JP2009297952A - Method for manufacturing composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for simply manufacturing a high-quality composite material without being peeled at a high temperature. <P>SOLUTION: The method for manufacturing the composite material combines a polymer material A and a polymer material B as a condition where the ratio B/A that is the thickness of the polymer material B/the thickness of the polymer material A is less than 0.5, a linear expansion coefficient (expressed by CTEc) of the composite material derived from the composite rule is set to be 10 ppm/°C or less, and an anneal temperature is within a specified range. The polymer material A has a modulus of elongation of 5 GPa or more, the linear expansion coefficient (expressed by CTEa) of -10 to +20 ppm/°C, and no glass transition point at 400°C or less. The polymer material B has the modulus of elongation of 5 GPa or less, the linear expansion coefficient (expressed by CTEb) of 10-250 ppm/°C and the difference (CTEb-CTEa) between CTEb and CTEa of 10 ppm/°C or more, and the glass transition point within the range of 150-400°C. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a production method in which compounding and annealing at a specific temperature are used in combination such as lamination of a polymer material such as a polyimide film and another polymer material. More specifically, the present invention relates to a compounding method in a case where materials having a large difference in CTE (linear expansion coefficient) are compounded.

  Polyimide films have very little change in physical properties over a wide temperature range from −269 ° C. to 300 ° C., and therefore, applications and uses in the electric and electronic fields are expanding. In the electric field, for example, it is used for coil insulation of vehicle motors, industrial motors, etc., insulation of aircraft electric wires and superconducting wires. On the other hand, in the electronic field, for example, it is used for a flexible printed circuit board, a base film of a film carrier for semiconductor mounting, and the like. Thus, the polyimide film is widely used in the electrical and electronic fields as a highly reliable film among various functional polymer films. Recently, however, problems have become apparent with the refinement of the electric and electronic fields. For example, a printed circuit board made of a polyimide film base material in which copper is copper-clad by vapor deposition or plating or the like has a tendency that the adhesive force of the copper layer is lowered due to a change with time and an environmental change, and further peeling occurs.

In addition, ceramic has been conventionally used as a material for base materials of electronic components such as information communication equipment (broadcast equipment, mobile radio equipment, portable communication equipment, etc.), radar, high-speed information processing devices, and the like. A base material made of ceramic has heat resistance, and can cope with an increase in the frequency band (reaching the GHz band) of information communication equipment in recent years. However, ceramics are not flexible and cannot be thinned, so the fields that can be used are limited.
For this reason, studies have been made to use a film made of an organic material as a base material for an electronic component, and a film made of polyimide and a film made of polytetrafluoroethylene have been proposed.
A film made of polyimide has excellent heat resistance and has the advantage that the film can be thin because it is tough. However, there are concerns about problems such as low signal strength and signal transmission delay when applied to high-frequency signals. However, the tensile strength at break and the tensile modulus are still insufficient, and the linear expansion coefficient is too large. A film made of polytetrafluoroethylene can handle high frequencies, but the tensile modulus is low, so the film cannot be made thin, the adhesion to metal conductors and resistors on the surface is poor, and the coefficient of linear expansion However, it is problematic in that it is not suitable for the production of a circuit having fine wiring due to a large dimensional change due to temperature change. Thus, a film having sufficient physical properties for a substrate having heat resistance, high mechanical properties, and flexibility has not been obtained yet.
As a polyimide film having a high tensile modulus, a polyimide benzoxazole film made of polyimide having a benzoxazole ring in the main chain has been proposed (see Patent Document 1). A printed wiring board using the polyimide benzoxazole film as a dielectric layer has also been proposed (see Patent Document 2 and Patent Document 3).
Polyimide benzoxazole films consisting of polyimides with these benzoxazole rings in the main chain have improved tensile tensile strength and tensile elastic modulus and are within the range of satisfactory linear expansion coefficients. In spite of its physical properties, it has problems such as insufficient surface properties in terms of adhesion.

Various proposals have been made to improve the adhesion of polyimide with excellent physical properties. For example, a polyimide film that has a thermoplastic resin layer on at least one surface of a polyimide film that does not have adhesion (see Patent Document 4), a polyimide film And at least a two-layer film in which a film made of polyamide resin is laminated (see Patent Document 5).
Even though those with a thermoplastic resin layer on these polyimide films can be satisfied in improving the adhesiveness, the low heat resistance of these thermoplastic resins will ruin the heat resistance of the folded polyimide film. Had a trend.
Japanese Patent Laid-Open No. 06-56992 Japanese National Patent Publication No. 11-504369 Japanese National Patent Publication No. 11-505184 Japanese Patent Laid-Open No. 09-169088 JP, 07-186350, A In these conventional disclosure techniques, paying attention to the difference in CTE between one material of the composite material and the other material, and considering the composite temperature, annealing temperature, etc. There is nothing that was made by paying attention to the stress at the composite interface of the composite material obtained, and the composite material that has been composited may peel off or wrinkle between materials due to the temperature at which it is used. There was a problem in reliability.

