JP2012006149A - Polyimide board, metal-laminated polyimide board, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide board which is excellent in heat resistance, dimensional stability, and adhesion, has a minute through hole in the thickness direction, and prevents the peeling of a metal layer even after a cooling impact cycle test when the metal layer is laminated on the wall surface of the through hole.SOLUTION: In the polyimide board in which a plurality of non-thermoplastic polyimide films (A) are laminated on each other through a thermoplastic resin (B) and which has a through hole of 10-200 μm in diameter in the thickness direction, its linear expansion coefficient in the surface direction is -5 to 15 ppm/°C; its thickness is 50-3,000 μm, and the diameter ratio of holes penetrating the layer (A) and the layer (B) [the diameter (average value) of the holes penetrating the layer (A)/the diameter (average value) of the holes penetrating the layer (B)] is 75-99%.

Description

The present invention relates to a polyimide board having excellent heat resistance, dimensional stability, and adhesiveness and having fine through holes in the thickness direction. More specifically, when a metal layer is laminated on the wall surface of the through holes, The present invention relates to a polyimide board in which peeling of a metal layer does not occur even after a thermal shock cycle test.

  The polyimide film has a very small change in physical properties in a wide temperature range from −269 ° C. to 300 ° C., and therefore, applications and uses in the electric / electronic field 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 electric / electronic field as a highly reliable film among various functional polymer films.

The polyimide film is mainly manufactured by solution casting by casting, and it is difficult to produce a thick film due to its manufacturing method, or the productivity is extremely inferior.
As an improvement technique, a polyimide board is proposed in which thermoplastic polyimide films having a relatively low glass transition point are directly heat-pressed without using an adhesive. This polyimide board has the heat resistance, dimensional stability, adhesiveness, drilling workability, migration resistance, and thermal and thermal shock cycle resistance required when used as a core material in the electrical / electronic field, for example, multilayer printed wiring boards. I was not satisfied. Furthermore, it has been pointed out that when the thickness is increased, the adhesiveness is further lowered and the warpage is increased. (See Patent Document 1)

In order to solve this problem, a polyimide board in which a plurality of non-thermoplastic polyimide films are laminated with an acrylic resin adhesive or an epoxy resin adhesive has been proposed. Although this polyimide board has sufficient adhesiveness, it is not practical because the heat resistance is remarkably lowered. Furthermore, the dimensional stability was not sufficient.

Also proposed is a polyimide board in which multiple non-thermoplastic polyimide films are laminated with a thermoplastic adhesive consisting of at least one of polyimide siloxane and epoxy resin, bismaleimide-triazine resin, bismaleimide resin, cyanate resin, or acrylate resin. Has been. Although this polyimide board had sufficient adhesiveness and heat resistance, it did not satisfy dimensional stability. (See Patent Document 2)

In addition, a polyimide board is proposed in which two or more thermocompression-bonding multilayer polyimide films (surface layer: thermoplastic polyimide, base layer: non-thermoplastic polyimide) are thermocompression bonded. Similarly, this polyimide board did not satisfy the dimensional stability. (See Patent Document 3)

As these improvements, a polyimide board has been proposed in which at least two polyimide films subjected to plasma surface treatment are stacked and directly heat-pressed without using an adhesive. Since this polyimide board does not involve an adhesive between layers, heat resistance, dimensional stability, and adhesiveness are sufficient, but for example, when a through hole is made in the thickness direction and the wall surface is plated with copper Since there is a large difference between the coefficient of linear expansion in the thickness direction of the polyimide board and the coefficient of linear expansion of copper (16 ppm / ° C.), there is a risk of peeling during use. (See Patent Document 4)

Japanese Patent Publication No. 5-59815 Japanese Patent No. 4168562 Japanese Patent No. 4123665 JP 2002-234126 A

The present invention has excellent heat resistance, dimensional stability and adhesiveness, has fine through holes in the thickness direction, and has a metal layer even after a thermal shock cycle test when a metal layer is laminated on the wall surface of the through hole. It is an object of the present invention to provide a polyimide board that does not peel off.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, this invention consists of the following structures.
1. In a polyimide board in which a plurality of (A) non-thermoplastic polyimide films are alternately laminated via (B) a thermoplastic resin and have a through hole having a diameter of 10 μm to 200 μm in the thickness direction, The linear expansion coefficient is −5 ppm / ° C. to 15 ppm / ° C., the thickness is 50 μm to 3000 μm, and the diameter ratio of the holes passing through the layers (A) and (B) {the diameter of the holes penetrating the layers (A) ( (Average value) / (B) A polyimide board having a diameter (average value) of holes penetrating the layer of 75% to 99%.
2. 1. Difference of 5% weight loss temperature of layer (A) and layer (B) {5% weight loss temperature of layer (A) −5% weight loss temperature of layer (B)} is 5 ° C. to 100 ° C. Polyimide board.
3. (A) Thickness ratio to the whole layer [(A) total thickness of layer / {(A) total thickness of layer + (B) total thickness of layer}] is 40% to 98%. Or 2. Polyimide board.
4). (A) A non-thermoplastic polyimide film is a polyimide film obtained by a reaction between an aromatic tetracarboxylic acid and an aromatic diamine having a benzoxazole structure, and has a linear expansion coefficient in the plane direction of −10 ppm / ° C. 1 ppm / ° C. and a thickness of 5 μm to 75 μm ~ 3. Any polyimide board.
5. (B) The thermoplastic resin is one or more resins selected from the group consisting of polyaryl ketones, thermoplastic polyimides, polyetherimides, and polyamideimides, and has a thickness of 0.1 μm to 50 μm. ~ 4. Any polyimide board.
6). (A) (B) The peel strength between layers is 3 N / cm or more. ~ 5. Any polyimide board.
7). 1. A through hole is formed by a laser. ~ 6. Any polyimide board.
8). 1. A through hole is formed by a drill. ~ 6. Any polyimide board.
9.1. ~ 8. A metal-laminated polyimide board in which a metal layer is laminated on any polyimide board.
10. 8. The metal is copper or a copper-based metal. Metal laminated polyimide board.
11.1. ~ 8. 8. any polyimide board, or -10. Printed wiring board using any metal laminated polyimide board.
12.1. ~ 8. 8. any polyimide board, -10. 10. Any metal laminated polyimide board, or Multilayer printed wiring board using the printed wiring board as a core material.

As will be apparent from the results of Examples and the like described later, by the above means, heat resistance, dimensional stability and adhesiveness, which were impossible with a conventional polyimide board, were further improved. When a metal layer is laminated on the wall surface, it is possible to obtain a polyimide board that does not peel off the metal layer even after the thermal shock cycle test.

The present invention is described in detail below.
The (A) non-thermoplastic polyimide film used in the present invention includes, for example, aromatic tetracarboxylic acids (anhydrides, acids, and amide bond derivatives are collectively referred to below) and aromatic diamines (amine, And a polyamide film obtained by casting, drying, and heat-treating (imidizing) a polyamic acid solution obtained by reacting amide bond derivatives and generically referred to below as the same). Here, the non-thermoplastic polyimide means (1) a high concentration of imide units in repeating units in the polymer chain, and (2) a rigid molecule in which planar aromatic imide groups are arranged linearly or planarly. By forming a chain, it means one that does not exhibit a clear melting point and glass transition temperature because the molecules are in a strongly associated state.
Although the said polyimide is not specifically limited, The combination of the following aromatic diamine and aromatic tetracarboxylic acid (anhydride) is mentioned as a preferable example.
A. Combination with aromatic tetracarboxylic acid having pyromellitic acid residue and aromatic diamine having benzoxazole structure.
B. A combination of an aromatic diamine having a phenylenediamine skeleton and an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton.
C. A combination of an aromatic diamine having a diphenyl ether skeleton and an aromatic tetracarboxylic acid having a pyromellitic acid residue.
Above all, A. A polyimide film having an aromatic diamine residue having a benzoxazole structure is preferred.

  The molecular structure of the aromatic diamines having the benzoxazole structure is not particularly limited, and specific examples include the following. These diamines are preferably 70 mol% to 100 mol%, more preferably 80 mol% to 100 mol% of the total diamine.

  Among these, from the viewpoint of easy synthesis, each isomer of amino (aminophenyl) benzoxazole is preferable, and 5-amino-2- (p-aminophenyl) benzoxazole is more preferable. 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.

  Furthermore, as long as it is 30 mol% or less of the total diamine, one or more of the diamines exemplified below may be used in combination. Examples of such diamines include 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, and 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-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3′-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-dia Nodiphenyl sulfide, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 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-amino) Phenoxy) phenyl] ethane, 1,1-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, , 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-a Minophenoxy) -3-methylphenyl] propane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2- Bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexa Fluoropropane, 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-amino) Enoxy) 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} fe Sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethyl Benzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluoro) Phenoxy) -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′-dipheno Cibenzophenone, 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′-diamino-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-bi) Phenoxybenzoyl) 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] benzonitrile and some or all of the hydrogen atoms on the aromatic ring of the aromatic diamine are halogen atoms, An alkyl group having 1 to 3 carbon atoms, an alkoxyl group, a cyano group, or an alkyl group or an alkoxyl group having 1 to 3 carbon atoms in which some or all of the hydrogen atoms of the alkyl group or alkoxyl group are substituted with halogen atoms. Examples thereof include substituted aromatic diamines.

  The molecular structure of the aromatic tetracarboxylic acid anhydrides is not particularly limited, and specific examples include the following. These acid anhydrides are preferably 70 mol% to 100 mol%, more preferably 80 mol% to 100 mol% of the total acid anhydride.

These tetracarboxylic dianhydrides may be used alone or in combination of two or more.
Furthermore, as long as it is 30 mol% or less of the total tetracarboxylic dianhydrides, one or more of the non-aromatic tetracarboxylic dianhydrides exemplified below may be used in combination. Examples of such tetracarboxylic acid anhydrides include butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, and cyclobutanetetracarboxylic acid. Acid dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclohex-1-ene-2,3 5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3 -(1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride 1-ethylcyclohexane -(1,2), 3,4-tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane- 1- (2,3), 3- (2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] Heptane-2,3,5,6-tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1 -(2,3), 3- (2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane -2,3,5,6-tetracarboxylic dianhydride, bisic [2.2.2] Octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride An anhydride etc. are mentioned.

  The solvent used when reacting (polymerizing) the aromatic tetracarboxylic acid and the aromatic diamine to obtain a polyamic acid is particularly suitable as long as it can dissolve both the raw material monomer and the produced polyamic acid. Although not limited, 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 Examples include sulfoxide, hexamethylphosphoric amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, and halogenated phenols. 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% by weight to 40% by weight. %, More preferably 10% by weight to 30% by weight.

