CN101652244B

CN101652244B - Metal-resin laminate

Info

Publication number: CN101652244B
Application number: CN2008800115332A
Authority: CN
Inventors: 井冈崇明; 小住尚论
Original assignee: Asahi Chemical Co Ltd
Current assignee: Asahi Kasei Corp
Priority date: 2007-04-18
Filing date: 2008-04-17
Publication date: 2013-06-26
Anticipated expiration: 2028-04-17
Also published as: TW200909202A; TWI393629B; JP4896219B2; CN101652244A; JPWO2008133182A1; WO2008133182A1

Abstract

It is intended to provide a metal-resin laminate, which contains a metal foil having a small surface roughness and a thermoplastic polyimide having a high adhesiveness and a low hygroscopic expansion coefficient, and is useful as a material particularly for a flexible printed wiring board. The laminate of the invention is characterized by comprising a metal foil with a surface having an arithmetic average roughness Ra of 0.20 [mu]m or less and/or a ten-point average roughness Rz of 0.70 [mu]m or less; a thermoplastic polyimide layer containing a specific chemical structure provided on the surface of the metal foil; and a resin layer provided on the thermoplastic polyimide layer.

Description

Metal-resin laminate

Technical field

The present invention relates to a kind of metal-resin laminate that is particularly useful for the material that flexible printing patch panel uses.

Background technology

About being used in the metal-resin laminate of flexible printing patch panel, its main flow is to be situated between by tack coat, metal forming to be bonded at least one side of polyimide film.Such layered product is owing between polyimide film and metal forming, using tack coat, so the character of the bonded layer of the characteristic of this layered product institute left and right.Again, the characteristic of tack coat also affects the flexible printing patch panel that has used such layered product.

As tack coat, main flow is acrylic resin binding agent and epoxy resin binding agent, wishes to improve heat resistance, resistance to chemical reagents, moisture-proof, dimensional stability, mechanical properties etc.

Therefore, study use and thering is the TPI of high-fire resistance, resistance to chemical reagents, mechanical properties, electrical characteristics as tack coat.; TPI is due to the caking property of shortage with metal; so in order to obtain practical caking property; adopt following gimmick: use the arithmetic surface roughness Ra to surpass the such metal forming with large surface roughness of 0.70 μ m over 0.2 μ m or 10 mean roughness Rz; main by fixing (anchor) effect, improve caking property.

And, along with the densification of the assembling of electronic equipment, the microspur of the distribution of flexible printing patch panel is in development.In the situation that large such as the surface roughness of the metal forming of conductor layer, microspurization must produce boundary.Also have, produce following problem, increase along with the process information amount of electronic equipment, the frequency gets higher of transmission of signal, therefore the phenomenon (skin effect) of near surface of density deflection conductor that flows through the electric current of conductor becomes significantly, and the surface roughness of conductor is brought bad impact to the transmission of signal.

Due to these situations, so wish to use metal forming that surface roughness is less as the conductor layer for flexible printing patch panel.Due to above-mentioned situation, so expect that a kind of use has the layered product that has high-adhesion between the metal-resin of metal forming of little surface roughness.

Again, for the dimensional stability that makes layered product improves, and the moisture expantion coefficient of expectation tack coat is low., the moisture expantion coefficient of the moisture expantion coefficient ratio polyimide film of general TPI is high.

So far, people the research Copper Foil of surface roughness below certain value with take the laminate (patent documentation 1,2) of the thermoplastic polyimide layer that tetracarboxylic dianhydride with specific chemical constitution is raw material., the TPI of patent documentation 1 record is because its structural symmetry is high, and the degree of orientation of polymer molecule is high, so have and the inadequate possibility of the caking property of Copper Foil.Again, the TPI of patent documentation 2 record is owing to having the structure that softness and polarity are high, and, in order to improve caking property, take epoxy resin as essential component, so the possibility that the moisture expantion coefficient is high is arranged.

Again, the metal forming of surface roughness below certain value with take the laminate of the thermoplastic polyimide layer that specific diamines is raw material also for example, in studied (, patent documentation 3).The thermoplastic polyimide layer that has high-adhesion for SUS (stainless steel) is disclosed in patent documentation 3., generally all know that caking property between Copper Foil-polyimides, than the caking property between stainless steel-polyimides obviously bad (non-patent literature 1), expects to occur the layered product high with the caking property of copper.Again, the TPI of patent documentation 3 records is because the symmetry of its structure is low, and the degree of orientation of polymer molecule is low, so the possibility that the moisture expantion coefficient is high is arranged.Due to above-mentioned situation, so expect that a kind of metal forming for having little surface roughness has high-adhesion and has the TPI of low moisture expantion coefficient.

Patent documentation 1: Japanese Patent Laid-Open 2004-82495 communique

Patent documentation 2: No. 2003/006553 brochure of International Publication

Patent documentation 3: Japanese Patent Laid-Open 2006-142834 communique

Non-patent literature 1: wide Tian Xing controls and waits work " adherence of Tu work System film To おけ Ru is followed property system and driven とそ Evaluation value " technical information association of Co., Ltd. of Japan in May, 2005, p27～29

Summary of the invention

Given this, the object of the present invention is to provide a kind of especially suitable be used as (metal-resin) layered product towards the material of flexible printing patch panel (below, referred to as layered product), it contains TPI, and this TPI has with respect to the high-adhesion of the metal forming with little surface roughness and low moisture expantion coefficient.

The present invention is in order to solve above-mentioned problem, carry out repeatedly wholwe-hearted research, the TPI that the tetracarboxylic dianhydride who found that to have ad hoc structure is raw material, controlled the degree of orientation of molecule can take into account low moisture expantion coefficient and with the good caking property of the metal forming with little surface roughness, thereby completed the present invention.

Namely, layered product of the present invention, it contains metal forming and thermoplastic polyimide layer, it is characterized in that, and the surface of this metal forming is low roughness, and the moisture expantion coefficient of this thermoplastic polyimide layer is below 16ppm/%RH.

In layered product of the present invention, it is desirable to, the arithmetic average roughness Ra on the surface of described metal forming below 0.20 μ m and/or 10 mean roughness Rz below 0.70 μ m.

In layered product of the present invention, it is desirable to, the tetracarboxylic dianhydride's that repetitive B, (iii) that described thermoplastic polyimide layer contains the tetracarboxylic dianhydride that the repetitive A, (ii) that are selected from the tetracarboxylic dianhydride that (i) come self-drifting (1) to mean come self-drifting (2) to mean comes self-drifting (3) to mean repetitive C's is at least two or more

[changing 1]

In formula (1), R ₁mean hydrogen, the alkyl of carbon number 1～6 or the alkoxyl of carbon number 1～6, n means the integer more than 2,

[changing 2]

In formula (2), R ₂mean the alkyl of carbon number 1～6 or the alkoxyl of carbon number 1～6,

[changing 3]

In layered product of the present invention, it is desirable to, described repetitive A is the repetitive from the tetracarboxylic dianhydride of following general formula (4) expression,

[changing 4]

In formula (4), R ₃, R ₄mean independently respectively the alkyl of hydrogen, carbon number 1～6 or the alkoxyl of carbon number 1～6.

In layered product of the present invention, it is desirable to, described general formula (4) is two (trimellitic acid monoesters) dianhydrides of 4,4 '-bis-phenylenes that formula (5) means.

[changing 5]

In layered product of the present invention, it is desirable to, described repetitive B is the repetitive from the tetracarboxylic dianhydride of following general formula (6) expression,

[changing 6]

In formula (6), R ₅mean the alkyl of carbon number 1～6 or the alkoxyl of carbon number 1～6.

In layered product of the present invention, it is desirable to, described general formula (6) is 2 of formula (7) expression, two (trimellitic acid monoesters) dianhydrides of 5-benzal.

[changing 7]

In layered product of the present invention, it is desirable to, the tetracarboxylic dianhydride's that described repetitive A comes self-drifting (4) to mean repetitive, and described repetitive B carrys out the tetracarboxylic dianhydride's of self-drifting (6) expression repetitive.

In layered product of the present invention, it is desirable to, the repetitive of the diamines that described thermoplastic polyimide layer contains to come self-drifting (8) to mean,

[changing 8]

H ₂N-X-NH ₂ (8)

In formula, X is the divalent group that is selected from following formula group (9),

[changing 9]

In layered product of the present invention, it is desirable to, the diamines that the contained above-mentioned general formula (8) of described thermoplastic polyimide layer means is the diamines that formula (10) means.

[changing 10]

In layered product of the present invention, it is desirable to the repetitive of the diamines that also contains to come self-drifting (11) to mean in above-mentioned thermoplastic polyimide layer.

[changing 11]

In layered product of the present invention, it is desirable to, the diamines that described general formula (11) means is 1 of formula (12) expression, two (3-amino-benzene oxygen) benzene of 3-.

[changing 12]

In layered product of the present invention, it is desirable to, also possess resin bed on above-mentioned thermoplastic polyimide layer.

In layered product of the present invention, it is desirable to, the moisture expantion coefficient of described resin bed is below 16ppm/%RH.

In layered product of the present invention, it is desirable to, described resin bed is polyimide film.

In layered product of the present invention, it is desirable to, described polyimide film contains from PMDA and/or 3, and 3 ', 4, the repetitive of 4 '-biphenyl tetracarboxylic dianhydride is as constituent.

In layered product of the present invention, it is desirable to, described metal forming is Copper Foil.

Flexible printing patch panel of the present invention, is characterized in that, above-mentioned layered product is carried out distribution processing and forms.

Layered product of the present invention, it contains metal forming and thermoplastic polyimide layer, it is characterized in that, the arithmetic average roughness Ra on the surface of described metal forming below 0.20 μ m and/or 10 mean roughness Rz below 0.70 μ m, the tetracarboxylic dianhydride's that described thermoplastic polyimide layer at least contains to come self-drifting (2) to mean repetitive B, and the moisture expantion coefficient is below 16ppm/%RH.

In layered product of the present invention, it is desirable to the tetracarboxylic dianhydride's that described repetitive B comes self-drifting (6) to mean repetitive.

According to the present invention, can manufacture following flexible printing patch panel: use the metal forming with little surface roughness, there is good caking property simultaneously, and excellent in dimensional stability.

The accompanying drawing explanation

Fig. 1 is the infrared absorption spectroscopy of the TPI of embodiment 4 records.

The specific embodiment

Below, the present invention is specifically described.

