

(Production of Polyimide Resin) The polyimide resin can be obtained by dehydrating and ring-closing a corresponding precursor polyamic acid polymer. The polyamic acid polymer is obtained by reacting an acid dianhydride component and a diamine component in substantially equimolar amounts.

As a typical procedure of the reaction, there is a method of dissolving or diffusing one or more diamine components in an organic polar solvent and then adding one or more acid dianhydride components to obtain a polyamic acid solution. The order of addition of each monomer is not particularly limited, and the acid dianhydride component may be added to the organic polar solvent first, and the diamine component may be added to prepare a solution of the polyamic acid polymer, or the diamine component may be added to the organic polar solvent. A solution of the polyamic acid polymer may be prepared by first adding an appropriate amount therein, then adding an excess acid dianhydride component, and then adding an excess amount of a diamine component. Besides this, there are various addition methods known to those skilled in the art. The term "dissolved" as used herein refers to a state in which the solute is substantially dissolved by being uniformly dispersed or dispersed in the solvent, in addition to the case where the solvent completely dissolves the solute. Including cases.

Examples of the organic polar solvent used in the polyamic acid polymerization reaction include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and N, N-.
Formamide solvents such as dimethylformamide and N, N-diethylformamide, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone, phenol, o Examples thereof include phenol solvents such as-, m- or p-cresol, xylenol, halogenated phenol, and catechol, hexamethylphosphoramide, and γ-butyrolactone. Furthermore, if necessary, these organic polar solvents may be used in combination with an aromatic hydrocarbon such as xylene or toluene.

The polyamic acid solution obtained above is dehydrated and ring-closed by a thermal or chemical method to obtain a polyimide. A thermal method in which the polyamic acid solution is heat-treated and dehydrated,
Any of the chemical methods of dehydrating with a dehydrating agent can be used. Further, a method of heating under reduced pressure for imidization can also be used. Each method will be described below.

As a method of thermally dehydrating and ring-closing, a method of carrying out an imidization reaction of the above polyamic acid solution by heat treatment and at the same time evaporating a solvent can be exemplified. By this method, a solid polyimide resin can be obtained. The heating conditions are not particularly limited, but it is preferable to perform the heating at a temperature of 300 ° C. or less for a time of about 5 minutes to 200 minutes.

As a method of chemically performing dehydration ring closure, a method of performing a dehydration reaction by evaporating an organic solvent by adding a stoichiometric or more dehydrating agent and a catalyst to the above polyamic acid solution can be exemplified. Thereby, a solid polyimide resin can be obtained. Examples of the dehydrating agent by a chemical method include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, heterocyclic primary amines such as pyridine, α-picoline, β-picoline, γ-picoline and isoquinoline. Examples include tertiary amines. The conditions for the chemical dehydration ring closure are 100
Temperature below ℃ is preferable, evaporation of organic solvent is 200 ℃
It is preferable to carry out the treatment at the following temperature for a time of about 5 minutes to 120 minutes. Further, as another method for obtaining a polyimide resin, there is a method in which the solvent is not evaporated in the above-mentioned method of thermally or chemically performing dehydration ring closure. In particular,
A polyimide resin solution obtained by performing a thermal imidization treatment or a chemical imidization treatment with a dehydrating agent is poured into a poor solvent to precipitate a polyimide resin, and the unreacted monomer is removed to purify and dry the solid polyimide. It is a method of obtaining a resin. As the poor solvent, a material that is well mixed with the solvent but has a property that the polyimide is difficult to dissolve is selected, and examples thereof include acetone, methanol, ethanol, isopropanol, benzene, methyl cellosolve, and methyl ethyl ketone, but are not limited thereto. Not done.

Next, there is a method of heating under a reduced pressure for imidization. According to this imidization method, water generated by imidization can be positively removed to the outside of the system. Can be suppressed and a high molecular weight polyimide can be obtained. Further, according to this method, the ring-opened product on one side or both sides present as an impurity in the acid dianhydride as the raw material is re-closed, so that a further improvement effect of the molecular weight can be expected.

