JPH1110664A - Method for processing thermoplastic polyimide film with release film and thermoplastic polyimide film with release film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thin and uniform thermoplastic polyimide film easy to handle by directly casting and coating a heat resistant release film with thermoplastic polyimide, and further executing removal of solvent by drying. SOLUTION: Thermoplastic polyimide is obtained by polycondensing diamine such as 1,3-bis(3-aminophenoxy)benzene and 3,3',4,4'diphenylether tetracarboxylic dianhydride. As heat resistant release film, a polyimide film is uniformly and continuously directly cast and coated with thermoplastic polyimide varnish by using a knife coater, solvent-removed and imide-derived completely in a nitrogen atmosphere drying furnace. As a result, the thermoplastic polyimide film 11 with release film made of release film 12 and non-thermoplastic polyimide film 13 is obtained. Since the film 11 is thin and uniform and the film 12 has a high strength, it is easily handled.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a thermoplastic polyimide film with a release film, wherein the heat-resistant film is used as a release film. And a thermoplastic polyimide film with a release film obtained by the processing method.

[0002]

2. Description of the Related Art Conventionally, an adhesive resin such as an epoxy resin or an acrylic resin is applied to both sides of a heat-resistant film such as a non-thermoplastic commercially available polyimide film, and the resin is used as an adhesive to form a heat-resistant adhesive sheet or an adhesive. How to get a tape
It has attracted attention as a bonding method for obtaining heat-resistant bonded products.

However, in these cases, the use temperature is limited because the adhesive has a lower heat-resistant temperature than the heat-resistant base film. Another problem is that insulation reliability decreases during long-term use due to ionic impurities in the adhesive. Further, the production of a thin adhesive sheet or adhesive tape was difficult due to the presence of the heat-resistant film.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a release film in which a non-thermoplastic heat-resistant film which does not have the above-mentioned problems in processing a thermoplastic polyimide film with a release film is used as a release film. It is an object of the present invention to provide a method for processing a thermoplastic polyimide film having a release film, a method for processing a secondary processed product thereof, and a thermoplastic polyimide film having a release film obtained by the processing method.

[0005]

Means for Solving the Problems The present inventors have intensively studied to solve the above-mentioned problems, and have developed a thermoplastic polyimide obtained by polycondensing a specific diamine and a specific tetracarboxylic dianhydride, A thermoplastic polyimide / non-thermoplastic film laminate obtained by directly casting and coating a heat-resistant non-thermoplastic film (hereinafter, referred to as a non-thermoplastic film) and further removing the solvent by drying, It has been found that it can be peeled off with a non-thermoplastic film.

Further, the peeled thermoplastic polyimide is an excellent film having a uniform thickness (hereinafter referred to as a thermoplastic polyimide film), and the thermoplastic polyimide film can be heated and pressed at a temperature equal to or higher than the glass transition point. Thus, the present invention has been completed.

The above objects and objects are solved and achieved by the present invention described below. That is, the present invention provides a method for processing a thermoplastic polyimide film with a release film, in which a thermoplastic polyimide solution is directly cast and applied on the release film, and dried to form a thermoplastic polyimide film with a release film. Characterized by obtaining a processing method of a thermoplastic polyimide film with a release film, a processing method to add a further processing to a secondary processed product, and a thermoplastic polyimide film with a release film obtained by the processing method It is disclosed.

According to the present invention, an adhesive layer, an adhesive sheet or an adhesive plate (hereinafter, collectively referred to as an adhesive sheet) made of a thermoplastic polyimide having excellent heat resistance can be obtained. A processing method having high industrial value by performing the heat-press bonding processing has also become possible.

That is, the first processing method of the present invention is characterized in that a thermoplastic polyimide solution is directly cast on a release film and dried to obtain a thermoplastic polyimide film with a release film. This is a method for processing a thermoplastic polyimide film with a release film.

A second processing method is characterized in that the thermoplastic polyimide film with the release film and the adherend are heated and pressed to transfer the thermoplastic polyimide film to the adherend. This is a method for processing a thermoplastic polyimide film.

In a third processing method, a punched product, a slit process and / or a cut-off process are performed on the above-mentioned thermoplastic polyimide film with a release film to obtain a processed product, and then the processed product and the adherend are heated and pressed. A method of processing a thermoplastic polyimide film with a release film, wherein the thermoplastic polyimide film having a desired shape is transferred to the adherend.

A fourth processing method is characterized in that, in the above-described method, the thermoplastic polyimide film transferred onto the adherend is used as an adhesive film, and the adherend and another adherend are adhered by heat and pressure. This is a processing method capable of obtaining a secondary processed product.

A fifth processing method is the method described above, in which the thermoplastic polyimide film transferred onto the adherend functions as an adhesive film, as well as electrical insulation, radiation resistance, and the like.
This is a processing method capable of obtaining a secondary processed product, characterized by adding at least one of heat insulation and chemical resistance.

[0014]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below. Raw materials for the thermoplastic polyimide according to the present invention include a specific diamine and a specific tetracarboxylic dianhydride.

