CN101652244A - metal-resin laminate - Google Patents

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 expansioncoefficient, 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 arithmeticaverage 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 on the one side at least of polyimide film.Such layered product is owing to using tack coat, so about the character institute of the bonded layer of the characteristic of this layered product between polyimide film and metal forming.Again, the characteristic of tack coat also influences 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 hear resistance, resistance to chemical reagents, moisture-proof, dimensional stability, mechanical properties etc.

Therefore, studying use and having the TPI of high-fire resistance, resistance to chemical reagents, mechanical properties, electrical characteristics as tack coat.; TPI is because the caking property of shortage and metal; so in order to obtain practical caking property; adopt following gimmick: use the arithmetic surface roughness Ra to surpass the such metal forming of 0.70 μ m with big surface roughness above 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 microspurization of the distribution of flexible printing patch panel is in development.Under the big such situation of surface roughness as 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, transmit the frequency gets higher of signal, therefore near the phenomenon (skin effect) of density deflection surface of conductors that flows through the electric current of conductor becomes significantly, and the surface of conductors roughness brings bad influence for the transmission of signal.

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

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 height of the moisture expantion coefficient ratio polyimide film of general TPI.

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

Again, the metal forming of surface roughness below certain value also is being studied (for example, patent documentation 3) with the laminate that with specific diamines is the thermoplastic polyimide layer of raw material.The thermoplastic polyimide layer that has high-adhesion for SUS (stainless steel) is disclosed in patent documentation 3., generally all know caking property between Copper Foil-polyimides than the caking property between stainless steel-polyimides obviously bad (non-patent literature 1), the high layered product of caking property with copper appears in expectation.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 high possibility of moisture expantion coefficient is arranged.Because above-mentioned situation, so expect a kind ofly to have high-adhesion and have the TPI of low moisture expantion coefficient for metal forming with little surface roughness.

Patent documentation 1: the Japan Patent spy opens the 2004-82495 communique

Patent documentation 2: the international brochure that discloses No. 2003/006553

Patent documentation 3: the Japan Patent spy opens the 2006-142834 communique

Non-patent literature 1: wide Tian Xing controls and waits work " the imperial と そ Evaluation value of property system is followed in the adherence of Tu worker System film To お け Ru " 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, abbreviate layered product as), 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, found that with tetracarboxylic dianhydride with ad hoc structure be raw material, the TPI of having controlled the degree of orientation of molecule can take into account low moisture expantion coefficient and with the good caking property of metal forming with little surface roughness, thereby finished the present invention.

Just, 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 a 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 the 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, described thermoplastic polyimide layer contain be selected from (i) come the tetracarboxylic dianhydride's of self-drifting (1) expression repetitive A, (ii) come the tetracarboxylic dianhydride's of self-drifting (2) expression repetitive B, (iii) come the tetracarboxylic dianhydride's of self-drifting (3) expression repetitive C two or more at least

[changing 1]

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

[changing 2]

In the formula (2), R ₂The alkyl of expression 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 the formula (4), R ₃, R ₄Represent the alkyl of hydrogen, carbon number 1～6 or the alkoxyl of carbon number 1～6 respectively independently.

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

[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 the formula (6), R ₅The alkyl of expression 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, described repetitive A comes the tetracarboxylic dianhydride's of self-drifting (4) expression repetitive, and described repetitive B comes the tetracarboxylic dianhydride's of self-drifting (6) expression repetitive.

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

[changing 8]

H ₂N-X-NH ₂????????(8)

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

[changing 9]

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

[changing 10]

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

[changing 11]

In layered product of the present invention, it is desirable to, the diamines of described general formula (11) expression 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, on above-mentioned thermoplastic polyimide layer, also possess resin bed.

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 a 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 a Copper Foil.

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

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 the 0.20 μ m and/or 10 mean roughness Rz below 0.70 μ m, described thermoplastic polyimide layer contains to come the tetracarboxylic dianhydride's of self-drifting (2) expression repetitive B at least, and the moisture expantion coefficient is below 16ppm/%RH.

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

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.

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

Description of drawings

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 metal forming with particular surface roughness and the thermoplastic polyimide layer that contains the particular chemical structure that is arranged on the above-mentioned metal forming.

＜metal forming 〉

The used metal forming of layered product of the present invention 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 is meant that the arithmetic average roughness (Ra) on the surface (single face) of above-mentioned metal forming is below the 0.20 μ m and/or 10 mean roughness (Rz) are below the 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.The scope of better Ra is below the 0.15 μ m, again from the close-burning viewpoint of TPI, Ra it is desirable to more than the 0.01 μ m, better is more than the 0.03 μ m.Again, the scope of better Rz is below the 0.60 μ m, from the close-burning viewpoint of TPI, Rz it is desirable to more than the 0.20 μ m, better is more than the 0.30 μ m, it is desirable to especially more than the 0.40 μ m.Here, Ra and Rz are the values of measuring with JIS B0601:1994 defined method.

There is no particular limitation to the kind of the used metal forming of layered product of the present invention, gets final product so long as have the metal forming of above-mentioned Ra and/or Rz, 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 the Copper Foil of electrolytic copper foil, rolled copper foil, band carrier copper foil etc.Example as the Copper Foil that is fit to use, trade name U-WZ is arranged for example, and (the Furukawa サ of Japan one キ Star ト Off オ イ Le Co., Ltd. makes, Ra=0.11 μ m, Rz=0.60 μ m), (Mitsu Mining ﹠ Smelting Co., Ltd of Japan makes trade name NA-DFF, Ra=0.11 μ m, Rz=0.60 μ m), trade name HLS (Nippon Denkai, Ltd. of Japan makes, Rz=0.60 μ m), trade name HLP (Nippon Mining and Metals Co., Ltd of Japan makes, Rz=0.70 μ m) etc.

Viewpoints such as the easness that the thickness of metal forming is handled when making, the resistance to bend(ing) when using product or folding Qu Xing it is desirable to 0.5～50 μ m, and that better is 1～35 μ m, further it is desirable to 5～20 μ m.