The heating condition of the method of heating and imidizing under reduced pressure is preferably 80 to 400 ° C., but more preferably 100 ° C. or higher, more preferably 120 ° C., which enables efficient imidization and efficient removal of water. That is all. The maximum temperature is preferably equal to or lower than the thermal decomposition temperature of the intended polyimide, and the normal imidization completion temperature, that is, 250 to 350.
℃ degree is usually applied.

The condition of the pressure for reducing the pressure is preferably as small as possible, but specifically, it is 0.9 to 0.001 atm, preferably 0.8 to 0.001 atm, more preferably 0.7 to 10.
It is 0.01 atm.

The polyimide resin thus obtained has a glass transition temperature at a relatively low temperature, but in order for the resin composition of the present invention to obtain particularly good processing characteristics, the glass transition temperature of the polyimide resin is 350 ° C. The following is preferable, 320 ° C or less is more preferable, and 28 is particularly preferable.
It is 0 ° C or lower.

(Thermosetting Resin) Examples of the thermosetting resin include bismaleimide resin, bisallylnadiimide resin, phenol resin, cyanate resin, epoxy resin, acrylic resin, methacryl resin, triazine resin, hydrosilyl curing resin and allyl curing resin. , Unsaturated polyester resins and the like, and these can be used alone or in combination.

In addition to the above thermosetting resin, a side chain reactive group type heat having a reactive group such as an epoxy group, an allyl group, a vinyl group, an alkoxysilyl group or a hydrosilyl group on the side chain or terminal of the polymer chain. It is also possible to use curable polymers as thermosetting components. Among the above-mentioned thermosetting resins, it is preferable to use an epoxy resin because it has excellent adhesiveness, low-temperature processability, and can improve heat resistance and solder heat resistance. The epoxy resin will be described below. As the epoxy resin, any epoxy resin can be used in the present invention. For example, bisphenol epoxy resin, halogenated bisphenol epoxy resin,
Phenol novolac epoxy resin, halogenated phenol novolac epoxy resin, alkylphenol novolac epoxy resin, polyphenol epoxy resin, polyglycol epoxy resin, cycloaliphatic epoxy resin, cresol novolac epoxy resin, glycidyl amine epoxy resin, urethane A modified epoxy resin, a rubber modified epoxy resin, an epoxy modified polysiloxane, etc. can be used.

(Production of Adhesive Composition) The mixing ratio of the thermosetting resin in the adhesive composition is preferably 1 to 70 parts by weight, more preferably 5 to 60 parts by weight, based on 100 parts by weight of the polyimide resin. Is. If it is too small, the adhesive strength may be lowered, and if it is too large, flexibility or heat resistance may be lowered.

In a preferred embodiment, the adhesive layer of the laminate exhibits an excellent low water absorption rate of 1.5% or less, more preferably 1.3% or less, and particularly preferably 1.0% or less. Is possible.

In a preferred embodiment, the adhesive composition contains at least one solvent. The solvent is not particularly limited as long as it can dissolve the polyimide resin and the epoxy resin, but a type and amount capable of suppressing the residual volatile content after curing of the adhesive to 3% by weight or less are preferable.
In addition, the boiling point is 160 ℃ in consideration of economical efficiency and workability.
The following low boiling point solvents are preferred. A solvent having a boiling point of 130 ° C. or lower is more preferable, and further preferably 105 ° C.
It is a solvent having the following boiling points. Such a low boiling point solvent is preferably tetrahydrofuran (hereinafter, TH
Abbreviated as F. Boiling point 66 ° C.), 1,4-dioxane (hereinafter,
Abbreviated as dioxane. A boiling point of 103 ° C.), monoglyme (boiling point of 84 ° C.) and dioxolane (boiling point of 76 ° C.) can be used. These may be used alone or in combination of two or more.

Further, in the adhesive composition, if necessary, water-absorbing property, heat resistance, adhesive property and the like, generally used acid curing agents such as acid dianhydrides, amine curing agents, imidazole curing agents, etc. Accelerators and various coupling agents may be used in combination. Further, a thermosetting resin other than an epoxy resin, a phenol resin, a cyanate resin or the like may be used in combination.