As a specific diamine, 1,3-bis (3
-Aminophenoxy) benzene (hereinafter abbreviated as APB), 4,4'-bis (3-aminophenoxy) biphenyl (hereinafter abbreviated as m-BP) and 3,3'-diaminobenzophenone (hereinafter abbreviated as DABP) At least one diamine selected from the group consisting of

As a specific tetracarboxylic dianhydride,
3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride (hereinafter abbreviated as ODPA), 3,3', 4,4'-
Benzophenone tetracarboxylic dianhydride (hereinafter BT)
DA), pyromellitic dianhydride (hereinafter referred to as PMD)
A) and at least one tetracarboxylic dianhydride selected from the group consisting of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter abbreviated as BPDA).

In other words, the thermoplastic polyimide of the present invention comprises at least one diamine component selected from the diamine group consisting of APB, m-BP and DABP, and ODPA, BTDA and PMD as tetracarboxylic dianhydrides.
A, a polycondensation polymer obtained using at least one tetracarboxylic dianhydride component selected from the group consisting of BPDA. The reaction molar ratio of the diamine and the tetracarboxylic dianhydride is usually in the range of 0.75 to 1.25,
Preferably it is in the range of 0.8 to 1.2.

Examples of the amine compound that can partially substitute the above-mentioned diamine include, for example, 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 (4-aminophenyl) sulfone, 3,4′-diaminobenzophenone,
4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 3,4'-diaminodiphenylether, 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] sulfoxide, bis [4- (aminophenoxy) phenyl] sulfoxide, bis [ 4-
(3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) 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] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, bis [4- {4
-(4-Aminophenoxy) phenoxydiphenyl] sulfone, 1,4-bis [4- (4-aminophenoxy)
-Α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, and the like, alone or in combination of two or more. May be used.

The substitution amount by the amine compound is usually in the range of 0 to 50 mol% of the above-mentioned diamine.

Examples of the anhydride which can partially replace the above-mentioned tetracarboxylic dianhydride include, for example, ethylene tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanecarboxylic dianhydride, Two,
2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride Anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis ( 2,3-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,
3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride,
4 '-(p-phenylenedioxy) diphthalic dianhydride, 4,4'-(m-phenylenedioxy) diphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-Naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3, Examples include 4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride and the like. And these alone,
Alternatively, two or more kinds may be used in combination. The replacement amount by the anhydride is usually in the range of 0 to 50 mol% of the above-mentioned tetracarboxylic dianhydride.

For the purpose of sealing the polymer end of the thermoplastic polyimide relating to the thermoplastic polyimide layer of the present invention,
Dicarboxylic anhydride may be added.

The dicarboxylic anhydride used includes:
Phthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, 3,4-benzophenone dicarboxylic anhydride, 2,
3-dicarboxyphenylphenyl ether anhydride,
2,3-biphenyldicarboxylic anhydride, 3,4-biphenyldicarboxylic anhydride, 2,3-dicarboxyphenylphenylsulfone anhydride, 3,4-dicarboxyphenylphenylsulfone anhydride, 2,3-dicarboxy Phenylphenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride,
1,2-anthracene dicarboxylic anhydride, 2,3-anthracene dicarboxylic anhydride, and 1,9-anthracene dicarboxylic anhydride. These dicarboxylic anhydrides may be substituted with a group having no reactivity with amine or dicarboxylic anhydride. The amount of the dicarboxylic anhydride to be added is usually 0.0001 relative to the total amount of 100 moles of the main raw materials of diamine and tetracarboxylic dianhydride.
The range is from 0.5 to 0.5 mol, preferably from 0.005 to 0.25 mol.

Similarly, a monoamine may be added for the purpose of sealing the polymer end of the thermoplastic polyimide. The monoamines used include the following.
For example, aniline, o-toluidine, m-toluidine,
p-Toluidine, 2,3-xylidine, 2,4-xylidine, 2,5-xylidine, 2,6-xylidine, 3,4-
Xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroallynine, m-nitroaniline, p-nitro Aniline, o-aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-
Anisidine, p-anisidine, o-phenetidine, m-
Phenetidine, p-phenetidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-amino Biphenyl, 4-aminobiphenyl, 2-aminophenol phenyl ether, 3
-Aminophenol phenyl ether, 4-aminophenol phenyl ether, 2-aminobenzophenone,
3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenol phenyl sulfide, 3-aminophenol phenyl sulfide, 4-aminophenol phenyl sulfide, 2-aminophenol phenyl sulfone, 3-aminophenol phenyl sulfone,
4-aminophenol phenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2-amino-1-naphthol, 4-amino-1-
Naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-
Examples thereof include amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene.

These monoamines may be used alone or in combination of two or more. The amount of monoamine added
Usually, it is in the range of 0.001 to 0.5 mol, preferably 0.005 to 0.25 mol, per 100 mol of the total amount of diamine and tetracarboxylic dianhydride as the main raw materials. The dicarboxylic anhydride and the monoamine may be used in combination.