For improving purposes such as caking property or rustless property, can be in surface treatments such as 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 use the low metal forming of surface roughness,, can improve the visuognosis degree so can improve the transparency of the flexible wiring sheet that uses layered product making of the present invention.Therefore, locate easily when carrying semiconductor wafer, be fit to the purposes of High Density Packaging material.

＜thermoplastic polyimide layer 〉

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

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

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

[changing 13]

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

[changing 14]

(in the formula (2), R ₂Be C 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 n=2～4 expression, better is 2～3 expressions, further it is desirable to the tetracarboxylic dianhydride from following general formula (4) expression.

[changing 16]

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

R in the 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 hear resistance of TPI and the viewpoint of the moisture-proof coefficient of expansion, better is hydrogen or methyl.

In above-mentioned general formula (1), it is desirable to especially, repetitive A is from two (trimellitic acid monoesters) dianhydrides of 4,4 '-two phenylenes of following formula (5) expression.

[changing 17]

R in the 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, better is methyl.Again, the tetracarboxylic dianhydride of general formula (2) expression, 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 of repetitive B from following formula (6) expression.It is desirable to especially, repetitive B is from 2 of following (7) expression, two (trimellitic acid monoesters) dianhydrides of 5-benzal.

[changing 18]

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

[changing 19]

The tetracarboxylic dianhydride of above-mentioned general formula (3) expression, 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 caking property of metal forming or the viewpoint of moisture expantion coefficient, this TPI contains repetitive B and repetitive C is more suitable.This moment repetitive C content from the viewpoint of physical properties balance such as the caking property of metal forming or glass transition temperature, with repetitive B100mol% is benchmark, it is desirable to more than the 10mol%, below the 1000mol%, better is more than the 25mol%, below the 500mol%, it is desirable to especially more than the 50mol%, below the 200mol%.

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

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

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

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 makes the reduction of moisture expantion coefficient., have the polyimides of above-mentioned repetitive A or C separately because there are following problem in the upright and outspoken degree of its structure and the height of orientation: do not manifest thermoplasticity, even perhaps 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 uses usually., by importing the high structure of such bendability, 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 more than 2 kinds for reaching above-mentioned problem.Present embodiment contains the tetracarboxylic dianhydride of 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 among this tetracarboxylic dianhydride, moderately control the orientation of TPI molecule, realize high caking property with 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 the 16ppm/%RH, it is desirable to below 14ppm/%RH, and better is below 13ppm/%RH, further it is desirable to below 12ppm/%RH, it is desirable to below 10ppm/%RH especially.The moisture expantion coefficient can be controlled by the content of above-mentioned each repetitive or to the selection of diamines.

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

The content that repeats unit B is not limited especially, but from considering with the viewpoint of rerum natura balances such as the caking property of metal forming or glass transition temperature, the repetitive 100mol% from tetracarboxylic dianhydride contained with TPI is benchmark, the content of repetitive B it is desirable to more than the 1mol%, below the 99mol%, better is more than the 10mol%, below the 95mol%, further it is desirable to it is desirable to especially more than the 50mol%, below the 80mol% more than the 30mol%, below the 90mol%.

As mentioned above, the tetracarboxylic dianhydride's of containing upright and outspoken (gathering) phenylene two ester groups the TPI existence and the low problem of caking property of other materials have been used separately.Present embodiment is kept the low moisture expantion coefficient that upright and outspoken phenylene diester base band is come by one side, 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 to be possible.

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

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

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

As tetracarboxylic dianhydride in addition, can use known.Particularly, the compound that can have the acid dianhydride that contains the structure that following tetrabasic carboxylic acid cyclodehydration forms and all or part of hydrogen atom in these compounds to be replaced for example 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-1,4-phenylene ester, 3,3 ', 4,4 '-diphenyl sulfone tetrabasic carboxylic acid, 2,3,6, the 7-naphthalene tetracarboxylic acid, 1,2,4, the 5-naphthalene tetracarboxylic acid, 1,4,5, the 8-naphthalene tetracarboxylic acid, 1,2,5, the 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, 1, two (3, the 4-di carboxyl phenyloxy) benzene of 3-, 1,4-two (3, the 4-di carboxyl phenyloxy) benzene, 4,4 '-two (3, the 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, the 6-tetrabasic carboxylic acid, 1-methyl-3-ethyl cyclohexane-3-(1,2), 5, the 6-tetrabasic carboxylic acid, 1-methyl-3-ethyl hexamethylene-1-alkene-3-(1,2), 5, the 6-tetrabasic carboxylic acid, 1-ethyl cyclohexane-1-(1,2), 3, the 4-tetrabasic carboxylic acid, 1-propyl cyclohexane-1-(2,3), 3, the 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, consider, it is desirable to 3 from the viewpoint of thermal coefficient of expansion, glass transition temperature, hear resistance etc., 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 separately also and can and use.

There is no particular limitation for the content from above-mentioned tetracarboxylic dianhydride's repetitive, but from considering with the such viewpoint of caking property, glass transition temperature, the moisture expantion coefficient of metal forming, the all repetitive 100mol% from tetracarboxylic dianhydride contained with TPI is benchmark, content from above-mentioned tetracarboxylic dianhydride's repetitive it is desirable to below 90mol%, better is below 80mol%, further it is desirable to below 50mol%, it is desirable to below 20mol% especially.