  The present invention maintains the excellent mechanical and thermal properties of the polymer A when the polymer A and the polymer B having a low linear expansion coefficient are in a specific range and excellent in heat resistance. In addition, the polymer B having excellent adhesion and the like has a linear expansion coefficient in a specific range in which the composite and annealing are used in combination and in a specific temperature range, and the surface properties such as adhesion and the adhesive properties are improved, and The present invention provides a method for producing a composite material that does not cause peeling or wrinkles at the interface during use in a conventional composite material.

In composite materials, there are many cases where there are large differences in the elastic modulus, CTE, and glass transition temperature between the composite materials, especially when materials with large differences in CTE are combined, depending on the temperature change. In many cases, each material expands and contracts and a large stress is generated at the interface between the materials, leading to separation of the interface and destruction of the composite material.
It is known that the CTE of a composite material follows the composite law. When a material having a large CTE and a material having a small CTE are combined, if the temperature rises, a compressive stress is generated in a material having a large CTE, and a tensile stress is generated in a material having a small CTE, and the stress increases as the temperature increases. . On the other hand, mechanical properties such as the elastic modulus of the material decrease with increasing temperature. Combined with the increase in stress and the decrease in physical properties of the material, destruction of the composite material such as destruction of the material itself and separation at the joint surface occurs. Therefore, it can be said that controlling the change of the stress accompanying the temperature change is an important issue in considering the life of the composite material.
The present invention is intended to solve the above problems and provide a method for producing a composite material by a method not disclosed in the prior art.

As a result of intensive studies, the present inventors have found that the mechanical properties of the polymer A are excellent when the polymer A and the polymer B, which have a low linear expansion coefficient and have excellent heat resistance, are combined. The coefficient of linear expansion has improved surface characteristics such as adhesion by combining polymer B with excellent adhesion and the like, maintaining thermal properties, and combining and annealing in a specific temperature range. It has been found that a composite material that is in a specific range and does not cause peeling or wrinkles at the interface when used in the conventional composite material can be obtained.
That is, this invention consists of the following structures.
1. The polymer material A having a tensile modulus of 5 GPa or more, a linear expansion coefficient (expressed by CTEa) of −10 to +20 ppm / ° C. and having no glass transition point at 400 ° C. or less, and a tensile modulus of elasticity Less than 5 GPa, linear expansion coefficient (denoted as CTEb) of 10 to 250 ppm / ° C., difference between CTEb and CTEa (CTEb−CTEa) of 10 ppm / ° C. or more, and glass transition in the range of 150 to 400 ° C. This is a method of producing a composite material by combining (stacking) and annealing a polymer material B having points, and the ratio B / A of the thickness of the polymer material B / the thickness of the polymer material A is <0. .5, the linear expansion coefficient (expressed as CTEc) of the composite material derived by the composite law is 10 ppm / ° C. or less, the composite (lamination) temperature T1 (° C.), the glass transition temperature Tga (° C.) of the polymer material A, high Molecular material The glass transition temperature Tgb of (° C.), when the annealing temperature Tal (° C.),
<< T1 ≤ Tgb ≤ Tal ≤ Tga
A method for producing a composite material, comprising: combining (lamination) and annealing so as to satisfy the following relationship.
2. 1. Polymer material A is polyimide resin Of manufacturing composite materials.
3. 1. Polymer material B is a thermosetting resin ~ 2. A method of manufacturing any composite material.