  The conditions for the polymerization reaction for obtaining the polyamic acid (hereinafter also simply referred to as “polymerization reaction”) may be conventionally known conditions. As a specific example, in a temperature range of 0 ° C. to 80 ° C. in an organic solvent, Stirring and / or mixing continuously for 10 minutes to 30 hours. If necessary, the polymerization reaction may be divided or the temperature may be increased or decreased. In this case, the order of adding both monomers is not particularly limited, but it is preferable to add aromatic tetracarboxylic acid anhydrides to the solution of aromatic diamines. The viscosity of the polyamic acid solution obtained by the polymerization reaction is preferably 10 Pa · s to 2000 Pa · s, more preferably 100 Pa · s from the viewpoint of the stability of the liquid feeding as measured with a Brookfield viscometer (25 ° C.). s to 1000 Pa · s.

Vacuum defoaming during the polymerization reaction is effective for producing a good quality polyamic acid solution. 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.
In order to form a polyimide film from the polyamic acid solution obtained by the polymerization reaction, a green film (a self-supporting precursor film is obtained by applying the polyamic acid solution on a support and drying, then, Examples of the method of imidization reaction by subjecting the green film to heat treatment include, but are not limited to, application of the polyamic acid solution to the support, including casting from a slit-attached base and extrusion by an extruder. A conventionally known solution coating means can be appropriately used.

  There are no particular limitations on the conditions for drying the polyamic acid coated on the support to obtain a green sheet. Examples of the temperature include 70 ° C. to 150 ° C. Examples of the drying time include 5 minutes to 180 minutes. A conventionally known drying apparatus that satisfies such conditions can be applied, and examples thereof include hot air, hot nitrogen, far infrared rays, and high frequency induction heating. Next, in order to obtain a target polyimide film from the obtained green sheet, an imidization reaction is performed. As a specific method thereof, a conventionally known imidation reaction can be appropriately used. For example, there may be mentioned a method (so-called thermal ring closure method) in which an imidization reaction proceeds by subjecting it to a heat treatment after performing a stretching treatment as necessary using a polyamic acid solution containing no ring closure catalyst or a dehydrating agent. The heating temperature in this case is exemplified by 100 ° C. to 500 ° C. From the viewpoint of film physical properties, more preferably, the treatment is performed at 150 ° C. to 250 ° C. for 3 minutes to 20 minutes, and then 350 ° C. to 500 ° C. for 3 minutes to 20 minutes. A two-stage heat treatment is mentioned.

  Another example of the imidization reaction is a chemical ring closure method in which a polyamic acid solution contains a ring closure catalyst and a dehydrating agent, and the imidization reaction is performed by the action of the ring closing catalyst and the dehydrating agent. In this method, after the polyamic acid solution is applied to the support, the imidization reaction is partially advanced to form a film having self-supporting property, and then imidization can be performed completely by heating. In this case, the condition for partially proceeding with the imidization reaction is preferably a heat treatment at 100 ° C. to 200 ° C. for 3 minutes to 20 minutes, and the condition for causing the imidization reaction to be completely performed is preferably 200 ° C. Heat treatment at ˜400 ° C. for 3 minutes to 20 minutes.

The thickness of the (A) non-thermoplastic polyimide film is preferably 5 μm to 75 μm, more preferably 10 μm to 75 μm, and still more preferably 20 μm to 75 μm. If the film thickness is greater than 75 μm, there will be variations in the amount of residual solvent on the film surface and inside in the film-forming / drying step, and the quality and physical properties may be reduced. On the other hand, if the film thickness is thinner than 5 μm, handling is difficult. In addition, in order to obtain a polyimide board having a thickness of 100 μm to 1000 μm of the present invention, it is necessary to stack a large number of sheets, which may complicate the process.

The linear expansion coefficient (value in the MD direction and the average value in the TD direction) in the surface direction of the (A) non-thermoplastic polyimide film is preferably −10 ppm / ° C. to 10 ppm / ° C., More preferably, it is −7.5 ppm / ° C. to 7.5 ppm / ° C., and further preferably −5 ppm / ° C. to 5 ppm / ° C. If the linear expansion coefficient exceeds this range, the dimensions expand or contract during high temperature exposure such as soldering, which may cause distortion and wrinkles.
The difference between the linear expansion coefficient in the MD direction and the linear expansion coefficient in the TD direction is preferably as small as possible.

The linear expansion coefficient in the thickness direction of the (A) non-thermoplastic polyimide film is not particularly limited, but is preferably 10 ppm / ° C to 200 ppm / ° C, more preferably 15 ppm / ° C to 175 ppm / ° C, Preferably, it is 20 ppm / ° C. to 150 ppm / ° C. If the linear expansion coefficient in the thickness direction is too large, the connection reliability between the conductive layers may be lowered when a printed wiring board is processed.
Originally, the difference between the linear expansion coefficient in the thickness direction and the linear expansion coefficient in the plane direction is preferably as small as possible, but the non-thermoplastic polyimide film is oriented in the plane direction. The coefficient of linear expansion is generally large.

The (A) 5% weight loss temperature of the non-thermoplastic polyimide film is not particularly limited, and it is generally known that when the non-thermoplastic polyimide having the above composition is used, a value of 550 ° C. to 650 ° C. is taken. Yes.

The tensile break strength (value in the MD direction and the average value in the TD direction) of the (A) non-thermoplastic polyimide film is not particularly limited, but is preferably 200 MPa or more, more preferably 300 MPa or more. More preferably, it is 400 MPa or more. If the tensile strength at break is lower than 200 MPa, film breakage is likely to occur during conveyance, and the yield may be reduced.
The tensile elongation at break (average value in MD direction and average value in TD direction) of the non-thermoplastic polyimide film (A) is not particularly limited, but is preferably 10% or more, more preferably It is 15% or more, more preferably 20% or more. When the tensile elongation at break is lower than 10%, film breakage is likely to occur during conveyance, and the yield may be reduced.
The (A) tensile elastic modulus (value in MD direction and average value in TD direction) of the non-thermoplastic polyimide film is not particularly limited, but is preferably 6.0 GPa or more, more preferably 6.5 GPa or more, more preferably 7.0 GPa or more. When the tensile elastic modulus is lower than 6.0 GPa, the polyimide board of the present invention inevitably has a low tensile elastic modulus. For example, when used as a core material of a multilayer printed wiring board, the reinforcing effect may not be sufficient. is there.
It is preferable that the difference between the tensile rupture strength, tensile rupture elongation, and tensile elastic modulus in the MD direction and the tensile rupture strength, tensile rupture elongation, and tensile elastic modulus in the TD direction is as small as possible.

The non-thermoplastic polyimide film (A) is treated with a coupling agent (amino silane, epoxy silane, etc.), sand blast treatment, wet blast treatment, corona treatment, atmospheric pressure plasma treatment as necessary to improve adhesion. , Vacuum plasma treatment, ion gun treatment, etching treatment, flame treatment, etc. Of these, atmospheric pressure plasma treatment and vacuum plasma treatment are preferred, and vacuum plasma treatment is more preferred. These treatments may be performed alone or in combination of two or more.

The plasma treatment of the non-thermoplastic polyimide film (A) is performed in an internal electrode type low-temperature plasma generator by applying a discharge voltage of at least 1,000 volts between the electrodes to perform glow discharge, and the polyimide film surface is subjected to low-temperature plasma. A method of contacting with the atmosphere is preferred. Plasma gases for low temperature plasma treatment include helium, neon, argon, nitrogen, oxygen, air, nitrous oxide, nitrogen monoxide, nitrogen dioxide, carbon monoxide, carbon dioxide, ammonia, water vapor, hydrogen, sulfurous acid gas , Hydrogen cyanide and the like are exemplified, and these can be used alone or in admixture of two or more. Among these, use of oxygen-containing inorganic gas is preferable, and carbon dioxide and water vapor are more preferable. The pressure of the gas atmosphere in the apparatus is preferably in the range of 0.001 Torr to 10 Torr, more preferably 0.1 Torr to 1.0 Torr. Under such gas pressure, for example, a stable glow discharge can be performed by applying power of 10 W to 100 KW at a high frequency of 10 KHz to 2 GHz between discharge electrodes, and the discharge frequency band is low in addition to the high frequency. Frequency, microwave, direct current or the like can be used. The low-temperature plasma generator is preferably an internal electrode type, but may be an external electrode type depending on the case, and may be either capacitive coupling such as a coil furnace or inductive coupling. The shape of the electrode is not particularly limited, and it can be various shapes such as a flat plate shape, a ring shape, a rod shape, and a cylinder shape, and further has a shape in which the metal inner wall of the processing apparatus is grounded as one electrode. May be. In order to apply a voltage of 1,000 volts or more between the electrodes and maintain a stable low temperature plasma state, it is necessary to apply an insulating coating having a considerable withstand voltage to the input electrode. When the polyimide film is subjected to plasma surface treatment in this way, the film surface to be plasma-treated may be one side, but it is preferable to perform plasma surface treatment on both sides.

Examples of the thermoplastic resin (B) used in the present invention include polyaryl ketones {polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ketone ketone (PEEKK), etc. }, Thermoplastic polyimide (TPI), polyetherimide (PEI), polyamideimide (PAI), fluororesin {tetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene -Hexafluoropropylene copolymer (FEP), tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPE), tetrafluoroethylene-ethylene copolymer (ETFE), polymer Vinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), etc.}, sulfone resin {polyphenylene sulfide (PPS), polysulfone (PSU), polyethersulfone (PES) etc., liquid crystal polymer (LCP) and the like.
Among these, polyaryl ketones, thermoplastic polyimides, polyether imides, and polyamide imides having high adhesiveness with non-thermoplastic polyimide films are preferable, and thermoplastic polyimides are more preferable. Moreover, these thermoplastic resins may be used independently and may use 2 or more types together.

The thickness of the (B) thermoplastic resin is preferably 0.1 μm to 50 μm, more preferably 0.5 μm to 50 μm, and still more preferably 1 μm to 50 μm. When the film thickness is larger than 50 μm, the linear expansion coefficient in the surface direction is generally larger than that of the non-thermoplastic polyimide film, and the thickness ratio of the thermoplastic resin is increased. There is a risk that the linear expansion coefficient may increase and warping may occur. On the other hand, if the film thickness is thinner than 0.1 μm, sufficient adhesion may not be obtained.