Layered product of the present invention comprises the metal forming with particular surface roughness and is arranged on the thermoplastic polyimide layer that contains specific chemical constitution on above-mentioned metal forming.

Layered product of the present invention metal forming used is from the viewpoint of the processing of microspur distribution, skin effect etc., it is desirable to use the Copper Foil of low roughness, here, low roughness refers to that the arithmetic average roughness (Ra) on the surface (single face) of above-mentioned metal forming is below 0.20 μ m and/or 10 mean roughness (Rz) are below 0.70 μ m.Especially Ra is that the following and Rz of 0.20 μ m is that the following metal forming of 0.70 μ m is suitable.More preferably the scope of Ra is below 0.15 μ m, again from the close-burning viewpoint with TPI, more than Ra it is desirable to 0.01 μ m, more preferably more than 0.03 μ m.Again, more preferably the scope of Rz is below 0.60 μ m, from the close-burning viewpoint with TPI, more than Rz it is desirable to 0.20 μ m, more preferably more than 0.30 μ m, particularly desirably more than 0.40 μ m.Here, Ra and Rz are the values of measuring by JIS B0601:1994 defined method.

To layered product of the present invention, there is no particular limitation for the kind of metal forming used, so long as have the metal forming of above-mentioned Ra and/or Rz, gets final product, and known metal forming, Alloy Foil all are suitable for.Particularly, can use Copper Foil, aluminium foil, stainless steel foil etc.Wherein, from the viewpoint of cost aspect, the property obtained, processability, it is desirable to electrolytic copper foil, rolled copper foil, with the Copper Foil of carrier copper foil etc.Example as the Copper Foil that is applicable to using, trade name U-WZ is arranged for example, and (the Furukawa サ of Japan mono-キ Star ト Off オイ Le Co., Ltd. manufactures, Ra=0.11 μ m, Rz=0.60 μ m), (Mitsu Mining & Smelting Co., Ltd of Japan manufactures trade name NA-DFF, Ra=0.11 μ m, Rz=0.60 μ m), (Nippon Denkai, Ltd. of Japan manufactures trade name HLS, Rz=0.60 μ m), trade name HLP (Nippon Mining and Metals Co., Ltd of Japan manufacture, Rz=0.70 μ m) etc.

The viewpoints such as the easness that the thickness of metal forming is processed when manufacturing, the resistance to bend(ing) while using product or folding Qu Xing, it is desirable to 0.5～50 μ m, and more preferably 1～35 μ m, further it is desirable to 5～20 μ m.

For improving the purposes such as caking property or rustless property, can be in surface treatments such as the electroplating processes such as metal foil surface enforcement, chromate processing, aluminium-alcohol salt processing, aluminium chelate compound processing, silane coupler processing.

In the present invention, owing to using the low metal forming of surface roughness, so can improve the transparency of the flexible wiring sheet that uses layered product making of the present invention, can improve the visuognosis degree.Therefore, while carrying semiconductor wafer, easily locate, be applicable to the purposes of High Density Packaging material.

The layered product the present invention relates to, is characterized in that, in above-mentioned metal forming, being laminated into Ra is below 0.20 μ m and/or Rz is that 0.70 μ m following face and thermoplastic polyimide layer join.

The TPI the present invention relates to be take at least one of at least one and diamines of tetracarboxylic dianhydride and is made as raw material.Here " thermoplasticity " refers to that the scope at 100 ℃～400 ℃ has glass transition temperature, the melt-flow by the heating more than glass transition temperature, and processing can be shaped.

As the first embodiment of the present invention, contain the tetracarboxylic dianhydride's who is selected from self-drifting (1) to mean repetitive A, tetracarboxylic dianhydride's the repetitive B, tetracarboxylic dianhydride's repetitive C at least two or more of coming self-drifting (3) to mean that comes self-drifting (2) to mean in the molecule of this TPI.

[changing 13]

(in formula (1), R ₁mean hydrogen, the alkyl of carbon number 1～6 or the alkoxyl of carbon number 1～6, n means the integer more than 2),

[changing 14]

(in formula (2), R ₂c ₁～C ₆alkyl, C ₁～C ₆alkoxyl),

[changing 15]

In above-mentioned general formula (1), repetitive A is from the deliquescent viewpoint of raw material acid dianhydride monomer or TPI precursor, it is desirable to that n=2～4 means, more preferably 2～3 mean, further it is desirable to the tetracarboxylic dianhydride who means from following general formula (4).

[changing 16]

(in formula (4), R ₃, R ₄mean independently respectively the alkyl of hydrogen, carbon number 1～6 or the alkoxyl of carbon number 1～6),

R in above-mentioned general formula (1) ₁and the R in (4) ₃, R4 it is desirable to hydrogen, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, from the heat resistance of TPI and the viewpoint of the moisture-proof coefficient of expansion, more preferably hydrogen or methyl.

In above-mentioned general formula (1), particularly desirably, repetitive A is two (trimellitic acid monoesters) dianhydrides of 4,4 '-bis-phenylenes that mean from following formula (5).

[changing 17]

R in above-mentioned general formula (2) ₂it is desirable to methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, from the stable on heating viewpoint of TPI, more preferably methyl.Again, the tetracarboxylic dianhydride that general formula (2) means, there are three kinds of ortho position bodies, a position body, contraposition body in the isomers of the substituted phenylene that it is central, but the viewpoint from the moisture expantion coefficient is reduced it is desirable to the contraposition body.

In above-mentioned general formula (2), it is desirable to the tetracarboxylic dianhydride that repetitive B means from following formula (6).Particularly desirably, repetitive B from following (7), mean 2, two (trimellitic acid monoesters) dianhydrides of 5-benzal.

[changing 18]

(in formula (6), R ₅mean the alkyl of carbon number 1～6 or the alkoxyl of carbon number 1～6),

[changing 19]

The tetracarboxylic dianhydride that above-mentioned general formula (3) means, there are three kinds of ortho position bodies, a position body, contraposition body in the isomers of the phenylene that it is central, but the viewpoint from the moisture expantion coefficient is reduced it is desirable to the contraposition body.

In the present embodiment, from the viewpoint of the caking property with metal forming or moisture expantion coefficient, this TPI contains repetitive B and repetitive C is more suitable.Now the content of repetitive C is from the viewpoint of the balance of the physical property such as the caking property with metal forming or glass transition temperature, take repetitive B100mol% as benchmark, more than it is desirable to 10mol%, below 1000mol%, more preferably 25mol% above, below 500mol%, particularly desirably 50mol% above, below 200mol%.

In the present embodiment, from the viewpoint of the caking property with metal forming or moisture expantion coefficient, this TPI contains repetitive A and repetitive B is also suitable.Now to the content that repeats unit B, there is no particular limitation, but from the close-burning viewpoint with metal forming, take repetitive A100mol% as benchmark, more than it is desirable to 25mol%, below 400mol%, more preferably 33mol% above, below 300mol%, more preferably 50mol% above, below 200mol%, particularly desirably above, the following such scope of 150mol% of 65mol%.

In embodiment, this TPI can repetitive A, repetitive B, repetitive C all contains.Now to the content that repeats unit B and C, there is no particular limitation, but from the close-burning viewpoint with metal forming, take repetitive A100mol% as benchmark, more than it is desirable to 25mol%, below 400mol%, more preferably 33mol% above, below 300mol%, more preferably 50mol% above, below 200mol%, particularly desirably above, the following such scope of 150mol% of 65mol%.

In the present embodiment, to the content sum of repetitive A, repetitive B and repetitive C, there is no particular limitation, but the viewpoint from the caking property with metal forming, glass transition temperature, moisture expantion coefficient, the contained whole repetitive 100mol% from the tetracarboxylic dianhydride of the TPI of take are benchmark, it is desirable to more than 10mol%, more preferably more than 20mol%, further it is desirable to more than 50mol%, particularly desirably more than 80mol%.

Known generally by with a kind of tetracarboxylic dianhydride of containing upright and outspoken (gather) phenylene two ester groups, the orientation of raising polyimide molecule, make the reduction of moisture expantion coefficient., there is separately the polyimides of above-mentioned repetitive A or C due to the upright and outspoken degree of its structure and the height of orientation, have following problem: do not manifest thermoplasticity, even or thermoplasticity, with the caking property of other materials also step-down.Therefore, for the close-burning purpose that improves polyimides, the tetracarboxylic dianhydride that copolymerization contains the structure with bendability, used usually., by importing the structure that such bendability is high, the orientation of polyimide molecule reduces, and the moisture expantion coefficient rises.Generally believe that the polyimides that high-adhesion and low moisture expantion coefficient is provided and deposits is difficult.

In the past, failed to expect to share the tetracarboxylic dianhydride of containing upright and outspoken (gathering) phenylene ester group of more than two kinds for reaching above-mentioned problem.The tetracarboxylic dianhydride that present embodiment contains upright and outspoken (gathering) phenylene two ester groups by use, the moisture expantion coefficient is reduced, and by share the different two or more monomer of structure of (gathering) phenylene in this tetracarboxylic dianhydride, moderately control the orientation of TPI molecule, realize and the high caking property of metal forming with this, can make low moisture expantion coefficient and high-adhesion and deposit.

In the present embodiment, the moisture expantion coefficient that can make TPI is below 16ppm/%RH, it is desirable to below 14ppm/%RH, more preferably below 13ppm/%RH, further it is desirable to below 12ppm/%RH, particularly desirably below 10ppm/%RH.The moisture expantion coefficient can or be controlled the selection of diamines by the content of above-mentioned each repetitive.

As the second embodiment of the present invention, the tetracarboxylic dianhydride's of at least containing to come self-drifting (2) to mean in the molecule of this TPI repetitive B.

To the content that repeats unit B without particular limitation of, but consider from the viewpoint of the physical property balances such as the caking property with metal forming or glass transition temperature, the contained 100mol% of the repetitive from the tetracarboxylic dianhydride of the TPI of take is benchmark, more than the content of repetitive B it is desirable to 1mol%, below 99mol%, more preferably 10mol% above, below 95mol%, further it is desirable to 30mol% above, below 90mol%, particularly desirably 50mol% above, below 80mol%.