The polymer material A and the polymer material B of the present invention have at least a tensile elastic modulus of 5 GPa or more, a linear expansion coefficient (expressed by CTEa) of −10 to +20 ppm / ° C., and a glass of 400 ° C. or less. Polymer material A having no transition point, tensile elastic modulus of less than 5 GPa, linear expansion coefficient (expressed as CTEb) of 10 to 250 ppm / ° C. and difference between CTEb and CTEa (CTEb−CTEa) of 10 ppm / A method of producing a composite material by combining (lamination) and annealing a polymer material B having a glass transition point in the range of 150 to 400 ° C. Thickness ratio B / A of polymer material A is <0.5, CTEc derived by the compounding rule is 10 ppm / ° C. or less, compounding (lamination) temperature T 1 (° C.), glass transition temperature of polymer material A Tga ° C.), the glass transition temperature Tgb of a polymer material B (° C.), when the annealing temperature Tal (° C.),
<< T1 ≤ Tgb ≤ Tal ≤ Tga
By combining (lamination) and annealing so as to satisfy the following relationship, the stress exerted on the other at the composite interface between the polymer material A and the polymer material B is adjusted, and at least between T1 ≤ Tal At the time of use, the occurrence of peeling and wrinkles due to both stresses is suppressed.
The composite material obtained by the present invention, such as a laminated film, is a laminate with a metal layer (foil) using these as a substrate, has improved adhesion, and is peeled off at a high temperature such as soldering or high temperature use. Therefore, a composite material having excellent quality can be produced efficiently and relatively easily, and is extremely effective industrially.

The polymer A of the present invention is a polymer having a tensile modulus of 5 GPa or more, a linear expansion coefficient (expressed by CTEa) of −10 to +20 ppm / ° C., and having no glass transition point at 400 ° C. or less. Although there is no particular limitation as long as it is present, examples thereof include high melting point and non-melting polymers such as polyamideimide, polyimide, polybenzazole, and aramid.
Among these, a polyimide obtained by reacting an aromatic diamine and an aromatic tetracarboxylic acid is preferable, and a polyimide obtained from an aromatic diamine having a benzoxazole skeleton and an aromatic tetracarboxylic acid is more preferable.
In addition, a film or a thin layer can be preferably applied to the polymer material in the present invention.
Hereinafter, the composition using a film (thin layer) as a polymer material will be described in detail, but the present invention is not limited thereto.
The polymer A of the present invention can be obtained, for example, by casting a solution containing a polymer, drying and heat-treating it to form a film. Examples of the solvent used for the solution containing these polymers include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, methylene chloride, tetrahydrofuran, methanol, and metacresol.
Examples of the polymer solution preferably used in the present invention include N-methyl-2-pyrrolidone solution of polyamideimide, N, N-dimethylacetamide solution, N-methyl-2-pyrrolidone solution of polyamide acid which is a polyimide precursor, N , N-dimethylacetamide solution, N-methyl-2-pyrrolidone solution of solvent-soluble polyimide, N, N-dimethylacetamide solution, N-methyl-2-pyrrolidone solution of aramid, and the like.
In the case of a polyimide film, a solution containing these polyimides or their precursor polyimide (polyamic acid) is cast, dried and heat-treated to form a film. Examples of the solvent used for the solution containing these polyimides include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, methylene chloride, tetrahydrofuran, methanol, and metacresol.

The method for producing a polyimide film as the polymer A that can be preferably applied in the present invention is a polyimide precursor, particularly an N-methyl-2-pyrrolidone solution of polyamic acid, an N, N-dimethylacetamide solution, or a precursor of polyimide benzoxazole. It can be most preferably applied in the case of a wet (casting) film forming method using a solution of polyamic acid such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide.
The reaction between an aromatic diamine for obtaining a polyimide film, which can be preferably applied to the present invention, and an aromatic tetracarboxylic acid is carried out by reacting an aromatic diamine and an aromatic tetracarboxylic acid (anhydride) in a solvent. (Ring-opening) Polyamide acid solution that is a polyimide precursor is obtained by polyaddition reaction, and then a precursor film (green film) is formed from this polyamic acid solution, followed by drying, heat treatment, dehydration condensation (imide) Manufactured).

Although the polyimide film in this invention is not specifically limited, The combination of the following aromatic diamine and aromatic tetracarboxylic acid (anhydride) is mentioned as a preferable example.
A. A combination of an aromatic diamine having a benzoxazole structure and an aromatic tetracarboxylic acid.
B. A combination of an aromatic diamine having a diaminodiphenyl ether skeleton and an aromatic tetracarboxylic acid having a pyromellitic acid skeleton.
C. A combination of an aromatic diamine having a phenylenediamine skeleton and an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton.
D. A combination of one or more of the above ABCs.
Examples of the aromatic diamine having a benzoxazole structure that can be most preferably used in the present invention include the following compounds.