The glass transition temperature when the (B) thermoplastic resin is an amorphous polymer is not particularly limited, but is preferably 200 ° C to 450 ° C, more preferably 225 ° C to 450 ° C, and still more preferably. 250 ° C to 450 ° C. If the glass transition temperature is lower than 200 ° C., the thermoplastic resin softens during high-temperature exposure such as soldering, which may cause displacement or peeling. On the other hand, when the glass transition temperature is higher than 450 ° C., a processing temperature of 450 ° C. to 500 ° C. is required for thermocompression bonding, and the non-thermoplastic polyimide may be thermally decomposed.

The melting point when the thermoplastic resin (B) is a crystalline polymer is not particularly limited, but is preferably 250 ° C to 450 ° C, more preferably 275 ° C to 450 ° C, and still more preferably 300 ° C to 450 ° C. If the melting point is lower than 250 ° C., the thermoplastic resin flows during high-temperature exposure such as soldering, which may cause displacement or peeling. On the other hand, if the melting point is higher than 450 ° C., a processing temperature of 450 ° C. to 500 ° C. is required for thermocompression bonding, and the non-thermoplastic polyimide may be thermally decomposed.

The 5% weight reduction temperature of the (B) thermoplastic resin is preferably 400 ° C to 600 ° C, more preferably 450 ° C to 650 ° C, and further preferably 500 ° C to 600 ° C. If the 5% weight loss temperature is lower than 400 ° C., the heat resistance of the polyimide board of the present invention is remarkably lowered, which is not practical. On the other hand, it is practically difficult to produce a resin having a 5% weight loss temperature of 600 ° C. or higher and thermoplasticity and adhesiveness.

The thermoplastic resin (B) is optionally treated with a coupling agent (aminosilane, epoxysilane, etc.), sand blasting, wet blasting, corona treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, ion gun treatment, etching. You may use for a process, a frame process, etc. Of these, atmospheric pressure plasma treatment and vacuum plasma treatment are preferred, and vacuum plasma treatment is more preferred. These treatments may be performed alone or in combination of two or more.

(A) Although the method of laminating | stacking a non-thermoplastic polyimide film alternately via (B) thermoplastic resin is not specifically limited, For example, when (B) thermoplastic resin is a thermoplastic polyimide resin, The following methods can be considered.
(A) Polyamic acid solution of (A) and (B) Polyamic acid solution obtained by co-extrusion (A) (B) A method of imidizing a multilayer polyamic acid film (green film) together, and then heat-compression bonding. (A) Polyamide acid solution obtained by co-extrusion of polyamic acid solution of (A) and polyimide solution of (B) (A) (B) A method of imidizing a multilayer polyamic acid film (green film) and then thermocompression bonding. Method of casting the polyamic acid solution of (B) on the film surface, drying and imidizing, and then thermocompression bonding. Casting the polyimide solution of (B) on the polyimide film surface of (A) and drying. Method of thermocompression bonding after that-Casting the polyamic acid solution of (B) on the polyamic acid film surface of (A), drying together and imidizing, then heating pressure Method of wearing-Method of casting the polyimide solution of (B) on the surface of the polyamic acid film of (A), drying and imidizing, and then thermocompression bonding-The polyimide film of (A) and the polyimide film of (B) Method of thermocompression bonding

Above all, from the viewpoint of physical properties, quality, and cost of the obtained polyimide board. Method of casting the polyamic acid solution of (B) on the polyimide film surface of (A), drying and imidizing, and then thermocompression bonding. The method of casting the polyimide solution of (B) on the polyimide film surface of (), drying and then thermocompression bonding. The method of thermocompression bonding of the polyimide film of (A) and the polyimide film of (B) is preferred.
The polyimide board of the present invention can be obtained by combining these means alone or in combination.

The thermocompression bonding apparatus used when alternately laminating (A) non-thermoplastic polyimide film via (B) thermoplastic resin is also particularly limited as long as it is an apparatus for laminating by applying pressure to the material to be laminated. For example, a single-action press apparatus, a multistage press apparatus, a single-action vacuum press apparatus, a multistage vacuum press apparatus, an autoclave apparatus, a hot roll laminator, a double belt press machine, and the like can be given. Among these, a single-acting vacuum press apparatus and a multistage vacuum press apparatus are preferable because defects such as bubbles are less likely to occur in the obtained laminate. In order to reduce in-plane pressure unevenness, a mirror plate, a cushion plate or the like may be used above or below the polyimide board.
The heating method in the apparatus is not particularly limited as long as it can be heated at a predetermined temperature, and examples thereof include a heat medium circulation method, a hot air heating method, and a dielectric heating method. Further, the pressurization method is not particularly limited as long as a predetermined pressure can be applied, and examples thereof include a hydraulic method, a pneumatic method, a gap pressure method, and the like.

As the thermocompression bonding conditions, any conditions can be selected depending on the type of thermoplastic resin to be used. In order to use the thermoplastic resin which has, it is preferable that heating temperature is 250 degreeC-500 degreeC, a pressure is 1 MPa-20 MPa, and heating time is 5 minutes-120 minutes.

As for the thickness of the polyimide board of this invention, 50 micrometers-3000 micrometers are preferable, More preferably, they are 75 micrometers-2000 micrometers, More preferably, they are 100 micrometers-1000 micrometers. It is not realistic in terms of cost to manufacture a polyimide board having a thickness of more than 3000 μm by the method of the present invention. On the other hand, when the film thickness is less than 50 μm, a non-thermoplastic polyimide film can be formed by a conventional general solution film formation, so that the effect of using the polyimide board of the present invention is small.

  The thickness ratio [total thickness of (A) layer / {total thickness of (A) layer + total thickness of (B) layer}] with respect to the entire (A) layer in the polyimide board is 40% to 98. % Is preferable, more preferably 50% to 95%, still more preferably 55% to 90%. When the thickness ratio is less than 40%, the polyimide of the present invention generally has a higher volume ratio of (B) thermoplastic resin than (A) non-thermoplastic polyimide film, which has a larger linear expansion coefficient in the surface direction. There is a risk that the coefficient of linear expansion in the direction of the board surface will increase and warpage may occur. On the other hand, if the thickness ratio is larger than 98%, the film thickness of the (B) thermoplastic resin is inevitably reduced, and there is a possibility that sufficient adhesion cannot be obtained.

The linear expansion coefficient in the surface direction of the polyimide board (the average value in the MD direction and the value in the TD direction) is preferably −5 ppm / ° C. to 15 ppm / ° C., more preferably −2. 5 ppm / ° C. to 12.5 ppm / ° C., more preferably 0 ppm / ° C. to 10 ppm / ° C. If the linear expansion coefficient exceeds this range, the dimensions expand or contract during high temperature exposure such as soldering, which may cause distortion and wrinkles.
The difference between the linear expansion coefficient in the MD direction and the linear expansion coefficient in the TD direction is preferably as small as possible.

The linear expansion coefficient in the thickness direction of the polyimide board is not particularly limited, but is preferably 10 ppm / ° C to 300 ppm / ° C, more preferably 15 ppm / ° C to 250 ppm / ° C, and still more preferably 20 ppm / ° C to 200 ppm / ° C.
Originally, the difference between the linear expansion coefficient in the thickness direction and the linear expansion coefficient in the plane direction is preferably as small as possible, but the non-thermoplastic polyimide film is oriented in the plane direction. The coefficient of linear expansion is generally large. Therefore, the polyimide board of the present invention formed by laminating a non-thermoplastic polyimide film inevitably has a linear expansion coefficient in the thickness direction> a linear expansion coefficient in the plane direction.

The peel strength between the (A) and (B) layers in the polyimide board is preferably 3 N / cm or more, more preferably 4 N / cm, and even more preferably 5 N / cm or more.
If the peel strength is less than 3 N / cm, peeling may occur during the manufacturing process (particularly during drilling with a drill or a laser) or during use.

The polyimide board of the present invention needs to have through holes in the thickness direction in addition to the above physical properties.
The diameter of the through hole is preferably 10 μm to 200 μm, more preferably 20 μm to 150 μm, and still more preferably 30 μm to 100 μm. When the diameter is smaller than 10 μm, drilling with a laser and a drill becomes difficult. On the other hand, if the diameter is larger than 200 μm, the performance (design rule) when used for a multilayer substrate is not satisfied.
In addition, the diameter of the through-hole here is an average value of the diameter of the space | gap (circle) formed in the surface of a polyimide board by a through-hole, and the space | gap (circle) formed in the back surface of a polyimide board.

On the inner wall of the through hole, it is necessary to form macro unevenness (bamboo-like structure) in order to improve adhesion to through-hole plating.
The diameter ratio of the holes penetrating the layer (A) and the layer (B) {the diameter of the holes penetrating the layer (A) (average value) / the diameter of the holes penetrating the layer (B) (average value)} is: It is preferably 75% to 99%, more preferably 80% to 99%, still more preferably 85% to 99%. If the diameter ratio is within the above range, a mismatch occurred between the linear expansion coefficient in the thickness direction of the polyimide board and the linear expansion coefficient of the metal layer when the metal layer was formed on the inner wall of the through hole. Even in this case, peeling and cracking do not occur even after the thermal shock cycle test due to the anchor effect by the macro unevenness (bamboo structure) formed on the inner wall of the through hole. When the diameter ratio is smaller than 75%, a short circuit occurs between through holes when the multilayer substrate is manufactured, and the substrate cannot be processed. On the other hand, when the diameter ratio is larger than 99%, clear irregularities are not formed on the inner wall of the through hole, and an effect of improving the adhesiveness due to the anchor effect cannot be expected.

  The difference between the 5% weight reduction temperature of the (A) layer and the (B) layer in the polyimide board {5% weight reduction temperature of the (A) layer−5% weight reduction temperature of the (B) layer} is 5 ° C. to 100 ° C. It is preferable that it is degreeC, More preferably, it is 5 to 90 degreeC, More preferably, it is 5 to 80 degreeC. If the difference in 5% weight loss temperature is less than 5 ° C., clear irregularities are not formed on the inner wall of the through hole, and the effect of improving the adhesion due to the anchor effect cannot be expected. On the other hand, if it is higher than 100 ° C., it does not have the heat resistance necessary for the substrate and is not suitable for the reflow process.

  The method for forming the through hole is not particularly limited, and examples thereof include discharge treatment such as plasma etching, chemical treatment such as alkali etching, physical treatment such as blast or laser, and machining such as drill. Among these, drilling and laser processing are preferable because they are suitable for microhole processing, and carbon dioxide laser, UV laser, and excimer laser are more preferable from the viewpoint of achieving both micromachining and processing costs.

It is preferable that the surface and the inner wall of the through hole have no altered layer such as burrs and smears. A burr and an altered layer are formed on the surface and inner wall of the through hole after laser or drilling, and this can be removed by a general desmear process. The desmear process is not particularly limited, and examples thereof include discharge treatment such as plasma etching, chemical treatment such as alkali etching, and physical treatment such as blasting. By performing these processes, burrs and smears can be completely removed.