With above-mentioned tetracarboxylic dianhydride and diamines is the TPI that raw material can obtain the present invention relates to, and there is no particular limitation to diamines, can use known.For example can have 1 for example, the 4-phenylenediamine, 1, the 3-phenylenediamine, 2, the 4-diaminotoluene, the xyxylene diamines, the diaminonaphthalene class, the diaminoanthraquinone-class, 2, two (4-aminophenyl) propane of 2-, 2-(3-aminophenyl)-2-(4-aminophenyl) propane, 2, two (3-aminophenyl) propane of 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, 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-, 1, two (3-aminobenzoyl) benzene of 3-, 1, two (4-aminobenzoyl) benzene of 3-, 1, two (3-aminobenzoyl) benzene of 4-, 1, two (3-aminobenzoyl) benzene of 4-, α, α '-two (4-aminophenyl)-1, the 4-diisopropyl benzene, α, α '-two (4-aminophenyl)-1, the 3-diisopropyl benzene, 4,4 '-two (4-amino-benzene oxygen) benzophenone, 4,4 '-two (3-amino-benzene oxygen) benzophenone, 4,4 '-two (4-amino-benzene oxygen) diphenyl sulfone, 4,4 '-two (3-amino-benzene oxygen) diphenyl sulfone, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, 2, 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-, 4,4 '-two (4-amino-benzene oxygen) diphenyl ether, 4,4 '-two (3-amino-benzene oxygen) diphenyl ether, 1, two (4-(3-amino-benzene oxygen) benzoyl) benzene of 3-, 4,4 '-two (4-(4-amino-benzene oxygen) benzoyl) diphenyl ether, 9, two (4-aminophenyl) fluorenes of 9-, trans and cis-1, the 4-DACH, trans and cis-1, the 3-DACH, trans and cis-1, the 2-DACH, 3-methyl-trans and cis-1, the 4-DACH, 3-methyl-3-amino methyl-5, the 5-dimethyl cyclohexyl amine, 1, the two amino methyl cyclohexanes of 3-, two (4,4 '-aminocyclohexyl) methane, two (3,3 '-methyl-4,4 '-aminocyclohexyl) methane, two (amino methyl) norbornane, two (amino methyl)-three 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.Again, the diamines after the group that also can use the part of the contained hydrogen atom of above-mentioned two amines to be selected from methyl, ethyl and halogen replaces.These diamines can use a kind of respectively or suitably make up more than 2 kinds and use.

Wherein, from with the caking property of metal forming, the viewpoint of the low moisture expantion coefficient of TPI is seen, it is desirable to 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (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 '-two (4-aminophenyl)-1, the 4-diisopropyl benzene, α, α '-two (4-aminophenyl)-1,3-diisopropyl benzene, 2, two (4-aminophenyl) propane of 2-, 2, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-, 4,4 '-two (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, from with the viewpoint of the thermal coefficient of expansion of the caking property of 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-, two (3-amino-benzene oxygen) benzene, 1 of 4-, at least a diamines and 2 of two (4-amino-benzene oxygen) benzene of 4-, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-are also used also effective.

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

Again, the end of TPI can be the structure after ending with terminal sealing agent envelope such as dicarboxylic anhydride or monoamine.There is no particular limitation to terminal sealing agent, can use known.

Be used for terminal envelope dicarboxylic acid anhydride only for example phthalic anhydride can be arranged for example, 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-phenylacetylene base phthalic anhydride, 3-phenylacetylene base phthalic anhydride, phenylacetylene base naphthalene dicarboxylic acids acid anhydride, phenylacetylene base biphenyltetracarboxyacid acid acid anhydride, phenylacetylene base diphenyl ether dicarboxylic anhydride, phenylacetylene base benzophenone dicarboxylic anhydride, phenylacetylene base diphenyl sulfone dicarboxylic anhydride, phenylacetylene base anthracene dicarboxylic anhydride or on these aromatic rings, have substituent compound.These dicarboxylic anhydrides can use separately, also can merge use more than 2 kinds.

Being used for terminal envelope monoamine only for example has 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 use separately, also can merge use more than 2 kinds.

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

Scolding tin is used in being connected of distribution in the flexible printing patch panel and device usually.So the fusing point that the vitrifying transition temperature of the TPI that the present invention relates to it is desirable at SnPb63 is that further, in order to use more dystectic Pb-free solder, better is that glass transition temperature is more than 200 ℃ more than 183 ℃.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.

Make above-mentioned tetracarboxylic dianhydride and diamines at least a equimolar amounts in fact be dissolved in the organic solvent, make it reaction and obtain polyamic acid, this polyamic acid as precursor, is carried out imidization reaction again, and the TPI that obtains the present invention relates to.

As the solvent that is used 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, N, N-dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, cresols, dimethyl sulfoxide (DMSO), gamma-butyrolacton etc.From the viewpoints such as easness of security, processing, specially suitable is N, N-dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolacton.Benzene, the dimethylbenzene, 1,3 that can in these solvents, mix arbitrary proportion, 5-trimethylbenzene, hexane, chlorobenzene, oxolane, 1,4-diox, acetonitrile, phenylcyanide equal solvent.

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

What the degree of polymerization of resulting polyamic acid was suitable is 2～600.In addition, this degree of polymerization can be calculated according to the weight average molecular weight that GPC measures.The same can the control of situation of the adjustment of the degree of polymerization and common polycondensation based polymer 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 use 0.9～1.1mol diamines for 1mol acid composition.

Known general macromolecule quantize to the mechanical strength that improves polyimides effectively the key element that descends of the caking property of (" Japanese Port リ イ ミ De research association compile up-to-date Port リ イ ミ De～basic Foundation と ying with～" (the エ ヌ テ イ one エ ス of Co., Ltd. of Japan) p.106) and polyimides be the low-molecular-weight thing that has near interface (" inferior generation エ レ Network ト ロ ニ Network ス Electricity material To can be paid skill Intraoperative to the high Machine of the new い of け Port リ イ ミ De development と " (skill Intraoperative feelings Reported Association meeting) p.20).In the present invention, there is no particular limitation to the weight average molecular weight (Mw) of resulting polyamic acid, but viewpoint from the moisture expantion coefficient of easy coating, TPI, when this TPI does not contain repetitive A, suitable is 1000～300000, more suitably is 50000～200000.When containing repetitive A, suitable is 10000～200000, more suitably is 50000～100000.