  2,2′-p-phenylenebis (5-aminobenzoxazole), 2,2′-p-phenylenebis (6-aminobenzoxazole), 1- (5-aminobenzoxazolo) -4- (6- Aminobenzoxazolo) benzene, 2,6- (4,4′-diaminodiphenyl) benzo [1,2-d: 5,4-d ′] bisoxazole, 2,6- (4,4′-diaminodiphenyl) ) Benzo [1,2-d: 4,5-d ′] bisoxazole, 2,6- (3,4′-diaminodiphenyl) benzo [1,2-d: 5,4-d ′] bisoxazole, 2,6- (3,4'-diaminodiphenyl) benzo [1,2-d: 4,5-d '] bisoxazole, 2,6- (3,3'-diaminodiphenyl) benzo [1,2- d: 5,4-d '] bisoxazole, 2 6- (3,3'-diaminodiphenyl) benzo [1,2-d: 4,5-d '] bis-oxazole.

  Among these, amino (aminophenyl) benzoxazole isomers are preferable from the viewpoint of ease of synthesis. Here, “each isomer” refers to each isomer in which two amino groups of amino (aminophenyl) benzoxazole are determined according to the coordination position (eg, the above “formula 1” to “formula 4”). Each compound described in the above. These diamines may be used alone or in combination of two or more.

The polyimide film in the present invention is not limited to the above, and the following aromatic diamines may be used as long as the total diamines are less than 30 mol%, more preferably less than 10 mol%.
For example, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3 -Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3 , 3,3-hexafluoropropane, m-aminobenzylamine, p-aminobenzylamine,

3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4'- Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'- Diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4 -(4-aminophenoxy) phenyl] ethane, 1, -Bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane 2,2-bis [4- (4-aminophenoxy) phenyl] propane,

1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) Phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) Phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3-methylphenyl] propane, 2- [4- ( 4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphen Le] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,

1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) ) Biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- ( 4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) ) Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3 Aminophenoxy) benzoyl] benzene, 4,4′-bis [(3-aminophenoxy) benzoyl] benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 3,4'-diaminodiphenyl sulfide,

2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] methane, 1,1 -Bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 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, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3 -Bis [4- (4-amino-6-fluorophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl Benzene, 1,3-bis [4- (4-amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene,

3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino 5,5′-diphenoxybenzophenone, 3,4′-diamino-4,5′-diphenoxybenzophenone, 3,3 '-Diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone 3,4'-diamino-5'-phenoxybenzophenone, 3,3'- Diamino-4,4′-dibiphenoxybenzophenone, 4,4′-diamino-5,5′-dibiphenoxybenzophenone, 3,4′-diamino-4,5′-dibiphenoxybenzophenone, 3,3′-diamino- 4-biphenoxybenzophenone, 4,4′-diamino-5-biphenoxybenzophenone, 3,4′- Amino-4-biphenoxybenzophenone, 3,4′-diamino-5′-biphenoxybenzophenone, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4 -Phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino- 4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis ( 4-amino-5-biphenoxybenzoyl) benzene, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy Some or all of the hydrogen atoms on the aromatic ring in benzonitrile and the aromatic diamine are halogen atoms, alkyl groups having 1 to 3 carbon atoms or alkoxyl groups, cyano groups, or some hydrogen atoms of alkyl groups or alkoxyl groups. Or the aromatic diamine etc. which were substituted by the C1-C3 halogenated alkyl group or alkoxyl group by which all were substituted by the halogen atom are mentioned.

As aromatic tetracarboxylic acids which can be preferably used in the polyimide film of the present invention, aromatic tetracarboxylic acids having a pyromellitic acid skeleton, that is, pyromellitic acid and anhydrides or halides thereof, aromatic tetracarboxylic acids having a biphenyltetracarboxylic acid skeleton Examples include acids, i.e. biphenyltetracarboxylic acid and anhydrides or halides thereof.
Without being limited thereto, the following aromatic tetracarboxylic acids may be used.

これらのテトラカルボン酸は単独で用いてもよいし、二種以上を併用してもよい。

These tetracarboxylic acids may be used alone or in combination of two or more.

  The solvent used when polyamic acid is obtained by polymerizing aromatic diamines and aromatic tetracarboxylic acid anhydrides is particularly limited as long as it dissolves both the raw material monomer and the polyamic acid to be produced. Although not preferred, polar organic solvents are preferred, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide Hexamethylphosphoric amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, halogenated phenols and the like, among which N-methyl-2-pyrrolidone and N, N-dimethylacetamide are preferably applied. These solvents can be used alone or in combination. The amount of the solvent used may be an amount sufficient to dissolve the monomer as a raw material. As a specific amount used, the weight of the monomer in the solution in which the monomer is dissolved is usually 5 to 40% by mass, The amount is preferably 10 to 20% by mass.

