JP2003011308A - Film-shaped laminated member - Google Patents

Abstract

(57) [Summary] [Problem] Temporary crimping at a temperature and pressure lower than the temperature and pressure at the time of final crimping (when used), that is, low temperature and low pressure, is excellent in heat resistance and electrical reliability, Further, a film-like laminated member excellent in adhesive strength, workability, and workability at the time of final pressure bonding is provided. SOLUTION: The film-shaped laminated member has a polyimide film and an adhesive layer applied to at least one surface of the polyimide film. The adhesive layer is obtained by, for example, casting and applying a solution obtained by dissolving at least a thermoplastic polyimide and a thermosetting resin in an organic solvent to at least one surface of a polyimide film, and then drying. The film-like laminated member has an adhesive strength of 1 when thermocompression bonded to a polyimide film to be applied at a temperature of 150 ° C. or less, a pressure of 5 kgf / cm ² or less, and a linear velocity of 0.5 m / min or less.
0 gf / cm or more and 100 gf / cm or less.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to main pressure bonding (when used).
The present invention relates to a film-like laminated member capable of temporary pressure bonding at a temperature / pressure lower than the temperature / pressure at the time of pressure bonding, that is, at low temperature and low pressure, and having excellent adhesive strength, workability, and workability during main pressure bonding is there. The film-like laminated member of the present invention, for example,
It can be suitably used for a laminated material such as a multilayer flexible printed circuit board (multilayer FPC) which is required to have pressure-bonding property at low temperature and low pressure, heat resistance and adhesiveness.

[0002]

2. Description of the Related Art In recent years, electronic devices have become more sophisticated, have higher performance,
Miniaturization is advancing, and miniaturization and weight reduction are required for electronic components used with them. Therefore, semiconductor device packaging methods and wiring materials or wiring components for mounting them are also required to have higher density, higher functionality and higher performance. In particular, semiconductor packages, COL and LOC packages, MCM (M
There is a demand for a material having excellent heat resistance, electrical reliability, and adhesiveness, which can be suitably used as a high-density mounting material such as an ulti chip module) or a printed wiring board material such as a multilayer FPC.

In this field, polyimide adhesive materials are gradually being used as adhesive materials having flexibility not possessed by phenolic and epoxy adhesive materials and heat resistance not possessed by acrylic adhesive materials. It is being used. In particular, in multi-layer FPC, which has recently been rapidly increasing in applications to small electronic devices such as mobile phones, as a material replacing the conventional epoxy resin-impregnated prepreg,
Attention is being paid to the market for polyimide-based adhesive materials.

[0004]

However, although the polyimide-based adhesive material is excellent in heat resistance and electric reliability, it requires a high temperature of about 300 ° C. and a high pressure in order to exhibit sufficient adhesiveness. It is not suitable for applications that require workability and workability at extremely low temperatures. In addition, in the manufacturing process of the multilayer FPC, when the layers are temporarily pressure-bonded to each other at a temperature and a pressure lower than the temperature and pressure at the time of the main pressure-bonding before the main pressure-bonding of the layers, that is, at the time of the main pressure-bonding. In some cases, temporary pressure bonding may be performed with an adhesive strength lower than the adhesive strength of. However, the polyimide-based adhesive material that requires high temperature and high pressure to develop adhesiveness has a problem that it is difficult to perform temporary pressure bonding because it cannot exhibit sufficient adhesiveness at low temperature and low pressure. ing. Further, if the glass transition temperature of polyimide is set extremely low in order to improve the adhesiveness at low temperature and low pressure, there is a problem that the heat resistance of the adhesive material is impaired.

Furthermore, since polyimides generally have very low solubility in organic solvents, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP). )
It can be dissolved only in a very limited (several kinds) high boiling point solvent such as. Therefore, the adhesive material solution using these high boiling point solvents cannot completely remove the solvent when applied on a film and dried. It has been clarified that the solvent remaining in the adhesive material causes foaming, deterioration of heat resistance and the like.

Further, as a method for improving the solubility of polyimide in an organic solvent (solubilization method), a method of introducing a siloxane moiety into the structure, a method of introducing a long chain alkyl group, a bulky side chain substituent A method for introducing the is generally known. However, when a siloxane moiety or a long-chain alkyl group is introduced in order to improve the solubility of the polyimide to such an extent that the polyimide has good solubility in a cyclic ether solvent, the heat resistance of the polyimide decreases. That is, the above method cannot achieve both good solubility and good heat resistance of the polyimide. Also,
Introducing bulky side chain substituents into polyimide requires special raw materials. Therefore, the molecular design of the polyimide becomes complicated, and it becomes difficult to balance with other physical properties.

An adhesive material consisting only of a thermosetting resin is excellent in workability at low temperatures, but inferior in heat resistance.

The present invention has been made in view of the above conventional problems, and an object thereof is a temperature / pressure lower than a temperature / pressure at the time of main pressure bonding (in use), that is, at a low temperature and a low pressure. An object of the present invention is to provide a film-like laminated member that can be pressure-bonded, has excellent heat resistance and electrical reliability, and has excellent adhesive strength, workability, and workability during main pressure-bonding.

[0009]

Means for Solving the Problems In order to solve the above problems, a film-like laminated member of the present invention comprises a polyimide film and at least a thermoplastic polyimide and a thermosetting resin applied to at least one surface of the polyimide film. A film-like laminated member having an adhesive layer obtained by drying a solution obtained by dissolving a resin in an organic solvent, wherein the temperature is 150 ° C. or lower, the pressure is 5 kgf / cm ² or lower, and the linear velocity is 0.
Adhesive strength when thermocompression-bonded to a polyimide film to be worn at 5 m / min or less, 10 gf / cm or more, 100 gf / c
It is characterized by being m or less.

In order to solve the above-mentioned problems, the film-like laminated member of the present invention has a glass transition temperature (Tg) of 200 ° C. or less of the thermoplastic polyimide, and the thermoplastic polyimide is a cyclic ether type. It is characterized by being a soluble thermoplastic polyimide showing a solubility of 10% or more of solid content concentration (SC) in a solvent. In order to solve the above problems, the film-shaped laminated member of the present invention is characterized in that the thermosetting resin contains a plurality of epoxy groups in its structure. The film-like laminated member of the present invention,
In order to solve the above problems, the thickness of the adhesive layer is 2 to 20.
It is characterized in that it is in the range of μm.