The reaction for producing the polyamic acid which is a precursor of the thermoplastic polyimide is usually carried out in an organic solvent. As the organic solvent used in this reaction, for example, N-methyl-
2-pyrrolidone, N, N-dimethylacetamide, N, N
-Dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N, N-diethylacetamide, N, N-
Dimethylmethoxyacetamide, dimethylsulfoxide, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylurea, N-methylcaprolactam, ptyrrolactam, tetrahydrofuran, m-dioxane, p-dioxane, 1,2-dimethoxyethane, bis (2- Methoxyethyl) ether, 1,2-bis (2
-Methoxyethoxy) ethane, bis 2- (2-methoxyethoxy) ethyl ether, tetrahydrofuran,
3-dioxane, 1,4-dioxane, pyridine, picoline, dimethylsulfoxide, dimethylsulfone, o-
Cresol, m-cresol, p-cresol, cresylic acid, p-chlorophenol, phenol, anisole and the like can be mentioned. These organic solvents can be used alone or
A combination of more than one species may be used.

The thermoplastic polyimide of the present invention may be a thermoplastic polyimide solution, a polyamic acid solution which is a precursor of a thermoplastic polyimide, or a mixed solution of a thermoplastic polyimide and a polyamic acid which is a precursor of a thermoplastic polyimide (hereinafter, these are referred to as A thermoplastic polyimide varnish (collectively referred to as a thermoplastic polyimide varnish) is cast and applied to a non-thermoplastic film plate, and then heated and dried in order to remove the solvent, complete the imidization reaction, and remove volatile impurities.

In addition, a method of applying a powder of thermoplastic polyimide powder isolated from the thermoplastic polyimide varnish, a method of granulating the thermoplastic polyimide powder, and then heating and melting the thermoplastic polyimide particles for casting. There is.

The method for producing the polyamic acid which is a precursor of the thermoplastic polyimide of the present invention is not particularly limited, and the diamine and the tetracarboxylic dianhydride component are reacted in the above-mentioned organic solvent at a uniform reaction temperature. What is necessary is just to polymerize, keeping it. If necessary, the above-mentioned dicarboxylic anhydride or monoamine can be added and reacted.

The reaction temperature for producing the polyamic acid which is the precursor of the thermoplastic polyimide according to the present invention is usually 0
It is in the range of -60C, preferably in the range of 0-50C.
The reaction pressure is not particularly limited, and normal pressure is sufficient. The reaction time varies depending on the molar ratio of tetracarboxylic dianhydride and diamine used, the type of solvent and the reaction temperature,
The reaction is allowed to proceed for a time sufficient to complete the formation of the polyamic acid. Usually, 4 to 24 hours are sufficient.

The polyamic acid, which is a precursor of the thermoplastic polyimide obtained by the above polycondensation reaction, is mixed with 100 to 30
A method of imidizing by heating at 0 ° C. for 0.5 to 24 hours, or a method of imidizing using a tertiary amine such as pyridine, γ-picoline, imidazole, and tritylamine as a catalyst, is used to convert the polyimide. A reaction mixture containing is obtained. The reaction conditions in this case are as follows, using an imidizing agent such as acetic anhydride, at a temperature in the range of room temperature to 200 ° C, preferably in the range of room temperature to 100 ° C.
The reaction time is between 0.5 and 24 hours. This may be used as a thermoplastic polyimide varnish.

Further, the reaction mixture is precipitated into a poor solvent of the thermoplastic polyimide, or is precipitated by adding the poor solvent into the reaction system. Solvent mixed in the reaction system other than the plastic polyimide, remove the catalyst, etc. by heating and reduced pressure, or after isolating the thermoplastic polyimide by any method, the isolated thermoplastic polyimide, this thermoplastic polyimide The thermoplastic polyimide varnish may be adjusted by dissolving the powder in a solvent that dissolves the powder, and the thermoplastic polyimide varnish may be used substantially as a thermoplastic polyimide. Examples of the solvent used here include the solvents listed above as the polymerization solution.

Specific examples of the poor solvent include N-methyl-2
-Pyrrolidone, N, N-dimethylacetamide, N, N-
Dimethylformamide, 1,3-dimethyl-2-imidazolidinone, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethylsulfoxide,
Pyridine, dimethyl sulfone, hexamethylphosphoramide, tetramethylurea, N-methylcaplactam, butyrolactam, tetrahydrofuran, m-dioxane,
p-dioxane, 1,2-dimethoxyethane, bis (2
-Methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis2- (2-methethoxyethoxy) ethyl ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline,
Examples include dimethyl sulfoxide, dimethyl sulfone, o-cresol, m-cresol, p-cresol, cresylic acid, p-chlorophenol, phenol, anisole and the like.

These organic solvents may be used alone or in combination of two or more. After the thermoplastic polyimide is isolated from the reaction system, it can be washed with an alcohol such as methanol or ethanol to remove impurities and the like, and dried at a temperature at which the used alcohol can be removed.