As mentioned above, used separately the tetracarboxylic dianhydride's of containing upright and outspoken (gathering) phenylene two ester groups TPI to have the problem low with the caking property of other materials.Present embodiment maintains by one side the low moisture expantion coefficient that upright and outspoken phenylene diester base band is come, import substituting group on the phenylene of one side in this tetracarboxylic dianhydride, moderately control the orientation of TPI molecule, realize and the high caking property of metal forming, make low moisture expantion coefficient and high-adhesion and be saved as possibility.

In present embodiment, the moisture expantion coefficient that can make TPI is below 16ppm/%RH, it is desirable to below 14ppm/%RH, more preferably below 13ppm/%RH, further it is desirable to below 12ppm/%RH, particularly desirably below 10ppm/%RH.The moisture expantion coefficient can or be controlled the selection of diamines by the content of above-mentioned repetitive B.

It is desirable to, the moisture expantion coefficient of the resin bed possessed on the thermoplastic polyimide layer of chatting after the moisture expantion coefficient ratio of TPI is low.

TPI of the present invention can consist of following such repetitive, be that the repetitive from the tetracarboxylic dianhydride in molecule all is selected from above-mentioned repetitive A, B, C, or also can contain the repetitive from the tetracarboxylic dianhydride beyond above-mentioned repetitive A, B, C.

As tetracarboxylic dianhydride in addition, can use known.Particularly, there can be exemplified the compound that the acid dianhydride that contains the structure that following tetrabasic carboxylic acid cyclodehydration forms and all or part of hydrogen atom in these compounds are replaced by other substituting groups such as alkyl, haloalkyl, halogen atom, alkoxyl, halogenated alkoxy.Described tetrabasic carboxylic acid has pyromellitic acid for example, the benzene tertacarbonic acid, the cyclobutane tetrabasic carboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 2,3,2 ', 3 '-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-benzophenone tetrabasic carboxylic acid, 2,2 ', 3,3 '-benzophenone tetrabasic carboxylic acid, 2,2 ', 3,3 '-oxygen, two phthalic acids, 3,3 ', 4,4 '-oxygen, two phthalic acids, 1,3-dihydro-1,3-dioxo-5-isobenzofuran carboxylic acid-Isosorbide-5-Nitrae-phenylene ester, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,4,5-naphthalene tetracarboxylic acid, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 4,4 '-(isopropylidene) two phthalic acids, 4,4 '-(hexafluoro isopropylidene) two phthalic acids, 4,4 '-(4,4 '-isopropylidene, two phenoxy groups) two phthalic acids, 4,4 '-(4,4 '-hexafluoro isopropylidene, two phenoxy groups) two phthalic acids, two (3,4-dicarboxyl phenyl) sulfide, two (3,4-dicarboxyl phenyl) methane, two (3, the 4-di carboxyl phenyloxy) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3,4-di carboxyl phenyloxy) benzene, 4,4 '-bis-(3,4-di carboxyl phenyloxy) biphenyl, butane-1,2,3, the 4-tetrabasic carboxylic acid, pentane-1,2,4, the 5-tetrabasic carboxylic acid, pentamethylene-1,2,3, the 4-tetrabasic carboxylic acid, cyclohexane-1,2,4, the 5-tetrabasic carboxylic acid, 1-cyclohexene-2,3,5, the 6-tetrabasic carboxylic acid, 3-ethyl hexamethylene-1-alkene-3-(1,2), 5,6-tetrabasic carboxylic acid, 1-methyl-3-ethyl cyclohexane-3-(1,2), 5,6-tetrabasic carboxylic acid, 1-methyl-3-ethyl hexamethylene-1-alkene-3-(1,2), 5,6-tetrabasic carboxylic acid, 1-ethyl cyclohexane-1-(1,2), 3,4-tetrabasic carboxylic acid, 1-propyl cyclohexane-1-(2,3), 3,4-tetrabasic carboxylic acid, 1,3-dipropyl cyclohexane-1-(2,3), 3-(2,3)-tetrabasic carboxylic acid, dicyclohexyl-3,4,3 ', 4 '-tetrabasic carboxylic acid, two ring [2.2.1] heptane-2,3,5, the 6-tetrabasic carboxylic acid, two ring [2.2.2] octanes-2,3,5, the 6-tetrabasic carboxylic acid, two ring [2.2.2]-7-octenes-2,3,5, the 6-tetrabasic carboxylic acid, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-cyclohexene-1, the 2-dicarboxylic acids, ethylenebis (trimellitic acid monoesters), bisphenol-A two (trimellitic acid monoesters), polyethylene glycol two (trimellitic acid monoesters) etc.Wherein, from the viewpoint of thermal coefficient of expansion, glass transition temperature, heat resistance etc., consider, it is desirable to 3,4,3 ', 4 '-biphenyl tetracarboxylic dianhydride, PMDA, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-oxygen, two O-phthalic acid dianhydrides, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride.These tetracarboxylic dianhydrides can use also and can be used together separately.

For the content of the repetitive from above-mentioned tetracarboxylic dianhydride, there is no particular limitation, but consider from the caking property with metal forming, glass transition temperature, the such viewpoint of moisture expantion coefficient, the contained all repetitive 100mol% from the tetracarboxylic dianhydride of the TPI of take are benchmark, content from above-mentioned tetracarboxylic dianhydride's repetitive it is desirable to below 90mol%, more preferably below 80mol%, further it is desirable to below 50mol%, particularly desirably below 20mol%.

Take the TPI that above-mentioned tetracarboxylic dianhydride and diamines can obtain the present invention relates to as raw material, to diamines, there is no particular limitation, can use known.There can be exemplified for example Isosorbide-5-Nitrae-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, the xyxylene diamines, the diaminonaphthalene class, the diaminoanthraquinone-class, two (4-aminophenyl) propane of 2,2-, 2-(3-aminophenyl)-2-(4-aminophenyl) propane, two (3-aminophenyl) propane of 2,2-, 4,4 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 3,3 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 4,4 '-hydroxy diphenylamine, 3,4 '-hydroxy diphenylamine, 3,3 '-hydroxy diphenylamine, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3-amino-benzene oxygen) benzene, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, two (3-aminobenzoyl) benzene of 1,3-, two (4-aminobenzoyl) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(3-aminobenzoyl) benzene, Isosorbide-5-Nitrae-bis-(3-aminobenzoyl) benzene, α, α '-bis-(4-aminophenyl)-Isosorbide-5-Nitrae-diisopropyl benzene, α, α '-bis-(4-aminophenyl)-1,3-diisopropyl benzene, 4,4 '-bis-(4-amino-benzene oxygen) benzophenone, 4,4 '-bis-(3-amino-benzene oxygen) benzophenone, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl sulfone, 4,4 '-bis-(3-amino-benzene oxygen) diphenyl sulfone, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, two (4-(4-amino-benzene oxygen) phenyl) propane of 2,2-, two (4-(3-amino-benzene oxygen) phenyl) propane of 2,2-, two (3-(3-amino-benzene oxygen) phenyl) propane of 2,2-, 4,4 '-bis-(4-amino-benzene oxygen) diphenyl ether, 4,4 '-bis-(3-amino-benzene oxygen) diphenyl ether, two (4-(3-amino-benzene oxygen) benzoyl) benzene of 1,3-, 4,4 '-bis-(4-(4-amino-benzene oxygen) benzoyl) diphenyl ether, two (4-aminophenyl) fluorenes of 9,9-, trans and cis-Isosorbide-5-Nitrae-DACH, trans and cis-1, the 3-DACH, trans and cis-1, the 2-DACH, 3-methyl-trans and cis-Isosorbide-5-Nitrae-DACH, 3-methyl-3-amino methyl-5, the 5-dimethyl cyclohexyl amine, the two amino methyl cyclohexanes of 1,3-, two (4,4 '-aminocyclohexyl) methane, two (3,3 '-methyl-4,4 '-aminocyclohexyl) methane, two (amino methyl) norbornane, two (amino methyl)-tri-rings [5,2,1,0 ^2.6] decane, 3,4-diaminourea benzoic acid, 3,5-diaminourea benzoic acid, 3,4-diaminourea benzoic acid methyl esters, 3,5-diaminourea benzoic acid methyl esters etc.Diamines after the group that also can use the part of the contained hydrogen atom of above-mentioned Diamines to be selected from methyl, ethyl and halogen again, replaces.These diamines can be used respectively a kind of or suitably combine two or more and used.

Wherein, from the caking property with metal forming, the viewpoint of the low moisture expantion coefficient of TPI is seen, it is desirable to 4, 4 '-bis-(4-amino-benzene oxygen) biphenyl, 4, 4 '-bis-(3-amino-benzene oxygen) biphenyl, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 4-, α, α '-bis-(4-aminophenyl)-1, the 4-diisopropyl benzene, α, α '-bis-(4-aminophenyl)-1, the 3-diisopropyl benzene, 2, two (4-aminophenyl) propane of 2-, 2, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-, 4, 4 '-bis-(4-amino-benzene oxygen) diphenyl sulfone, 9, the compound that contains ehter bond and/or aliphatic quaternary carbon atom of two (4-aminophenyl) fluorenes of 9-etc., especially it is desirable to 2, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-.Again, viewpoint from the thermal coefficient of expansion of the caking property with metal forming, TPI, to be selected from 1, two (3-amino-benzene oxygen) benzene, 1 of 3-, two (4-amino-benzene oxygen) benzene, 1 of 3-, the diamines of at least one of two (3-amino-benzene oxygen) benzene of 4-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene and two (4-(4-amino-benzene oxygen) phenyl) propane of 2,2-are also used also effective.

To the not special regulation of the content of the repetitive from these diamines, but the viewpoint from the low moisture expantion coefficient of the caking property with metal forming, TPI, since from TPI, whole repetitive 100mol% of contained diamines are benchmark, more than it is desirable to 10mol%, more preferably more than 20mol%, more than further it is desirable to 50mol%, particularly desirably more than 80mol%.

Again, the end of TPI can be the structure after stopping by the end sealing agents such as dicarboxylic anhydride or monoamine envelope.To the end sealing agent, there is no particular limitation, can use known.