According to the above-mentioned constitution, the adhesive layer of the film-like laminated member comprises, for example, a solution prepared by dissolving at least a thermoplastic polyimide and a thermosetting resin in an organic solvent,
It is obtained by coating on at least one side of a polyimide film and then drying. Therefore, the adhesive layer of the film-like laminated member is provided with both the heat resistance of the thermoplastic polyimide and the processability at low temperature of the thermosetting resin in a good state. Further, the adhesive layer of the film-like laminated member can exhibit adhesiveness at low temperature and low pressure, and can have stronger adhesiveness at high temperature and high pressure. Therefore, it is possible to perform temporary crimping at a temperature and pressure lower than the temperature and pressure at the time of main pressure bonding (in use), that is, at low temperature and low pressure, with excellent heat resistance and electrical reliability, and at the time of main pressure bonding. It is possible to provide a film-like laminated member having excellent adhesive strength, workability, and workability.

In particular, a soluble thermoplastic polyimide having a glass transition temperature of 200 ° C. or lower and having solubility in a cyclic ether solvent, and a thermosetting resin containing a plurality of epoxy groups in its structure, For example, when used in combination with an epoxy resin, the processing temperature for forming the adhesive layer can be further lowered, and the organic solvent can be easily removed under the condition that the curing of the epoxy resin does not proceed excessively. can do. Moreover, the temperature at the time of the main pressure bonding can be further lowered, and the workability can be further improved. For this reason, it is possible to provide a film-like laminated member that can be subjected to temporary pressure bonding at a lower temperature and a lower pressure, and that has a higher adhesive strength than the adhesive strength during temporary pressure bonding during main pressure bonding.

Further, since the film-like laminated member of the present invention has the release film on at least one adhesive layer, it has good workability such as workability during use.

Further, the film-like laminated member of the present invention is
To solve the above problems, thermoplastic polyimide,
Formula (1)

[0015]

[Chemical 4]

(Wherein, X represents a saturated hydrocarbon divalent group having 1 to 10 carbon atoms or an aromatic ring-containing divalent group), and the ester acid dianhydride is represented by 50% of the total acid dianhydride component. Mol%
Equation (2) above

[0017]

[Chemical 5]

(In the formula, Y is independently -CO-, -SO ₂
-, - O -, - S -, - (CH 2) k -, - NHCO-,
_{-C (CH 3) 2 -,} - C (CF 3) 2 -, - COO- or a single bond, k and m are 1 to 5 of the represented diamine compound integer is) the total diamine component Of 50
It is characterized in that it is a thermoplastic polyimide obtained by using more than mol%.

In order to solve the above problems, the film-like laminated member of the present invention further comprises a thermoplastic polyimide,
Formula (3)

[0020]

[Chemical 6]

(In the formula, Z is independently -CO-, -SO ₂
-, - O -, - S -, - (CH 2) q -, - NHCO-,
_{-C (CH 3) 2 -,} - C (CF 3) 2 -, - COO- or a single bond, R ₁ is a hydroxyl group or carboxyl group independently, p is 1 or 2, n and q It is a thermoplastic polyimide obtained by using a diamine compound represented by 1 or more and 5 or less) in an amount of 5 mol% or more of all diamine components.

According to the above constitution, the thermoplastic polyimide obtained by using the ester dianhydride represented by the formula (1) and the diamine compound represented by the formula (2) is a cyclic ether solvent. In addition to exhibiting good solubility, it can exhibit sufficient heat resistance. Further, by using the above ester dianhydride, the water absorption of the thermoplastic polyimide obtained can be lowered. Furthermore, equation (3)
5 mol% of the total diamine component represented by
By using the above, the obtained thermoplastic polyimide and a thermosetting resin, for example, an epoxy resin can be reacted and crosslinked. Therefore, it is possible to provide a film-like laminated member having more excellent adhesiveness and heat resistance.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION A film-like laminated member according to the present invention has a polyimide film and an adhesive layer applied on at least one side of the polyimide film. The adhesive layer is obtained by, for example, casting and coating a solution prepared by dissolving at least a thermoplastic polyimide and a thermosetting resin in an organic solvent on at least one side of a polyimide film, and then drying.

The thermoplastic polyimide (polyimide resin) used in the present invention is not particularly limited, but in order to keep the processability of the solution better and to develop the adhesiveness at a lower temperature and a lower pressure, a glass is used. Transition temperature (below,
Tg) is 200 ° C. or less, and the solid content concentration (hereinafter, SC) with respect to the cyclic ether solvent 10
More preferably, it is a soluble thermoplastic polyimide that exhibits a solubility of at least%. The thermoplastic polyimide has, for example, the formula (1)

[0025]

[Chemical 7]

(Wherein, X represents a saturated hydrocarbon divalent group having 1 to 10 carbon atoms or an aromatic ring-containing divalent group), and the ester acid dianhydride is represented by 50% of the total acid dianhydride component. Mol%
Equation (2) above

[0027]

[Chemical 8]

(In the formula, Y is independently -CO-, -SO ₂
-, - O -, - S -, - (CH 2) k -, - NHCO-,
_{-C (CH 3) 2 -,} - C (CF 3) 2 -, - COO- or a single bond, k and m are 1 to 5 of the represented diamine compound integer is) the total diamine component Of 50
It can be obtained by reacting with mol% or more. still,
Examples of the saturated hydrocarbon divalent group include an alkylene group and an alkylidene group.

The proportion of the ester acid dianhydride represented by the above formula (1) is less than 50 mol% of the total acid dianhydride component, or the proportion of the diamine compound represented by the above formula (2) is the total diamine. When it is less than 50 mol% of the components, the solubility of the obtained thermoplastic polyimide in a cyclic ether solvent may decrease.