Further, as another method for forming the thermoplastic polyimide of the present invention on a non-thermoplastic film, a method of applying a powder of a thermoplastic polyimide powder isolated from the above-mentioned reaction system, or a method of applying the thermoplastic polyimide powder to After granulation, there is a method in which the thermoplastic polyimide particles are heated and melted at a melting temperature (hereinafter referred to as Tm) or a temperature at which thermal decomposition does not occur, preferably in a temperature range of Tm to 400 ° C., and applied by casting. However, in this case, it is necessary to perform at a temperature at which the non-thermoplastic film serving as the base material does not deteriorate and deteriorate.

The temperature and time for heating and drying the above-mentioned thermoplastic polyimide varnish differ depending on the kind of the thermoplastic polyimide, the amount of the remaining solvent and the coating thickness. Boiling point of solvent to 50
The heating temperature is in the range of 0 ° C., preferably 15 ° C. higher than the boiling point of the solvent to 420 ° C., and heating as short as possible is industrially preferable. When the coating thickness is 25 μm, it is usually 0.1 seconds to 6 hours, preferably 2 seconds to 1 hour, and more preferably 5 seconds to 30 minutes. In order to prevent oxidation of the non-thermoplastic film plate, it is preferable to heat and dry in an inert gas such as nitrogen gas or argon gas.

Further, the solvent removal and imidization reaction of the thermoplastic polyimide film layer of the present invention need not necessarily be completed on the release film. Because, the polyimide varnish according to the present invention formed on the release film,
This is because, after the transfer to the adherend, the remaining solvent and the remaining volatile impurities can be removed by heating, or the imidization reaction can be completed.

To the melt of the thermoplastic polyimide varnish or polyimide powder of the present invention, a coupling agent is added to increase the adhesion to the adherend, and a surfactant is added to increase the surface smoothness. It may be added, or an additive or a filler for changing the characteristics of the polyimide may be added. The thermoplastic polyimide thus obtained is
The glass transition point can be controlled in the range of 160 to 280 ° C.

The method for casting and coating the thermoplastic polyimide varnish or the polyimide powder melt of the present invention on a non-thermoplastic film is not limited. The coating is performed using a conventionally known coating apparatus such as a comma coater, a die coater, a roll coater, a knife coater, a reverse coater, a gravure coater, a blade coater, and a spin coater. Thereafter, heating and drying are performed for a sufficient time and temperature to complete the solvent removal and the imidization reaction.

The thickness of the non-thermoplastic film of the present invention is 1 μm.
Considering the strength, weight, workability, and the presence of pinholes, the thickness is preferably 2 μm to 5 mm. The shape may be a plate, a film, a ribbon, or a sheet (hereinafter, collectively referred to as a film). Industrially, a roll-shaped film is preferable because it is suitable for continuous production.

The non-thermoplastic film used in the present invention comprises:
Examples include a polyimide film, an aramid film, a polyetheretherketone film, and a polyetherethersulfone film. When processed and used below the glass transition point, a thermoplastic polyimide film may be used.

The adherend used in the present invention is not particularly limited as long as it does not cause deterioration or deterioration in the use environment and the processing environment.

The thermoplastic polyimide film with the release film obtained here is heated and pressed on the adherend as it is through the surface of the thermoplastic polyimide film, and the release film is mechanically peeled off. Only the polyimide film layer is transferred to the adherend. Further, when the thermoplastic polyimide with the release film is previously cut or punched and transferred to an adherend, a thermoplastic polyimide film layer having a desired shape can be obtained.

Further, the thermoplastic polyimide film layer on the adherend obtained by the above method may be used as a heat-resistant adhesive or a heat-resistant insulating adhesive layer, a radiation-resistant adhesive layer, a chemical-resistant adhesive layer, a heat-resistant adhesive layer. By using as, a secondary processed product having a desired shape can be obtained.

Further, by repeating the above operation a plurality of times, it is possible to obtain a multilayer laminate in which the adhesive layer composed of the thermoplastic polyimide film layer and the adherend are alternated.

The transfer method of the thermoplastic polyimide film of the present invention by thermocompression bonding is not particularly limited. A hot press method, a vacuum press method, an autoclave press method, a hot roll press method, a jogging press method, or the like is used. In particular, a hot roll press method and a jogging press method, which enable continuous processing of a long length and facilitate transfer of a thermoplastic film, are industrially preferable. Further, a hot roll press using an elastic roll is particularly preferable because uniform heat pressing can be performed.

The conditions of the thermocompression bonding for transferring the thermoplastic film to the adherend are not particularly limited, and are in a range necessary and sufficient for lamination and not hindering practical use such as deterioration of materials used and hot press equipment. Then, the pressure, temperature, and time may be selected. The preferred temperature is not higher than the glass transition point of the thermoplastic polyimide according to the present invention, and more preferably in the range of 50 ° C. lower than the glass transition point to the glass transition temperature.