There can be exemplified for example phthalic anhydride for end envelope dicarboxylic acid anhydride only, maleic anhydride, the benzophenone dicarboxylic anhydride, the diphenyl ether dicarboxylic anhydride, the diphenyl dicarboxylic acid acid anhydride, the diphenyl sulfone dicarboxylic anhydride, the naphthalene dicarboxylic acids acid anhydride, the anthracene dicarboxylic anhydride, 4-phenylene-ethynylene phthalic anhydride, 3-phenylene-ethynylene phthalic anhydride, phenylene-ethynylene naphthalene dicarboxylic acids acid anhydride, phenylene-ethynylene biphenyltetracarboxyacid acid acid anhydride, phenylene-ethynylene diphenyl ether dicarboxylic anhydride, phenylene-ethynylene benzophenone dicarboxylic anhydride, phenylene-ethynylene diphenyl sulfone dicarboxylic anhydride, phenylene-ethynylene anthracene dicarboxylic anhydride or there is substituent compound on these aromatic rings.These dicarboxylic anhydrides can be used separately, also can two or more merge use.

For end envelope monoamine only, for example have for example, aniline, amino-phenol, the 2-aminobphenyl, the 3-aminobphenyl, the 4-aminobphenyl, ortho-aminotoluene, meta-aminotoluene, para-totuidine, 2, the 3-xylidine, 2, the 6-xylidine, 3, the 4-xylidine, 3, the 5-xylidine, 2-ADP base ether, 3-ADP base ether, 4-ADP base ether, the 2-aminobenzophenone, the 3-aminobenzophenone, the 4-aminobenzophenone, 2-ADP base sulfone, 3-ADP base sulfone, 4-ADP base sulfone, alpha-naphthylamine, beta-naphthylamine, the 1-amino anthracene, the 2-amino anthracene.These monoamines can be used separately, also can two or more merge use.

The viewpoint of the drying of the solvent from close-burning viewpoint and manufacturing process, the ideal thickness of the thermoplastic polyimide layer the present invention relates to be 0.1～30 μ m, more preferably 0.3～15 μ m, further it is desirable to 0.5～8 μ m, particularly desirably 1～5 μ m.

Scolding tin is used in distribution in flexible printing patch panel and the connection of device usually.The fusing point that the vitrifying transition temperature of the TPI therefore the present invention relates to it is desirable at SnPb63 is that more than 183 ℃, further, in order to use more dystectic Pb-free solder, more preferably glass transition temperature is more than 200 ℃.Here, glass transition temperature is the value of measuring with thermomechanical analysis (TMA).

Then, to the TPI that the present invention relates to and the synthetic method of precursor be described.

At least one that makes above-mentioned tetracarboxylic dianhydride and diamines is dissolved in organic solvent in fact equimolar amounts, make it reaction and obtain polyamic acid, using this polyamic acid as precursor, then carry out imidization reaction, and the TPI that obtains the present invention relates to.

As the solvent for this reaction, so long as get final product for the solvent of inertia for reaction, there is no particular limitation, can use N, dinethylformamide, DMA, METHYLPYRROLIDONE, cresols, dimethyl sulfoxide (DMSO), gamma-butyrolacton etc.From the viewpoints such as easness of security, processing, specially suitable is DMA, METHYLPYRROLIDONE, gamma-butyrolacton.Benzene, the dimethylbenzene, 1,3 that can in these solvents, mix arbitrary proportion, 5-trimethylbenzene, hexane, chlorobenzene, oxolane, Isosorbide-5-Nitrae-dioxs, acetonitrile, phenylcyanide equal solvent.

Reaction is usually carried out under 5～80% solute concentration, the temperature of-20 ℃～150 ℃, the scope of 10 minutes～24 hours.The above-mentioned end sealing agent can be added in reaction system as required.

What the degree of polymerization of resulting polyamic acid was suitable is 2～600.In addition, the weight average molecular weight that this degree of polymerization can be measured according to GPC is calculated.The situation of the adjustment of the degree of polymerization and common polycondensation based polymer is the same can be controlled by the mol ratio of adjusting monomer component.For example, for 1mol acid composition, use two amine components of 0.8～1.2mol.It is desirable to, for 1mol acid composition, use 0.9～1.1mol diamines.

The mechanical strength that known general macromolecule quantizes improving polyimides is effective, (" Japanese Port リイミ De research association compile up-to-date Port リイミ De～Ji Foundation と ying with～", (the エヌテイ mono-エス of Co., Ltd. of Japan) p.106) and the key element that descends of the caking property of polyimides be near low-molecular-weight thing Presence of an interface, (" inferior generation エレ Network トロニ Network ス Electricity material To can be paid Ji Intraoperative to the new い of け Port リイミド development と Gao Machine ", (Ji Intraoperative Qing Reported Association meeting) p.20).In the present invention, to the weight average molecular weight (Mw) of resulting polyamic acid, there is no particular limitation, but the viewpoint from the moisture expantion coefficient of easy coating, TPI, when this TPI does not contain repetitive A, suitable is 1000～300000, is more suitably 50000～200000.While containing repetitive A, suitable is 10000～200000, is more suitably 50000～100000.

It is desirable to, the viscosity of the solution of resulting polyamic acid is 0.2～200,000mPas, and more preferably 0.3～50000mPas, further it is desirable to 0.5～30000mPas.The viscosity of polyamic acid solution is to use Zhui Xing & Plate (cone& Plate) value that rotation viscometer (E type viscosimeter) obtains at 23 ℃ of lower instrumentations.

When TPI is solvent soluble, can carry out in advance the imidization reaction of above-mentioned polyamic acid in solution.Thus, the stability that has solution improves or can simplify heat treated advantage during film coated described later.Here, " solvent soluble " refers to more than temperature range 1 % by weight of room temperature to 100 ℃ and is dissolved in the solvent of use.

For the method for carrying out imidization reaction in solution, there is no particular limitation, can use known method.Particularly, can use by heating makes it carry out the method for imidization reaction or following method, the catalyst of the representatives such as the chemical converting agent (dehydrating agent) represented by interpolation anhydrous acetic acid, trifluoroacetic acid, polyphosphoric acid, five phosphorous oxide, phosphorus pentachloride, thionyl chloride etc., isoquinolin, beta-picoline, pyridine, gamma-valerolactone, promote the cyclodehydration reaction of polyamic acid, imidizate is carried out.

On the other hand, when TPI is not solvent soluble, need to carry out imidization reaction in the coating of polyamic acid solution, after dry.This is narrated in the manufacture method of the layered product of back.

In addition, for the stability-enhanced purpose that makes polyimides precursor solution, also can replace polyamic acid with poly amic acid ester or polyisoimide.This gimmick for example is documented in " the up-to-date Port リ of the Japanese Port リイミ De Knitting of research association イミ De～Ji Foundation と ying use～" (the エヌテイ mono-エス of Co., Ltd. of Japan).

Can in the solution of TPI or its precursor, further add the surface modifiers such as the fillers such as dehydrating agent as additive, silica and silane coupler.Again, in order to make imidization reaction described later, effectively carry out, can in the solution of TPI precursor, add imidizate promoter.

The resin bed possessed on<thermoplastic polyimide layer >

In the present invention, from viewpoints such as the thermal coefficient of expansion of layered product, heat resistance, elastic modelling quantity, tearing strength, tension failure ductility, it is desirable to except above-mentioned thermoplastic polyimide layer, also use and be arranged to the resin bed joined with this thermoplastic polyimide layer.To this resin bed, there is no particular limitation, can use knownly, it is desirable to polyimide film, more preferably non-thermoplastic polyimide film.Here, " non-thermal plasticity " refers to is not having glass transition temperature below 400 ℃, even glass transition temperature is perhaps arranged, thereby elastic modelling quantity can not plastic (not melt-flow) not occur significantly descending owing to being heated to more than glass transition temperature yet.

Polyimide film is to take the film that tetracarboxylic dianhydride and diamines obtain as raw material, it is formed to there is no particular limitation, can use known.ユ mono-ピレ Star Network ス (registration mark) S that the example of commercially available suitable polyimide film has Ube Industries, Ltd of Japan to manufacture for example, ユ mono-ピレ Star Network ス (registration mark) SGA, ユ mono-ピレ Star Network ス (registration mark) SN, カプト Application (registration mark) H that east レデユ Port Application Co., Ltd. of Japan manufactures, カプト Application (registration mark) V, カプト Application (registration mark) EN, アピカ Le (registration mark) AH that the カネカ of Co., Ltd. of Japan manufactures, アピカ Le (registration mark) NPI, アピカ Le (registration mark) NPP, アピカ Le (registration mark) HP, アピカ Le (registration mark) FP etc.These are all non-thermal plasticities.

From the close-burning viewpoint between thermoplastic polyimide layer and polyimide film, more preferably, above-mentioned polyimide film contains from PMDA and/or 3, and 3 ', 4, the repetitive of 4 '-biphenyl tetracarboxylic dianhydride.

The ideal thickness of the resin bed the present invention relates to be 2 μ m above, below 125 μ m.The viewpoint of the easness of processing from the rigidity of layered product, film, more preferably more than 5 μ m.From the filming of printing distributing board, the viewpoint of bending easness, more preferably, below 75 μ m, further it is desirable to below 25 μ m, particularly desirably below 17 μ m again.

From the viewpoint of the dimensional stability of further raising layered product, more preferably the moisture expantion coefficient of this resin bed is also below 16ppm/%RH.

The resin bed the present invention relates to, can be processed with gimmick effects on surfaces such as sandblast, wet blasting (wet blast) or polishing grindings, or processed with gimmick effects on surfaces such as Corona discharge Treatment, plasma discharge processing or UV ozone treatment.For these processing, make film surface physics roughening, or chemically form the functional group that is of value to bonding of carboxyl etc., make thus caking property improve further.

Corona discharge Treatment can adopt known method.As electrode, the known electrodes such as applicable stainless steel electrode, aluminium electrode, quartzy electrode, roller electrode, wire electrode.Again, the known process rollers such as the applicable silicon liner roller for the treatment of tube, EPT liner roller, hypo grand (Hypalon) liner roller, ceramic-lined roller, silicon sleeve roll.To the Corona discharge Treatment atmosphere gas, there is no particular limitation to process density.For the Corona discharge Treatment condition, can select any condition, but it is desirable in electric discharge output, divided by speed of production and the resulting value of processing width, be that power-discharging density is 40Wmin/m ²carrying out electric treatment under above condition, is more preferably 80Wmin/m at power-discharging density ²carry out electric treatment under above condition.