Conventionally known conditions may be applied for the polymerization reaction for obtaining the polyamic acid (hereinafter also simply referred to as “polymerization reaction”). As a specific example, in a temperature range of 0 to 80 ° C., 10 Stirring and / or mixing continuously for 30 minutes.
Moreover, you may perform superposition | polymerization by adding a small amount of terminal blockers to aromatic diamines before a polymerization reaction. Examples of the end capping agent include compounds having a carbon-carbon double bond such as maleic anhydride. The amount of maleic anhydride used is preferably 0.001 to 1.0 mol per mol of aromatic diamine.
As imidization / heat treatment, a polyamic acid solution that does not contain a ring-closure (imidization) catalyst or a dehydrating agent is used, and the imidization reaction is advanced by subjecting to a heat treatment (so-called thermal ring closure method) or ring closure in the polyamic acid solution. Examples thereof include a chemical ring closure method in which a catalyst and a dehydrating agent are contained and an imidization reaction is performed by the action of the above ring closing catalyst and the dehydrating agent.

The thickness of a polyimide film is not specifically limited, It can apply in the range of 1.5-150 micrometers. In consideration of use for a printed wiring board base substrate described later, the thickness is 1.5 to 60 μm, preferably 1.5 to 15 μm. Furthermore, when particularly high performance is required, the range of 1.5 to 9.0 μm, more preferably 2.0 to 6.0 μm is still more preferable. This thickness can be easily controlled by the amount of the polyamic acid solution applied to the support and the concentration of the polyamic acid solution. The polyimide film is preferably provided with a lubricant in the polyimide to give fine irregularities on the film surface to improve the slipping property of the film.
As the lubricant, inorganic or organic fine particles having an average particle diameter of about 0.03 μm to 3 μm can be used. Specific examples include titanium oxide, alumina, silica, calcium carbonate, calcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate, Examples include magnesium oxide, calcium oxide, and clay minerals.

In the present invention, the polymer material B has a tensile modulus of less than 5 GPa, a linear expansion coefficient (expressed as CTEb) of 10 to 250 ppm / ° C., and a difference between CTEb and CTEa (CTEb−CTEa) of 10 ppm / The polymer is not particularly limited as long as it is a polymer having a glass transition point in the range of 150 ° C to 400 ° C.
Specific examples include thermoplastic polymers and thermosetting polymers having these physical properties, preferably thermosetting polymers that are thermosetting and excellent in heat resistance and adhesiveness. If it is, it will not specifically limit.
As the thermosetting polymer used in the present invention, epoxy-based, urethane-based, acrylic-based, silicone-based, polyester-based, imide-based, polyamide-imide-based, etc. can be used, mainly flexible resin such as polyamide resin and phenol. Examples include those containing a hard material such as epoxy resin, imidazoles and the like as a main component, dimer acid based polyamideimide resin, room temperature solid phenol, room temperature liquid epoxy etc. It can be illustrated.
The thermosetting polymer can also control the cured state to a semi-cured state, and as a method for controlling the cured state, for example, heating with hot air when applying and drying these on the polymer material A, distant / Heating by near infrared rays, electron beam irradiation, etc. In the control by heating, it is preferable to heat at 100 to 200 ° C. for 1 to 60 minutes, more preferably at 130 to 160 ° C. for 5 to 10 minutes. The cured state can also be controlled by heat treatment for several hours to several hundred hours at a relatively low temperature of, for example, about 40 to 90 ° C. while the FPC or TAB tape is wound into a roll. The conditions for controlling the cured state are preferably determined in consideration of the composition of the polymer material B, the curing mechanism, and the curing rate. In this way, by controlling the cured state, it is possible to obtain a semi-cured polymer material B.

  It should be noted that before the thermosetting polymer as the polymer material B is composited (coated) on the polyimide film as the polymer material A, the polyimide film surface is subjected to plasma treatment, corona treatment, and alkali treatment. This is a preferable method for enhancing the plasma, and the plasma is an inert gas plasma. As the inert gas, nitrogen gas, Ne, Ar, Kr, or Xe is used. There is no particular limitation on the method for generating plasma, and an inert gas may be introduced into the plasma generator to generate plasma.