(Adhesive Layer) As an adhesive, the above resin composition is dissolved in a solvent such as THF, dioxane, monoglyme or dioxolane. The concentration is not particularly limited, but is preferably 5 to 50% by weight. The obtained resin solution is
After coating on the surface of the polymer film, it is dried. Alternatively, after casting on a support and removing the solvent into a sheet,
It can also be obtained by pasting onto a polymer film.

The thickness of the adhesive layer is not particularly limited, but is 1
˜50 μm, preferably 1 to 30 μm, more preferably 1 to 20 μm.

(Polymer Film) Next, the polymer film used in the laminate of the present invention will be described. In the flexible copper-clad laminate of the present invention, the polymer film forms the insulating layer together with the adhesive layer, so that the insulating layer is prevented from being extremely thin and a uniform insulating layer thickness is realized.

As the polymer film used in the present invention,
A material excellent in dimensional stability, heat resistance and mechanical properties is preferable. For example, polyolefins such as polyethylene, polypropylene and polybutene; ethylene-vinyl alcohol copolymer, polystyrene, polyethylene terephthalate, polybutylene terephthalate, ethylene-2,6
-Polyester such as naphthalate; further, nylon-6, nylon-11, aromatic polyamide, polyamideimide resin, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyketone resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin Examples thereof include fluororesins, polyarylate resins, liquid crystal polymer resins, polyphenylene ether resins, and polyimide resins.

Here, the polymer film preferably has a tensile elastic modulus of 5 GPa or more, in order to impart sufficient rigidity to the flexible copper-clad laminate of the present invention, and 6 GP.
It is more preferably a or more.

The thickness of the polymer film is preferably 50 μm or less for forming a small-diameter via hole, and is 35 μm.
m or less is more preferable, and 25 μm or less is further preferable. It is preferably 1 μm or more, more preferably 2 μm or more. A polymer film having a small thickness and ensuring sufficient electric insulation is desirable.

Further, the flexible copper clad laminate is processed.
In this case, thermal stability is required, so polymer film
Dimensional stability is desired. Therefore, 2.0 × 10
^-Five/ ° C. or less, more preferably 1.5 × 10^-Five/ ° C or less,
More preferably 1.0 x 10 ^-FiveThe coefficient of linear expansion below
A polymer film having is desirable. In addition, heat during processing
To prevent defects such as swelling due to low water absorption.
Polymer films are preferred. According to ASTM-D570
The water absorption rate of the polymer film measured by
It depends on the size of the film, but the absorption of the 25 μm thick film
The water content is preferably 1.5% or less, more preferably 1.
A polymer film having a composition of 2% or less is desired.
Yes.

A polyimide film is mentioned as a film satisfying the above-mentioned various characteristics. The polyimide film is obtained from a polyamic acid polymer solution which is its precursor. This polyamic acid polymer solution can be produced by a method commonly used by those skilled in the art. That is, one or more tetracarboxylic dianhydride components and one or more diamine components are used in substantially equimolar amounts and polymerized in an organic polar solvent to obtain a polyamic acid polymer solution.

Typical tetracarboxylic dianhydride components used in the production of the polyimide film include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3'. 3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 1,4
5,8-naphthalenetetracarboxylic dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride,
4,4'-oxydiphthalic anhydride, 3,3 ', 4
4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 4,
4'-hexafluoroisopropylidene diphthalic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, p -Aromatic tetracarboxylic dianhydrides such as phenylene bis (trimellitic acid monoester anhydride) and p-phenylenediphthalic anhydride.

Among these tetracarboxylic dianhydrides, the tensile elastic modulus is 5 GPa or more and the linear expansion coefficient is 2.0 ×.
As a preferred combination for obtaining a polyimide film having a water absorption of 10 ⁻⁵ / ° C. or less and a water absorption of 1.5% or less, pyromellitic dianhydride as a tetracarboxylic dianhydride is 0 to 80 mol%, And p-phenylene bis (trimellitic acid monoester anhydride) 100 to 20
The case of using mol% is mentioned.