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

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

There is no particular limitation for the method for carrying out imidization reaction in solution, can use known method.Particularly, can use by heating makes it carry out the method for imidization reaction or following method, the catalyst of representatives such as the chemical converting agent (dehydrating agent) by adding representatives such as anhydrous acetic acid, trifluoroacetic acid, polyphosphoric acid, five phosphorous oxide, phosphorus pentachloride, thionyl chloride, 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 carry out imidization reaction in the coating of polyamic acid solution, after dry.This is narrated in the laminated body manufacturing method 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 poly-different acid imide.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 usefulness～" (the エ ヌ テ イ one エ ス of Co., Ltd. of Japan).

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

The resin bed that possesses on＜the thermoplastic polyimide layer 〉

In the present invention, from viewpoints such as the thermal coefficient of expansion of layered product, hear 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 that joins with this thermoplastic polyimide layer.There is no particular limitation to this resin bed, can use knownly, it is desirable to polyimide film, and better is non-thermoplastic polyimide film.Here, " non-thermal plasticity " is meant is not having glass transition temperature below 400 ℃, even glass transition temperature is perhaps arranged, thereby elastic modelling quantity can descend significantly not plastic (not melt-flow) not occur owing to being heated to yet more than the glass transition temperature.

Polyimide film is to be the film that raw material obtains with tetracarboxylic dianhydride and diamines, it is formed there is no particular limitation, can use known.ユ one ピ レ Star Network ス (registration mark) S that the example of commercially available suitable polyimide film has Ube Industries, Ltd of Japan to make for example, ユ one ピ レ Star Network ス (registration mark) SGA, ユ one 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 makes, 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 makes, 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 all are non-thermal plasticities.

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

The ideal thickness of the resin bed that the present invention relates to be 2 μ m above, below the 125 μ m.The viewpoint of the easness of handling from the rigidity of layered product, film, better is more than the 5 μ m.Again, from the filming of printing distributing board, the viewpoint of bending easness, better is below the 75 μ m, further it is desirable to it is desirable to especially below the 17 μ m below the 25 μ m.

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

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

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

The plasma discharge processing method adopts 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, can at random select, but utilize the plasma discharge treatment of light emitting discharge, it is desirable to discharge and be output as 20～2000Wmin/m for the plasma discharge treatment condition ², pressure is below the 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 reactant gases such as mist more than 2 kinds.

The polishing milled processed can be used known device, to polishing roll, polishing press, 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.

＜laminated body manufacturing method 〉

Laminated body manufacturing method of the present invention is described.

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

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 the method for solution coat on resin bed with TPI or its precursor, 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 one タ one), contrary roll coater, engraved roll coater, scraper plate coating machine (リ Star プ コ one タ one), hat type coating machine (キ ヤ Star プ コ one タ one), scraping strip coating machine, extrusion coating machine (ス Network イ ズ コ one タ one), slope stream coating machine, the heavy curtain coating machine carries out.

Behind the solution of coating thermoplastic polyimides or its precursor, make it dry.To drying means or condition without limits, for example, use hot blast or infrared ray, it is desirable to more than the boiling point of solvent (usually 100 ℃～400 ℃ scopes) heating 10 seconds～10 hours.

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

When making the single-sided flexible printing distributing board, at the single face formation thermoplastic polyimide layer of resin bed.When making the double-faced flexible printing distributing board, at the two-sided formation thermoplastic polyimide layer of resin bed.At this moment, composition, the thickness that is formed at the thermoplastic polyimide layer on two sides can be the same or different.

Thermoplastic polyimide layer by making the resin laminate that is obtained by said method and the Ra of metal forming be below the 0.20 μ m and/or the face of Rz below 0.70 μ m contacts, crimping, and it is integrated to carry out lamination, 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, better is bilayer zone pressure application, roll-in force method.There is no particular limitation to the condition of pressure, it is desirable under the temperature that TPI fully flows, and 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, press between zone face and it is desirable to 1～10MPa, that better is 2～6MPa.In the roll-in force method, pressure it is desirable to 1～500N/mm between the hot-rolling line, and that better is 10～300N/mm.In order to prevent the hot deterioration of metal forming or resin, thermo-compressed also can be carried out in atmosphere of inert gases such as nitrogen or argon gas.

In addition, also can according to above-mentioned opposite lamination order, promptly according to following order: on metal forming, form thermoplastic polyimide layer, thermoplastic polyimide layer is contacted with resin bed, carry out crimping, lamination is integrated, makes the layered product that the present invention relates to.At this moment, 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 that 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 the above-mentioned layered product that obtains is carried out distribution processing.Distribution processing can be undertaken by following at least operation.

On the metal forming of layered product, form resist layer with dry film photoresist or resist China ink etc.Then develop, resist layer is carved into the pattern of desired shape.With soups such as copper chloride or iron chloride the Copper Foil that exposes by development is partly dissolved, removes resist layer.

Again, when making the two sides flexible printing patch panel,, carry out following operation again,, again the side in hole is electroplated, make the two sides conducting by offering the hole of the conducting between the metal forming that is used to carry out the two sides except above-mentioned operation.

Usually, in flexible printing patch panel, for following viewpoint: make adding under the shock environment reducing of fault when the substrate that is assembled with parts after distribution forms handled or reducing of fault when under the crooked environment of high-frequency, handling 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, better is 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.

By removing thermoplastic polyimide layer and resin bed, can measure the Ra and the Rz on the surface of metal forming from layered product or the flexible printing patch panel that the present invention relates to.The method of removing thermoplastic polyimide layer and resin bed from layered product can be used and peel off, dissolving, etching, oxidation Decomposition, thermal decomposition and their combination.Especially polyimides can use the etching of aqueous slkali, so when resin bed is polyimide film, by layered product is carried out alkaline etching, the surface of metal forming is exposed.Also have according to the difference of the kind of resin bed and can not use etched situation, but measure 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, perhaps (c) destroys in the aggegation of the inside of thermoplastic polyimide layer.(a) situation can directly be measured the Ra and the Rz of metal forming like this, and (b) or (c) situation can be removed the thermoplastic polyimide layer that remains on the metal forming by etching, and the surface of metal forming is exposed, and can measure Ra and Rz.The value of Ra of Ce Dinging and Rz is got Ra and the roughly the same value of Rz with the raw material metal paper tinsel usually like this.

