JPH0625401A - Film for printed circuit - Google Patents

Abstract

(57) [Summary] [Object] To provide a film for a flexible printed circuit made of a polycarbonate resin, which has improved heat resistance without impairing excellent mechanical properties, electrical properties, dimensional stability and the like. A film for a printed circuit, comprising an aromatic polycarbonate resin containing 70 to 95 mol% of 9,9-bis (4-oxyphenylene) fluorene structural unit and having a specific viscosity of 0.19 or more.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin film for printed circuits. More specifically, it relates to a film for a flexible printed circuit made of a polycarbonate resin, which is excellent in mechanical strength, electrical characteristics, dimensional stability, and particularly excellent in heat resistance.

[0002]

2. Description of the Related Art Conventionally, polyimide films exhibiting excellent heat resistance have been widely used for flexible printed circuit films. However, the polyimide film is extremely expensive. On the other hand, a polycarbonate resin obtained by reacting a carbonate precursor substance with 2,2-bis (4-hydroxyphenyl) propane is excellent in mechanical properties, electrical properties, and dimensional stability, and is therefore often used as an engineering plastic. Widely used in the field. However, such a polycarbonate resin does not have heat resistance suitable for soldering. On the other hand,
A polycarbonate resin obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene with a carbonate precursor is known, and it is also known that this polymer has good heat resistance. For example, JP-A-63-182336
The publication describes a method for producing a homopolycarbonate resin from 9,9-bis (4-hydroxyphenyl) fluorenes. However, when synthesizing this homopolymer, a large amount of components insoluble in the solvent are generated,
The yield of the solvent-soluble component was at most 60 to 70%, which was poor in practicality.

[0003]

The present inventors have found that the aromatic polycarbonate resin has excellent mechanical properties, electrical properties, and
An object of the present invention is to provide a film for a flexible printed circuit made of a polycarbonate resin, which has improved heat resistance without impairing dimensional stability and the like.

The inventors of the present invention have conducted extensive studies to achieve this object. As a result, a polycarbonate copolymer having a specific proportion of 9,9-bis (4-oxyphenylene) fluorene structural units introduced therein is a film for flexible printed circuits. As a result, they have found that it is extremely effective and have completed the present invention.

[0005]

The present invention provides the following general formula [1]:

[0006]

[Chemical 3]

[Wherein R _{1 to} R ₄ are a hydrogen atom, a halogen atom, a phenyl group or an alkyl group having 1 to 3 carbon atoms,
It may be the same or different. ] And the following general formula [2]

[0008]

[Chemical 4]

[Wherein W is a single bond, an alkylidene group, a cycloalkylidene group, a phenyl group-substituted alkylidene group, a sulfone group, a sulfide group or an oxide group, and R ₅ and R ₆ are a hydrogen atom, a halogen atom, a phenyl group, It is an alkyl group having 1 to 3 carbon atoms and may be the same or different, and m and n are each an integer of 1 to 4. ] The structural unit represented by the general formula [1] is contained in an amount of 70 to 95 mol%, and 0.7 g of the structural unit is dissolved in 100 ml of methylene chloride to obtain a specific viscosity measured at 20 ° C. 0.1
The present invention relates to a printed circuit film made of a polycarbonate resin of 9 or more.

Polycarbonate resins of interest in the present invention are prepared by reacting 9,9-bis (4-hydroxyphenyl) fluorenes with one or more other dihydric phenol compounds, endcapping agents and carbonate precursor materials. Manufactured. It is usually produced by an interfacial polycondensation method using phosgene or a transesterification reaction using a carbonic acid diester.

9,9-bis (4-hydroxyphenyl)
Examples of fluorenes include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, and 9,9-bis (3-ethyl-4-hydroxyphenyl). ) Fluorene and the like, and particularly 9,9-bis (4-hydroxyphenyl) fluorene is preferable.

Other dihydric phenols include, for example, bis (4-hydroxyphenyl) methane and 2,2-bis (4
-Hydroxyphenyl) propane [commonly known as bisphenol A], 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy) -3,5
-Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) oxide, bis (3,5
-Dichloro-4-hydroxyphenyl) oxide,
4,4'-dihydroxydiphenyl, 3,3'-dichloro-4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (4 -Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide and the like are mentioned, and bisphenol A is particularly preferable. A monohydric phenol such as p-tert-butylphenol is used as the terminal stopper.
The amount used is usually 0.01 with respect to the dihydric phenol used.
It is -10 mol%, preferably 0.03-8 mol%.

In the interfacial polycondensation reaction using phosgene,
Usually, 9,9-bis (4-hydroxyphenyl) fluorenes and other dihydric phenol are dissolved in an aqueous solution of an acid binder and reacted in the presence of an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used, and as the organic solvent, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. The reaction is usually 0 to 40 ° C, preferably 20 to
It takes about 10 minutes to 10 hours to finish at 30 ° C. It is preferable to keep the pH of the reaction system at 10 or higher as the reaction progresses. A catalyst may be used to accelerate the reaction, and examples of the catalyst include triethylamine and tetra-n.
Examples include tertiary amines such as -butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds. Further, if necessary, an antioxidant such as hydrosulfite can be added.