The combination of tetracarboxylic dianhydrides described here is only one specific example for obtaining a polyimide film suitable for the polymer film constituting the flexible copper-clad laminate of the present invention. Not limited to these combinations, it is possible to adjust the characteristics of the polyimide film by changing the combination and the usage ratio of the tetracarboxylic dianhydride used.

On the other hand, as the diamine component, 4,4'-
Diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 2,2-bis (4-aminophenoxyphenyl) propane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene , 1,3-bis (3-aminophenoxy)
Benzene, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy)
Phenyl) sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) hexafluoropropane, 4,4'-
Diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 9,9-bis (4-aminophenyl) fluorene, bisaminophenoxyketone, 4,
4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4'-(1,3-phenylenebis (1-methylethylidene)) bisaniline, metaphenylenediamine, paraphenylenediamine, 4, 4 '
-Diaminobenzanilide, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 3,3'-dimethoxy-
Aromatic diamines such as 4,4′-diaminobiphenyl, and other aliphatic diamines can be mentioned.

Of these diamine components, preferred is a polyimide film having a tensile elastic modulus of 5 GPa or more, a linear expansion coefficient of 2.0 × 10 ^-5 / ° C. or less, and a water absorption rate of 1.5% or less. As an example of the combination, paraphenylenediamine and / or 4,4′-diaminobenzanilide is added in an amount of 20 to 80 mol% of the diamine component and 4,4′-
The case where 80 to 20 mol% of diaminodiphenyl ether is used is mentioned.

The combination of the diamine components described here is one specific example for obtaining a polyimide film suitable for the polymer film constituting the flexible copper-clad laminate of the present invention. Not limited to these combinations, the characteristics of the polyimide film can be adjusted by changing the combination of the diamine components used and the usage ratio.

When a polyimide film is used as the polymer film constituting the flexible copper-clad laminate of the present invention, the number average molecular weight of its precursor polyamic acid is 1
It is desirable that it is from 10,000 to 1,000,000. If the average molecular weight is less than 10,000, the resulting film may become brittle. On the other hand, if the number average molecular weight exceeds 1,000,000, the viscosity of the polyamic acid varnish, which is a polyimide precursor, may become too high, and handling may become difficult.

Further, various organic additives to polyamic acid,
Alternatively, inorganic fillers or various reinforcing materials may be added to form a composite polyimide film.

Examples of the organic polar solvent used in the reaction for producing the polyamic acid copolymer include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; formamide such as N, N-dimethylformamide and N, N-diethylformamide. System solvent; acetamide system solvent such as N, N-dimethylacetamide, N, N-diethylacetamide; N-methyl-2-pyrrolidone,
Pyrrolidone-based solvents such as N-vinyl-2-pyrrolidone;
Phenol-based solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol and catechol; or hexamethylphosphoramide, γ-butyrolactone and the like can be mentioned. These are preferably used alone or as a mixture. Further, an aromatic hydrocarbon such as xylene or toluene may be partially mixed with the solvent and used.

The polyamic acid copolymer is contained in the above organic polar solvent in an amount of 5 to 40% by weight, preferably 10 to 3%.
It is desirable that 0% by weight is dissolved from the viewpoint of handling.

In order to obtain a polyimide film from this polyamic acid copolymer solution, either a thermal method of thermally dehydrating or a chemical method using a dehydrating agent may be used. It is preferable because the polyimide film has excellent mechanical properties such as elongation and tensile strength.

An example of producing a polyimide film by a chemical method will be described below. A solution prepared by adding a stoichiometric or more stoichiometric dehydrating agent and a catalytic amount of a tertiary amine to the above polyamic acid polymer or a solution thereof is cast or coated on a drum or an endless belt to form a film. ℃
Dry at a temperature below for about 5 to 90 minutes to obtain a self-supporting polyamic acid film. Then, this is peeled off from the support and the end is fixed. After that, by gradually heating to about 100 to 500 ° C., imidization is performed, and after cooling, the fixing of the end portion is released to obtain a polyimide film. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and the like.
Heterocyclic tertiary amines such as pyridine, picoline, isoquinoline and the like can be mentioned.