Specific examples of the ester acid dianhydride represented by the above formula (1) include the following formulas:

[0031]

[Chemical 9]

2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4 represented by
4'-tetracarboxylic dianhydride, p-phenylene bis (trimellitic acid monoester anhydride), the following formula

[0033]

[Chemical 10]

3,3 ', 4,4'-ethylene glycol benzoate tetracarboxylic dianhydride represented by:
4,4'-biphenylene bis (trimellitic acid monoester anhydride), 1,4-naphthalene bis (trimellitic acid monoester anhydride), 1,2-ethylenebis (trimellitic acid monoester anhydride), 1 , 3-trimethylene bis (trimellitic acid monoester anhydride), 1,4
-Tetramethylene bis (trimellitic acid monoester anhydride), 1,5-pentamethylene bis (trimellitic acid monoester anhydride), 1,6-hexamethylene bis (trimellitic acid monoester anhydride), etc. To be Of the above-exemplified ester dianhydrides, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride and 3,3', 4 , 4'-Ethylene glycol benzoate tetracarboxylic dianhydride is particularly preferred. These ester acid dianhydrides may be used alone or in combination of two or more.

Specific examples of the acid dianhydride other than the ester acid dianhydride represented by the above formula (1) include pyromellitic dianhydride and 2,3,6,7-naphthalenetetrahydride. Carboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ′, 3,3 ′
-Biphenyltetracarboxylic dianhydride, 3,3 ',
4,4'-benzophenone tetracarboxylic dianhydride,
Examples include oxydiphthalic acid dianhydride, p-phenylene bis (trimellitic acid monoester acid anhydride), biphenyl bis (trimellitic acid monoester acid anhydride), and analogs (derivatives) of these acid dianhydrides. .

Specific examples of the diamine compound represented by the above formula (2) include 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 3,3'-bis (aminophenoxyphenyl) sulfone, 2,2'-bis [4- (3-aminophenoxy) phenyl] propane and the like can be mentioned.
These diamine compounds may be used alone,
Moreover, you may use together 2 or more types. In the diamine compound represented by the formula (2), since the amino group is bonded to the meta position, the solubility of the resulting thermoplastic polyimide in an organic solvent is improved, and the thermoplastic polyimide is added to the organic solvent. The processability of the solution obtained by dissolving in is better. As a compound having a structure similar to that of the diamine compound represented by the formula (2), a diamine compound in which an amino group is bonded to the ortho position or the para position instead of the meta position can be mentioned. It may be difficult to achieve the above effects.

The thermoplastic polyimide obtained by using the ester acid dianhydride represented by the above formula (1) and the diamine compound represented by the above formula (2) is suitable for cyclic ether solvents. It can exhibit solubility and sufficient heat resistance. Further, by using the above ester dianhydride, the water absorption of the thermoplastic polyimide obtained can be lowered.

Thermoplastic polyimides may also include, for example:
Formula (3)

[0039]

[Chemical 11]

(In the formula, Z is independently -CO-, -SO ₂
-, - O -, - S -, - (CH 2) q -, - NHCO-,
_{-C (CH 3) 2 -,} - C (CF 3) 2 -, - COO- or a single bond, R ₁ is a hydroxyl group or carboxyl group independently, p is 1 or 2, n and q It is more preferable that the diamine compound represented by the formula (1 is an integer of 1 or more and 5 or less) is used to react with 5 mol% or more of all diamine components. As a result, the thermoplastic polyimide and a thermosetting resin such as an epoxy resin can be reacted and crosslinked, so that a film-like laminated member having more excellent adhesiveness and heat resistance can be obtained.

The proportion of the diamine compound represented by the above formula (3) in all the diamine components is more preferably in the range of 5 to 40 mol%. This makes it possible to react and crosslink the obtained thermoplastic polyimide with a thermosetting resin such as an epoxy resin. Therefore, it is possible to obtain a film-like laminated member having more excellent adhesiveness and heat resistance. When the ratio is less than 5 mol%, the effect of using the diamine compound represented by the formula (3) becomes poor. On the other hand, when the ratio exceeds 40 mol%, the Tg of the thermoplastic polyimide exceeds 200 ° C., or
The solubility of the resulting thermoplastic polyimide in a cyclic ether solvent may decrease.

Specific examples of the diamine compound represented by the above formula (3) include 3,3'-dihydroxy-4,4'-diaminobiphenyl and 3,5-diaminobenzoic acid. . These diamine compounds may be used alone or in combination of two or more.

Specific examples of the diamine other than the diamine compounds represented by the above formulas (2) and (3) include, for example,
3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-dichlorobenzidine, 4,4 '
-Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 4,4'-diaminodiphenylsilane, 4,4'-diaminodiphenylethylphosphine oxide, 1 , 4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene, 1,2-diaminobenzene, 4,4′-diaminobenzanilide, 3,4′-diaminobenzanilide, and diamines thereof. Examples include analogs (derivatives) and the like.

The thermoplastic polyimide according to the present invention can be obtained by dehydrating and ring-closing a polyamic acid polymer which is a precursor thereof. The polyamic acid polymer solution contains, for example, 50 mol% or more of the total acid dianhydride component of the ester acid dianhydride represented by the formula (1) in an inert gas atmosphere such as helium, argon, or nitrogen. The diamine compound represented by the above formula (2) in an amount of 50 mol% of all diamine components.
As described above, if necessary, the diamine compound represented by the formula (3) is used in an amount of 5 mol% or more of the total diamine component so that the total acid dianhydride component and the total diamine component are substantially equimolar. It is obtained by using and polymerizing in an organic polar solvent.

Specific examples of the organic polar solvent used in the above polymerization include sulfoxide type solvents such as dimethyl sulfoxide and diethyl sulfoxide; formamide type solvents such as N, N-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-cresol, m-cresol, p
-Cresol, xylenol, halogenated phenol,
Phenolic solvents such as catechol; hexamethylphosphoramide, γ-butyrolactone; and the like. These organic polar solvents may be used alone, or two or more kinds may be appropriately mixed and used. Further, an aromatic hydrocarbon such as toluene or xylene can be used as a mixture with an organic polar solvent as long as the polymerization is not hindered.

The addition method (sequence) and polymerization method for adding the acid dianhydride component and the diamine component to the organic polar solvent are not particularly limited, and various known methods can be adopted. For example, a solution of a polyamic acid polymer may be obtained by adding all diamine components to an organic polar solvent to which all acid dianhydride components have been added in advance and polymerizing, and a part of the diamine components has been added in advance. You may obtain a solution of a polyamic-acid polymer by adding the whole acid dianhydride component to an organic polar solvent and polymerizing, and then adding the remaining diamine component and polymerizing. The polymerization conditions are
It is not particularly limited.