When the release film is mechanically peeled off after pressing under the above conditions, the transfer of the thermoplastic film to the adherend is completed.

There is no particular limitation on the transfer method by heating and pressing to another adherend via the thermoplastic polyimide film layer of the adherend obtained by the above method. That is, a hot press method, a vacuum press method, an autoclave press method, a hot roll press method, a jogging press method, or the like is used. In particular, a hot roll press method and a jogging press method, which enable continuous processing of a long length and facilitate transfer of a thermoplastic film, are industrially preferable. further,
A hot roll press using an elastic roll is particularly preferable because uniform heat pressing can be performed.

Further, there is no particular limitation on the conditions for heat-pressing the adherend and the other adherend via the transferred thermoplastic polyimide film layer. The pressure, temperature, and time may be selected as long as they are necessary and sufficient for lamination and do not hinder practical use such as deterioration of the materials used and the hot press equipment. The preferred temperature is in the range of the glass transition point of the thermoplastic polyimide according to the present invention to 500 ° C., more preferably a temperature 10 ° C. higher than the glass transition point to 430 ° C.
Range.

The thermoplastic polyimide film layer obtained by the above transfer has higher radiation resistance, heat resistance and moisture resistance than ordinary electric insulators, for example, epoxy resin.
Excellent electrical insulation, low dielectric constant, and low dielectric loss.
Therefore, it can be suitably used for highly reliable environment resistance or composite materials and components for high frequency devices.

[0051]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments based on the drawings, but the present invention is not limited to these embodiments. (Synthesis Example 1) 2920 g (10 mol) of APB and N, N
24560 g of -dimethylacetamide was stirred and dissolved at room temperature under a nitrogen atmosphere. In addition, BTDA's 3197
g (9.99 mol) were added in four portions, and the mixture was stirred at room temperature for 24 hours. The polyad acid thus obtained has a viscosity of 70 poise at 23 ° C. and an logarithmic viscosity of 0.7 dl / g.
(23 ° C., 0.5% in N, N-dimethylacetamide solvent)
Logarithmic viscosity measured at a concentration, using an E-type viscometer; hereinafter, this value is referred to as logarithmic viscosity).

(Synthesis Example 2) 2920 g (10 mol) of APB and 24560 g of N, N-dimethylacetamide
Was stirred and dissolved at room temperature under a nitrogen atmosphere. In addition, BT
3197 g (9.99 mol) of DA was added in four portions, and the mixture was stirred at room temperature for 24 hours. Thereafter, 11.184 g (0.8 mol) of phthalic anhydride was added, and the mixture was stirred at room temperature for 3 hours. The polyad acid thus obtained had a viscosity at 23 ° C. of 68 poise and an logarithmic viscosity of 0.54 dl / g.

Synthesis Example 3 2920 g (10 mol) of APB and 24560 g of N, N-dimethylacetamide
Was stirred and dissolved at room temperature under a nitrogen atmosphere. In addition, BT
3197 g (9.99 mol) of DA was added in four portions, and the mixture was stirred at room temperature for 24 hours. Thereafter, 11.184 g (0.8 mol) of phthalic anhydride was added, and the mixture was stirred at room temperature for 3 hours. The polyad acid thus obtained had a viscosity at 23 ° C. of 68 poise and an logarithmic viscosity of 0.54 dl / g. 408 g of acetic anhydride (4
Mol) and 150 g of triethylamine were added dropwise, and the mixture was stirred at room temperature for 10 hours. 10,000 g of the obtained reaction mixture
Of methanol under vigorous stirring, and the precipitate was separated by filtration. The obtained powdery precipitate was further washed with methanol and dried at 180 ° C. for 12 hours to obtain a polyimide powder.

(Synthesis Example 4) 200 g of the polyimide powder obtained in Synthesis Example 1 was mixed with 800 g of N-methyl-2-pyrrolidone.
g (concentration: 20% by weight) to obtain a thermoplastic polyimide varnish.

(Synthesis Example 5) 292 g (1 mol) of APB
And 1839 g of N, N-dimethylacetamide were stirred and dissolved at room temperature under a nitrogen atmosphere. ODPA 7
6.9 g (0.26 mol) and 225.3 g (0.2%) of BTDA.
(70 mol) was added in four portions, each being careful to raise the temperature, and the mixture was stirred at room temperature for about 20 hours. Thereafter, 1.1184 g (0.08 mol) of phthalic anhydride was added, and the mixture was further stirred at room temperature for 3 hours. The polyamic acid thus obtained had a logarithmic viscosity of 0.49 dl / g. Then, the solution was heated and treated at the reflux temperature of N, N-dimethylacetamide for 6 hours. Further, the removal of 1000 g of N, N-dimethylacetamide was continued for 6 hours to obtain a thermoplastic polyimide waste.

(Synthesis Example 6) The ODPA of Synthesis Example 5 (0.2
6 mol) was changed to BPDA (0.25 mol), and a thermoplastic polyimide varnish was obtained under the same conditions as in Synthesis Example 5.