In the transesterification reaction using a carbonic acid diester, 9,9-bis (4-hydroxyphenyl) fluorene and another dihydric phenol compound are formed by stirring the carbonic acid diester while heating in an inert gas atmosphere. It is carried out by distilling alcohol or phenol.
The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 350 ° C.
In the latter stage of the reaction, the system is depressurized to facilitate the distillation of the alcohol or phenol produced and complete the reaction. Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable.

A polymerization catalyst can also be used to accelerate the polymerization rate. As the polymerization catalyst, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide and potassium hydroxide, and hydroxides of boron and aluminum can be used. Alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, alkali metal and alkaline earth metal alkoxides, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, silicon Compounds,
Germanium compounds, organotin compounds, lead compounds,
It is possible to use a catalyst which is usually used for an esterification reaction or a transesterification reaction of antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. The catalyst may be used alone or in combination of two or more kinds. The amount of these catalysts used is 0.0001 to 1% by weight, preferably 0.
It is selected in the range of 0005 to 0.5% by weight.

The molecular weight of the polycarbonate resin is 0.19 or more, preferably 0.26 to, expressed as a specific viscosity measured at 20 ° C. in a methylene chloride solution having a concentration of 0.7 g / dl.
0.45. If it is less than 0.19, the obtained film becomes brittle, which is not suitable.

The polycarbonate resin in the present invention is
The content ratio of the structural unit represented by the general formula [1] and the structural unit represented by the general formula [2] is 70 to 95 mol% of the former and 30 to 5 mol% of the latter. When the content of the structural unit represented by the general formula [1] is less than 70 mol%, the heat resistance required for soldering is not recognized, and when it exceeds 95 mol%, the resin yield is deteriorated.

Any method may be adopted for molding the thus obtained polycarbonate resin into a film, but the casting method is most suitable. If necessary, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, diphenyl hydrogen phosphite, Irganox 1076 may be used in forming the film.
[Stearyl-β- (3,5-di-tert-butyl-4-
Additives such as stabilizers such as hydroxyphenyl) propionate], colorants, antistatic agents, lubricants, release agents and the like may be added.

The polycarbonate resin film of the present invention obtained as described above has remarkably improved heat resistance without impairing the excellent mechanical properties, electrical properties, dimensional stability and the like of the aromatic polycarbonate resin. It is extremely effective as a film for flexible printed circuits.

[0020]

EXAMPLES The present invention will be further described with reference to the following examples. The parts and% in the examples are parts by weight and% by weight, unless otherwise specified. The specific viscosity and glass transition point (T
g) was measured by the following method.

Specific viscosity: 0.7 g of the polymer was dissolved in 100 ml of methylene chloride and measured at 20 ° C. Glass transition point (Tg): Measured by 910 type DSC manufactured by DuPont.

[0022]

Example 1 9,9-bis (4-hydroxyphenyl)
Fluorene 19.0 parts, bisphenol A 4.1 parts, 4
23.8 parts of 8.5% caustic soda aqueous solution and distilled water 360
A part was charged into a reactor equipped with a stirrer and dissolved. To this, 160 parts of methylene chloride was added, the mixed solution was cooled to 20 ° C., and 10 parts of phosgene was blown in for 40 minutes. After that, 0.11 parts of p-tert-butylphenol was added to the reaction solution as a solution dissolved in methylene chloride, 3.0 parts of 48.5% caustic soda aqueous solution and 0.5 parts of triethylamine were added, and stirring was continued for 2 hours to allow reaction. finished. After the reaction is completed, the methylene chloride solution of the lower layer polycarbonate is separated from the reaction solution,
This solution was washed with an aqueous hydrochloric acid solution and distilled water, and then methylene chloride was removed by evaporation to obtain a polycarbonate powder. The obtained powder had a specific viscosity of 0.863 and a Tg of 256 ° C.

[0023]

Example 2 9,9-bis (4-hydroxyphenyl)
22.8 parts of fluorene and 1.6 of bisphenol A
A powder was obtained in the same manner as in Example 1 except that part of the powder was used. The powder has a specific viscosity of 0.820 and a Tg of 274 ° C.
Met.

[0024]

[Comparative Example 1] Bisphenol A polycarbonate powder having a specific viscosity of 0.451 [Panlite manufactured by Teijin Chemicals Ltd.]
L-1250] had a Tg of 150 ° C.

[0025]

The polycarbonate resin film for flexible printed circuits of the present invention is excellent in mechanical properties, electrical properties, dimensional stability and the like and exhibits extremely high heat resistance.
Further, the polycarbonate resin used in the present invention is easier to form a film than a polyimide resin.

Claims (1)

[Claims] 1. The following general formula [1]: [In the formula, R _{1 to} R ₄ are a hydrogen atom, a halogen atom, a phenyl group or an alkyl group having 1 to 3 carbon atoms and may be the same or different. ] And the following general formula [2] [Wherein W is a single bond, an alkylidene group, a cycloalkylidene group, a phenyl group-substituted alkylidene group, a sulfone group, a sulfide group or an oxide group, and R ₅ and R ₆ are a hydrogen atom, a halogen atom, a phenyl group, and a carbon number of 1 ~ 3 alkyl groups, which may be the same or different, and m and n are integers of 1 to 4, respectively. ] The structural unit represented by general formula [1] is 70-95.
A film for a printed circuit comprising a polycarbonate resin containing 0.7% by mol of 100% methylene chloride and having a specific viscosity of 0.19 or more measured at 20 ° C.