A thermoplastic polyimide is obtained by subjecting the obtained polyamic acid polymer to dehydration ring closure by a thermal or chemical method, that is, by imidization. Specific examples of the imidization include a thermal method of heat-treating a solution of a polyamic acid polymer to dehydrate it, and a chemical method of dehydrating it using a dehydrating agent and a catalyst. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, and aromatic acid anhydrides. As the catalyst, for example, aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline,
Examples include heterocyclic tertiary amines such as pyridine and isoquinoline.

The thermoplastic polyimide obtained by the chemical method can be used in the state of a solution dissolved in an organic polar solvent, but can also be taken out and used as a solid thermoplastic polyimide. As a method of taking out the thermoplastic polyimide from the solution, for example, while uniformly mixing with an organic polar solvent, by adding the solution to a poor solvent which is difficult to dissolve the thermoplastic polyimide, it is possible to precipitate the thermoplastic polyimide and A method of removing the acid dianhydride component and the diamine component of the reaction for purification, and then drying is mentioned. Examples of the poor solvent include acetone, methyl alcohol, ethyl alcohol, isopropyl alcohol, benzene, methyl cellosolve, methyl ethyl ketone, and the like, but are not particularly limited.

Examples of the thermal method include a method in which a polyamic acid polymer is placed in a vacuum oven and is imidized by heating under reduced pressure, and is taken out as a solid thermoplastic polyimide. In particular, when the diamine compound represented by the above formula (3) is used as the diamine component, the polyamic acid polymer has a plurality of hydroxyl groups or carboxyl groups. Reacts with carboxyl groups. Therefore, in this case, it is preferable to perform imidization by a thermal method.

The thermosetting resin used in the present invention is not particularly limited, but from the viewpoint of adhesiveness,
Including a plurality of epoxy groups in the structure, that is,
More preferably, it is an epoxy resin. Specific examples of the epoxy resin include Epicoat 828.
Bisphenol A type resin (made by Yuka Shell Co., Ltd.); Epicoat 180S65 (made by Yuka Shell Co., Ltd.)
Orthocresol novolac type resin such as Epicoat 1
57S70 (produced by Yuka Shell Co., Ltd.) and other bisphenol A novolac resins; Epicoat 1032H60 (produced by Yuka Shell Co., Ltd.) and other trishydroxyphenylmethane novolac resins; ESN375 (produced by Nippon Steel Chemical Co., Ltd.) and naphthalene. Aralkyl novolak type resin;
Tetraphenylolethane 1031S (made by Yuka Shell Co., Ltd.), YGD414S (made by Toto Kasei Co., Ltd.), trishydroxyphenylmethane EPPN502H (made by Nippon Kayaku Co., Ltd.), special bisphenol VG3101L
(Mitsui Chemicals, Inc.), Special Naphthol NC7000
(Manufactured by Nippon Kayaku Co., Ltd.), TETRAD-X, TETR
Glycidyl amine type resins such as AD-C (manufactured by Mitsubishi Gas Chemical Co., Inc.); and the like. These epoxy resins are
Only one type may be used, or two or more types may be used in combination.

By using the thermosetting resin, the adhesive layer of the film-like laminated member is in a state in which both the heat resistance of the thermoplastic polyimide and the processability at low temperature of the thermosetting resin are good. I will prepare for it. The mixing ratio of the thermoplastic polyimide and the thermosetting resin is not particularly limited, but the ratio of the thermosetting resin to 100 parts by weight of the thermoplastic polyimide is within the range of 10 to 100 parts by weight. Is more preferable, and the range of 20 to 70 parts by weight is further preferable. If the proportion of the thermosetting resin is less than 10 parts by weight, the resulting film-like laminated member may not exhibit sufficient adhesiveness at low temperature and low pressure, that is, it may be difficult to perform temporary pressure bonding. is there. If the proportion of the thermosetting resin is more than 100 parts by weight, the resulting film-like laminated member may not be able to exhibit sufficient flexibility and heat resistance.

The thermosetting resin curing agent used in the present invention is not particularly limited. For example, when an epoxy resin is used as the thermosetting resin, phthalic anhydride, maleic anhydride or the like is used. Acid dianhydride curing agent;
Amine-based curing agents such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, m-phenylenediamine and p-phenylenediamine; imidazole-based curing agents such as ethylmethylimidazole Generally used epoxy curing agents such as; Of the above-exemplified curing agents, 4,4′-diaminodiphenyl sulfone is more preferable. Furthermore, in order to further reduce the water absorption of the obtained adhesive layer and further improve heat resistance and adhesiveness,
Various accelerators and coupling agents can also be used.

The adhesive layer of the film-like laminated member according to the present invention is a solution (hereinafter referred to as an adhesive solution) formed by dissolving the above-mentioned thermoplastic polyimide, thermosetting resin and its curing agent in an organic solvent. After that, for example, the adhesive solution is obtained by, for example, casting and coating on at least one surface of the polyimide film, and then drying. Alternatively, the adhesive layer of the film-like laminated member according to the present invention is obtained by, for example, casting and coating the above adhesive solution on a support, drying the solution, and then peeling it from the support. When the adhesive layer is formed by using the support, the sheet-shaped adhesive layer separated from the support is attached (applied) to the polyimide film to obtain a film-like laminated member. As the support, for example, a polyethylene terephthalate (PET) film or the like is suitable, but the support is not particularly limited. The method of peeling the adhesive layer from the support is not particularly limited. Further, the sheet-shaped adhesive layer separated from the support can be used alone, that is, the adhesive layer (single-layer sheet) itself can be used as an adhesive sheet (film-like laminated member).

The kind and thickness of the polyimide film are not particularly limited. Examples of the method for applying the adhesive solution include, but are not limited to, methods using a bar coater, a spin coater, a gravure coater, or the like. The thickness of the adhesive layer obtained after drying is more preferably in the range of 2 to 20 μm.