(Synthesis Example 7) A thermoplastic polyimide varnish was obtained under the same conditions as in Synthesis Example 1 except that APB (10 mol) in Synthesis Example 1 was changed to m-BP (10 mol).

(Synthesis Example 8) The thermoplastic polyimide varnishes of Synthesis Example 1 and Synthesis Example 4 were mixed in an amount of 2000 g each for 3 hours to prepare a mixture of thermoplastic polyimide and polyamic acid which is a precursor of the thermoplastic polyimide. A plastic polyimide varnish was obtained.

Synthesis Example 9 APB (1 mol) and N, N-
2456 g of dimethylacetamide was stirred and dissolved at room temperature under a nitrogen atmosphere. To this, BDPA (0.95 mol) was added in four portions, and the mixture was stirred at room temperature for 20 hours. Thereafter, phthalic anhydride (0.04 mol) was added, and the mixture was added at room temperature for 3 hours.
After stirring for an hour, a thermoplastic polyimide varnish made of polyamic acid, which is a precursor of the thermoplastic polyimide, was obtained.

(Synthesis Example 10) A thermoplastic polyimide varnish was obtained under the same conditions as in Synthesis Example 1 except that APB (10 mol) in Synthesis Example 1 was changed to DABP (10 mol).

(Synthesis Example 11) A thermoplastic polyimide varnish was obtained under the same conditions as in Synthesis Example 4 except that APB (10 mol) in Synthesis Example 4 was changed to PMDA (1 mol).

Example 1 FIG. 1 (a) is a schematic sectional view showing one example of a thermoplastic polyimide film with a release film according to the present invention.

As an example of a heat-resistant release film, a thickness of 5
Using a knife coater, the thermoplastic polyimide varnish of Synthesis Example 1 was directly and uniformly and directly cast coated on a 0 μm, 508 mm wide polyimide film (trade name: Upilex S, manufactured by Ube Industries, Ltd.). In a drying furnace under a nitrogen atmosphere at a temperature of 250 ° C., the solvent is removed and the imidization reaction is completed with a residence time of about 25 minutes, and the release film 12 and the non-thermoplastic polyimide as shown in FIG. A thermoplastic polyimide film 11 with a release film comprising the film 13 was obtained. This thermoplastic polyimide film 13
Had a thickness of 25 μm.

Example 2 A heat-resistant release film (1)
2) As an example, the thermoplastic polyimide varnish of Synthesis Example 2 is uniformly and continuously applied on a polyimide film (trade name: Apical NPI, manufactured by Kanegafuchi Chemical Co., Ltd.) having a thickness of 25 μm and a width of 35 mm using a roll coater. Typically, coating width 26m
m, and in a drying oven under a nitrogen atmosphere at a maximum temperature of 300 ° C., the solvent is removed and the imidization reaction is completed with a residence time of about 5 minutes. ) Got. The thickness of this thermoplastic polyimide film (13) was 10 μm.

Example 3 A heat-resistant release film (1)
As an example of 2), the thermoplastic polyimide varnish of Synthesis Example 11 is directly and uniformly applied directly onto a 38 μm-thick aramid film (trade name: Aramica, manufactured by Asahi Kasei Corporation) using a die coater. Then, in a drying furnace under a nitrogen atmosphere at a maximum temperature of 280 ° C., the solvent was removed and the imidization reaction was completed at a residence time of about 15 minutes to obtain a thermoplastic polyimide film (11) with a release film. The thickness of this thermoplastic polyimide film (13) was 8 μm.

Example 4 A heat-resistant release film (1)
As an example of 2), Synthesis Example 1 was formed on a 100 μm-thick polyetheretherketone film (trade name: Talpa 2000, manufactured by Mitsui Toatsu Chemicals, Inc.) using a knife coater.
Directly cast and apply a uniform thermoplastic polyimide varnish,
The solvent was removed and the imidization reaction was completed in a drying oven under a nitrogen atmosphere at a maximum temperature of 250 ° C. for a residence time of about 15 minutes, and the thermoplastic polyimide film (1
1) was obtained. The thickness of the thermoplastic polyimide film (13) was 15 μm.

Example 5 The thermoplastic polyimide varnish of Example 4 was replaced with the thermoplastic polyimide varnish of Synthesis Example 5.
In the same manner as in Example 4, a thermoplastic polyimide film (11) with a release film was obtained. The thickness of this thermoplastic polyimide film (13) was 25 μm.

Example 6 The thermoplastic polyimide varnish of Example 1 was replaced with the thermoplastic polyimide varnish of Synthesis Example 4.
In the same manner as in Example 1, a thermoplastic polyimide film (11) with a release film was obtained. The thickness of this thermoplastic polyimide film (13) was 25 μm.

Example 7 A heat-resistant release film (1)
2) As an example, the thermoplastic polyimide varnish of Synthesis Example 6 is uniformly and continuously applied on a 50 μm-thick and 1016 mm-wide polyimide film (trade name: Kapton H, manufactured by Dupont Toray) using a roll coater. , Effective coating width 1
The solvent was removed and the imidization reaction was completed in a drying furnace under a nitrogen atmosphere at a maximum temperature of 300 ° C. for a residence time of about 5 minutes. ) Got. The thickness of this thermoplastic polyimide film (13) was 18 μm.