Further, the polymer film may be subjected to various surface treatments for the purpose of improving the adhesion with the adhesive layer.

For example, on the surface of the polymer film, Cr, N
Method of forming metal oxide adhesive layer on polymer film surface by sputtering, plasma ion implantation, etc. of metal oxide such as i, Ti, Mo, thermosetting resin, thermoplastic resin, organic monomer, coupling The method of applying various organic substances such as agents as a primer, the method of surface treatment with metal hydroxide, organic alkali, etc., the method of plasma treatment, the method of corona treatment, the method of grafting the surface, etc. Examples include a method of processing. The surface of the polymer film may be treated by these methods alone or in various combinations. The surface treatment method can also be used to improve the adhesion to the adhesive layer on the other side.

(Copper Foil) The copper foil is not particularly limited, but the thickness of the copper foil is 12 μ in order to produce a sandwiched pitch circuit pattern.
m or less, more preferably 10 μm or less, and further preferably 5 μm or less. A copper foil provided with a peeling carrier is suitable for the present invention because it has excellent handleability. The carrier for peeling is not particularly limited, and polyester such as polyethylene terephthalate, polycarbonate, release paper, and metal foil such as copper foil, aluminum foil, and 42 alloy foil can be used. When using copper foil, it is preferable to use copper foil also for the peeling carrier. The thickness of the peeling carrier is not particularly limited, but preferably 1 to 100 μm, more preferably 5 to
It is 50 μm.

(Flexible Copper Clad Laminate) The flexible copper clad laminate of the present invention is provided with an adhesive layer on one side or both sides of the polymer film, and one side or both sides of the polymer film are provided through the adhesive layer. Made by laminating copper foil. By using the polymer film and the adhesive, it is possible to obtain a flexible copper-clad laminate having excellent mechanical strength, heat resistance, processability, and adhesiveness, and particularly excellent solder heat resistance. You can

(Manufacturing Method of Flexible Copper Clad Laminate) Hereinafter, a manufacturing method of the flexible copper clad laminate will be described. First,
The resin composition of the present invention composed of a polyimide resin and an epoxy resin is dissolved in a solvent to obtain a resin solution, which is then coated on the surface of a polymer film and dried to obtain a bonding sheet. Alternatively, the resin solution obtained as described above may be cast on a support, the solvent may be removed to form a sheet, and the sheet may be attached to a polymer film to obtain a bonding sheet. Next, the flexible copper clad laminate of the present invention can be obtained by laminating copper foil on both surfaces of the above-mentioned bonding sheet by a method such as pressing or rolling. The roll-to-roll method is preferable because the flexible copper-clad laminate can be efficiently manufactured. A protective film may be used for the flexible copper-clad laminate of the present invention for the purpose of protecting the surface.

The above-mentioned method for manufacturing the flexible copper-clad laminate is an example, and any method within the range that can be carried out by those skilled in the art is possible.

Although the flexible copper clad laminate of the present invention has been described above, the present invention is not limited to these, and various improvements can be made based on the knowledge of those skilled in the art without departing from the spirit of the present invention. Needless to say, the present invention can be carried out in a mode in which modifications, modifications and variations are added.

[0080]

EXAMPLES The present invention will be described in detail below with reference to Examples, but these Examples are intended to explain the present invention.
It is not meant to be limiting. Those skilled in the art may make various changes, modifications, and alterations without departing from the scope of the present invention.

Example 1 In a glass flask having a capacity of 2000 ml, dimethylformamide (hereinafter referred to as DMF) was added in an amount of 0.95 equivalent of 1,3-bis (3-aminophenoxy) benzene (hereinafter referred to as APB). And 0.
05 equivalents of 3,3′-dihydroxy-4,4′-diaminobiphenyl (manufactured by Wakayama Seika Co., Ltd.) were charged and dissolved under stirring in a nitrogen atmosphere. Furthermore, the inside of the flask was stirred under a nitrogen substitution atmosphere while cooling the solution with ice water, and 1 equivalent of 4, 4 '
-(4,4'-isopropylidenediphenoxy) bisphthalic anhydride (hereinafter referred to as IPBP) was added.
As described above, a polyamic acid polymer solution was obtained.
The amount of DMF used was such that the concentration of APB, 3,3′-dihydroxy-4,4′-diaminobiphenyl, and IPBP charged to the monomers was 30% by weight.