The plasma discharge processing method adopts the known methods such as light emitting discharge, for gaseous species, the air pressure of plasma discharge treatment, there is no particular limitation for processing density.Again, for the plasma discharge treatment condition, can at random select, but utilize the plasma discharge treatment of light emitting discharge, it is desirable to electric discharge and be output as 20～2000Wmin/m ², pressure is below 1Torr.The atmosphere gas of plasma discharge treatment also can at random be selected, but it is desirable to adopt tetrafluoromethane, oxygen, nitrogen, argon, helium, carbon dioxide, hydrogen or their non-reactive gas or the reactant gases such as mist of more than two kinds.

The polishing milled processed can be used known device, to polishing roll, polishing pressure, there is no particular limitation for the polishing roll rotating speed.

Can before Corona discharge Treatment or plasma discharge processing, carry out sandblast, wet blasting or polishing milled processed.

Can implement these surface treatments at the single face of resin bed, also can be two-sided at it.

The manufacture method of<layered product >

Manufacture method to layered product of the present invention is described.

As the manufacture method of layered product of the present invention, at first the solution of the above-mentioned TPI of coating or its precursor on metal forming or resin bed, then carry out drying, carries out as required imidization reaction, forms thus thermoplastic polyimide layer.

Below, the method for the solution of coating thermoplastic polyimides or its precursor on resin bed is described in detail.

There is no particular limitation for method for the solution coat by TPI or its precursor on resin bed, can use known various coating process, for example, use scraper (blade) coating machine, the metal mold coating machine, scraper plate (knife) coating machine, the impregnation coating machine, comma coating machine (コ Application マコ mono-タ mono-), contrary roll coater, engraved roll coater, scraper plate coating machine (リ Star プコ mono-タ mono-), hat type coating machine (キヤ Star プコ mono-タ mono-), scraping strip coating machine, extrusion coating machine (ス Network イズコ mono-タ mono-), slope stream coating machine, the heavy curtain coating machine carries out.

After the solution of coating thermoplastic polyimides or its precursor, make it dry.To drying means or not restriction of condition, for example, use hot blast or infrared ray, it is desirable to more than the boiling point of solvent (usually 100 ℃～400 ℃ scopes) and heat 10 seconds～10 hours.

During coating thermoplastic polyimides precursor solution, with the dry solvent while or after it, carry out imide reaction, convert the TPI precursor to TPI.This reaction promotes by heating usually.Reaction condition is had no particular limits, applicable known condition, under 100 ℃～400 ℃, heating is practical in 0.5 hour～24 hours usually.As required, can under the atmosphere of the inert gases such as nitrogen, argon, helium, carry out again.

While manufacturing the single-sided flexible printing distributing board, at the single face formation thermoplastic polyimide layer of resin bed.While manufacturing the double-faced flexible printing distributing board, at the two-sided formation thermoplastic polyimide layer of resin bed.Now, the composition, the thickness that are formed at the thermoplastic polyimide layer on two sides can be the same or different.

Thermoplastic polyimide layer by the resin laminate that makes to be obtained by said method below 0.20 μ m and/or the face of Rz below 0.70 μ m contacts, crimping, can carry out lamination integrated with the Ra of metal forming, obtains layered product of the present invention.

Method as carrying out crimping, it is desirable to pressure application.As pressure application, planar vacuum pressure application, dull and stereotyped antivacuum pressure application, roll-in force method, bilayer zone pressure application etc. are arranged for example, wherein, more preferably bilayer zone pressure application, roll-in force method.To the condition of pressure, there is no particular limitation, it is desirable at the temperature fully mobile at TPI, carries out hot pressing continuously by bilayer zone pressure application or roll-in force method and fetch and carry out.In the bilayer zone pressure application, between zone face, press and it is desirable to 1～10MPa, more preferably 2～6MPa.In the roll-in force method, between the hot-rolling line, pressure it is desirable to 1～500N/mm, more preferably 10～300N/mm.Deteriorated for the heat that prevents metal forming or resin, thermo-compressed also can be carried out in the atmosphere of inert gases such as nitrogen or argon gas.

In addition, also can be according to lamination order contrary to the above, according to following order: form thermoplastic polyimide layer on metal forming, then make thermoplastic polyimide layer contact with resin bed, carry out crimping, lamination is integrated, manufactures the layered product the present invention relates to.Now, the laminated thermoplastic polyimide layer is clamped the two sides of resin bed, can make towards the layered product of two sides flexible printing patch panel.

The layered product the present invention relates to is because the moisture expantion coefficient of TPI is low, so the dimensional stability of layered product is good.Therefore can improve the precision in the operation that distribution forms operation or assembled semiconductor integrated package etc., be suitable for the High Density Packaging material applications.

During flexible printing patch panel that making the present invention relates to, the metal forming of layered product obtained above is carried out to distribution processing.Distribution processing can be undertaken by least following operation.

Form resist layer with dry film photoresist or resist China ink etc. on the metal forming of layered product.Then developed, resist layer is carved into to the pattern of desired shape.With liquids such as copper chloride or iron chloride, the Copper Foil exposed by development is partly dissolved, removes resist layer.

Again, while making the two sides flexible printing patch panel, except above-mentioned operation, then carry out following operation, the side in the ，Zai Dui hole, hole by offering the conducting between the metal forming for carrying out two sides is electroplated, and makes the two sides conducting.

Usually, in flexible printing patch panel, for following viewpoint: make adding under shock environment reducing of fault when the substrate that is assembled with parts after distribution forms is processed or reducing of fault while under the crooked environment of high-frequency, processing the substrate after distribution forms, the caking property at conductor layer-resin bed interface (peel strength of the A regulation of JIS C64718.1) is high more satisfactory, more than 0.6N/mm, more preferably, more than 0.8N/mm, further it is desirable to more than 1.0N/mm.According to the present invention, can obtain the good flexible printing patch panel of caking property at conductor layer-resin bed interface.

Remove thermoplastic polyimide layer and resin bed by the layered product from the present invention relates to or flexible printing patch panel, can measure Ra and the Rz on the surface of metal forming.The method of from layered product, removing thermoplastic polyimide layer and resin bed can be used and peel off, dissolving, etching, oxidation Decomposition, thermal decomposition and their combination.Especially polyimides can be used the etching of aqueous slkali, so, when resin bed is polyimide film, by layered product is carried out to alkaline etching, can make the surface of metal forming expose.Also have and can not apply etched situation according to the difference of the kind of resin bed, but measured the words of the operation of peel strength described later, most situation is, (a) at the interface peel of thermoplastic polyimide layer and metal forming, perhaps (b) at the interface peel of thermoplastic polyimide layer and resin bed, or (c) in the aggegation of the inside of thermoplastic polyimide layer, destroys.(a) situation can directly be measured Ra and the Rz of metal forming like this, and (b) or (c) situation, can remove the thermoplastic polyimide layer remained on metal forming by etching, makes thus the surface of metal forming expose, and can measure Ra and Rz.The Ra measured like this and the value of Rz are got and the Ra of raw material metal paper tinsel and the roughly the same value of Rz usually.

(embodiment)

Below, by embodiment, the present invention is specifically described, but these examples are not limited in any way the present invention.In addition, the evaluation of physical property in following examples carries out as follows.

(1) peel strength

Copper Foil-resin laminate is cut into to long 140mm, wide 10mm, the vinyl tape of wide 1mm is bonded in to the length direction on copper-clad surface, carry out mask.When also there is copper foil layer in the back side, with being coated with the vinyl chloride insulating tape, mask is carried out in the whole back side.Be immersed in ferrous chloride aqueous solution (manufacture of Tsurumi Soda Co., Ltd. of Japan), copper foil layer is carried out to etch processes, after removing painting vinyl chloride insulating tape, washed, form the copper foil pattern of wide 1mm.Under 105 ℃, with air drier, by resulting samples dried 1 hour, then, with two-sided tape, be bonded in the glass epoxy substrate with the same size of layered product.One side is peeled off the copper foil pattern of wide 1mm from polyimide layer, one side is measured and peeled off required stress.Measure the method by A (the 90 ° of stripping methods) regulation of JIS C6471 8.1, peeling rate is set as 50mm/min.For same composition, measure 2 test films, using its mean value as peel strength.

(2) heat-proof aging

Under 150 ℃, the sample that the etch processes copper foil layer in above-mentioned (1) is obtained is made test film after carrying out heat treated 7 days the samely with (1), measures peel strength.

(3) moisture expantion coefficient

The Copper Foil of standing thickness 12 μ m on the metal coating cloth deck of 90 ℃ of insulations (trade name USLP-SE, Nippon Denkai, Ltd. of Japan), make tarnish (マ Star ト) face side for surface.With scraper, the solution of the TPI precursor of concentration 15 % by weight (varnish varnish) is coated on the Copper Foil frosted face.Afterwards, on coating cloth deck standing 10 minutes, then in the drying oven of air circulating type 120 ℃ of lower heat dryings 10 minutes, obtain thus the TPI precursor film (thickness is 45 μ m approximately) without crease (タ Star Network) property.Then, in hot-air drier, under nitrogen atmosphere, 5 ℃/min of programming rate, 150 ℃ are heated 30 minutes, and 200 ℃ are heated 60 minutes, and 350 ℃ are heated 60 minutes, carry out imidizate, obtain the thermoplastic polyimide film with Copper Foil.By being immersed in ferrous chloride aqueous solution (manufacture of Tsurumi Soda Co., Ltd. of Japan) with copper foil membrane, Copper Foil is removed in etching, obtains approximately (formation thermoplastic polyimide layer) thermoplastic polyimide film of 25 μ m of thickness.

Use the ア of Japan Le バ Star Network science and engineering Co., Ltd.'s thermo-mechanical analysis device (TM-9400) and humidity atmosphere adjusting device (HC-1), under 23 ℃, load 5g, the change in size of the thermoplastic polyimide film of wide 3mm, long 30mm (length 15mm between chuck) when mensuration changes to high humidity environment (70～80%RH) from low-humidity environment (10～30%RH), calculate the moisture expantion coefficient.

(4) thermal coefficient of expansion, glass transition temperature

The thermo-mechanical analysis device (TMA-50) that uses Shimadzu Scisakusho Ltd of Japan to make, under load 5g, measure the change in size of the above-mentioned thermoplastic polyimide film of wide 3mm, length 19mm (length 15mm between chuck), thermal coefficient of expansion and the glass transition temperature of calculating the scope of 100 ℃～200 ℃.

(5) heat decomposition temperature

The thermogravimetry device (TGA-50) that uses Shimadzu Scisakusho Ltd of Japan to make, under stream of nitrogen gas, 10 ℃/minutes of programming rates, the weight change of above-mentioned thermoplastic polyimide film while being determined at the interior intensification of 30～700 ℃ of scopes.