The obtained thermoplastic polyimide film (11) with a release film was slit to a width of 7.0 mm to obtain a heat-resistant adhesive tape for fixing electronic components for mounting semiconductor elements. By the following procedure, application processing of the thermoplastic polyimide film with the release film to automatic tape mounting of a semiconductor element was verified.

1) A desired shape (in this embodiment, a width of 7 m)
m, rectangle with a length of 4 mm)
Thermoplastic polyimide surface of plastic polyimide film and 42 d
A nickel alloy was temporarily bonded. Conditions for temporary bonding at this time
Is 220 ° C. × 10 kgf / cm ^Two(1080 kPa)
× 1 second, by changing the shape of the pressurizing mold
As a result, a cross section of the temporary bonding having a desired shape is obtained.

2) By peeling off the release film using a take-off machine, a thermoplastic polyimide layer having a desired shape was formed on the 42 nickel alloy layer.

3) A silicon wafer is placed on the above-mentioned thermoplastic polyimide layer, and the temperature is 300 ° C. × 20 kgf / cm
^Under a pressurizing condition of ² (2060 kPa) × 10 seconds, the 42 nickel alloy and the silicon wafer were fixed.

4) The secondary processed product was dried at 150 ° C. for 30 minutes and sealed with an epoxy resin. However, harmful defects such as warpage of the silicon wafer, cracks at the sealing material interface, and peeling were observed. Did not.

As described above, the secondary processing of the thermoplastic polyimide film with the release film of the present invention was easily performed. According to the present example, it was shown that the present invention is useful for automatic mounting of a semiconductor element by a tape automatic mounting (TAB) method.

Example 8 A heat-resistant release film (1
2) As an example, the thermoplastic polyimide varnish of Synthesis Example 7 is directly cast on a polyimide film (trade name: Kapton K, manufactured by Dupont Toray) having a thickness of 50 μm and a width of 508 mm using a roll coater. Coating, in a drying furnace under a nitrogen atmosphere at a maximum temperature of 275 ° C., a residence time of about 18
The solvent was removed and the imidization reaction was completed in 0 minutes to obtain a thermoplastic polyimide film (11) with a release film. The thickness of this thermoplastic polyimide film (13) is 5
It was 0 μm.

Example 9 A heat-resistant release film (1)
2) As an example, the thermoplastic polyimide varnish of Synthesis Example 5 is uniformly and continuously applied on a 125 μm-thick, 508 mm-wide polyimide film (trade name: Kapton V, manufactured by Dupont Toray) using a roll coater. , Effective coating width 5
Then, the solvent was removed and the imidization reaction was completed with a residence time of about 10 minutes in a drying furnace under a nitrogen atmosphere at a maximum temperature of 375 ° C. to complete the imidation reaction. ) Got. The thickness of this thermoplastic polyimide film (13) was 20 μm.

A heat-resistant adhesive tape obtained by slitting the obtained thermoplastic polyimide film with a release film to a width of 26.0 mm and punching a hole having a desired shape (5 mm square in this embodiment) is used. Obtained.

The following procedure was used to verify the continuous application of a long roll of the thermoplastic polyimide film with a release film.

1) The thermoplastic polyimide surface of the thermoplastic polyimide film with the release film having holes (5 mm square in this embodiment) having a desired shape formed of a roll,
8 μm, 35 mm wide rolled electrolytic copper foil (trade name: SLP
-18, manufactured by Nippon Electrolysis Co., Ltd.). The condition of the temporary bonding at this time is as follows, using a heating roll press machine.
220 ° C. × 10 kgf / cm ² (1080 kPa) × 1
Seconds. In addition, in order to prevent oxidation of the copper foil, the test was performed in a nitrogen atmosphere.

2) By peeling off the release film with a take-off machine, a thermoplastic polyimide layer having a desired shape is formed.
Formed on copper foil.

3) On the above-mentioned thermoplastic polyimide layer, a rolled all-polyimide flexible printed circuit board on which a circuit is formed is laminated, and 300 ° C. × 20 kgf / cm ² (206
By applying pressure continuously under a pressure of 0 kPa) × 10 seconds, an all-polyimide flexible multilayer circuit was obtained.

4) The electrolytic copper foil in contact with the punched portion of the thermoplastic polyimide of the secondary processed product has already secured conduction between the circuit layers of the applied polyimide flexible printed circuit board. In other words, through-hole processing can be performed without newly processing the polyimide, and thus continuous processing in a rolled state is possible.

5) A circuit was formed on the electrolytic copper foil layer of the secondary processed product, and ordinary circuit processing was performed to obtain a multilayer substrate made of all polyimide. This substrate is 300
It was an excellent printed circuit board having no change in the soldering heat test at 10 ° C. for 10 seconds. In this embodiment, processing by an existing tape automatic mounting apparatus was possible.