(embodiment)

Below, by embodiment the present invention is carried out specific description, but these examples are not done any qualification to the present invention.In addition, the evaluation of physical property in following examples is following carries out.

(1) peel strength

Copper Foil-resin laminate is cut into long 140mm, wide 10mm, the vinyl tape of wide 1mm is bonded in length direction on the copper-clad surface, carry out mask.When also there is copper foil layer in the back side, mask is carried out at the whole back side with being coated with the vinyl chloride insulating tape.Be immersed in ferrous chloride aqueous solution (manufacturing of Tsurumi Soda Co., Ltd. of Japan), copper foil layer is carried out etch processes, remove and be coated with after the vinyl chloride insulating tape, wash, form the copper foil pattern of wide 1mm.Under 105 ℃, with resulting samples dried 1 hour, then, be bonded in glass epoxy substrate with the same size of layered product with two-sided tape with air drier.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 with A (peeling off method for the 90 °) regulation of JIS C6471 8.1, peeling rate is set at 50mm/min.For same composition, measure 2 test films, with 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 carries out making test film with (1) after the heat treated 7 days the samely, measures peel strength.

(3) moisture expantion coefficient

On the metal coating cloth deck of 90 ℃ of insulations, leave standstill the Copper Foil (trade name USLP-SE, Nippon Denkai, Ltd. of Japan) of thickness 12 μ m, make tarnish (マ Star ト) face side be the surface.Be coated on the Copper Foil frosted face with the solution (varnish varnish) of scraper the TPI precursor of concentration 15 weight %.Afterwards, on coating cloth deck, left standstill 10 minutes 120 ℃ of following heat dryings 10 minutes in the drying oven of air circulating type again, the TPI precursor film (the about 45 μ m of thickness) of (the タ Star Network) property that obtains not having crease thus.Then, in hot-air drier, under the nitrogen atmosphere, 5 ℃/min of programming rate, 150 ℃ were heated 30 minutes, and 200 ℃ were heated 60 minutes, and 350 ℃ were heated 60 minutes, carried out imidizate, obtained the thermoplastic polyimide film with Copper Foil.By being immersed in ferrous chloride aqueous solution (manufacturing of Tsurumi Soda Co., Ltd. of Japan) with copper foil membrane, Copper Foil is removed in etching, obtains (formation thermoplastic polyimide layer) thermoplastic polyimide film of the about 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, (10～30%RH) change to high humidity environment, and (change in size of the thermoplastic polyimide film of wide 3mm, long 30mm (length 15mm between chuck) 70～80%RH) time is calculated the moisture expantion coefficient to mensuration from low-humidity environment.

(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 the load 5g, measure the change in size of the above-mentioned thermoplastic polyimide film of wide 3mm, length 19mm (length 15mm between chuck), the thermal coefficient of expansion and the glass transition temperature of calculating 100 ℃～200 ℃ scope.

(5) heat decomposition temperature

The thermogravimetry device (TGA-50) that uses Shimadzu Scisakusho Ltd of Japan to make, under stream of nitrogen gas, 10 ℃/minute of programming rates are determined at the weight change of above-mentioned thermoplastic polyimide film when heating up in 30～700 ℃ of scopes.

(6) tensile modulus of elasticity and tension failure ductility

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

Again, when sample is commercially available polyimide film, with 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 make, under the condition that the long 50mm of sample, test speed 50mm/ divide, tensile sample, the ductility of the sample when measuring fracture (below, rupture when for example the sample of 50mm is stretched as 100mm, then 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 one) tearing strength

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

(8) weight average molecular weight (Mw)

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

(9) infrared absorption spectroscopy

Use the Fourier transform infrared spectroscopy apparatus Spectrum One of the パ one キ Application エ Le マ of Co., Ltd. of Japan one ジ ヤ パ Application manufacturing to measure.

(embodiment 1)

At nitrogen replacement casing in, in the glass system helix tube of capacity 50ml, add 2, two (4-(4-amino-benzene oxygen) phenyl) propane (BAPP) 1.22g (3.0mmol) of 2-and N-N-methyl-2-2-pyrrolidone N-(dehydration) (manufacturing of Wako Pure Chemical Industries, Ltd. of Japan) (below, NMP) 14.1g, stir at normal temperatures, make it dissolving.Add 2 again, two (trimellitic acid monoesters) dianhydride (hereinafter referred to as the TAMHQ) 1.42g (3.0mmol) of 5-benzal, cover completely 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 the solution (varnish) of the TPI precursor of concentration 15 weight %.With NMP this varnish is diluted 150% again, obtain the varnish of concentration 10 weight %.

Using #22 wire rod that U.S. R.D.Specialties makes that the varnish of resulting concentration 10 weight % is coated on remains on the polyimide film (trade name ア ピ カ Le (registration mark) 17FP, the カ ネ カ of Co., Ltd. of Japan makes) of insulation on 80 ℃ level and smooth plate.Place after 10 minutes, in the drying oven of air circulating type, drying is 10 minutes under 120 ℃, again under nitrogen atmosphere, 150 ℃ of following heat treated 30 minutes, then 200 ℃ of following heat treated are 60 minutes, and then 350 ℃ of following heat treated are 60 minutes, carry out imidizate thus, form thermoplastic polyimide layer.