300 g of this polyamic acid solution was placed in a Teflon (R) -coated vat and placed in a vacuum oven for 2 hours.
The mixture was heated at 00 ° C for 180 minutes under reduced pressure at 665 Pa to obtain 80 g of a thermoplastic polyimide resin having a hydroxyl group. The polyimide resin powder obtained above, a novolac type epoxy resin (Epicoat 1032H60: manufactured by Yuka Shell Co., Ltd.), and 4,4′-diaminodiphenylsulfone (hereinafter, referred to as 4,4′-DDS) as a curing agent, respectively. It was dissolved in dioxolane to obtain a solution having a concentration of 20% by weight. Each of the resulting solutions was treated with polyimide, epoxy resin, 4,
The 4'-DDS was mixed at a weight ratio of 70: 30: 9 to obtain an adhesive solution. The adhesive solution thus obtained was applied to a polyimide film (Apical 12.5 HP, manufactured by Kanebuchi Kagaku Kogyo Co., Ltd.) with a gravure coater on each side and then 170 ° C.
And dried for 2 minutes to form an adhesive layer having a thickness of each adhesive layer of 5 μm. An electrolytic copper foil having a thickness of 35 μm and a carrier copper foil having a thickness of 5 μm on both sides of the obtained double-sided adhesive layer-attached polyimide film was placed at a temperature of 200 ° C. and a pressure of 3 M.
It was heated and pressed at Pa for 5 minutes to obtain a flexible copper-clad laminate. This flexible copper clad laminate was cured in a hot air oven at a temperature of 200 ° C. for 1 hour. In order to measure the peeling strength, electrolytic copper plating was further performed on the electrolytic copper foil so that the total copper thickness was 20 μm. When the peel strength between the copper layer and the adhesive layer was measured, it was 15 N / cm in the normal state, 12 N / cm after PCT, and the retention rate after PCT was 80%. Also, when a solder heat resistance test was conducted,
No blistering or peeling occurred at 300 ° C.

Example 2 To 500 g of a polyamic acid solution obtained in the same manner as in Example 1 was added β-picoline (35 g) and acetic anhydride (60 g), and the mixture was stirred for 1 hour and further stirred at 100 ° C. for 1 hour to perform imidization. Let Then, this solution was gradually added to methanol stirred at high speed to obtain a filamentous polyimide resin. After drying at 100 ° C for 30 minutes, pulverize with a mixer and wash with Soxhlet with methanol.
It was dried at 00 ° C. for 2 hours to obtain a polyimide powder.

A flexible copper clad laminate was obtained in the same manner as in Example 1 except that the polyimide resin powder obtained as described above was used, and the peel strength between the copper layer and the adhesive layer was measured. 14N / cm, after PCT 11N / cm, P
The retention rate after CT was 79%. Further, when a solder heat resistance test was conducted, swelling and peeling at 300 ° C. and no whitening occurred.

(Example 3) Polyimide, epoxy resin,
An adhesive solution was obtained in the same manner as in Example 1 except that the weight ratio of 4,4′-DDS was 50:50:15. Further, a flexible copper clad laminate was obtained in the same manner as in Example 1, and the peel strength between the copper layer and the adhesive layer was measured. As a result, it was 13 N / cm in the normal state and 9 N / cm after PCT.
The post-retention rate was 69%. Further, when a solder heat resistance test was conducted, swelling and peeling at 300 ° C. and no whitening occurred.