The above-mentioned organic solvent is not particularly limited, but the cyclic ether type solvent can easily remove the solvent because the temperature at the time of drying can be set low, and the cyclic ether type solvent can be easily removed. Curing does not proceed excessively, and
It is particularly preferable because it hardly remains in the adhesive layer. Specific examples of the cyclic ether solvent include tetrahydrofuran (THF), 1,4-dioxane, dioxolane and the like. These cyclic ether solvents may be used alone or in admixture of two or more kinds, but it is most preferable to use a low boiling cyclic ether solvent as a main component.

Furthermore, if necessary, a mixed solvent in which a cyclic ether solvent and an organic polar solvent are combined can be used. As the organic polar solvent, specifically,
For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide; acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide. And the like. When using a mixed solvent, the combination and type of the cyclic ether solvent and the organic polar solvent, the mixing ratio, etc.,
Although not particularly limited, the proportion of the cyclic ether solvent in the mixed solvent is particularly preferably 30% by weight or more. 30% by weight of cyclic ether solvent
If it is less than, there is a possibility that the thermosetting resin may be excessively cured because the temperature during drying cannot be set low, and it becomes difficult to perform temporary pressure bonding, or the adhesiveness, The bonding property with the release film may be deteriorated.

The addition method (sequence) for dissolving the thermoplastic polyimide, the thermosetting resin, and the curing agent thereof in the organic solvent, that is, the method for forming the adhesive solution is not particularly limited. For example, an adhesive solution may be obtained by dissolving a thermoplastic polyimide in an organic solvent and then dissolving a thermosetting resin and a curing agent, and the thermoplastic polyimide, the thermosetting resin and the curing agent may be separately prepared. An adhesive solution may be obtained by dissolving these in an organic solvent and then mixing these solutions. The conditions for the dissolution are not particularly limited, but if the thermoplastic polyimide is difficult to dissolve, the organic solvent may be heated if necessary. However, when a cyclic ether solvent is used as the organic solvent, the cyclic ether solvent has a low boiling point and is easily volatilized (evaporated). Therefore, it is desirable to keep the heating temperature and the heating time to the necessary minimum. Further, when the thermosetting resin is dissolved, it is preferable to refrain from heating the organic solvent as much as possible.

By forming the adhesive layer as described above, the film-like laminated member according to the present invention can be obtained.
Since the thermoplastic polyimide is used, the adhesive layer has excellent heat resistance. And, in particular, when a soluble thermoplastic polyimide having Tg of 200 ° C. or lower and having solubility in a cyclic ether solvent and an epoxy resin as a thermosetting resin are used in combination, the adhesive layer It is possible to further lower the processing temperature at the time of forming, and it is possible to easily remove the organic solvent under the condition that the curing of the epoxy resin does not proceed excessively. Further, the temperature at the time of main pressure bonding (in use) can be further lowered, and the workability can be further improved. Therefore, it is possible to obtain a film-like laminated member having an adhesive layer capable of exhibiting more sufficient adhesiveness at low temperature and low pressure. still,
The Tg of a general thermoplastic polyimide exceeds 200 ° C., and the Tg of the thermoplastic polyimide preferably used in the present invention is relatively low. Therefore, the above effect can be obtained.

Further, the film-like laminated member according to the present invention may have a release film on at least one adhesive layer, if necessary. As a result, handling such as workability during use becomes good. Specific examples of the material of the release film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), and the like. The thickness of the release film may be set according to the usage of the film-like laminated member and the like, and is not particularly limited.

It is more preferable that the surface of the release film, which is in contact with the adhesive layer, be subjected to a release treatment in order to facilitate the release operation of the release film during use. Examples of the treatment method include, but are not particularly limited to, silicon treatment and alkyd treatment.

The adhesive strength of the release film to the adhesive layer in the film-like laminated member is preferably in the range of 1 to 50 gf / cm, more preferably 5 to 20 gf / cm. Adhesive strength is 1gf / c
If it is lower than m, the release film may peel off from the adhesive layer before the use of the film-like laminated member (for example, during storage or transportation). When the adhesive strength is higher than 50 gf / cm, it becomes difficult to smoothly peel the release film from the adhesive layer. The method for laminating the release film and the adhesive layer (laminating method) is not particularly limited, but it is desirable to attach them while applying a certain pressure in order to prevent wrinkles and bubbles from entering. . Further, in order to prevent the release film and the adhesive layer from being bonded to each other with an adhesive strength more than necessary, the temperature during lamination is 170
It is desirable to keep the temperature below ℃.

The film-like laminated member obtained by the above-mentioned constitution is obtained by hot pressing (thermocompression bonding) with a polyimide film to be worn at a temperature of 150 ° C. or less and a pressure of 5 kgf / cm ² or less and a linear velocity of 0.5 m / min or less. Adhesive strength (hereinafter referred to as temporary pressure bonding strength) is 10 gf / cm or more, 100 gf / c
m or less. That is, the adhesive layer of the film-like laminated member can exhibit good adhesiveness at low temperature and low pressure.
Further, the adhesive layer has stronger adhesiveness at high temperature and high pressure. Therefore, it is possible to perform temporary crimping at a temperature and pressure lower than the temperature and pressure at the time of main pressure bonding (in use), that is, at low temperature and low pressure, with excellent heat resistance and electrical reliability, and at the time of main pressure bonding. It is possible to provide a film-like laminated member having excellent adhesive strength, workability, and workability.

The "temporary pressure bonding strength" in the present invention refers to the strength measured by the following method. That is, the "temporary pressure bonding strength" is the adhesive layer (one side) of the film-like laminated member and the polyimide film (Apical 25N) with a thickness of 25 μm
PI, manufactured by Kanegafuchi Chemical Industry Co., Ltd.), and using a thermal laminating apparatus equipped with a pair of the present laminating roll and slow cooling laminating roll (material: silicone rubber), a temperature of 150 ° C. or less and a pressure of 5 kgf / cm. ² or less,
After a pressure-bonded product is obtained by heating and pressurizing under the condition of a linear velocity of 0.5 m / min or less (tension against film, etc.), JIS C
Based on 6481, the peel strength between the adhesive layer and the polyimide film to be adhered in the pressure-bonded product is a numerical value measured at a width (peel width) of the adhered polyimide film of 10 mm.