With this thermoplastic polyimide layer and Copper Foil (trade name U-WZ, the manufacturing of the Furukawa サ of Japan one キ Star ト Off オ イ Le Co., Ltd.) surface roughness Ra is that the face of 0.11 μ m combines, under vacuum, 325 ℃, 4.4MPa, carried out punching press 30 minutes with vacuum press, then under 5.9MPa, carry out punching press 20 minutes, obtain Copper Foil-resin laminate thus.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 of the varnish of working concentration 15 weight % making 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 (trimellitic acid monoesters) dianhydride (hereinafter referred to as TAHQ) 0.55g (1.2mmol) replaces TAMHQ1.42g as the tetracarboxylic dianhydride, other carry out 1 identical operations with embodiment, 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 of the varnish of working concentration 15 weight % making 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 (manufacturing of Mitsubishi chemical Co., Ltd of Japan) (following BPDA) 0.44g (1.5mmol) replaces TAMHQ1.42g as outside the tetracarboxylic dianhydride, other carry out 1 identical operations with embodiment, 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 the 3 mouthfuls of flasks of glass system separated type heavy stone used as an anchor type agitator, capacity 1000ml that covered by polytetrafluoroethylene (PTFE), is used nitrogen replacement inside.Add BAPP16.2g (40mmol) and NMP199.0g at this flask, stir at normal temperatures and make it dissolving.Add TAHQ18.3g (40mmol) again, after at room temperature stirring 1 hour, be warming up to 80 ℃, stirred again 3 hours, make it reaction, obtain the varnish of concentration 15 weight %.With NMP this varnish is diluted 150% again, obtain the varnish of concentration 10 weight %.

Using #22 wire rod that U.S. R.D.Specialties makes that the varnish of resulting concentration 10 weight % is coated on remains on the polyimide film (trade name ア ピ カ Le (registration mark) 17FP, the カ ネ カ of Co., Ltd. of Japan makes) of insulation on 80 ℃ level and smooth plate.Place after 10 minutes, in the drying oven of air circulating type, drying is 10 minutes under 120 ℃, again under nitrogen atmosphere, 150 ℃ of following heat treated 30 minutes, then 200 ℃ of following heat treated are 60 minutes, and then 350 ℃ of following heat treated are 60 minutes, carry out imidizate thus, form thermoplastic polyimide layer.Thermoplastic polyimide layer is a gonorrhoea.

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

(comparative example 2)

Except using BPDA0.88g (3.0mmol) to replace TAMHQ1.42g as the tetracarboxylic dianhydride, other carry out 1 identical operations with embodiment, 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 of the varnish of working concentration 15 weight % making 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 1 identical operations with embodiment, 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 the 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 behind the heat-proof aging drops to 0.56N/mm in comparative example 1.Again, in the comparative example 2,3, peel strength all is lower than 0.6N/mm before and after heat-proof aging.

Table 1

(embodiment 4)

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

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

Using #22 wire rod that U.S. R.D.Specialties makes that the varnish of resulting concentration 10 weight % is coated on remains on the polyimide film (trade name ア ピ カ Le (registration mark) 17FP, the カ ネ カ of Co., Ltd. of Japan makes) of insulation on 80 ℃ level and smooth plate.Place after 10 minutes, in the drying oven of air circulating type, drying is 10 minutes under 120 ℃, again under nitrogen atmosphere, 150 ℃ of following heat treated 30 minutes, then 200 ℃ of following heat treated are 60 minutes, and then 350 ℃ of following heat treated are 60 minutes, carry out imidizate thus, form thermoplastic polyimide layer.

With this thermoplastic polyimide layer and thickness 9 μ m Copper Foil (trade name NA-DFF, the manufacturing of Mitsu Mining ﹠ Smelting Co., Ltd of Japan) surface roughness Rz is that the face of 0.60 μ m combines, under vacuum, 325 ℃, 4.4MPa, carried out punching press 30 minutes with vacuum press, then under 5.9MPa, carry out punching press 20 minutes, obtain Copper Foil-resin laminate thus.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 weight % is made is 8.6ppm/%RH.

(embodiment 5)

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

Using #22 wire rod that U.S. R.D.Specialties makes that the varnish of resulting concentration 10 weight % is coated on remains on the polyimide film (trade name ア ピ カ Le (registration mark) 17FP, the カ ネ カ of Co., Ltd. of Japan makes) of insulation on 80 ℃ level and smooth plate.Place after 10 minutes, in the drying oven of air circulating type, drying is 10 minutes under 120 ℃, again under nitrogen atmosphere, 150 ℃ of following heat treated 30 minutes, then 200 ℃ of following heat treated are 60 minutes, and then 350 ℃ of following heat treated are 60 minutes, carry out imidizate thus, form thermoplastic polyimide layer.

With this thermoplastic polyimide layer and thickness 9 μ m Copper Foil (trade name NA-DFF, the manufacturing of Mitsu Mining ﹠ Smelting Co., Ltd of Japan) surface roughness Rz is that the face of 0.60 μ m combines, under vacuum, 325 ℃, 4.4MPa, carried out punching press 30 minutes with vacuum press, then under 5.9MPa, carry out punching press 20 minutes, obtain Copper Foil-resin laminate thus.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, in the glass system helix tube of capacity 50ml, add BAPP1.23g (3.00mmol) and NMP16.1g, stir at normal temperatures, make it dissolving.Slowly add TABP1.60g (3.00mmol) again, cover completely, use magnetic stirrer, under stream of nitrogen gas,, make it reaction stirring at room 1 hour with the lid that nitrogen ingress pipe is installed.Obtain the solution (varnish) of the TPI precursor of concentration 15 weight % thus.With NMP this varnish is diluted 150% again, obtain the varnish of concentration 10 weight %.

Using #22 wire rod that U.S. R.D.Specialties makes that the varnish of resulting concentration 10 weight % is coated on remains on the polyimide film (trade name ア ピ カ Le (registration mark) 17FP, the カ ネ カ of Co., Ltd. of Japan makes) of insulation on 80 ℃ level and smooth plate.Place after 10 minutes, in the drying oven of air circulating type, drying is 10 minutes under 120 ℃, again under nitrogen atmosphere, 150 ℃ of following heat treated 30 minutes, then 200 ℃ of following heat treated are 60 minutes, and then 350 ℃ of following heat treated are 60 minutes, carry out imidizate thus, form thermoplastic polyimide layer.

With this thermoplastic polyimide layer and thickness 9 μ m Copper Foil (trade name NA-DFF, the manufacturing of Mitsu Mining ﹠ Smelting Co., Ltd of Japan) surface roughness Rz is that the face of 0.60 μ m combines, under vacuum, 325 ℃, 4.4MPa, carried out punching press 30 minutes with vacuum press, then under 5.9MPa, carry out punching press 20 minutes, obtain Copper Foil-resin laminate thus.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 with BAPP changed to 1.29g (3.14mmol), other carried out 1 identical operations with embodiment.