Example 4 0.95 equivalents of APB and 0.05 equivalents of 3,3'-dihydroxy-4,4'-diaminobiphenyl were added to 1 equivalent of bis [4- (3-aminophenoxy) phenyl]. A thermoplastic polyimide resin was obtained in the same manner as in Example 1 except that sulfone (hereinafter referred to as BAPS-M) was used. In the same manner as in Example 1, the weight ratio of polyimide, epoxy resin, and 4,4′-DDS was 70:30:
A flexible copper clad laminate was obtained in the same manner as in Example 1, and the peel strength between the copper layer and the adhesive layer was measured.
N / cm, 10 N / cm after PCT, retention rate after PCT is 77%
Met. In addition, when a solder heat resistance test was performed, it was 300
No blistering or peeling occurred at ℃.

Example 5 0.95 equivalents of APB and 0.05 equivalents of 3,3'-dihydroxy-4,4'-diaminobiphenyl were added to 0.8 equivalents of APB and 0.2 equivalents of 3,3. A thermoplastic polyimide resin was obtained in the same manner as in Example 1 except that'-dihydroxy-4,4'-diaminobiphenyl was used. Polyimide, as in Example 1
The weight ratio of epoxy resin and 4,4'-DDS is 70: 3.
An adhesive solution mixed so as to be 0: 9 was obtained, and a flexible copper-clad laminate was further obtained in the same manner as in Example 1, and the peel strength between the copper layer and the adhesive layer was measured. / cm, 11 N / cm after PCT, retention rate after PCT is 7
It was 9%. Moreover, when a solder heat resistance test was performed, it was 3
No blistering or peeling occurred at 00 ° C.

Comparative Example 1 A polyimide resin powder was obtained in the same manner as in Example 1 except that pyromellitic dianhydride (PMDA) was used as the acid dianhydride component and oxydianiline (ODA) was used as the diamine component.

This polyimide resin powder is DMF, TH
It was not dissolved in any of F, dioxane, and dioxolane.

Comparative Example 2 10 g of Pratabond M1276 (copolymerized nylon, manufactured by Nippon Rilsan Co., Ltd.), 20 g of Epicoat 1032H60 (manufactured by Yuka Shell Co., Ltd.) and 1 g of diaminodiphenyl sulfone were dissolved in 83 g of DMF. The obtained adhesive solution was applied to a polyimide film (Apical 12.5 HP, manufactured by Kaneka Kagaku Kogyo Co., Ltd.) with a gravure coater on each side, and dried at 100 ° C. for 4 minutes, and each adhesive layer had a thickness of 5 μm. An adhesive layer was formed. A 5 μm thick electrolytic copper foil with a 35 μm thick carrier copper foil is thermocompression bonded at a temperature of 200 ° C. and a pressure of 3 MPa for 5 minutes on both sides of the obtained double-sided adhesive layer-attached polyimide film to form a flexible copper-clad laminate. Obtained. This flexible copper clad laminate was cured in a hot air oven at a temperature of 200 ° C. for 1 hour. Further, electrolytic copper plating was performed on the electrolytic copper foil so that the total copper thickness was 20 μm. The peel strength between the copper layer and the adhesive layer was measured to be 12 N / cm in the normal state, 4 N / cm after PCT, and the retention rate after PCT was 33.
%Met. Moreover, when the solder heat resistance test was conducted, it was 30
Blistering and peeling occurred at 0 ° C, and whitening occurred.

Comparative Example 3 The acid dianhydride component was 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride and the diamine component was BAPS. A flexible copper-clad laminate was obtained in the same manner as in Comparative Example 2 except that -M (1 equivalent) was measured, and the peel strength between the copper layer and the adhesive layer was measured.
2N / cm, 5N / cm after PCT, retention rate after PCT is 38%
Met. In addition, when a solder heat resistance test was performed, it was 300
Swelling and peeling occurred at ℃, and whitening occurred.

The peel strength is measured according to JISC.
6481. Regarding the solder heat resistance test, the flexible copper clad laminate was tested at 40 ° C, humidity of 90%, 1
After the environmental test for 92 hours, it was immersed in a solder bath at 300 ° C. for 10 seconds, the copper foil on one surface was removed by etching, and then swelling, peeling, and whitening were visually judged.

PCT (Pressure Cooker Tes) which is a reliability test of electronic materials.
t) The processing conditions were 121 ° C., 100% humidity, and 96 hours.