  The taper of the through hole is {(surface hole diameter−back surface hole diameter) / polyimide board thickness} of the polyimide board. The taper is preferably smaller from the viewpoint of reliability when used for a multilayer substrate. However, control is generally performed according to the purpose of use, and the degree is not particularly limited.

The metal used in the present invention is not particularly limited as long as it is a conductive metal. For example, silver, copper, gold, platinum, rhodium, nickel, aluminum, iron, chromium, zinc, tin, brass, white copper, bronze, monel , Molybdenum, tungsten, tin-lead solder, tin-copper solder, tin-silver solder, or the like alone or an alloy thereof. Among these, copper is a preferred embodiment in terms of balance between performance and economy. These metals naturally cover the inner wall surface, but may completely fill the through hole. Further, an embodiment in which the inner wall of the through hole is covered with copper and then filled with solder is also preferable.

Although the thickness of the said metal layer is not specifically limited, It is preferable that they are 1 micrometer-50 micrometers, More preferably, they are 1 micrometer-25 micrometers, More preferably, they are 1 micrometer-18 micrometers.

Although the metal lamination | stacking method of the metal lamination polyimide board of this invention is not specifically limited, For example, the following methods can be considered.
・ Method of heat-bonding polyimide board and metal foil.
-A method of forming a metal layer on a polyimide board using vacuum coating techniques such as vapor deposition, sputtering, and ion plating.
A method of forming a metal layer on a polyimide board by a wet plating method such as electroless plating or electrolytic plating.
The metal laminated polyimide board of the present invention can be obtained by combining these means alone or in combination.

  The metal-laminated polyimide board of the present invention is coated with a photoresist on the side of a conductive metal layer, or, if necessary, a thick film metal layer formed later if necessary, and dried, followed by exposure, A wiring circuit pattern is formed by the steps of development, etching, and photoresist stripping. Further, if necessary, solder resist coating, plastic and electroless tin plating are performed, a flexible printed wiring board, a multilayer printed wiring board obtained by multilayering them, Further, a printed wiring board having a semiconductor chip directly mounted thereon can be obtained. There are no particular limitations on the method for creating these circuits, making them multi-layered, and mounting a semiconductor chip, and the methods may be appropriately selected from known methods.

An inorganic coating such as a single metal or a metal oxide may be formed on the surface of the metal layer or, if necessary, a thick film metal layer attached later. Also, if necessary, it can be used for treatment with a coupling agent (aminosilane, epoxysilane, etc.), sand blast treatment, wet blast treatment, corona treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, ion gun treatment, etching treatment, flame treatment, etc. Also good. These treatments may be performed alone or in combination of two or more.

The use of the polyimide board is not particularly limited, but is mainly used as a core material of a multilayer printed wiring board.

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.

1. 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. The thickness of the polyimide film and the polyimide board The thickness was measured using a micrometer (manufactured by Fine Reef, Millitron 1245D).

3. Tensile modulus, tensile breaking strength, tensile breaking elongation of polyimide film and polyimide board Tensile fracture test is conducted under the following conditions, and tensile modulus, tensile breaking strength, respectively in the flow direction (MD direction) and the width direction (TD direction), The tensile elongation at break was measured.
Device name: Autograph AG-5000A manufactured by Shimadzu Corporation
Sample length: 100mm
Sample width: 10mm
Pulling speed: 50mm / min
Distance between chucks: 40 mm

4). Linear expansion coefficient (CTE) in the surface direction of polyimide film and polyimide board
The stretch rate in the MD direction and the TD direction was measured under the following conditions, the stretch rate / temperature at intervals of 40 to 50 ° C., 50 to 60 ° C., and 10 ° C., and this measurement was performed up to 400 ° C. The average value of all measured values from ℃ to 350 ℃ was calculated as CTE (ppm / ℃).
Device name: TMA4000S manufactured by Bruker AXS
Sample length: 10mm
Sample width: 2mm
Initial load: 34.5 g / mm ²
Temperature rising start temperature: 30 ° C
Temperature rise end temperature: 350 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Argon

5. Linear expansion coefficient (CTE) in the thickness direction of polyimide film and polyimide board
The stretch rate in the thickness direction is measured under the following conditions, the stretch rate / temperature at intervals of 40 to 50 ° C., 50 to 60 ° C.,..., And 10 ° C. is measured. The average value of all measured values up to 350 ° C. was calculated as CTE (ppm / ° C.).
Device name: Q400 manufactured by TA instruments
Sample length: 10mm
Sample width: 10mm
Initial load: 0.1N
Temperature rise start temperature: -55 ° C
Temperature rise end temperature: 350 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Nitrogen

6). Glass transition temperature of polyimide film and thermoplastic resin Dynamic viscoelasticity measurement (DMA) was performed under the following conditions, and the temperature at which the tan δ peak reached the maximum value was defined as the glass transition temperature.
Device name: Rheogel-E4000 manufactured by UBM
Jig: Stretch jig
Sample length: 14mm
Sample width: 5mm
Frequency: 10Hz
Temperature rising start temperature: 30 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Nitrogen

7). Melting point of polyimide film and thermoplastic resin Differential scanning calorimetry (DSC) was performed under the following conditions, and a melting point (Tm) was determined in accordance with JIS K7121.
Device name: DSC3100S manufactured by MAC Science
Bread: Aluminum bread (non-airtight type)
Sample mass: 4mg
Temperature rising start temperature: 30 ° C
Temperature rise end temperature: 400 ° C
Temperature increase rate: 20 ° C / min
Atmosphere: Argon

8). 5% weight reduction temperature of polyimide film and thermoplastic resin Thermobalance measurement (TGA) is performed under the following conditions, the mass of the sample at 150 ° C. is taken as 100%, and the temperature at which the mass of the sample decreases by 5% from that point is 5% weight Decrease temperature.
Device name: TG-DTA2000S manufactured by MAC Science
Bread: Aluminum bread (non-airtight type)
Sample mass: 10mg
Temperature rising start temperature: 30 ° C
Temperature increase rate: 20 ° C / min
Atmosphere: Nitrogen

9. Peel strength measurement of polyimide board Immediately after production and after PCT treatment (121 ° C, 100%, 2 atoms, 96 hours) and after heat treatment (150 ° C, 168 hours) Sought by doing.
Device name: Autograph AG-IS, manufactured by Shimadzu Corporation
Sample length: 100mm
Sample width: 3mm
Measurement temperature: 25 ° C
Peeling speed: 50mm / min
Atmosphere: Atmosphere

<< Evaluation of Substrate >> Drilling Workability For each metal laminated polyimide board, using a drill (SSD, manufactured by Kyocera Corporation) with a drilling machine (ND-6N210, manufactured by Hitachi Via Mechanics), 2000 times / second 4000 through-holes with a diameter of 75 μm were drilled at a rotational speed of 100 m / sec to produce a perforated metal laminated polyimide board.
About the obtained perforated metal laminated polyimide board, the total number of processed holes is inspected by AOI (AI-328, manufactured by Optima), and the number of processing defects (hole size, misalignment, burrs, cutting clogs) with respect to the designed hole. Was measured, and the yield (1) (ratio without processing defects) was calculated. The criteria for determining the processing failure here are a hole diameter of 2 μm or more or −2 μm or less, a positional deviation of 3 μm or more or −3 μm or less, a burr of 5 μm or more or −5 μm or less, a cutting diameter of 75 μm as a design value. The clogging is 5 μm or more or −5 μm or less. The yield (1) obtained was evaluated as 99% or more as ◯, 90% or more and less than 99% Δ, and less than 90% as ×.
In addition, about 20 through holes randomly selected from the 4000 through holes, the microtome passes through the center points of both of the voids (circular) formed on the front and back surfaces of each metal laminated polyimide board by the through holes. Was cut in the thickness direction, and the cross section was photographed with a scanning electron microscope (SEM). From the obtained cross-sectional SEM image, the yield (2) {(A) (B) ratio without peeling and cracking between layers} was calculated. The obtained yield (2) was evaluated as 95% or more as ◯, 85% or more and less than 95% Δ, and less than 85% as ×.
Further, from the obtained cross-sectional SEM image, the diameter of the hole penetrating the layer (A) {number of layers of the (A) layer in the polyimide board × average value of ten through holes}, penetrating the layer (B). The hole diameter {number of layers (B) in polyimide board × average value of 10 through holes} was measured. From the obtained value, the ratio of the diameters of the holes penetrating the layers (A) and (B) {the diameter of the holes penetrating the layer (A) (average value) / the diameter of the holes penetrating the layer (average) Value)}.

<< Evaluation of Substrate >> Laser Drilling Workability For each metal laminated polyimide board, a laser processing machine (HIPPO, Spectra-Physics) is used, wavelength: 355 nm, frequency: 50 kHz, number of shots: 3500, output: 2.5 W Under the processing conditions of energy density: 0.72 J / cm ² , 4000 through-holes with a diameter of 75 μm were drilled to produce a perforated metal laminated polyimide board.
About the obtained perforated metal laminated polyimide board, the total number of processed holes is inspected by AOI (AI-328, manufactured by Optima), and the number of processing defects (hole size, misalignment, burrs, cutting clogs) with respect to the designed hole. Was measured, and the yield (1) (ratio without processing defects) was calculated. The criteria for determining the processing failure here are a hole diameter of 2 μm or more or −2 μm or less, a positional deviation of 3 μm or more or −3 μm or less, a burr of 5 μm or more or −5 μm or less, a cutting diameter of 75 μm as a design value. The clogging is 5 μm or more or −5 μm or less. The yield (1) obtained was evaluated as 99% or more as ◯, 90% or more and less than 99% Δ, and less than 90% as ×.
In addition, about 20 through holes randomly selected from the 4000 through holes, the microtome passes through the center points of both of the voids (circular) formed on the front and back surfaces of each metal laminated polyimide board by the through holes. Was cut in the thickness direction, and the cross section was photographed with a scanning electron microscope (SEM). From the obtained cross-sectional SEM image, the yield (2) {(A) (B) ratio without peeling and cracking between layers} was calculated. The obtained yield (2) was evaluated as 95% or more as ◯, 85% or more and less than 95% Δ, and less than 85% as ×.
Further, from the obtained cross-sectional SEM image, the diameter of the hole penetrating the layer (A) {number of layers of the (A) layer in the polyimide board × average value of ten through holes}, penetrating the layer (B). The hole diameter {number of layers (B) in polyimide board × average value of 10 through holes} was measured. From the obtained value, the ratio of the diameters of the holes penetrating the layers (A) and (B) {the diameter of the holes penetrating the layer (A) (average value) / the diameter of the holes penetrating the layer (average) Value)}.