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 weight % is made is 1.14N/mm.

(embodiment 7)

Except the use amount with BAPP changed to 1.26g (3.07mmol), other carried out 1 identical operations with embodiment.

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 weight % is made is 1.18N/mm.

(embodiment 8)

Except the use amount with BAPP changed to 1.22g (2.97mmol), other carried out 1 identical operations with embodiment.

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 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 the concentration 10 weight % that use obtains in embodiment 4, (east レ デ ユ Port Application Co., Ltd. of Japan makes 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 one) tearing strength: 60N/m, elastic modelling quantity: 5.6GPa (goods catalogue record value), maximum ductility: 81%, moisture expantion coefficient: 16.0ppm/%RH), make Copper Foil-resin laminate according to said method.The peel strength of Copper Foil-resin laminate is 1.36N/mm.

(embodiment 10)

At nitrogen replacement casing in, in the glass system helix tube of capacity 50ml, add BAPP0.96g (2.3mmol) and NMP14.8g, stir at normal temperatures, make it dissolving.Slowly add TABP0.64g (1.2mmol) again, cover completely, use magnetic stirrer, under stream of nitrogen gas,, make it reaction stirring at room 1 hour with the lid that nitrogen ingress pipe is installed.Add TAMHQ0.85g (1.8mmol) and 1 again, 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 the solution (varnish) of the TPI precursor of concentration 15 weight % thus.With NMP this varnish is diluted 150% again, obtain the varnish of concentration 10 weight %.

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

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

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, Mitsu Mining ﹠ Smelting Co., Ltd of Japan makes) surface roughness Ra be that 0.11 μ m and Rz are that the face of 0.60 μ m combines, with vacuum press in vacuum, 200 ℃, do not have to add to depress and carried out punching press 30 minutes, then under 325 ℃, 5.9MPa, carry out punching press 20 minutes, must arrive Copper Foil-resin laminate that the 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 weight % is made is 12.0ppm/%RH.

(embodiment 11)

At nitrogen replacement casing in, in the glass system helix tube of capacity 50ml, add BAPP0.72g (1.7mmol) and NMP14.8g, stir at normal temperatures, make it dissolving.Slowly add TABP0.64g (1.2mmol) again, cover completely, use magnetic stirrer, under stream of nitrogen gas,, make it reaction stirring at room 1 hour with the lid that nitrogen ingress pipe is installed.Add TAMHQ0.85g (1.8mmol) and APB0.34g (1.2mmol) again, under stream of nitrogen gas,, make it reaction, obtain the solution (varnish) of the TPI precursor of concentration 15 weight % thus stirring at room 1 hour.With NMP this varnish is diluted 150% again, obtain the varnish of concentration 10 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 of the varnish of working concentration 15 weight % making is 12.0ppm/%RH.

(embodiment 12)

At nitrogen replacement casing in, in the glass system helix tube of capacity 50ml, add BAPP0.81g (2.0mmol) and NMP14.8g, stir at normal temperatures, make it dissolving.Slowly add TABP0.64g (1.2mmol) again, cover completely, use magnetic stirrer, under stream of nitrogen gas,, make it reaction stirring at room 1 hour with the lid that nitrogen ingress pipe is installed.Add TAMHQ0.85g (1.8mmol) and 4 again, 4 '-two (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 the solution (varnish) of the TPI precursor of concentration 15 weight % thus.With NMP this varnish is diluted 150% again, obtain the varnish of concentration 10 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, in the glass system helix tube of capacity 50ml, add BAPP0.81g (2.0mmol) and NMP14.8g, stir at normal temperatures, make it dissolving.Slowly add TABP0.64g (1.2mmol) again, cover completely, use magnetic stirrer, under stream of nitrogen gas,, make it reaction stirring at room 1 hour with the lid that nitrogen ingress pipe is installed.Add TAMHQ0.85g (1.8mmol), m-BAPB0.21g (0.56mmol), APB0.082g (0.28mmol) again, under stream of nitrogen gas, stirring at room 1 hour, make it reaction, obtain the solution (varnish) of the TPI precursor of concentration 15 weight % thus.With NMP this varnish is diluted 150% again, obtain the varnish of concentration 10 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 1.32N/mm.

Table 4

(embodiment 14)

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

Using #22 wire rod that U.S. R.D.Specialties makes that the varnish of resulting concentration 10 weight % is coated on remains on the polyimide film (trade name ア ピ カ Le (registration mark) 17FP, the カ ネ カ of Co., Ltd. of Japan makes) of insulation on 80 ℃ level and smooth plate.Place after 10 minutes, in the drying oven of air circulating type, drying is 10 minutes under 120 ℃, again under nitrogen atmosphere, 150 ℃ of following heat treated 30 minutes, then 200 ℃ of following heat treated are 60 minutes, and then 350 ℃ of following heat treated are 60 minutes, carry out imidizate thus, form thermoplastic polyimide layer.