When the polymer material A and the polymer material B are combined, the ratio B / A of the thickness of the polymer material B / the thickness of the polymer material A is <0.5 and is derived according to the compounding rule. CTE is 10 ppm / ° C or less, composite (lamination) temperature T1 (° C), glass transition temperature Tga (° C) of polymer material A, glass transition temperature Tgb (° C) of polymer material B, annealing temperature Tal (° C) )), It is an essential requirement of the present invention to combine (stack) so as to satisfy the relationship of “T1 ≦ Tgb ≦ Tal ≦ Tga”.
The composite law in the present invention is, when the coefficient of linear expansion of the composite material is CTEc,
Am (GPa); Elastic modulus CTEa of polymer material A (ppm / ° C.); CTE of polymer material A
At (μm); Polymer material A thickness Bm (GPa); Polymer material B elastic modulus CTEb (ppm / ° C.); Polymer material B CTE
Bt (μm); When the thickness of the polymer material B is used, it is represented by the following formula.
CTEc (ppm / ° C.) = (Am × CTEa × At + Bm × CTEb × Bt) / (Am × At + Bm × Bt)

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited by a following example. In addition, the evaluation method of the physical property in the following examples is as follows. Reduced viscosity of polyamic acid (ηsp / C)
A solution dissolved in N-methyl-2-pyrrolidone (or N, N-dimethylacetamide) so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. with an Ubbelohde type viscosity tube. (When the solvent used for preparing the polyamic acid solution was N, N-dimethylacetamide, the polymer was dissolved using N, N-dimethylacetamide and measured.)
2. Film thickness Measured using a micrometer (Millitron (registered trademark) 1245D, manufactured by Finelfu).
3. Tensile Elastic Modulus of Polyimide Film A test piece was prepared by cutting a polyimide film to be measured into strips of 100 mm × 10 mm in the flow direction (MD direction) and the width direction (TD direction). Using a tensile tester (manufactured by Shimadzu Corp., Autograph (R) model name AG-5000A), the tensile modulus was measured in each of the MD and TD directions under the conditions of a tensile speed of 50 mm / min and a chuck distance of 40 mm. The average value of the values in the MD direction and the TD direction was used as the tensile modulus.

4). Glass-transition temperature
Viscoelasticity measurement was performed in the range from room temperature to 450 ° C., and the inflection point of E ′ was taken as the glass transition temperature. Details are as follows.

Measuring device: Solid viscoelastic device RSA-II (Rheometric)
Tension mode (auto tension)
Measurement temperature -30 ° C to 300 ° C / Temperature increase rate 5 ° C / min Frequency 10Hz

5. CTE: coefficient of linear expansion Measures the expansion / contraction ratio in the MD direction and TD direction under the following conditions, and measures the expansion ratio / temperature at intervals of 90 to 100 ° C., 100 to 110 ° C.,. It carried out to 250 degreeC and computed the average value of all the measured values from 100 degreeC to 200 degreeC as CTE (average value).
Device name: TMA4000S manufactured by MAC Science
Sample length: 10mm
Sample width: 2mm
Temperature rise start temperature: 25 ° C
Temperature rise end temperature: 250 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Argon Note that the adhesive was measured after it was formed into a film and cured.

6). Appearance inspection For laminates. 25 ° C to Table 4. A temperature cycle test was performed 50 times with the Tr shown in FIG. 2, and the appearance inspection was observed with the naked eye, and the presence or absence of swelling (peeling on the adhesive surface) of the laminate was observed.

[Reference Example 1]
(Preparation of polyamic acid solution)
1.22 parts by mass of amorphous silica spherical particles Seahoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.), 420 parts by mass of N-methyl-2-pyrrolidone, the wetted part of the container, and the infusion pipe are austenitic stainless steel The mixture was placed in a container of SUS316L and stirred with a homogenizer T-25 basic (manufactured by IKA Labortechnik) at a rotation speed of 1000 rpm for 1 minute to obtain a preliminary dispersion. The average particle size in the preliminary dispersion was 0.11 μm.
A nitrogen inlet tube, a thermometer, a liquid contact part of a container equipped with a stirring rod, and a pipe for infusion were substituted with nitrogen in the reaction container made of austenitic stainless steel SUS316L, and then 223 parts by mass of 5-amino-2- ( p-Aminophenyl) benzoxazole was added. Next, 4000 parts by mass of N-methyl-2-pyrrolidone was added and completely dissolved, and then the preliminary dispersion obtained above was added with 420 parts by mass and 217 parts by mass of pyromellitic dianhydride. When the mixture was stirred at ° C for 24 hours, a brown viscous polyamic acid solution PAc1 was obtained. The reduced viscosity (ηsp / C) was 3.8.