(6) tensile modulus of elasticity and tension failure ductility

After the varnish with spin coating concentration 15 % by weight on the silicon chip of aluminium film by splash method film forming, under 100 ℃, drying is 20 minutes, and the TPI precursor layer of thickness 17 μ m is set.Then, 150 ℃ of heating 30 minutes, 200 ℃ of heating 60 minutes, 350 ℃ of heating 60 minutes, carry out imidizate.Use die sinking cutter to obtain to be cut into 3mm with the TPI silicon chip wide, be immersed in 2N hydrochloric acid, etching aluminium, peel off TPI.Washed afterwards, under 80 ℃ dry 1 hour, as sample.

Again, when sample is commercially available polyimide film, using this polyimide film cutting 5mm * 50mm as sample.

The RTG-1210 type tensile test apparatus that uses the オリエ of Co., Ltd. of Japan Application テ Star Network to manufacture, under the condition of dividing at the long 50mm of sample, test speed 50mm/, tensile sample, the ductility of the sample while measuring fracture (below, for example, rupture when the sample of 50mm is stretched as 100mm, be designated as " tension failure ductility is 100% ").Tensile modulus of elasticity is calculated by the slope of 0.4～1.0% stress of stretching ductility of film.

(7) square (トラウザ mono-) tearing strength

Polyimide film is cut to 50mm * 150mm, as sample, the RTG-1210 type tensile test apparatus (UR-50N-D type dynamometry (load) sensor that same society manufactures is installed) that uses the オリエ of Co., Ltd. of Japan Application テ Star Network to manufacture, adopt the method for JIS K7128-1 record, measured under test speed 50mm/ divides.

(8) weight average molecular weight (Mw)

Use gel permeation chromatography, dimethyl formamide is measured as developping solution, calculate the weight average molecular weight under polystyrene standard.

(9) infrared absorption spectroscopy

Use the Fourier transform infrared spectroscopy apparatus Spectrum One of the パ of Co., Ltd. of Japan mono-キ Application エ Le マ mono-ジヤパ Application manufacture to be measured.

(embodiment 1)

At nitrogen replacement casing in, add 2 in the glass of capacity 50ml helix tube processed, two (4-(4-amino-benzene oxygen) phenyl) propane (BAPP) 1.22g (3.0mmol) of 2-and METHYLPYRROLIDONE (dehydration) (manufacture of Wako Pure Chemical Industries, Ltd. of Japan) (below, NMP) 14.1g, stir at normal temperatures, make it to dissolve.Add again 2, two (trimellitic acid monoesters) dianhydride (hereinafter referred to as the TAMHQ) 1.42g (3.0mmol) of 5-benzal, with the lid that nitrogen ingress pipe is installed, cover tightly, use magnetic stirrer, under stream of nitrogen gas, stirring at room 1 hour, make it reaction, obtain the solution (varnish) of the TPI precursor of concentration 15 % by weight.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.

The #22 wire rod that uses U.S. R.D.Specialties to manufacture is coated on the varnish of resulting concentration 10 % by weight to be held on the polyimide film (trade name アピカ Le (registration mark) 17FP, the カネカ of Co., Ltd. of Japan manufactures) of insulation on the level and smooth plate of 80 ℃.Place after 10 minutes, in the drying oven of air circulating type, under 120 ℃, drying is 10 minutes, again under nitrogen atmosphere, 150 ℃ of lower heat treated 30 minutes, then 200 ℃ of lower heat treated are 60 minutes, and then 350 ℃ of lower heat treated are 60 minutes, carry out thus imidizate, form thermoplastic polyimide layer.

By this thermoplastic polyimide layer and Copper Foil (trade name U-WZ, the manufacture of the Furukawa サ of Japan mono-キ Star ト Off オイ Le Co., Ltd.) face that surface roughness Ra is 0.11 μ m combines, carry out punching press 30 minutes by vacuum press under vacuum, 325 ℃, 4.4MPa, then carry out punching press 20 minutes under 5.9MPa, obtain thus Copper Foil-resin laminate.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record.

Again, the moisture expantion coefficient of TPI in 10%RH～80%RH that the varnish of working concentration 15 % by weight is made is 15.5ppm/%RH.Again, thermal coefficient of expansion is 64ppm/ ℃.

(embodiment 2)

Except the mixture that uses TAMHQ0.85g (1.8mmol) and TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters) dianhydride (hereinafter referred to as TAHQ) 0.55g (1.2mmol) replaces TAMHQ1.42g as the tetracarboxylic dianhydride, other carry out the operation identical with embodiment 1, obtain Copper Foil-resin laminate and thermoplastic polyimide film.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record.Again, the moisture expantion coefficient of TPI in 10%RH～80%RH that the varnish of working concentration 15 % by weight is made is 12.5ppm/%RH.Again, thermal coefficient of expansion is 60ppm/ ℃.

(embodiment 3)

Except using TAMHQ0.71g (1.5mmol) and 3,3 ', 4, the mixture of 4 '-biphenyl tetracarboxylic dianhydride (manufacture of Mitsubishi chemical Co., Ltd of Japan) (following BPDA) 0.44g (1.5mmol) replaces TAMHQ1.42g as outside the tetracarboxylic dianhydride, other carry out the operation identical with embodiment 1, obtain Copper Foil-resin laminate.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record.

(comparative example 1)

Nitrogen ingress pipe is installed being equipped with on covered by polytetrafluoroethylene (PTFE) heavy stone used as an anchor type agitator, 3 mouthfuls of flasks of glass capacity 1000ml separated type processed, is used nitrogen replacement inside.Add BAPP16.2g (40mmol) and NMP199.0g at this flask, stir at normal temperatures and make it to dissolve.Add again TAHQ18.3g (40mmol), after at room temperature stirring 1 hour, be warming up to 80 ℃, then stir 3 hours, make it reaction, obtain the varnish of concentration 15 % by weight.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.

The #22 wire rod that uses U.S. R.D.Specialties to manufacture is coated on the varnish of resulting concentration 10 % by weight to be held on the polyimide film (trade name アピカ Le (registration mark) 17FP, the カネカ of Co., Ltd. of Japan manufactures) of insulation on the level and smooth plate of 80 ℃.Place after 10 minutes, in the drying oven of air circulating type, under 120 ℃, drying is 10 minutes, again under nitrogen atmosphere, 150 ℃ of lower heat treated 30 minutes, then 200 ℃ of lower heat treated are 60 minutes, and then 350 ℃ of lower heat treated are 60 minutes, carry out thus imidizate, form thermoplastic polyimide layer.Thermoplastic polyimide layer is gonorrhoea.

(comparative example 2)

Except using BPDA0.88g (3.0mmol) to replace TAMHQ1.42g as the tetracarboxylic dianhydride, other carry out the operation identical with embodiment 1, obtain Copper Foil-resin laminate.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record.Again, the moisture expantion coefficient of TPI in 10%RH～80%RH that the varnish of working concentration 15 % by weight is made is 19.9ppm/%RH.

(comparative example 3)

Except using 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (hereinafter referred to as BTDA) 0.97g (3.0mmol) replaces TAMHQ1.42g as outside the tetracarboxylic dianhydride, and other carry out the operation identical with embodiment 1, obtain Copper Foil-resin laminate.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record.

The result of embodiment 1～3 and comparative example 1～3 is illustrated in table 1.In embodiment 1～3, any one peel strength all surpasses 0.6N/mm before and after heat-proof aging.And the peel strength after heat-proof aging drops to 0.56N/mm in comparative example 1.Again, in comparative example 2,3, peel strength before and after the heat-proof aging all lower than 0.6N/mm.

Table 1

(embodiment 4)

At nitrogen replacement casing in, add BAPP1.23g (3.00mmol) and NMP15.4g in the glass of capacity 50ml helix tube processed, stir at normal temperatures, make it to dissolve.Slowly add again two (trimellitic acid monoesters) dianhydride (hereinafter referred to as the TABP) 0.64g (1.2mmol) of 4,4 '-bis-phenylenes, cover tightly with the lid that nitrogen ingress pipe is installed, use magnetic stirrer, under stream of nitrogen gas, stirring at room 1 hour, make it reaction.Add again TAMHQ0.85g (1.8mmol), under stream of nitrogen gas, stirring at room 1 hour, make it reaction, obtain thus the solution (varnish) of the TPI precursor of concentration 15 % by weight.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.

The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 8.2 * 10 ⁴.

By this thermoplastic polyimide layer and thickness 9 μ m Copper Foil (trade name NA-DFF, the manufacture of Mitsu Mining & Smelting Co., Ltd of Japan) face that surface roughness Rz is 0.60 μ m combines, carry out punching press 30 minutes by vacuum press under vacuum, 325 ℃, 4.4MPa, then carry out punching press 20 minutes under 5.9MPa, obtain thus Copper Foil-resin laminate.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record, its measurement result is 1.38N/mm.

The moisture expantion coefficient of TPI in 30%RH～70%RH that the varnish of working concentration 15 % by weight is made is 8.6ppm/%RH.

(embodiment 5)

At nitrogen replacement casing in, add BAPP1.23g (3.00mmo1) and NMP15.6g in the glass of capacity 50ml helix tube processed, stir at normal temperatures, make it to dissolve.Slowly add again TABP0.96g (1.8mmol), cover tightly with the lid that nitrogen ingress pipe is installed, use magnetic stirrer, under stream of nitrogen gas, stirring at room 1 hour, make it reaction.Add again TAMHQ0.57g (1.2mmol), under stream of nitrogen gas, stirring at room 1 hour, make it reaction, obtain thus the solution (varnish) of the TPI precursor of concentration 15 % by weight.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.

By this thermoplastic polyimide layer and thickness 9 μ m Copper Foil (trade name NA-DFF, the manufacture of Mitsu Mining & Smelting Co., Ltd of Japan) face that surface roughness Rz is 0.60 μ m combines, carry out punching press 30 minutes by vacuum press under vacuum, 325 ℃, 4.4MPa, then carry out punching press 20 minutes under 5.9MPa, obtain thus Copper Foil-resin laminate.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record, its measurement result is 1.00N/mm.