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

With this thermoplastic polyimide layer and thickness 9 μ m Copper Foil (trade name NA-DFF, Mitsu Mining ﹠ Smelting Co., Ltd of Japan makes) surface roughness Ra be that 0.11 μ m and Rz are that the face of 0.60 μ m combines, under vacuum, 325 ℃, 4.4MPa, carried out punching press 30 minutes with vacuum press, then under 5.9MPa, carry out punching press 20 minutes, obtain Copper Foil-resin laminate thus.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 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 the 3 mouthfuls of flasks of glass system separated type heavy stone used as an anchor type agitator, capacity 1000ml that covered by polytetrafluoroethylene (PTFE), 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 dissolving.Add TAMHQ24.1g (51.0mmol) again, under stream of nitrogen gas,, stirred 3 hours down at 80 ℃ again, make it reaction, obtain the solution (varnish) of concentration 15 weight % TPI precursors stirred in water bath 1 hour.With NMP this varnish is diluted 150% again, obtain the varnish of concentration 10 weight %.The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 10.1 * 10 ⁴

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

The glass transition temperature of the TPI that the varnish of working concentration 15 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 the 3 mouthfuls of flasks of glass system separated type heavy stone used as an anchor type agitator, capacity 1000ml that covered by polytetrafluoroethylene (PTFE), 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 dissolving.Add BPDA17.8g (60.5mmol) again, under stream of nitrogen gas,, stirred 3 hours down at 80 ℃ again, make it reaction, obtain the solution (varnish) of concentration 15 weight % TPI precursors stirred in water bath 1 hour.With NMP this varnish is diluted 150% again, obtain the varnish of concentration 10 weight %.The weight average molecular weight (Mw) of the TPI precursor that varnish is contained is 8.4 * 10 ⁴

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

Table 5

(embodiment 16)

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

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

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, Mitsu Mining ﹠ Smelting Co., Ltd of Japan makes) surface roughness Ra be that 0.11 μ m and Rz are that the face of 0.60 μ m combines, with vacuum press in vacuum, 200 ℃, do not have to add to depress and carried out punching press 30 minutes, then under 325 ℃, 5.9MPa, carry out punching press 20 minutes, must arrive Copper Foil-resin laminate that the 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 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 weight % dilution 150% was obtained the varnish of concentration 10 weight %, (in addition γ-BL) replace NMP as solvent, carried out the operation the same with embodiment 16 to use gamma-butyrolacton.The peel strength of the Copper Foil-resin laminate that obtains is 1.31N/mm.

(comparative example 6)

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

Using #22 wire rod that U.S. R.D.Specialties makes that the varnish of resulting concentration 10 weight % is coated on remains on the polyimide film (trade name ア ピ カ Le (registration mark) 17FP, the カ ネ カ of Co., Ltd. of Japan makes) of insulation on 80 ℃ level and smooth plate.Place after 10 minutes, in the drying oven of air circulating type, drying is 10 minutes under 120 ℃, again under nitrogen atmosphere, 150 ℃ of following heat treated 30 minutes, then 200 ℃ of following heat treated are 60 minutes, and then 350 ℃ of following heat treated are 60 minutes, carry out imidizate thus, form thermoplastic polyimide layer.

Copper Foil (trade name U-WZ with this thermoplastic polyimide layer and thickness 9 μ m, the Furukawa サ of Japan one キ Star ト Off オ イ Le Co., Ltd. makes) surface roughness Ra be that 0.11 μ m and Rz are that the face of 0.60 μ m combines, under vacuum, 325 ℃, 4.4MPa, carried out punching press 30 minutes with vacuum press, then under 5.9MPa, carry out punching press 20 minutes, obtain Copper Foil-resin laminate thus.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 usefulness.

Utilizability on the 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 (21)

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

2. layered product as claimed in claim 1 is characterized in that, the arithmetic average roughness Ra on the surface of described metal forming below the 0.20 μ m and/or 10 mean roughness Rz below 0.70 μ m.

3. as claim 1 or the described layered product of claim 2, it is characterized in that described thermoplastic polyimide layer contains and is selected from

(i) come the tetracarboxylic dianhydride of self-drifting (1) expression repetitive A,

(ii) come the tetracarboxylic dianhydride of self-drifting (2) expression repetitive B,

(iii) come the tetracarboxylic dianhydride of self-drifting (3) expression repetitive C,

Two or more at least,

[changing 1]

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

[changing 2]

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

[changing 3]

4. layered product as claimed in claim 3, described repetitive A are the repetitives from the tetracarboxylic dianhydride of following general formula (4) expression,

[changing 4]

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

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

[changing 5]

6. layered product as claimed in claim 3, described repetitive B are the repetitives from the tetracarboxylic dianhydride of following general formula (6) expression,

[changing 6]

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

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

[changing 7]

8. layered product as claimed in claim 3, described repetitive A come the tetracarboxylic dianhydride's of self-drifting (4) expression repetitive, and described repetitive B comes the tetracarboxylic dianhydride's of self-drifting (6) expression repetitive.

9. layered product as claimed in claim 3 is characterized in that, described thermoplastic polyimide layer contains to come the repetitive of the diamines of self-drifting (8) expression,

[changing 8]

H ₂N-X-NH ₂????????????????????????(8)

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

[changing 9]

10. layered product as claimed in claim 9 is characterized in that, the diamines of described general formula (8) expression that described thermoplastic polyimide layer is contained is the diamines of formula (10) expression.

[changing 10]

11. layered product as claimed in claim 10 is characterized in that, also contains to come the repetitive of the diamines of self-drifting (11) expression in the thermoplastic polyimide layer of claim 10 record.

[changing 11]

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

[changing 12]

13. layered product as claimed in claim 3 is characterized in that, also possesses resin bed on described thermoplastic polyimide layer.

14. layered product as claimed in claim 13 is characterized in that, the moisture expantion coefficient of described resin bed is below 16ppm/%RH.

15. layered product as claimed in claim 14 is characterized in that, described resin bed is a polyimide film.

16. layered product as claimed in claim 15 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.

17. layered product as claimed in claim 3 is characterized in that, described metal forming is a Copper Foil.

18. a flexible printing patch panel carries out distribution processing and forms the layered product of each record in claim 1～claim 17.

19. 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 the 0.20 μ m and/or 10 mean roughness Rz below 0.70 μ m, described thermoplastic polyimide layer contains to come the tetracarboxylic dianhydride's of self-drifting (2) expression repetitive B at least, and the moisture expantion coefficient is below 16ppm/%RH.

20. layered product as claimed in claim 19 is characterized in that, described repetitive B comes the tetracarboxylic dianhydride's of self-drifting (6) expression repetitive.

21. layered product as claimed in claim 20 is characterized in that, described general formula (6) is 2 of formula (7) expression, two (trimellitic acid monoesters) dianhydrides of 5-benzal.

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