Example 10 In the same manner as in Example 1 except that the thermoplastic polyimide varnish of Example 1 was replaced with the thermoplastic polyimide varnish of Synthesis Example 9, a thermoplastic polyimide film (11) with a release film (12) was used. ) Got. The thickness of this thermoplastic polyimide film (13) was 8 μm.

FIG. 1B is a schematic plan view showing one embodiment of a primary processed product 21 obtained by subjecting a thermoplastic polyimide film 11 with a release film obtained in this embodiment to punching and cutting. It is.

In the figure, reference numeral 22 denotes a punched hole (hole for transporting the base material), reference numeral 23 denotes a punched hole, and reference numeral 24 denotes a punched hole.
Indicates a cutting trace. Such a cut is for detecting the movement of the film with a sensor or the like, and the cut itself may be in an I-shape as in this example, but may be in another form, for example, a V-shape. However, there is no problem.

FIG. 1C is a view taken along the line AA ′ in FIG.
FIG. FIG. 1D shows the state shown in FIG.
3 is a schematic cross-sectional view taken along the line BB 'of FIG. 1, showing a state in which both the release film 12 and the thermoplastic polyimide film 13 have been removed by punching and cutting.

FIG. 1E is a view similar to that of FIG.
FIG. 4B is a schematic cross-sectional view taken along line −B ′, in which only the thermoplastic polyimide film 13 is partially removed by punching and cutting. In this case, the release film 12 may be partially damaged by the punching process.

FIG. 1F is a view taken in the direction of arrow C- in FIG.
It is a schematic cross section in C '. This embodiment is an example applied to a tape automatic mounting (TAB) method.

[0091]

According to the present invention, a thin and uniform thermoplastic polyimide film can be obtained by forming a thermoplastic polyimide film on a release film, and the thermoplastic polyimide film is easy to handle because the release film has high strength. Can be obtained.

Further, the thermoplastic polyimide film in a state where the release film is adhered is punched, cut,
Processing of slits and the like can be performed extremely easily, and a processed product of high industrial value suitable for continuous processing can be obtained.

Further, by transferring a thermoplastic polyimide film having a desired shape to an object to be bonded, a heat-resistant insulating adhesive layer having a complicated shape can be obtained, and a laminated product through the thermoplastic polyimide layer can be easily processed. A remarkable effect such as a product can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a thermoplastic polyimide film with a release film. (However, (a) is a schematic cross-sectional view of the film, (b) is a schematic plan view of a primary processed product in which the film is punched and cut, and (c) is an arrow A in (b). FIG. 4D is a schematic cross-sectional view taken along the line BB ′ in FIG. 4B, from which both the release film 12 and the thermoplastic polyimide film 13 have been removed. Is also BB 'in the direction of arrow (b).
(F) is a schematic cross-sectional view in which only the thermoplastic polyimide film 13 is partially removed, and FIG.
FIG. )

[Explanation of symbols]

REFERENCE SIGNS LIST 11 thermoplastic polyimide film with release film 12 release film 13 thermoplastic polyimide film 21 processed thermoplastic polyimide film with release film 22 punched holes (substrate transport holes) 23 punched holes 24 cut marks 25 slits Processing direction

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukihiro Kumamoto 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Mitsui Toatsu Chemicals Co., Ltd.

Claims (6)

[Claims] 1. A method for processing a thermoplastic polyimide film with a release film, wherein a thermoplastic polyimide solution is directly cast-coated on the release film and dried to form a thermoplastic polyimide film with a release film. A method for processing a thermoplastic polyimide film with a release film, characterized in that it is obtained. 2. The method according to claim 1, wherein the thermoplastic polyimide film with the release film is heat-pressed to the adherend to transfer the thermoplastic polyimide film to the adherend. Processing method of thermoplastic polyimide film. 3. A processed product is obtained by subjecting the thermoplastic polyimide film with a release film to punching, slitting, and / or cutting, and the processed product is heated and pressure-bonded to the adherend. 2. The method for processing a thermoplastic polyimide film with a release film according to claim 1, wherein a thermoplastic polyimide film having a desired shape is transferred onto the substrate. 4. A secondary processed product, wherein the thermoplastic polyimide film transferred onto the adherend is used as an adhesive film, and the adherend and another adherend are adhered to each other by heat and pressure to form a secondary processed product. A method for processing a thermoplastic polyimide film with a release film according to claim 2 or 3. 5. The thermoplastic polyimide film transferred onto the adherend has at least one function of electrical insulation, radiation resistance, heat insulation, and chemical resistance in addition to the function as an adhesive film. The method for processing a thermoplastic polyimide film with a release film according to claim 2 or 3, wherein the processed product is a secondary processed product. 6. A release film, characterized in that a thermoplastic polyimide film with a release film is obtained by the method for processing a thermoplastic polyimide film with a release film according to any one of claims 1 to 5. With thermoplastic polyimide film.