The film-like laminated member according to the present invention can be thermocompression-bonded again after being once peeled off. Therefore, since the film-shaped laminated member can be reattached many times during the temporary pressure bonding step, for example, in a manufacturing process of a laminated material such as a multilayer flexible printed circuit board (multilayer FPC),
Prior to the main compression bonding of the layers, temporary compression bonding may be performed at a temperature / pressure lower than the temperature / pressure at the time of the main compression bonding, and the alignment may be performed many times.

[0065]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. Tg of thermoplastic polyimide is
Differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC
CELL SCC-41) was used in a nitrogen stream at a heating rate of 10 ° C./min in the temperature range from room temperature to 400 ° C.

Various physical properties (characteristics) of the film-like laminated members in Examples and Comparative Examples, that is, bondability with a release film (hereinafter referred to as bondability), temporary pressure bonding strength, and final pressure bonding The adhesive strength (hereinafter referred to as main pressure bonding strength) was measured (evaluated) by the following method.

"Laminating Property" The adhesive layer of the film-like laminated member and the release film are superposed on each other, and a thermal laminating apparatus provided with a pair of the main laminating roll and the slow cooling laminating roll (material: silicone rubber) is used. , Temperature 1
00-170 ° C, pressure 3kgf / cm ² , linear velocity 0.3m
The pieces were laminated together under the condition of / min (tensile force against the film or the like; none). And the adhesiveness between the adhesive layer and the release film,
In addition, when the release film had good releasability, the result was evaluated as “◯”, and the other cases were evaluated as “x”.

[Temporary compression strength] The adhesive layer (one side) of the film-like laminated member and a 25 μm-thick polyimide film to be adhered (Apical 25 NPI, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) were overlaid, and the above thermal laminating apparatus was used. Using a temperature of 9
0 to 150 ° C (change in increments of 10 ° C), pressure 3 kgf / c
After heating and pressurizing under a condition of m ² and a linear velocity of 0.3 m / min (tension against film etc .; no), a crimped product is obtained.
Based on C6481, the peel strength between the adhesive layer and the polyimide film to be adhered in the pressure-bonded product was measured at a width (peel width) of the adhered polyimide film of 10 mm. Therefore, the peeling strength was measured 7 times in total while changing the temperature in steps of 10 ° C. Then, the largest value among the measured values was defined as "temporary pressure bonding strength". Also, 10
The lowest temperature at which a measured value of gf / cm or more is obtained is
"Temporary pressure bonding temperature" was set.

"Main pressure bonding strength" Adhesive layers (both sides) of the film-like laminated member and rolled copper foils (2 sheets) having a thickness of 18 μm,
After laminating the film-like laminated members with rolled copper foils, and heating and pressurizing for 5 minutes under the condition of a temperature of 200 ° C. and a pressure of 3 MPa to obtain a pressure-bonded product (copper-bonded flexible laminated plate), JIS C 6481 Based on the peel strength of the adhesive layer and the rolled copper foil on one side of the pressure-bonded product,
The width of the rolled copper foil (peeling width) was measured at 3 mm, and the measured value was defined as "main pressure bonding strength".

Example 1 A glass flask having a capacity of 1000 ml was charged with 326 g of N, N-dimethylformamide (DMF) as an organic polar solvent and 1,3-bis (as a diamine compound represented by the formula (2). 3-aminophenoxy) benzene (hereinafter referred to as APB) 0.19 mol,
3,3′-as the diamine compound represented by the formula (3)
Dihydroxy-4,4′-diaminobiphenyl (hereinafter,
(Hereinafter referred to as HAB) 0.01 mol, and while stirring under a nitrogen atmosphere, 3,3 ′, 4,4′-ethylene glycol benzoate tetracarboxylic acid as an ester acid dianhydride represented by the formula (1) 0.20 mol of dianhydride (hereinafter referred to as TMEG) was gradually added. After the addition, the solution was stirred in an ice bath for 30 minutes, and the viscosity of the solution was 150 Pa · s (15
When it reached 00 poise), the stirring was stopped. As a result, a solution of the polyamic acid polymer was obtained.

300 g of this polyamic acid polymer solution was transferred to a vat coated with a fluororesin and placed in a vacuum oven at 180 ° C. and a pressure of 665 Pa (5 mmHg, about 0.00
After heating under reduced pressure at (7 atm) for 3 hours, it was taken out of the vacuum oven. As a result, 84 g of powdery thermoplastic polyimide was obtained. The Tg of the thermoplastic polyimide was 80 ° C.

12 g of this thermoplastic polyimide, Epicoat 1032H6 as a thermosetting resin (epoxy resin)
0 (made by Yuka Shell Co., Ltd.) 8 g, 4, as a curing agent
4'-diaminodiphenyl sulfone (hereinafter referred to as 4,4'-
2.4 g of DDS) was added to 89.6 g of dioxolane as an organic solvent (cyclic ether solvent), and the mixture was stirred and dissolved. Thereby, a varnish (SC; 20%) as an adhesive solution was obtained.

The resulting varnish was cast on a polyimide film (Apical 12.5 NPI, manufactured by Kaneka Kagaku Kogyo Co., Ltd.) having a thickness of 12.5 μm, and dried at 60 ° C. for 2 minutes.
Next, a varnish was cast on the back surface of the polyimide film in the same manner, and dried at 60 ° C. for 2 minutes. Then, this polyimide film was fixed to a metal frame and dried at 150 ° C. for 5 minutes. As a result, a film-like laminated member having a thickness of 22.5 μm (adhesive layer thickness 5 μm × 2) was obtained. The results of measuring various physical properties of the film-like laminated member are shown in Table 1.

Example 2 In a glass flask having a capacity of 1000 ml, 327 g of DMF, 0.19 mol of APB and H were added.
While charging 0.01 mol of AB and stirring under a nitrogen atmosphere, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, as an ester acid dianhydride represented by the formula (1), 0.20 mol of 4,4'-tetracarboxylic dianhydride (hereinafter referred to as ESDA) was gradually added. After the addition, the mixture was stirred in an ice bath for 30 minutes, and when the viscosity of the solution reached 150 Pa · s (1500 poise), the stirring was stopped. As a result, a solution of the polyamic acid polymer was obtained.