<< Evaluation of Substrate >> For each metal laminated polyimide board with heat and heat resistance, using a laser processing machine (HIPPO, Spectra-Physics), wavelength: 355 nm, frequency: 50 kHz, number of shots: 3500, output: 2.5 W, energy density : Under the processing conditions of 0.72 J / cm ² , 4000 through-holes with a diameter of 75 μm were drilled to prepare a perforated metal laminated polyimide board. A through-hole plating having a thickness of 10 μm was formed on the obtained perforated metal laminated polyimide board by a desmear process (Table 1), an electroless copper plating process (Table 2), and an electrolytic copper plating process (Table 3).
In accordance with JEDEC-STD020-C, the obtained through-hole plating perforated metal laminated polyimide board was baked in an oven (DKM300, manufactured by Yamato Scientific Co., Ltd.) at 125 ° C. for 24 hours, a constant temperature and humidity chamber (SH-221). , Manufactured by ESPEC Co., Ltd.), and conditioned at 30 ° C.-60% RH for 192 hours, and reflowed at 260 ° C. for 30 seconds in a reflow oven (FT05, manufactured by CIF) three times. Inspect the appearance after the test, ○ that does not show any blisters, wrinkles, warping, or discoloration, △, swollen, wrinkles, warpage, discoloration that is slightly seen, △, swollen, wrinkles, warpage, discoloration Was evaluated as x.
In addition, about 20 through holes randomly selected from the 4000 through holes, the microtome passes through the center points of both of the voids (circular) formed on the front and back surfaces of each metal laminated polyimide board by the through holes. Was cut in the thickness direction, and the cross section was photographed with a scanning electron microscope (SEM). From the obtained cross-sectional SEM image, the case where there was no peeling or disconnection of through-hole plating was evaluated as “◯”, and the case where there was peeling or disconnection of through-hole plating was evaluated as “x”.

<< Evaluation of Substrate >> Cold / Heat Shock Cycle Resistance For each metal laminated polyimide board, using a laser processing machine (HIPPO, Spectra-Physics), wavelength: 355 nm, frequency: 50 kHz, number of shots: 3500, output: 2.5 W Under the processing conditions of energy density: 0.72 J / cm ² , 4000 through-holes with a diameter of 75 μm were drilled to produce a perforated metal laminated polyimide board. A through-hole plating having a thickness of 10 μm was formed on the obtained perforated metal laminated polyimide board by a desmear process (Table 1), an electroless copper plating process (Table 2), and an electrolytic copper plating process (Table 3).
According to JEDEC-STD020-C, the obtained through-hole plating perforated metal laminated polyimide board was baked in an oven (DKM300, manufactured by Yamato Scientific Co., Ltd.) at 125 ° C. for 24 hours, a constant temperature and humidity chamber (SH-221). , Manufactured by ESPEC Co., Ltd.) at 30 ° C.-60% RH for 192 hours, and reflow oven (FT05, manufactured by CIF) at 260 ° C. for 30 seconds 3 times, a thermal shock device (TSE-11) A, manufactured by ESPEC Co., Ltd.) was subjected to 1000 cycles of -55 ° C for 15 minutes to 125 ° C for 15 minutes as one cycle. Inspect the appearance after the test, ○ that does not show any blisters, wrinkles, warping, or discoloration, △, swollen, wrinkles, warpage, discoloration that is slightly seen, △, swollen, wrinkles, warpage, discoloration Was evaluated as x.
In addition, about 20 through holes randomly selected from the 4000 through holes, the microtome passes through the center points of both of the voids (circular) formed on the front and back surfaces of each metal laminated polyimide board by the through holes. Was cut in the thickness direction, and the cross section was photographed with a scanning electron microscope (SEM). From the obtained cross-sectional SEM image, the case where there was no peeling or disconnection of through-hole plating was evaluated as “◯”, and the case where there was peeling or disconnection of through-hole plating was evaluated as “x”.

[Reference Examples 1-3]
(Creation of non-thermoplastic polyimide films A1 to A3)
The inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole and 4400 parts by mass of N, N-dimethylacetamide were added. 40.5 parts by mass of Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.) (containing 8.1 parts by mass of silica), pyromellitic acid, which is prepared by completely dissolving the colloidal silica in dimethylacetamide. When 217 parts by mass of dianhydride was added and stirred for 24 hours at a reaction temperature of 25 ° C., a brown and viscous polyamic acid solution A was obtained. This reduced viscosity was 3.9 dl / g.
This polyamic acid solution A was coated on a stainless steel endless continuous belt mirror-finished using a die coater (coating width 1240 mm) and dried at 110 ° 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 interval is adjusted so as not to break and unnecessary tarmi is generated, and the final pin sheet interval is 1140 mm. The first sheet is conveyed at 170 ° C. for 2 minutes, and the second sheet is 230 mm. The imidization reaction was allowed to proceed by heating for 2 minutes at 3 ° C and 4 minutes at 485 ° C for the third stage. Then, it cooled to room temperature in 2 minutes, the part where the flatness of the both ends of a film was bad was cut off with the slitter, it rolled up into roll shape, and the non-thermoplastic polyimide films A1-A3 which exhibit brown were obtained.
Table 4 shows the physical property values of the obtained non-thermoplastic polyimide films A1 to A3.
Next, the non-thermoplastic polyimide films A1 to A3 were set in a plasma processing machine and evacuated to a vacuum, and then oxygen gas was introduced to cause discharge to obtain double-sided plasma-treated nonthermoplastic polyimide films A1 to A3. The processing conditions are a degree of vacuum of 30 Pa, a gas flow rate of 1.5 SLM, an applied voltage of 110 kHz, and a discharge power density of 300 Wmin / m ² .

[Reference Example 4]
(Preparation of non-thermoplastic polyimide film B)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, 108 parts by mass of paraphenylenediamine and 4000 parts by mass of N-methyl-2-pyrrolidone were added and completely dissolved, and then colloidal silica. 40.5 parts by mass (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.) 40.5 parts by mass (including 8.1 parts by mass of silica), 3,3 ′, 4,4′-biphenyltetracarboxylic When 292.5 parts by mass of acid dianhydride was added and stirred for 24 hours at a reaction temperature of 25 ° C., a brown viscous polyamic acid solution B was obtained. This reduced viscosity was 4.2 dl / g.
This polyamic acid solution B was coated on a stainless steel endless continuous belt mirror-finished using a die coater (coating width 1240 mm) and dried at 110 ° 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 interval is adjusted so as not to break and unnecessary tarmi is generated, and the final pin sheet interval is 1140 mm. The first sheet is conveyed at 150 ° C. for 2 minutes, and the second sheet is 220 minutes. The imidization reaction was allowed to proceed by heating under conditions of 2 minutes at 0 ° C and 4 minutes at 460 ° C for the third stage. Then, it cooled to room temperature in 2 minutes, the part with bad flatness of the both ends of a film was cut off with the slitter, it rolled up into the roll shape, and the non-thermoplastic polyimide film B which exhibits brown was obtained.
Table 4 shows the physical property values of the obtained non-thermoplastic polyimide film B.
Next, the non-thermoplastic polyimide film B was set in a plasma processing machine and evacuated to a vacuum. Then, oxygen gas was introduced to cause discharge, and a double-sided plasma-treated non-thermoplastic polyimide film B was obtained. The processing conditions are a degree of vacuum of 30 Pa, a gas flow rate of 1.5 SLM, an applied voltage of 110 kHz, and a discharge power density of 300 Wmin / m ² .

[Production Example 5]
(Preparation of non-thermoplastic polyimide film C)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 200 parts by mass of diaminodiphenyl ether and 4170 parts by mass of N-methyl-2-pyrrolidone were added and completely dissolved, and then colloidal silica was added. 40.5 parts by mass of Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.) dispersed in dimethylacetamide (containing 8.1 parts by mass of silica), 217 parts by mass of pyromellitic dianhydride were added, and 25 ° C. When the mixture was stirred at the reaction temperature of 24 hours, a brown viscous polyamic acid solution C was obtained. This reduced viscosity was 3.6 dl / g.
This polyamic acid solution C was coated on a stainless steel endless continuous belt mirror-finished using a die coater (coating width 1240 mm) and dried at 110 ° 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 interval is adjusted so as not to break and unnecessary tarmi is generated, and the final pin sheet interval is 1140 mm. The first sheet is conveyed at 150 ° C. for 2 minutes, and the second sheet is 220 minutes. The imidation reaction was allowed to proceed by heating at 400C for 4 minutes at 400C for 3 minutes at 3 ° C. Then, it cooled to room temperature in 2 minutes, the part with bad flatness of the both ends of a film was cut off with the slitter, it rolled up into the roll shape, and the non-thermoplastic polyimide film C which exhibits brown was obtained.
Table 4 shows the physical property values of the obtained non-thermoplastic polyimide film C.
Next, the non-thermoplastic polyimide film C was set in a plasma processing machine and evacuated to a vacuum, and then oxygen gas was introduced to cause discharge to obtain a double-sided plasma-treated non-thermoplastic polyimide film C. The processing conditions are a degree of vacuum of 30 Pa, a gas flow rate of 1.5 SLM, an applied voltage of 110 kHz, and a discharge power density of 300 Wmin / m ² .

Hereinafter, PI-A1 for non-thermoplastic polyimide film A1, PI-A2 for non-thermoplastic polyimide film A2, PI-A3 for non-thermoplastic polyimide film A3, PI-B for non-thermoplastic polyimide film B, non-thermoplastic polyimide Film C is abbreviated as PI-C.

[Reference Examples 6 to 16]
(B) The following were used as the thermoplastic resin.

-TPI film D: Midfil NS, manufactured by Kurabo Industries-TPI varnish E: Rika Coat PN20A, manufactured by Shin Nippon Rika Co., Ltd.-TPI precursor varnish F: Skybond 705, manufactured by IST-PEI film G: Ultem1000, manufactured by General Electric PAI varnish H: Viromax HR16NN, manufactured by Toyobo Co., Ltd., PAI varnish I: Viromax HR14ET, manufactured by Toyobo Co., Ltd., PEEK film J: APTIV, manufactured by Victrex, Inc., PEEK + PEI film K: IBUKI, manufactured by Mitsubishi Plastics, Inc., PFA film L: NEOFLON PFA, manufactured by Daikin Industries, Ltd./FEP film M: NEOFLON FEP, manufactured by Daikin Industries, Ltd./ETFE film N: NEOFLON ETFE, manufactured by Daikin Industries, Ltd.