(comparative example 4)

At nitrogen replacement casing in, add BAPP1.23g (3.00mmol) and NMP16.1g in the glass of capacity 50ml helix tube processed, stir at normal temperatures, make it to dissolve.Slowly add again TABP1.60g (3.00mmol), cover tightly with the lid that nitrogen ingress pipe is installed, use magnetic stirrer, under stream of nitrogen gas, stirring at room 1 hour, make it reaction.Obtain thus the solution (varnish) of the TPI precursor of concentration 15 % by weight.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.

By this thermoplastic polyimide layer and thickness 9 μ m Copper Foil (trade name NA-DFF, the manufacture of Mitsu Mining & Smelting Co., Ltd of Japan) face that surface roughness Rz is 0.60 μ m combines, carry out punching press 30 minutes by vacuum press under vacuum, 325 ℃, 4.4MPa, then carry out punching press 20 minutes under 5.9MPa, obtain thus Copper Foil-resin laminate.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record, its measurement result is 0.27N/mm.

Table 2

(embodiment 6)

Except the use amount by BAPP changes to 1.29g (3.14mmol), other carry out the operation identical with embodiment 1.

The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 5.6 * 10 ⁴.

The peel strength of Copper Foil-resin laminate that the varnish of working concentration 10 % by weight is made is 1.14N/mm.

(embodiment 7)

Except the use amount by BAPP changes to 1.26g (3.07mmol), other carry out the operation identical with embodiment 1.

The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 6.9 * 10 ⁴.

The peel strength of Copper Foil-resin laminate that the varnish of working concentration 10 % by weight is made is 1.18N/mm.

(embodiment 8)

Except the use amount by BAPP changes to 1.22g (2.97mmol), other carry out the operation identical with embodiment 1.

The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 8.1 * 10 ⁴.

The peel strength of Copper Foil-resin laminate that the varnish of working concentration 10 % by weight is made is 1.29N/mm.

Table 3

	B/A (mol ratio)	Mw/10 ⁴	Peel strength/Nmm-1
				Embodiment 6	1.05	5.6	1.14
Embodiment 7	1.02	6.9	1.18
				Embodiment 4	1.00	8.2	1.38
Embodiment 8	0.99	8.1	1.29

(embodiment 9)

The varnish of concentration 10 % by weight that use obtains in embodiment 4, (east レデユ Port Application Co., Ltd. of Japan manufactures to use カプト Application (registration mark) 80EN, thickness 20 μ m, as constituent, contain from 3,3 ', 4, the repetitive of 4 '-biphenyl tetracarboxylic dianhydride, square (De ラウザ mono-) tearing strength: 60N/m, elastic modelling quantity: 5.6GPa (goods catalogue record value), maximum ductility: 81%, moisture expantion coefficient: 16.0ppm/%RH), according to said method, make Copper Foil-resin laminate.The peel strength of Copper Foil-resin laminate is 1.36N/mm.

(embodiment 10)

At nitrogen replacement casing in, add BAPP0.96g (2.3mmol) and NMP14.8g in the glass of capacity 50ml helix tube processed, stir at normal temperatures, make it to dissolve.Slowly add again TABP0.64g (1.2mmol), cover tightly with the lid that nitrogen ingress pipe is installed, use magnetic stirrer, under stream of nitrogen gas, stirring at room 1 hour, make it reaction.Add again TAMHQ0.85g (1.8mmol) and 1, two (3-amino-benzene oxygen) benzene of 3-(below, be called APB) 0.17g (0.58mmol), under stream of nitrogen gas, stirring at room 1 hour, make it reaction, obtain thus the solution (varnish) of the TPI precursor of concentration 15 % by weight.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.

The #22 wire rod that uses U.S. R.D.Specialties to manufacture is coated on the varnish of resulting concentration 10 % by weight to be held on the polyimide film (trade name アピカ Le (registration mark) 17FP, the カネカ of Co., Ltd. of Japan manufactures) of insulation on the level and smooth plate of 80 ℃.Place after 10 minutes, in the drying oven of air circulating type, under 120 ℃ dry 10 minutes.According to same order, also carry out coating and the drying of varnish on the face to the opposition side of polyimide film.Again under nitrogen atmosphere, 150 ℃ of lower heat treated 30 minutes, then 200 ℃ of lower heat treated are 60 minutes, and then 350 ℃ of lower heat treated are 60 minutes, carry out thus imidizate, on the two sides of polyimides, form thermoplastic polyimide layer.

Clamp above-mentioned polyimide film with two Copper Foils, make this thermoplastic polyimide layer and thickness 9 μ m Copper Foil (trade name NA-DFF, the manufacture of Mitsu Mining & Smelting Co., Ltd of Japan) surface roughness Ra is that the face that 0.11 μ m and Rz are 0.60 μ m combines, by vacuum press in vacuum, 200 ℃, without adding to depress, carry out punching press 30 minutes, then under 325 ℃, 5.9MPa, carry out punching press 20 minutes, must arrive Copper Foil-resin laminate that two sides has Copper Foil thus.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record, its measurement result is 1.19N/mm.

The moisture expantion coefficient of thermoplastic polyimide film in 30%RH～70%RH that the varnish of working concentration 15 % by weight is made is 12.0ppm/%RH.

(embodiment 11)

At nitrogen replacement casing in, add BAPP0.72g (1.7mmol) and NMP14.8g in the glass of capacity 50ml helix tube processed, stir at normal temperatures, make it to dissolve.Slowly add again TABP0.64g (1.2mmol), cover tightly with the lid that nitrogen ingress pipe is installed, use magnetic stirrer, under stream of nitrogen gas, stirring at room 1 hour, make it reaction.Add again TAMHQ0.85g (1.8mmol) and APB0.34g (1.2mmol), under stream of nitrogen gas, stirring at room 1 hour, make it reaction, obtain thus the solution (varnish) of the TPI precursor of concentration 15 % by weight.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.

The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 6.6 * 10 ⁴.

Carry out operation similarly to Example 10, make Copper Foil-resin laminate.Peel strength is 1.28N/mm.

Again, the moisture expantion coefficient of thermoplastic polyimide film in 30%RH～70%RH that the varnish of working concentration 15 % by weight is made is 12.0ppm/%RH.

(embodiment 12)

At nitrogen replacement casing in, add BAPP0.81g (2.0mmol) and NMP14.8g in the glass of capacity 50ml helix tube processed, stir at normal temperatures, make it to dissolve.Slowly add again TABP0.64g (1.2mmol), cover tightly with the lid that nitrogen ingress pipe is installed, use magnetic stirrer, under stream of nitrogen gas, stirring at room 1 hour, make it reaction.Add again TAMHQ0.85g (1.8mmol) and 4,4 '-bis-(3-amino-benzene oxygen) biphenyl (below, be called m-BAPB) 0.31g (0.85mmol), under stream of nitrogen gas, stirring at room 1 hour, make it reaction, obtain thus the solution (varnish) of the TPI precursor of concentration 15 % by weight.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.

The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 6.2 * 10 ⁴.

Carry out operation similarly to Example 10, make Copper Foil-resin laminate.Peel strength is 1.12N/mm.

(embodiment 13)

At nitrogen replacement casing in, add BAPP0.81g (2.0mmol) and NMP14.8g in the glass of capacity 50ml helix tube processed, stir at normal temperatures, make it to dissolve.Slowly add again TABP0.64g (1.2mmol), cover tightly with the lid that nitrogen ingress pipe is installed, use magnetic stirrer, under stream of nitrogen gas, stirring at room 1 hour, make it reaction.Add again TAMHQ0.85g (1.8mmol), m-BAPB0.21g (0.56mmol), APB0.082g (0.28mmol), under stream of nitrogen gas, stirring at room 1 hour, make it reaction, obtain thus the solution (varnish) of the TPI precursor of concentration 15 % by weight.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.

Carry out operation similarly to Example 10, make Copper Foil-resin laminate.Peel strength is 1.32N/mm.

Table 4

(embodiment 14)

Nitrogen ingress pipe is installed being equipped with on covered by polytetrafluoroethylene (PTFE) heavy stone used as an anchor type agitator, 3 mouthfuls of flasks of glass capacity 1000ml separated type processed, is used nitrogen replacement inside.Add BAPP20.9g (50.8mmol) and NMP250mL at this flask, stir under stream of nitrogen gas, under normal temperature and make it to dissolve.Add again TAHQ14.2g (30.9mmol) and TAMHQ9.72g (20.6mmol), under stream of nitrogen gas, stirred in water bath 1 hour, then stir 3 hours under 80 ℃, make it reaction, obtain the solution (varnish) of concentration 15 % by weight TPI precursors.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 8.5 * 10 ⁴.

By this thermoplastic polyimide layer and thickness 9 μ m Copper Foil (trade name U-WZ, the manufacture of the Furukawa サ of Japan mono-キ Star ト Off オイ Le Co., Ltd.) surface roughness Ra is that the face that 0.11 μ m and Rz are 0.60 μ m combines, carry out punching press 30 minutes by vacuum press under vacuum, 325 ℃, 4.4MPa, then carry out punching press 20 minutes under 5.9MPa, obtain thus Copper Foil-resin laminate.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record, its measurement result is 1.48N/mm.

By this thermoplastic polyimide layer and thickness 9 μ m Copper Foil (trade name NA-DFF, the manufacture of Mitsu Mining & Smelting Co., Ltd of Japan) surface roughness Ra is that the face that 0.11 μ m and Rz are 0.60 μ m combines, carry out punching press 30 minutes by vacuum press under vacuum, 325 ℃, 4.4MPa, then carry out punching press 20 minutes under 5.9MPa, obtain thus Copper Foil-resin laminate.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record, its measurement result is 1.49N/mm.

The moisture expantion coefficient of TPI in 30%RH～70%RH that the varnish of working concentration 15 % by weight is made is 9.1ppm/%RH.Glass transition temperature is 200 ℃, and thermal coefficient of expansion is 54ppm/ ℃, and 1% weight reduces temperature (T _d1%) be 421 ℃, 5% weight reduces temperature (T _d5%) be 462 ℃.Tensile modulus of elasticity 3.3GPa, tension failure ductility is 126%.

(embodiment 15)

Nitrogen ingress pipe is installed being equipped with on covered by polytetrafluoroethylene (PTFE) heavy stone used as an anchor type agitator, 3 mouthfuls of flasks of glass capacity 1000ml separated type processed, is used nitrogen replacement inside.Add BAPP20.7g (50.3mmol) and NMP250ml at this flask, under stream of nitrogen gas, stir at normal temperatures and make it to dissolve.Add again TAMHQ24.1g (51.0mmol), under stream of nitrogen gas, stirred in water bath 1 hour, then stir 3 hours under 80 ℃, make it reaction, obtain the solution (varnish) of concentration 15 % by weight TPI precursors.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 10.1 * 10 ⁴.