300 g of this polyamic acid polymer solution was transferred to a vat coated with a fluororesin and placed in a vacuum oven at 200 ° C. under a pressure of 665 Pa (5 mmHg) for 3 hours.
After heating under reduced pressure, it was taken out of the vacuum oven. As a result, 85 g of powdery thermoplastic polyimide was obtained. The Tg of the thermoplastic polyimide was 175 ° C.

12 g of this thermoplastic polyimide, Epicoat 1032H60; 8 g, 4,4'-DDS 2.4 g
Was added to 89.6 g of dioxolane and dissolved by stirring. Thereby, a varnish (SC; 20%) was obtained.

The same operation as in Example 1 was performed using the obtained varnish to obtain a film-like laminated member having a thickness of 22.5 μm (adhesive layer thickness 5 μm × 2). The results of measuring various physical properties of the film-like laminated member are shown in Table 1.

Example 3 In a glass flask having a capacity of 1000 ml, 388 g of DMF and 3,3′-bis (aminophenoxyphenyl) sulfone (hereinafter referred to as BAPS-M) as a diamine compound represented by the formula (2) were used. ) 0.
19 mol and 0.01 mol of HAB were charged, and 0.20 mol of TMEG was gradually added while stirring under a nitrogen atmosphere. After the addition, the mixture was stirred in an ice bath for 30 minutes, and the solution had a viscosity of 1
When it reached 50 Pa · s (1500 poise), the stirring was stopped. As a result, a solution of the polyamic acid polymer was obtained.

300 g of this polyamic acid polymer solution was transferred to a vat coated with a fluororesin and placed in a vacuum oven at 200 ° C. under a pressure of 665 Pa (5 mmHg) for 3 hours.
After heating under reduced pressure, it was taken out of the vacuum oven. As a result, 85 g of powdery thermoplastic polyimide was obtained. The Tg of the thermoplastic polyimide was 174 ° C.

12 g of this thermoplastic polyimide, Epicoat 1032H60; 8 g, 4,4'-DDS 2.4 g
Was added to 89.6 g of dioxolane and dissolved by stirring. Thereby, a varnish (SC; 20%) was obtained.

The same operation as in Example 1 was performed using the obtained varnish to obtain a film-like laminated member having a thickness of 22.5 μm (adhesive layer thickness 5 μm × 2). The results of measuring various physical properties of the film-like laminated member are shown in Table 1.

Comparative Example 1 12 g of thermoplastic polyimide obtained by carrying out the same reaction and operation as in Example 1,
Epicoat 1032H60; 8g, 4,4'-DDS
2.4 g was added to DMF89.6 g and dissolved by stirring. Thereby, a varnish (SC; 20%) was obtained.

The obtained varnish was cast on a polyimide film (Apical 12.5 NPI) having a thickness of 12.5 μm and dried at 60 ° C. for 2 minutes. Next, cast a varnish on the back side of the polyimide film in the same manner, and
Dry for minutes. Then, this polyimide film was fixed to a metal frame and dried at 200 ° C. for 5 minutes. This allows
A film-like laminated member having a thickness of 22.5 μm (adhesive layer thickness 5 μm × 2) was obtained. The results of measuring various physical properties of the film-like laminated member are shown in Table 1.

Comparative Example 2 A glass flask having a capacity of 1000 ml was charged with 353 g of DMF and 0.20 mol of 3,3′-diaminodiphenylsulfone (3,3′-DDS), and ESDA0 was stirred under a nitrogen atmosphere while stirring. .20
Molar was added slowly. After the addition, the mixture was stirred in an ice bath for 30 minutes, and when the viscosity of the solution reached 150 Pa · s (1500 poise), the stirring was stopped. As a result, a solution of the polyamic acid polymer was obtained.

300 g of this polyamic acid polymer solution was transferred to a vat coated with a fluororesin and placed in a vacuum oven at 200 ° C. under a pressure of 665 Pa (5 mmHg) for 3 hours.
After heating under reduced pressure, it was taken out of the vacuum oven. As a result, 85 g of powdery thermoplastic polyimide was obtained. The Tg of the thermoplastic polyimide was 227 ° C.

12 g of this thermoplastic polyimide, Epicoat 1032H60; 8 g, 4,4'-DDS 2.4 g
Was added to 89.6 g of dioxolane and dissolved by stirring. Thereby, a varnish (SC; 20%) was obtained.

The same operation as in Example 1 was carried out using the obtained varnish to obtain a film-like laminated member having a thickness of 22.5 μm (adhesive layer thickness 5 μm × 2). The results of measuring various physical properties of the film-like laminated member are shown in Table 1.

Comparative Example 3 A glass flask having a capacity of 1000 ml was charged with 356 g of DMF, 0.10 mol of BAPS-M, and 0.10 mol of α, ω-bis (3-aminopropyl) polydimethylsiloxane, and the mixture was placed under a nitrogen atmosphere. While stirring, 0.20 mol of ESDA was gradually added. After the addition, stir in an ice bath for 30 minutes to give a solution with a viscosity of 150P.
The stirring was stopped at the time of reaching a · s (1500 poise). As a result, a solution of the polyamic acid polymer was obtained.

300 g of this polyamic acid polymer solution was transferred to a vat coated with a fluororesin and placed in a vacuum oven at 200 ° C. under a pressure of 665 Pa (5 mmHg) for 3 hours.
After heating under reduced pressure, it was taken out of the vacuum oven. As a result, 84 g of powdery thermoplastic polyimide was obtained. The Tg of the thermoplastic polyimide was 45 ° C.

12 g of this thermoplastic polyimide, Epicoat 1032H60; 8 g, 4,4'-DDS 2.4 g
Was added to 89.6 g of dioxolane and dissolved by stirring. Thereby, a varnish (SC; 20%) was obtained.

The same procedure as in Example 1 was carried out using the obtained varnish to obtain a film-like laminated member having a thickness of 22.5 μm (adhesive layer thickness 5 μm × 2). The results of measuring various physical properties of the film-like laminated member are shown in Table 1.