Here, TPI is thermoplastic polyimide, PEI is polyetherimide, PAI is polyamideimide, PEEK is polyetheretherketone, PFA is tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, FEP is tetrafluoroethylene / hexafluoropropylene Copolymer and ETFE are tetrafluoroethylene / ethylene copolymers, respectively.
The glass transition temperature, melting point, and 5% weight loss temperature were evaluated after the varnish sample was formed into a film. The film forming conditions are as follows.
-TPI varnish E: TPI varnish E was used on a non-lubricant surface of a polyethylene terephthalate film (A-4100, manufactured by Toyobo Co., Ltd.) having a thickness of 188 μm using a Baker type applicator (SA-201, manufactured by Tester Sangyo Co., Ltd.). After coating at 100 ° C. for 10 minutes, the TPI film was peeled from the polyethylene terephthalate film. The obtained TPI film was heat-treated in an inert oven (DN6101, manufactured by Yamato Scientific Co., Ltd.) at 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 30 minutes to obtain a TPI film E having a thickness of 20 μm. It was.

TPI precursor varnish F: TPI precursor varnish F was applied to a 188 μm-thick polyethylene terephthalate film (A-4100, manufactured by Toyobo Co., Ltd.) on a non-lubricant surface using a Baker type applicator (SA-201, Tester Sangyo Co., Ltd.). The TPI precursor film was peeled from the polyethylene terephthalate film after drying at 100 ° C. for 10 minutes. The obtained TPI precursor film was heat treated in an inert oven (DN6101, manufactured by Yamato Scientific Co., Ltd.) at 120 ° C. for 60 minutes, 200 ° C. for 10 minutes, 250 ° C. for 60 minutes, and 350 ° C. for 30 minutes. A TPI film F having a thickness of 20 μm was obtained.

PAI varnish H, I: PAI varnish H, I was applied on a non-lubricant surface of a polyethylene terephthalate film (A-4100, manufactured by Toyobo Co., Ltd.) having a thickness of 188 μm, and a Baker type applicator (SA-201, Tester Sangyo Co., Ltd.) The film was dried at 100 ° C. for 10 minutes, and then the PAI film was peeled from the polyethylene terephthalate film. The obtained PAI film was heat-treated in an inert oven (DN6101, manufactured by Yamato Scientific Co., Ltd.) at 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 30 minutes to obtain a PAI film H, I having a thickness of 20 μm. Got.

Tables 5 and 6 show physical property values of the obtained thermoplastic resins.

TPI film D is TPI-D, TPI varnish E is TPI-E, TPI precursor varnish F is TPI-F, PEI film G is PEI-G, PAI varnish H is PAI-H, PAI varnish I is PAI- I, PEEK film J are abbreviated as PEEK-J, PEEK + PEI film K as PEEK-K, PFA film L as PFA-L, FEP film M as FEP-M, and ETFE film N as ETFE-N.

[Example 1]
Double-sided plasma-treated PI-A2 cut out to a size of 150 mm □ and TPI-D having a thickness of 15 μm are arranged so as to be D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D. Then, using a small vacuum press machine (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing was performed at 380 ° C. and 5 MPa for 15 minutes to obtain a polyimide board having a thickness of 225 μm.
On the other hand, double-sided plasma treatment PI-A2, cut out to a size of 150 mm □, TPI-D having a thickness of 15 μm, and electrolytic copper foil having a thickness of 12 μm (U-WZ, manufactured by Furukawa Electric Co., Ltd.) / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / copper foil, and then placed at 380 ° C. using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho) Vacuum heating and pressure molding was performed at 5 MPa for 15 minutes to obtain a metal laminated polyimide board having a thickness of 249 μm.
Table 7 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