[Reference Example 2]
(Preparation of polyamic acid solution)
7.6 parts by mass of amorphous silica spherical particles Seahoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.), 390 parts by mass of N-methyl-2-pyrrolidone, and the infusion part are austenitic stainless steel SUS316L And stirred for 1 minute at a rotation speed of 1000 rpm with a homogenizer T-25 basic (manufactured by IKA Labortechnik) to obtain a preliminary dispersion.
The liquid contact part of the vessel equipped with a nitrogen introduction tube, a thermometer, a stirring rod, and the pipe for infusion were substituted with nitrogen in the reaction vessel made of austenitic stainless steel SUS316L, and then 200 parts by mass of diaminodiphenyl ether was added. Next, after 3800 parts by mass of N-methyl-2-pyrrolidone was added and completely dissolved, 390 parts by mass and 217 parts by mass of pyromellitic dianhydride were added to the preliminary dispersion obtained above. When the mixture was stirred at 0 ° C. for 5 hours, a brown viscous polyamic acid solution PAc2 was obtained. The reduced viscosity (ηsp / C) was 3.7.

[Reference Example 3]
(Preparation of polyamic acid solution)
3.7 parts by weight of amorphous silica spherical particle Seahoster KE-P10 (manufactured by Nippon Shokubai Co., Ltd.), 420 parts by weight of N-methyl-2-pyrrolidone, the liquid contact part of the container, and the infusion pipe are austenitic stainless steel SUS316L And stirred for 1 minute at a rotation speed of 1000 rpm with a homogenizer T-25 basic (manufactured by IKA Labortechnik) to obtain a preliminary dispersion.
The wetted part of the vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod, and the infusion piping were substituted with nitrogen in the reaction vessel made of austenitic stainless steel SUS316L, and then 108 parts by mass of phenylenediamine was added. Next, after 3600 parts by mass of N-methyl-2-pyrrolidone was added and completely dissolved, 420 parts by mass and 292.5 parts by mass of biphenyltetracarboxylic dianhydride were added to the preliminary dispersion obtained above. After stirring for 12 hours at 25 ° C., a brown viscous polyamic acid solution PAc3 was obtained. This reduced viscosity (ηsp / C) was 4.5.

Each polyamic acid solution obtained in Reference Examples 1 to 3 was applied onto a stainless steel endless continuous belt mirror-finished using a die coater, and dried at 90 to 115 ° C. for 10 minutes. The polyamic acid film which became self-supporting after drying was peeled off from the support and cut at both ends to obtain respective green films.
The obtained green film is passed through a pin tenter having a pin sheet in which pins are arranged so that the pin interval is constant when the pin sheets are arranged, and is gripped by inserting the film end into the pin. The pin sheet spacing is adjusted so that it does not break and unnecessary tarmi is generated, and the first stage is 170 ° C. for 2 minutes, the second stage is 230 ° C. for 2 minutes, and the third stage 485 is 6 minutes. In order to allow the imidization reaction to proceed, cool to room temperature in 2 minutes, cut off the poor flatness at both ends of the film with a slitter, roll up into a roll, and exhibit a brown color ( Polyimide films of polyamic acid solution PAc1), B (from polyamic acid solution PAc2), and cocoon (from polyamic acid solution PAc3) were obtained.
Table 1 shows the physical properties of these polyimide films.

The following adhesive was used as the polymer material B. These physical property values are shown in Table 2. Shown in
Adhesive a Acrylic / Epoxy Adhesive b Acrylic / Epoxy Adhesive c Polyetherimide / Epoxy Adhesive d Polyamideimide Adhesive e Phenolic Resin / Epoxy

(Prediction and actual measurement by the composite law of multilayer product production)
Two polyimide films each having a thickness of 10 μm were laminated so that adhesives d having different thicknesses were sandwiched. Table 3 shows the predicted value and the actual measurement value according to the CTE compound rule calculation formula of the laminate. Here, the laminated structure “A” d indicates that it has a three-layer structure in which the outer layer is polyimide A and the inner layer is adhesive d. It can be seen that the predicted value based on the compound rule and the actually measured value are almost the same.

* Example (CTE of laminated product)
Using the polyimide film Kou Oto and adhesives a to e, Table 4. A laminate was produced with the structure and processing temperature shown in FIG. The obtained laminate is 25 ° C. to Table 4. The temperature cycle test was conducted 50 times with the Tr shown in FIG. 5 and the presence or absence of swelling (peeling on the adhesive surface) of the laminate was observed by visual inspection.
Evaluated as “○ where no bulges were seen”, “△ where bulges per square meter are less than one”, and “×” where two or more bulges were observed per square meter. did.
The composite that has undergone the temperature history including the annealing of the present invention maintains a good appearance. However, when the annealing is not performed, the interface tends to be peeled off due to internal stress particularly in a high temperature range, and as a result, It turns out that it is easy to occur.