Comparative Example 4 A glass flask having a capacity of 1000 ml was charged with 304 g of DMF and 0.20 mol of BAPS-M, and 0.20 mol of pyromellitic dianhydride (PMDA) was gradually added while stirring under a nitrogen atmosphere. Was added to. After the addition, the mixture was stirred in an ice bath for 30 minutes, and the solution had a viscosity of 1
When it reached 50 Pa · s (1500 poise), the stirring was stopped. As a result, a solution of the polyamic acid polymer was obtained.

300 g of this polyamic acid polymer solution was transferred to a vat coated with a fluororesin and placed in a vacuum oven at 200 ° C. under a pressure of 665 Pa (5 mmHg) for 3 hours.
After heating under reduced pressure, it was taken out of the vacuum oven. As a result, 85 g of powdery thermoplastic polyimide was obtained. The Tg of the thermoplastic polyimide was 230 ° C.

12 g of this thermoplastic polyimide, Epicoat 1032H60; 8 g, 4,4'-DDS 2.4 g
Was added to 89.6 g of dioxolane and it was tried to dissolve it by stirring, but undissolved thermoplastic polyimide was left and a uniform varnish could not be obtained.

[0095]

[Table 1]

[0096]

As described above, the film-like laminated member of the present invention is prepared by dissolving a polyimide film and at least a thermoplastic polyimide and a thermosetting resin applied on at least one surface of the polyimide film in an organic solvent. A film-like laminated member having an adhesive layer obtained by drying the resulting solution, wherein the temperature is 150 ° C. or lower and the pressure is 5 kgf.
/ Cm ² or less and a linear velocity of 0.5 m / min or less, the adhesive strength when thermocompression-bonded to the polyimide film to be adhered is 10 gf / c
It is a structure of m or more and 100 gf / cm or less.

As a result, the adhesive layer of the film-like laminated member has both the heat resistance of the thermoplastic polyimide and the processability at low temperature of the thermosetting resin in a good condition. Further, the adhesive layer of the film-like laminated member can exhibit adhesiveness at low temperature and low pressure, and can have stronger adhesiveness at high temperature and high pressure. Therefore, it is possible to perform temporary crimping at a temperature and pressure lower than the temperature and pressure at the time of main pressure bonding (in use), that is, at low temperature and low pressure, with excellent heat resistance and electrical reliability, and at the time of main pressure bonding. The film-like laminated member having excellent adhesive strength, workability, and workability can be provided.

In particular, a soluble thermoplastic polyimide having a glass transition temperature of 200 ° C. or lower and having solubility in a cyclic ether solvent, and a thermosetting resin containing a plurality of epoxy groups in its structure, For example, when used in combination with an epoxy resin, the processing temperature for forming the adhesive layer can be further lowered, and the organic solvent can be easily removed under the condition that the curing of the epoxy resin does not proceed excessively. can do. Moreover, the temperature at the time of the main pressure bonding can be further lowered, and the workability can be further improved. For this reason, it is possible to provide a film-like laminated member that can be temporarily pressure-bonded at a lower temperature and a lower pressure, and that has a higher adhesive strength than the adhesive strength during temporary pressure-bonding during main pressure-bonding. Play.

Continued front page    F term (reference) 4F100 AK01B AK49A AK49B AK49K                       AK53B AL05B BA02 BA07                       GB43 JA05B JB13B JB16B                       JK06B JL01 JL05 JL11B                       YY00B                 4J004 AA16 AB01 AB03 CA06 CC02                       DB02 FA05 FA08                 4J040 EH031 GA11 JA09 JB02                       JB09 KA16 LA02 LA06 LA08                       NA19 NA20 PA23                 4J043 PA01 PA04 PB08 PB15 QB26                       QC02 RA08 RA34 SA06 SA47                       SA54 SA63 SA81 SB01 SB03                       TA22 TA32 TA71 TB01 UA11                       UA14 UA15 UA16 UA17 UA18                       VA01 VA05 VA06 XA13 XA16                       YA06 ZA02 ZB01 ZB50

Claims (7)

[Claims] 1. A film having a polyimide film and an adhesive layer obtained by drying a solution prepared by dissolving at least a thermoplastic polyimide and a thermosetting resin in an organic solvent, which is applied to at least one surface of the polyimide film. Laminated member having a temperature of 150 ° C. or less and a pressure of 5 kgf / cm ² or less and a linear velocity of 0.5 m / min or less and an adhesive strength of 10 gf / cm or more and 100 gf when thermocompression-bonded.
/ Cm or less, the film-like laminated member characterized by being. 2. A glass transition temperature (T
g) is 200 ° C. or lower, and the thermoplastic polyimide has a solid content concentration (SC) of 1 with respect to the cyclic ether solvent.
The film-like laminated member according to claim 1, which is a soluble thermoplastic polyimide exhibiting a solubility of 0% or more. 3. The film-shaped laminated member according to claim 1, wherein the thermosetting resin contains a plurality of epoxy groups in its structure. 4. The film-like laminated member according to claim 1, wherein the thickness of the adhesive layer is in the range of 2 to 20 μm. 5. The film-shaped laminated member according to claim 1, further comprising a release film on at least one adhesive layer. 6. A thermoplastic polyimide having the formula (1): (Wherein, X represents a saturated hydrocarbon divalent group having 1 to 10 carbon atoms or a divalent group containing an aromatic ring), and an ester acid dianhydride is represented by 50 mol% or more of all acid dianhydride components. , Formula (2) (Wherein, Y is independently _{-CO -, - SO 2 -,} - O-,
_{-S -, - (CH 2)} k -, - NHCO -, - C (CH 3)
_{2 -, - C (CF 3} ) 2 -, - COO- or a single bond, k and m are used 1 to 5 inclusive is an integer) in the represented diamine compound at least 50 mol% of the total diamine component The film-like laminated member according to any one of claims 1 to 5, which is a thermoplastic polyimide obtained as described above. 7. The thermoplastic polyimide further has the formula (3): (Wherein, Z is independently _{-CO -, - SO 2 -,} - O-,
_{-S -, - (CH 2)} q -, - NHCO -, - C (CH 3)
_{2 -, - C (CF 3} ) 2 -, - COO- or a single bond, R ₁ is independently a hydroxyl group or carboxyl group, p is 1 or 2, n and q is 1 to 5 integer It is a thermoplastic polyimide obtained by using 5 mol% or more of the total diamine component represented by the diamine compound represented by (4).