[Example 2]
Double-sided plasma-treated PI-A2 cut out to a size of 150 mm □ and TPI-D with a thickness of 15 μm are arranged so as to be A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2. Then, using a small vacuum press machine (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing was performed at 380 ° C. and 5 MPa for 15 minutes to obtain a polyimide board having a thickness of 225 μm.
The obtained polyimide board was set in a sputtering apparatus, and under the conditions of a frequency of 13.56 MHz, an output of 450 W, and a gas pressure of 0.4 Pa, a nickel-chromium (chromium 10 mass%) alloy target was used to perform DC in an argon atmosphere. A nickel-chromium alloy film (underlayer) having a thickness of 7 nm was formed at a rate of 1 nm / second by magnetron sputtering. Next, sputtering was performed to form a 0.25 μm-thick copper thin film to obtain a base metal thin film-formed polyimide board. Here, the thickness of the copper and NiCr layers was confirmed by a fluorescent X-ray method. A copper layer having a thickness of 5 μm was formed on the obtained base metal thin film-formed polyimide board using a copper sulfate plating bath. The electrolytic plating conditions were immersion in an electrolytic plating solution (copper sulfate 80 g / l, sulfuric acid 210 g / l, HCl, a small amount of brightener), and electricity was passed through 1.5 Adm ² . Subsequently, it was dried by heat treatment at 120 ° C. for 10 minutes to obtain a metal layer laminated polyimide board having a thickness of 235 μm.
Table 7 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 3
On both sides of the double-sided plasma treatment PI-A2, TPI-E is coated using a Baker type applicator (SA-201, manufactured by Tester Sangyo Co., Ltd.) so that the thickness after drying is 5 μm, and dried at 100 ° C. for 10 minutes. Then, heat treatment was performed in an inert oven (DN6101, manufactured by Yamato Scientific Co., Ltd.) at 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 30 minutes, and TPI-E / PI-A2 / TPI- having a thickness of 35 μm. A three-layer film of E was obtained. 6 layers of 3 layer film cut out to 150 mm □ size are stacked, and then vacuum heating and pressing are performed at 380 ° C. and 10 MPa for 15 minutes using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho). A polyimide board having a thickness of 210 μm was obtained.
On the other hand, after stacking six three-layer films cut to a size of 150 mm □, and further superposing a 12 μm thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric Co., Ltd.) on the front and back surfaces, a small vacuum press (IMC -11FD (manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing were performed at 380 ° C. and 10 MPa for 15 minutes to obtain a polyimide board having a thickness of 234 μm.
Table 7 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 4
On both sides of the double-sided plasma treatment PI-A2, TPI-F is coated using a Baker type applicator (SA-201, manufactured by Tester Sangyo Co., Ltd.) so that the thickness after drying is 5 μm, and dried at 100 ° C. for 10 minutes. Then, heat treatment was performed in an inert oven (DN6101, manufactured by Yamato Scientific Co., Ltd.) at 120 ° C. for 60 minutes, 200 ° C. for 10 minutes, 250 ° C. for 60 minutes, and 350 ° C. for 30 minutes, and a 35 μm thick TPI-F / A three-layer film of PI-A2 / TPI-F was obtained. 6 layers of 3 layer film cut out to 150 mm □ size are stacked, and then vacuum heating and pressing are performed at 380 ° C. and 10 MPa for 15 minutes using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho). A polyimide board having a thickness of 210 μm was obtained.
On the other hand, after stacking six three-layer films cut to a size of 150 mm □, and further superposing a 12 μm thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric Co., Ltd.) on the front and back surfaces, a small vacuum press (IMC -11FD (manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing were performed at 380 ° C. and 10 MPa for 15 minutes to obtain a polyimide board having a thickness of 234 μm.
Table 7 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 5
After arranging double-sided plasma treatment PI-A3 and PEI-G having a thickness of 50 μm cut to a size of 150 mm □ to be G / A3 / G / A3 / G, a small vacuum press (IMC-11FD, (Imoto Seisakusho Co., Ltd.) was used, and vacuum heating and pressure molding was performed at 380 ° C. and 10 MPa for 15 minutes to obtain a polyimide board having a thickness of 250 μm.
On the other hand, double-sided plasma treatment PI-A2, cut out to a size of 150 mm □, PEI-G having a thickness of 50 μm, and electrolytic copper foil having a thickness of 12 μm (U-WZ, manufactured by Furukawa Electric Co., Ltd.) / A3 / G / A3 / G / Copper foil, and then using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.) for 15 minutes at 380 ° C. and 10 MPa for vacuum heating and pressing. And a metal laminated polyimide board having a thickness of 274 μm was obtained.
Table 7 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 6
On both sides of the double-sided plasma treatment PI-A2, PAI-H was coated using a Baker type applicator (SA-201, manufactured by Tester Sangyo Co., Ltd.) so that the thickness after drying was 5 μm, and dried at 100 ° C. for 10 minutes. Thereafter, heat treatment was performed in an inert oven (DN6101, manufactured by Yamato Scientific Co., Ltd.) at 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 30 minutes, and PAI-H / PI-A2 / PAI- having a thickness of 35 μm was performed. A three-layer film of H was obtained. 6 layers of 3 layer film cut out to 150mm □ size are stacked, and then vacuum heating and pressing are performed at 330 ° C and 10MPa for 15 minutes using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho). A polyimide board having a thickness of 210 μm was obtained.
On the other hand, after stacking six three-layer films cut to a size of 150 mm □, and further superposing a 12 μm thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric Co., Ltd.) on the front and back surfaces, a small vacuum press (IMC -11FD (manufactured by Imoto Seisakusho Co., Ltd.) was used, and vacuum heating and pressure molding was performed at 330 ° C. and 10 MPa for 15 minutes to obtain a polyimide board having a thickness of 234 μm.
Table 7 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 7
After arranging double-sided plasma treatment PI-A3 cut into a size of 150 mm □ and PEEK-J having a thickness of 50 μm to be J / A3 / J / A3 / J, a small vacuum press (IMC-11FD, (Imoto Seisakusho Co., Ltd.) was used, and vacuum heating and pressing were performed at 380 ° C. and 5 MPa for 15 minutes to obtain a polyimide board having a thickness of 250 μm.
On the other hand, double-sided plasma treatment PI-A3 cut into a size of 150 mm □, PEEK-J with a thickness of 50 μm, and electrolytic copper foil with a thickness of 12 μm (U-WZ, manufactured by Furukawa Electric Co., Ltd.) / A3 / J / A3 / J / After being arranged to be copper foil, using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressure molding at 380 ° C., 5 MPa for 15 minutes. And a metal laminated polyimide board having a thickness of 274 μm was obtained.
Table 8 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 8
After arranging double-sided plasma treatment PI-A3 cut into a size of 150 mm □ and PEEK-K with a thickness of 50 μm to be K / A3 / K / A3 / K, a small vacuum press (IMC-11FD, (Imoto Seisakusho Co., Ltd.) was used, and vacuum heating and pressing were performed at 380 ° C. and 5 MPa for 15 minutes to obtain a polyimide board having a thickness of 250 μm.
On the other hand, double-sided plasma treatment PI-A3 cut into a size of 150 mm □, PEEK-K with a thickness of 50 μm, and electrolytic copper foil with a thickness of 12 μm (U-WZ, manufactured by Furukawa Electric Co., Ltd.) / A3 / K / A3 / K / copper foil, and then using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressure molding at 380 ° C., 5 MPa for 15 minutes. And a metal laminated polyimide board having a thickness of 274 μm was obtained.
Table 8 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 9
Double-sided plasma treatment PI-A2 cut out to a size of 150 mm □ and PFA-L with a thickness of 12.5 μm become L / A2 / L / A2 / L / A2 / L / A2 / L / A2 / L. Then, using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing were performed at 330 ° C. and 2 MPa for 30 minutes to obtain a polyimide board having a thickness of 200 μm.
Meanwhile, a double-sided plasma treatment PI-A2, cut into a size of 150 mm □, PFA-L with a thickness of 12.5 μm, and electrolytic copper foil with a thickness of 12 μm (U-WZ, manufactured by Furukawa Electric Co., Ltd.) / L / A2 / L / A2 / L / A2 / L / A2 / L / A2 / L / After arranging the copper foil, 330 is used using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.). Vacuum heating and pressure molding was performed at 2 ° C. for 30 minutes at a temperature of 2 ° C. to obtain a metal laminated polyimide board having a thickness of 224 μm.
Table 8 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 10
Double-sided plasma-treated PI-A2 cut out to a size of 150 mm □ and PFA-M with a thickness of 12.5 μm become M / A2 / M / A2 / M / A2 / M / A2 / M / A2 / M. Then, using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing were performed at 330 ° C. and 2 MPa for 30 minutes to obtain a polyimide board having a thickness of 200 μm.
On the other hand, a double-sided plasma treatment PI-A2, a 12.5 μm thick PFA-M, and a 12 μm thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric Co., Ltd.), cut into a size of 150 mm □, / M / A2 / M / A2 / M / A2 / M / A2 / M / A2 / M / Copper foil, and then arranged using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho) 330 Vacuum heating and pressure molding was performed at 2 ° C. for 30 minutes at a temperature of 2 ° C. to obtain a metal laminated polyimide board having a thickness of 224 μm.
Table 8 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 11
After arranging double-sided plasma treatment PI-A2 cut out to a size of 150 mm □ and TPI-D having a thickness of 15 μm so as to be D / A2 / D / A2 / D, a small vacuum press (IMC-11FD, (Imoto Seisakusho Co., Ltd.) was used, and vacuum heating and pressure molding was performed at 380 ° C. and 5 MPa for 15 minutes to obtain a polyimide board having a thickness of 95 μm.
On the other hand, double-sided plasma treatment PI-A2, cut out to a size of 150 mm □, TPI-D having a thickness of 15 μm, and electrolytic copper foil having a thickness of 12 μm (U-WZ, manufactured by Furukawa Electric Co., Ltd.) / A2 / D / A2 / D / copper foil, then vacuum heating and pressing using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho) at 380 ° C. and 5 MPa for 15 minutes. And a metal laminated polyimide board with a thickness of 119 μm was obtained.
Table 8 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 12
D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D on a double-sided plasma-treated PI-A2 cut into a size of 150 mm □ and a TPI-D with a thickness of 15 μm / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D and then using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho) Vacuum heating and pressing were performed at 380 ° C. and 5 MPa for 15 minutes to obtain a polyimide board having a thickness of 1015 μm.
On the other hand, double-sided plasma treatment PI-A2, cut out to a size of 150 mm □, TPI-D having a thickness of 15 μm, and electrolytic copper foil having a thickness of 12 μm (U-WZ, manufactured by Furukawa Electric Co., Ltd.) / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / A2 / D / After arranging to be copper foil, using a small vacuum press machine (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing at 380 ° C., 5 MPa for 15 minutes to form a metal laminate with a thickness of 1039 μm A polyimide board was obtained.
Table 8 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 13
On both sides of the double-sided plasma treatment PI-A2, TPI-E is coated using a baker type applicator (SA-201, manufactured by Tester Sangyo Co., Ltd.) so that the thickness after drying is 0.5 μm, and at 100 ° C. for 10 minutes. After drying, heat treatment was performed in an inert oven (DN6101, manufactured by Yamato Scientific Co., Ltd.) at 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 30 minutes to obtain a TPI-E / PI-A2 / 26 μm thick TPI-E / PI-A2 / A three-layer film of TPI-E was obtained. After eight layers of three-layer films cut to a size of 150 mm □ were stacked, vacuum heating and pressing were performed at 380 ° C. and 10 MPa for 15 minutes using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho). A polyimide board having a thickness of 208 μm was obtained.
On the other hand, after stacking 8 sheets of 3-layer film cut out to a size of 150 mm □, and further stacking 12 μm thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric) on the front and back surfaces, a small vacuum press (IMC -11FD (manufactured by Imoto Seisakusho Co., Ltd.) was used, and vacuum heating and pressing were performed at 380 ° C. and 10 MPa for 15 minutes to obtain a polyimide board having a thickness of 232 μm.
Table 9 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 14
On both sides of the double-sided plasma treatment PI-A2, TPI-E is coated using a Baker type applicator (SA-201, manufactured by Tester Sangyo Co., Ltd.) so that the thickness after drying is 1 μm, and dried at 100 ° C. for 10 minutes. Then, heat treatment was performed at 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 30 minutes in an inert oven (DN6101, manufactured by Yamato Scientific Co., Ltd.), and TPI-E / PI-A2 / TPI- having a thickness of 27 μm was performed. A three-layer film of E was obtained. After seven layers of three-layer films cut to a size of 150 mm □ were stacked, vacuum heating and pressing were performed at 380 ° C. and 10 MPa for 15 minutes using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho). A polyimide board having a thickness of 189 μm was obtained.
On the other hand, after seven layers of three-layer films cut out to a size of 150 mm □ were stacked, and a 12 μm thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric Co., Ltd.) was stacked on the front and back surfaces, a small vacuum press (IMC -11FD (manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing were performed at 380 ° C. and 10 MPa for 15 minutes to obtain a polyimide board having a thickness of 213 μm.
Table 9 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 15
On both sides of the double-sided plasma treatment PI-A2, TPI-E is coated using a Baker type applicator (SA-201, manufactured by Tester Sangyo Co., Ltd.) so that the thickness after drying is 2 μm, and dried at 100 ° C. for 10 minutes. Then, heat treatment was performed in an inert oven (DN6101, manufactured by Yamato Scientific Co., Ltd.) at 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 30 minutes, and TPI-E / PI-A2 / TPI- having a thickness of 29 μm A three-layer film of E was obtained. After seven layers of three-layer films cut to a size of 150 mm □ were stacked, vacuum heating and pressing were performed at 380 ° C. and 10 MPa for 15 minutes using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho). A polyimide board having a thickness of 203 μm was obtained.
On the other hand, after seven layers of three-layer films cut out to a size of 150 mm □ were stacked, and a 12 μm thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric Co., Ltd.) was stacked on the front and back surfaces, a small vacuum press (IMC -11FD (manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing were performed at 380 ° C. and 10 MPa for 15 minutes to obtain a polyimide board having a thickness of 227 μm.
Table 9 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.

Example 16 Multilayer Printed Wiring Board Using the metal laminated polyimide board obtained in Example 1, a 6-layer printed wiring board was produced.

After preparing two metal laminated boards and drilling holes for positioning pins on each, laminating a dry film resist on each side, through exposure, development, etching, resist stripping process, a predetermined circuit pattern Formed. Each of them is referred to as a patterned metal laminated polyimide board A and a patterned metal laminated polyimide board B for convenience. Then

Copper foil (thickness 12μm)
TPI film D (thickness 20μm)
Patterned metal laminated polyimide board A
TPI film D (thickness 40μm)
Patterned metal laminated polyimide board B
TPI film D (thickness 20μm)
Copper foil (thickness 12μm)

In this order, they were positioned and overlapped, and they were bonded together by vacuum pressing. Further, a through-hole having a diameter of 400 μm was drilled at a predetermined position with a laser, and the wall surface of the through-hole was made conductive by electroless copper plating according to a conventional method. After the through-hole was thickened by electrolytic copper plating, a dry film resist was used. Patterning was performed on the outermost copper foil by a tenting method to obtain a multilayer printed wiring board having six conductor layers. The obtained printed wiring board exhibited a good appearance without warping and sufficient stiffness. When the cross section of the obtained printed wiring board was observed, the hole diameter was 398 μm at the polyimide A2 portion and 407 μm at the TPI film D portion.

[Example 17] Build-up multilayer printed wiring board The six-layer multilayer printed wiring board obtained in Example 16 was used as a core layer, and two build-up layers were formed on both sides.
Specifically, first, the through-hole portion of the six-layer multilayer printed wiring board obtained in Example 16 was filled with an epoxy-based hole-filling material and cured, and then both sides of the epoxy system of Ajinomoto Fine Techno Co., Ltd. Laminated build-up material ABF, laser via drilling, base conductor formation by electroless plating, negative pattern formation by dry film resist, thickening by electrolytic copper plating, resist peeling and quick etching of base conductor A build-up layer was formed. Next, after blackening the copper foil surface of the first buildup layer, the second buildup layer is formed in the same manner by the semi-additive method. Finally, a photosensitive solder resist is formed, and a pillup-up printed wiring with 10 layers is formed. I got a plate. The obtained printed wiring board exhibited a good appearance without warping and sufficient stiffness.

[Comparative Example 1]
A laminate was prepared and evaluated in the same manner as in Example 1 except that double-sided plasma treatment PI-B was used instead of double-sided plasma treatment PI-A2.
Table 9 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.
(A) When the coefficient of linear expansion in the surface direction of the non-thermoplastic polyimide film is large, the coefficient of linear expansion in the surface direction of the resulting polyimide board also increases, and the dimensions expand or contract at high temperature exposure. , Warping occurred.

[Comparative Example 2]
A laminate was prepared and evaluated in the same manner as in Example 1 except that double-sided plasma treatment PI-C was used instead of double-sided plasma treatment PI-A2.
Table 9 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.
(A) When the coefficient of linear expansion in the surface direction of the non-thermoplastic polyimide film is large, the coefficient of linear expansion in the surface direction of the resulting polyimide board also increases, and the dimensions expand or contract at high temperature exposure. , Warping occurred. Furthermore, since there is no difference in the 5% weight loss temperature between (A) the non-thermoplastic polyimide film and (B) the thermoplastic resin, no clear irregularities are formed on the inner wall of the through hole, and after the heat and humidity resistance test and the thermal shock After the cycle test, peeling and disconnection of the through-hole plating occurred.