Fig. 1 to Fig. 2 show a conceptual diagram of stress-temperature in compounding.
FIG. Indicates changes in stress before and after annealing.
FIG. Indicates the change in stress after annealing.
In the figure, A1 to A12 are the stress values of the polymer material A in each temperature history. In the figure, B1 to B12 are the stress values of the polymer material B in each temperature history at the compounding temperature T1 (80 ° C.). When polymer material A (high Tg, low CTE) and polymer material B (low Tg, high CTE) are laminated, FIG. As shown in A1 and B1, the shrinkage of B is greater than the shrinkage of A on the lower temperature side than the compounding temperature, so that a compressive stress is applied to A and a tensile stress is applied to B.
When the temperature of the composite material is raised, the internal stress of both materials becomes a minimum value when the composite temperature is reached, and when the temperature is further raised, the stress direction is reversed as shown in A2 and B2, and A A tensile stress is applied to B and a compressive stress is applied to B. The absolute value of the stress applied to both increases as the temperature rises, and reaches a maximum immediately before reaching the glass transition temperature of the polymer material B (A3, B3). When the temperature is further raised and the Tg of the polymer material B is exceeded, the elastic modulus of the polymer material B decreases rapidly, and the CTE of the entire composite is dominated by the polymer material A, so the stress applied to both materials Becomes almost zero (A4, B5).
In the process of cooling the composite material heated above the glass transition temperature of the polymer material B (A5, A6, B6, B7), a compressive stress is applied to the polymer material A in the region below the glass transition temperature B of the polymer material. A tensile stress is applied to the polymer material B, and its absolute value increases as the temperature decreases.
For composites that have been annealed once, see FIG. As shown in FIG. 4, the stress is large near room temperature, and the stress decreases as the temperature increases. When the composite is annealed at a temperature higher than the glass transition temperature of the polymer material B, the stress near room temperature is greater than before the annealing, but in a high temperature region that does not exceed the glass transition temperature of the polymer material B. Conversely, the internal stress is smaller than that of the unannealed product.

The manufacturing method of the composite material in which the polymer material A and the polymer material B of the present invention are composited (laminated) and annealed is the other of both at the composite interface between the polymer material A and the polymer material B. The stress exerted on the surface is adjusted, and at the time of use at a temperature of at least T1 ≦ Tal, peeling and wrinkle generation due to both stresses are suppressed.
The composite material obtained by the present invention, such as a laminated film, is a laminate with a metal layer (foil) using these as a substrate, has improved adhesion, and is peeled off at a high temperature such as soldering or high temperature use. Therefore, a composite material having excellent quality can be produced efficiently and relatively easily, and is extremely effective industrially.

The change in stress before and after annealing is shown. The change of the stress after annealing treatment is shown.

Explanation of symbols

In the figure, A1 to A12 are stress values of the polymer material A in each temperature history.
In the figure, B1 to B12 are stress values of the polymer material B in each temperature history.

Claims (3)

The polymer material A having a tensile modulus of 5 GPa or more, a linear expansion coefficient (expressed by CTEa) of −10 to +20 ppm / ° C. and having no glass transition point at 400 ° C. or less, and a tensile modulus of elasticity Less than 5 GPa, linear expansion coefficient (denoted as CTEb) of 10 to 250 ppm / ° C., difference between CTEb and CTEa (CTEb−CTEa) of 10 ppm / ° C. or more, and glass transition in the range of 150 to 400 ° C. This is a method of producing a composite material by combining (stacking) and annealing a polymer material B having points, and the ratio B / A of the thickness of the polymer material B / the thickness of the polymer material A is <0. .5, the linear expansion coefficient (expressed as CTEc) of the composite material derived by the composite law is 10 ppm / ° C. or less, the composite (lamination) temperature T1 (° C.), the glass transition temperature Tga (° C.) of the polymer material A, high Molecular material The glass transition temperature Tgb of (° C.), when the annealing temperature Tal (° C.),
<< T1 ≤ Tgb ≤ Tal ≤ Tga
A method for producing a composite material, comprising: combining (lamination) and annealing so as to satisfy the following relationship.   The method for producing a composite material according to claim 1, wherein the polymer material A is a polyimide resin.   The method for producing a composite material according to claim 1, wherein the polymer material B is a thermosetting resin.

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