Make similarly to Example 14 Copper Foil-resin laminate.Measuring the result of peel strength, when Copper Foil is used U-WZ, is 1.01N/mm, while using NA-DFF, is 0.98N/mm.

The glass transition temperature of the TPI that the varnish of working concentration 15 % by weight is made is 204 ℃, and 1% weight reduces temperature (T _d1%) be 432 ℃, 5% weight reduces temperature (T _d5%) be 468 ℃.Tensile modulus of elasticity 2.6GPa, tension failure ductility is 131%.

(comparative example 5)

Nitrogen ingress pipe is installed being equipped with on covered by polytetrafluoroethylene (PTFE) heavy stone used as an anchor type agitator, 3 mouthfuls of flasks of glass capacity 1000ml separated type processed, is used nitrogen replacement inside.Add BAPP25.9g (63.1mmol) and NMP250ml at this flask, under stream of nitrogen gas, stir at normal temperatures and make it to dissolve.Add again BPDA17.8g (60.5mmol), under stream of nitrogen gas, stirred in water bath 1 hour, then stir 3 hours under 80 ℃, make it reaction, obtain the solution (varnish) of concentration 15 % by weight TPI precursors.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 8.4 * 10 ⁴.

Make similarly to Example 14 Copper Foil-resin laminate.Measuring the result of peel strength, when Copper Foil is used U-WZ, is 0.52N/mm, while using NA-DFF, is 0.53N/mm.

Table 5

(embodiment 16)

Nitrogen ingress pipe is installed being equipped with on covered by polytetrafluoroethylene (PTFE) heavy stone used as an anchor type agitator, 3 mouthfuls of flasks of glass capacity 1000ml separated type processed, is used nitrogen replacement inside.Add BAPP12.7g (31.0mmol), APB6.04g (20.7mmol) and NMP250ml at this flask, under stream of nitrogen gas, stir at normal temperatures and make it to dissolve.Add again TABP11.2g (20.9mmol), under stream of nitrogen gas, at room temperature stir 1 hour, then stir 1 hour under 80 ℃, make it reaction.After being cooled to room temperature, add TAMHQ14.8g (31.4mmol), at room temperature stir 1 hour, then stir 2 hours under 80 ℃, make it reaction, obtain the solution (varnish) of concentration 15 % by weight TPI precursors.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 5.3 * 10 ⁴.

The #22 wire rod that uses U.S. R.D.Specialties to manufacture is coated on the varnish of resulting concentration 10 % by weight to be held on the polyimide film (trade name アピカ Le (registration mark) 9FP, the カネカ of Co., Ltd. of Japan manufactures) of insulation on the level and smooth plate of 80 ℃.Place after 10 minutes, in the drying oven of air circulating type, under 120 ℃ dry 10 minutes, according to same order, also carry out coating and the drying of varnish on the face to the opposition side of polyimide film.Again under nitrogen atmosphere, 150 ℃ of lower heat treated 30 minutes, then 200 ℃ of lower heat treated are 60 minutes, and then 350 ℃ of lower heat treated are 60 minutes, carry out thus imidizate, on the two sides of polyimides, form thermoplastic polyimide layer.

Clamp above-mentioned polyimide film with two Copper Foils, make this thermoplastic polyimide layer and thickness 9 μ m Copper Foil (trade name NA-DFF, the manufacture of Mitsu Mining & Smelting Co., Ltd of Japan) surface roughness Ra is that the face that 0.11 μ m and Rz are 0.60 μ m combines, by vacuum press in vacuum, 200 ℃, without adding to depress, carry out punching press 30 minutes, then under 325 ℃, 5.9MPa, carry out punching press 20 minutes, must arrive Copper Foil-resin laminate that two sides has Copper Foil thus.Measure the peel strength of resulting Copper Foil-resin laminate by the method for above-mentioned record, its measurement result is 1.23N/mm.

The moisture expantion coefficient of thermoplastic polyimide film in 30%RH～70%RH that the varnish of working concentration 15 % by weight is made is 11.8ppm/%RH.Glass transition temperature is 192 ℃, and thermal coefficient of expansion is 61ppm/ ℃, and 1% weight reduces temperature (T _d1%) be 413 ℃, 5% weight reduces temperature (T _d5%) be 455 ℃.Tensile modulus of elasticity 3.1GPa, tension failure ductility is 108%.

(embodiment 17)

When the varnish of concentration 15 % by weight dilution 150% is obtained to the varnish of concentration 10 % by weight, use gamma-butyrolacton (γ-BL) to replace NMP as solvent, in addition, carry out the operation the same with embodiment 16.The peel strength of the Copper Foil-resin laminate obtained is 1.31N/mm.

(comparative example 6)

Nitrogen ingress pipe is installed being equipped with on covered by polytetrafluoroethylene (PTFE) heavy stone used as an anchor type agitator, 3 mouthfuls of flasks of glass capacity 1000ml separated type processed, is used nitrogen replacement inside.Add APB20.8g (71.1mmol) and NMP240ml at this flask, under stream of nitrogen gas, stir at normal temperatures and make it to dissolve.Add again TAHQ33.0g (71.9mmol), stirred in water bath 1 hour, then stir 3 hours under 80 ℃ under stream of nitrogen gas, make it reaction, obtain the solution (varnish) of concentration 15 % by weight TPI precursors.With NMP, this varnish is diluted to 150% again, obtain the varnish of concentration 10 % by weight.The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 21.7 * 10 ⁴.

Copper Foil (trade name U-WZ by this thermoplastic polyimide layer and thickness 9 μ m, the manufacture of the Furukawa サ of Japan mono-キ Star ト Off オイ Le Co., Ltd.) surface roughness Ra is that the face that 0.11 μ m and Rz are 0.60 μ m combines, carry out punching press 30 minutes by vacuum press under vacuum, 325 ℃, 4.4MPa, then carry out punching press 20 minutes under 5.9MPa, obtain thus Copper Foil-resin laminate.The caking property at the Copper Foil in resulting Copper Foil-resin laminate/TPI interface is very low, can not make the sample that peel strength is measured use.

Utilizability on industry

The present invention can be applied to the distribution base material of electronic equipment, especially can be applied to flexible printing patch panel.

Claims

1. a layered product, it contains metal forming and thermoplastic polyimide layer, it is characterized in that, the arithmetic average roughness Ra on the surface of described metal forming below 0.20 μ m and/or 10 mean roughness Rz below 0.70 μ m, and described thermoplastic polyimide layer contains and is selected from

The tetracarboxylic dianhydride's who (i) comes self-drifting (1) to mean repetitive A,

The tetracarboxylic dianhydride's who (ii) comes self-drifting (2) to mean repetitive B,

The tetracarboxylic dianhydride's who (iii) comes self-drifting (3) to mean repetitive C,

At least two or more, the moisture expantion coefficient of described thermoplastic polyimide layer below 16ppm/%RH,

[changing 1]

[changing 2]

[changing 3]

2. layered product as claimed in claim 1, described repetitive A is the tetracarboxylic dianhydride's that means from following general formula (4) repetitive,

[changing 4]

3. layered product as claimed in claim 2, is characterized in that, described general formula (4) is two (trimellitic acid monoesters) dianhydrides of 4,4 '-bis-phenylenes that formula (5) means.

[changing 5]

4. layered product as claimed in claim 1, described repetitive B is the tetracarboxylic dianhydride's that means from following general formula (6) repetitive,

[changing 6]

5. layered product as claimed in claim 4, is characterized in that, described general formula (6) is 2 of formula (7) expression, two (trimellitic acid monoesters) dianhydrides of 5-benzal.

[changing 7]

6. layered product as claimed in claim 1, the tetracarboxylic dianhydride's that described repetitive A comes self-drifting (4) to mean repetitive, and the described repetitive B tetracarboxylic dianhydride's that comes self-drifting (6) to mean repetitive.

7. layered product as claimed in claim 1, is characterized in that, the repetitive of the diamines that described thermoplastic polyimide layer contains to come self-drifting (8) to mean,

[changing 8]

H ₂N-X-NH ₂ (8)

[changing 9]

8. layered product as claimed in claim 7, is characterized in that, the diamines that the contained described general formula (8) of described thermoplastic polyimide layer means is the diamines that formula (10) means.

[changing 10]

9. layered product as claimed in claim 8, is characterized in that, the repetitive of the diamines that also contains to come self-drifting (11) to mean in the thermoplastic polyimide layer of claim 8 record.

[changing 11]

10. layered product as claimed in claim 9, is characterized in that, the diamines that described general formula (11) means is 1 of formula (12) expression, two (3-amino-benzene oxygen) benzene of 3-.

[changing 12]

11. layered product as claimed in claim 1, is characterized in that, also possesses resin bed on described thermoplastic polyimide layer.

12. layered product as claimed in claim 11, is characterized in that, the moisture expantion coefficient of described resin bed is below 16ppm/%RH.

13. layered product as claimed in claim 12, is characterized in that, described resin bed is polyimide film.

14. layered product as claimed in claim 13, is characterized in that, described polyimide film contains from PMDA and/or 3,3 ', 4, and the repetitive of 4 '-biphenyl tetracarboxylic dianhydride is as constituent.

15. layered product as claimed in claim 1, is characterized in that, described metal forming is Copper Foil.

16. a flexible printing patch panel, the layered product that any one in claim 1～claim 15 is put down in writing carries out distribution processing and forms.

A 17. layered product, it contains metal forming and thermoplastic polyimide layer, it is characterized in that, the arithmetic average roughness Ra on the surface of described metal forming below 0.20 μ m and/or 10 mean roughness Rz below 0.70 μ m, the tetracarboxylic dianhydride's that described thermoplastic polyimide layer at least contains to come self-drifting (2) to mean repetitive B, and the moisture expantion coefficient is below 16ppm/%RH.

18. layered product as claimed in claim 17, is characterized in that, the tetracarboxylic dianhydride's that described repetitive B comes self-drifting (6) to mean repetitive.

19. layered product as claimed in claim 18, is characterized in that, described general formula (6) is 2 of formula (7) expression, two (trimellitic acid monoesters) dianhydrides of 5-benzal.