[Comparative Example 3]
On both sides of the double-sided plasma treatment PI-A2, PAI-I was coated using a Baker type applicator (SA-201, manufactured by Tester Sangyo Co., Ltd.) so that the thickness after drying was 5 μm, and dried at 100 ° C. for 10 minutes. Then, heat treatment was performed in an inert oven (DN6101, manufactured by Yamato Scientific Co., Ltd.) at 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 30 minutes to give a PAI-I / PI-A2 / PAI- with a thickness of 35 μm. A three-layer film of I was obtained. 6 layers of 3 layer film cut out to 150mm □ size are stacked, and then vacuum heating and pressing are performed at 330 ° C and 10MPa for 15 minutes using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho). A polyimide board having a thickness of 210 μm was obtained.
On the other hand, after stacking six three-layer films cut to a size of 150 mm □, and further superposing a 12 μm thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric Co., Ltd.) on the front and back surfaces, a small vacuum press (IMC -11FD (manufactured by Imoto Seisakusho Co., Ltd.) was used, and vacuum heating and pressure molding was performed at 330 ° C. and 10 MPa for 15 minutes to obtain a polyimide board having a thickness of 234 μm.
Table 10 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.
(B) When the heat resistance of the thermoplastic resin was low, the heat resistance of the resulting polyimide board was also low, and swelling, wrinkles, warpage, and discoloration occurred during high temperature exposure. Furthermore, since the difference in 5% weight loss temperature between (A) non-thermoplastic polyimide film and (B) thermoplastic resin also increases, the diameter ratio of the holes passing through (A) layer and (B) layer becomes smaller, As a result, peeling and disconnection of through-hole plating occurred frequently.

[Comparative Example 4]
Double-sided plasma treatment PI-A2 cut out to a size of 150 mm □ and PFA-N with a thickness of 12.5 μm are N / A2 / N / A2 / N / A2 / N / A2 / N / A2 / N. Then, using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing were performed at 300 ° C. and 2 MPa for 30 minutes to obtain a polyimide board having a thickness of 200 μm.
Meanwhile, a double-sided plasma treatment PI-A2, a 12.5 μm thick PFA-N, and a 12 μm thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric Co., Ltd.), cut into a size of 150 mm □, 300 / N / A2 / N / A2 / N / A2 / N / A2 / N / A2 / N / copper foil, and then using a small vacuum press machine (IMC-11FD, manufactured by Imoto Seisakusho) 300 Vacuum heating and pressure molding was performed at 2 ° C. for 30 minutes at a temperature of 2 ° C. to obtain a metal laminated polyimide board having a thickness of 224 μm.
Table 10 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.
(B) When the heat resistance of the thermoplastic resin was low, the heat resistance of the resulting polyimide board was also low, and swelling, wrinkles, warpage, and discoloration occurred during high temperature exposure. Furthermore, since the difference in 5% weight loss temperature between (A) non-thermoplastic polyimide film and (B) thermoplastic resin also increases, the diameter ratio of the holes passing through (A) layer and (B) layer becomes smaller, As a result, peeling and disconnection of through-hole plating occurred frequently.

[Comparative Example 5]
D / A1 / D / A1 / D / A1 / D / A1 / D / A1 / D / A1 / D on a double-sided plasma treatment PI-A1 cut out to a size of 150 mm □ and TPI-D with a thickness of 15 μm / A1 / D / A1 / D, and then using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing at 380 ° C., 5 MPa for 15 minutes to obtain a thickness A 215 μm polyimide board was obtained.
Meanwhile, a double-sided plasma treatment PI-A1, a 15 μm-thick TPI-D, and a 12 μm-thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric Co., Ltd.), cut into a size of 150 mm □, / A1 / D / A1 / D / A1 / D / A1 / D / A1 / D / A1 / D / A1 / D / A1 / D / Small vacuum press machine (IMC-11FD) , Manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing were performed at 380 ° C. and 5 MPa for 15 minutes to obtain a metal laminated polyimide board having a thickness of 239 μm.
Table 10 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.
When the thickness ratio between the (A) non-thermoplastic polyimide film and the (B) thermoplastic resin is small, the coefficient of linear expansion in the surface direction of the resulting polyimide board increases, and the dimensions expand or contract at high temperature exposure. Swelling, wrinkles and warping occurred.

[Comparative Example 6]
Double-sided plasma treatment PI-A1 cut out to a size of 150 mm □ and TPI-D with a thickness of 25 μm are arranged so as to be D / A1 / D / A1 / D / A1 / D / A1 / D / A1 / D. Then, using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing were performed at 380 ° C. and 5 MPa for 15 minutes to obtain a polyimide board having a thickness of 200 μm.
On the other hand, a double-sided plasma treatment PI-A1, a 25 μm thick TPI-D, and a 12 μm thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric Co., Ltd.), cut into a size of 150 mm □, / A1 / D / A1 / D / A1 / D / A1 / D / A1 / D / After being arranged to be a copper foil, using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho), 380 ° C., Vacuum heating and pressure molding was performed at 5 MPa for 15 minutes to obtain a metal laminated polyimide board having a thickness of 224 μm.
Table 10 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.
When the thickness ratio between the (A) non-thermoplastic polyimide film and the (B) thermoplastic resin is small, the coefficient of linear expansion in the surface direction of the resulting polyimide board increases, and the dimensions expand or contract at high temperature exposure. Swelling, wrinkles and warping occurred.

[Comparative Example 7]
On both sides of the double-sided plasma treatment PI-A2, TPI-E was coated using a Baker type applicator (SA-201, manufactured by Tester Sangyo Co., Ltd.) so that the thickness after drying was 0.05 μm, and 10 minutes at 100 ° C. After drying, heat treatment was performed in an inert oven (DN6101, manufactured by Yamato Kagaku Co., Ltd.) at 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 250 ° C. for 30 minutes to obtain a TPI-E / PI- having a thickness of 25.1 μm. A three-layer film of A2 / TPI-E was obtained. After eight layers of three-layer films cut to a size of 150 mm □ were stacked, vacuum heating and pressing were performed at 380 ° C. and 10 MPa for 15 minutes using a small vacuum press (IMC-11FD, manufactured by Imoto Seisakusho). A polyimide board having a thickness of 200.8 μm was obtained.
On the other hand, after stacking 8 sheets of 3-layer film cut out to a size of 150 mm □, and further stacking 12 μm thick electrolytic copper foil (U-WZ, manufactured by Furukawa Electric) on the front and back surfaces, a small vacuum press (IMC -11FD, manufactured by Imoto Seisakusho Co., Ltd.), vacuum heating and pressing were performed at 380 ° C. and 10 MPa for 15 minutes to obtain a polyimide board having a thickness of 224.8 μm.
Table 10 shows the evaluation results of the obtained polyimide board and metal laminated polyimide board.
When the thickness of the (B) thermoplastic resin is small, the peel strength between the layers (A) and (B) becomes small, so that peeling occurred during drilling with a drill or a laser. Therefore, evaluation of subsequent heat-and-moisture resistance and cold-heat shock cycle properties has not been carried out.

In the polyimide board in which a plurality of (A) non-thermoplastic polyimide films of the present invention are alternately laminated via (B) a thermoplastic resin and have through holes having a diameter of 10 μm to 200 μm in the thickness direction, The linear expansion coefficient in the direction is −5 ppm / ° C. to 15 ppm / ° C., the thickness is 50 μm to 3000 μm, and the diameter ratio of the holes penetrating the layers (A) and (B) {the holes penetrating the layers (A) The polyimide board whose diameter (average value) / (B) diameter of the hole penetrating the layer (average value)} is 75% to 99% is excellent in heat resistance, dimensional stability and adhesiveness, and further has a thickness. When a through hole is made in the direction and a metal layer is laminated on the wall surface, the metal layer does not peel off even after the thermal shock cycle test.For example, it corresponds to higher wiring density and high reliability. Core material for multilayer printed wiring boards There is an advantage in that. Furthermore, it can be used effectively for mechanical jigs and components, sensors, probes, integrated circuits, and composite devices of these, and contributes greatly to the industry.

Claims (12)

  In a polyimide board in which a plurality of (A) non-thermoplastic polyimide films are alternately laminated via (B) a thermoplastic resin and have a through hole having a diameter of 10 μm to 200 μm in the thickness direction, The linear expansion coefficient is −5 ppm / ° C. to 15 ppm / ° C., the thickness is 50 μm to 3000 μm, and the diameter ratio of the holes passing through the layers (A) and (B) {the diameter of the holes penetrating the layers (A) ( (Average value) / (B) Diameter of holes penetrating the layer (average value)} is 75% to 99%. The difference between the 5% weight reduction temperature of the (A) layer and the (B) layer (5% weight reduction temperature of the (A) layer−5% weight reduction temperature of the (B) layer) is 5 ° C. to 100 ° C. 1. The polyimide board according to 1. (A) The thickness ratio of the entire layer [(A) total thickness of layer / {(A) total thickness of layer + (B) total thickness of layer}] is 40% to 98%. The polyimide board according to 1 or 2. (A) A non-thermoplastic polyimide film is a polyimide film obtained by a reaction between an aromatic tetracarboxylic acid and an aromatic diamine having a benzoxazole structure, and has a linear expansion coefficient in the plane direction of −10 ppm / ° C. The polyimide board according to claim 1, wherein the polyimide board has a thickness of 10 ppm / ° C. and a thickness of 5 μm to 75 μm. (B) The thermoplastic resin is one or more resins selected from the group consisting of polyaryl ketones, thermoplastic polyimides, polyetherimides, and polyamideimides, and has a thickness of 0.1 μm to 50 μm. 4. A polyimide board according to any one of the above. (A) (B) The peeling strength between layers is 3 N / cm or more, The polyimide board in any one of Claims 1-5. The polyimide board according to claim 1, wherein a through hole is formed by a laser. The polyimide board according to claim 1, wherein a through hole is formed by a drill.   A metal-laminated polyimide board obtained by laminating a metal layer on the polyimide board according to claim 1.   The metal laminated polyimide board according to claim 9, wherein the metal is copper or a metal containing copper as a main component.   The printed wiring board using the polyimide board in any one of Claims 1-8, or the metal lamination polyimide board in any one of Claims 9-10.   The multilayer printed wiring board using the polyimide board in any one of Claims 1-8, the metal lamination polyimide board in any one of Claims 9-10, or the printed wiring board of Claim 11 as a core material.