The peel strength retention rate after the PCT treatment was determined by setting the peel strength before the PCT treatment to F ₁
The peel strength after the treatment is defined as F ₂ , and the following formula: Retention rate of peel strength after PCT treatment (%) = F ₂ ÷ F ₁ × 10
It was calculated by 0.

[0095]

INDUSTRIAL APPLICABILITY The flexible copper-clad laminate of the present invention can be widely used in the production of flexible printed wiring boards and is industrially extremely useful as a material for electronics that requires high reliability and heat resistance. Has the advantage of being high.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F100 AB17B AB33B AK01A AK49                       AK49G AK53 AL05G AT00A                       BA02 CA02 CA02G CB02G                       GB43 JB13G JJ03 JK06                       JL11                 5E343 AA18 AA33 BB24 BB67 CC03                       CC04 CC06 DD53 EE22 GG02                       GG16

Claims (10)

[Claims] 1. A flexible copper-clad laminate comprising a polymer film provided with an adhesive layer on one side or both sides thereof, and a copper foil laminated on one side or both sides of the polymer film via the adhesive layer, wherein the adhesive is used. The agent layer is a resin composition containing a polyimide resin and a thermosetting resin obtained by reacting an acid dianhydride component containing an acid dianhydride represented by the following general formula (1) with a diamine component. A flexible copper-clad laminate characterized by the following. [Chemical 1] (In the formula, V is —O— or —O—T—O—
Represents a divalent organic group) 2. The flexible copper clad laminate according to claim 1, wherein the diamine component is a diamine component containing a diamine represented by the following general formula (2). [Chemical 2] (Wherein, Y is, -C (= O) -, - SO 2 -, - O-,
_{-S -, - (CH 2)} m -, - NHCO -, - C (C
_{H 3) 2 -, - C} (CF 3) 2 -, - C (= O) O-, or indicate binding. m and n are integers of 1 or more and 5 or less. ) 3. The flexible copper clad laminate according to claim 1, wherein the diamine component is a diamine component containing a diamine having a hydroxyl group and / or a carboxyl group. 4. The flexible copper clad laminate according to claim 1, wherein the diamine component is a diamine component represented by the general formula (2) and a diamine having a hydroxyl group and / or a carboxyl group. . 5. The diamine having a hydroxyl group is represented by the following formula (3):
It is 3,3'-dihydroxy-4,4'-diaminobiphenyl represented by these, The Claim 3 or 4 characterized by the above-mentioned.
The flexible copper clad laminate described. [Chemical 3] 6. T in the general formula (1) of the acid dianhydride component is And a group represented by (Wherein, Z _{is, -C Q H 2Q -, -} C (= O) -, - SO 2
It is a divalent group selected from the group consisting of-, -O- and -S-, and Q is an integer of 1 to 5. ] The group consisting of groups represented by the formula (1), wherein the acid dianhydride represented by the general formula (1) is at least one acid dianhydride selected from the group. The flexible copper clad laminate according to claim 5. 7. The polyimide resin comprises the diamine component represented by the general formula (2) in an amount of 60 to 99 mol% of the total diamine component, and 3,3′-dihydroxy-4,4′-diaminobiphenyl in the total diamine. The flexible copper clad laminate according to claim 5 or 6, which is a polyimide obtained by reacting a diamine component containing 40 to 1 mol% of the component. 8. The diamine represented by the general formula (2) is a diamine represented by the following formula (4) having an amino group at the meta position, and the diamine represented by the following formula (4): 7. The flexible copper-clad laminate according to any one of items 7 and 7. [Chemical 6] (Wherein, Y is, -C (= O) -, - SO 2 -, - O-,
_{-S -, - (CH 2)} m -, - NHCO -, - C (C
_{H 3) 2 -, - C} (CF 3) 2 -, - C (= O) O-, or indicate binding. m and n are integers of 1 or more and 5 or less. ) 9. The flexible copper-clad laminate according to claim 1, wherein the copper foil has a thickness of 5 μm or less. 10. The flexible copper-clad laminate according to any one of claims 1 to 9, wherein the polymer film is a polyimide film.