CN103694701B - Polyamic acid composition, polyimide compositions, circuit substrate and its application method and layered product and its manufacture method - Google Patents

Abstract

The present invention provides the manufacture method of a kind of polyamic acid composition, polyimide compositions, layered product, circuit substrate, its application method, the manufacture method of layered product and circuit substrate.Even if the present invention provides a kind of under the use environment being exposed to repeatedly in high temperature and oil component, the adhesion strength of metal level and resin base material is also difficult to the layered product and circuit substrate declined.Polyamic acid composition is included：Composition (A) weight average molecular weight is 10,000~150, polyamic acid and composition (B) acyclic compound in the range of 000, and contain relative to the parts by weight of (A) composition 100 (B) composition in the range of the parts by weight of 0.1 parts by weight~60.(A) amount of free-radical polymerised unsaturated bond present in every 1g weight of composition is below 3mmol, and the value of [quantity/molecular weight of (methyl) acryloyl group in 1 molecule] of (B) composition is more than 0.001.

Description

Polyamic acid composition, polyimide compositions, circuit substrate and its application method with Layered product and its manufacture method

Technical field

The present invention relates to a kind of polyamic acid composition that can be used for manufacture pliability printing distributing board etc., polyimides group Compound, layered product, circuit substrate, its application method, the manufacture method of the manufacture method of layered product and circuit substrate.

Background technology

In recent years, with e-machine miniaturization, lightweight, space saving progress, thin and light amount, with flexible Even if property and alternating bending also have pliability printing distributing board (the Flexible Printed of excellent durability Circuits, FPC) demand increase.FPC can also be three-dimensional in limited space and installed to high-density, therefore is for example existed Hard disk drive (Hard Disk Drive, HDD), digital versatile disc (Digital Versatile Disc, DVD), hand Constantly expand its purposes in the part such as the distribution or cable of the moving part of the e-machines such as machine, connector.

In the car, also from the viewpoint of lightweight is realized, at a variety of positions, such as engine (engine) week of automobile Side (specifically engine, inlet manifold (intake manifold), alternating current generator (alternator), radiator (radiator) etc.) or in gear-box (gearbox), speed changer (transmission) etc., FPC use increase.

Polyester-imides or polyimides are used in the insulating resin of base material as FPC mostly, as usage amount, is had The usage amount of the polyimides of heat resistance is definitely more.On the other hand, in conductive material, from for the aspect of excellent electric conductivity generally Use copper foil.As FPC materials, such as propose there is following pliability printed wiring substrate in patent document 1：In order to suppress Crispatura the generation of (curl), and the bottom contacted with conductor and with intermediate configurations basis of the conductor for the top layer of opposite side Layer, the basal layer is 30 × 10 comprising linear expansion coefficient^-6The low heat expansion polyimides system resins of (1/ DEG C) below, and Bottom is higher than the TPI system resin of basal layer with top layer comprising thermal expansivity.

In addition, in such as patent document 2, as the change relative to humidity environment, the few layered product of change in size, is carried Go out to have at least 1 layer layered product with low humidity dilatancy polyimides system resins layer of polyimides system resins layer, it is described low The resin bed of humidity expansion polyimides system is to make 4 containing 20 moles of more than %, 4 '-diaminourea -2,2 '-dimethyl diphenyl Diamino compounds reacted and obtained with tetracarboxylic compound, and line humidity expansion coefficient be 20 × 10-6/%RH with Under.

On the metal foil used in FPC, propose to use following metal foil in patent document 3：Wherein, in order to improve polyamides The peel strength of polyimide layer and copper foil in imine metal laminate, the zinc in the face contacted with polyimide layer of copper foil Adhesion amount is 0.07mg/dm²Below.

In addition, propose to have in patent document 4 to surface roughness Rz for the surface of 0.3 μm~1.0 μm of copper foil implement to The metal for less separating out nickel, zinc and cobalt separates out processing and the processing using coupling agent.In the patent document 2, separated out through metal The surface of the copper foil of processing is set to include the μ g/cm of nickel 5²~15 μ g/cm², the μ g/cm of zinc 1²~5 μ g/cm²And the μ g/cm of cobalt 0.1² ~5 μ g/cm²Surface.

[prior art literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 2005-259790 publications

[patent document 2] International Publication WO2001/028767

No. 3664708 publication of [patent document 3] patent

[patent document 4] 2011-No. 66431 publications of Japanese Patent Laid-Open

The content of the invention

Automobile with FPC in addition to being exposed to repeatedly in hot environment, also with oil (for example engine oil, speed changer use Oil etc.) contact chance more than feature.But, FPC is present when being exposed to repeatedly in oil, the adherence of resin base material and wiring layer Decline, the problem of wiring layer is easily peeled off.Therefore, automobile is with copper-clad laminate (the Copper Clad used in FPC Laminate, CCL) etc. in layered product, in addition to characteristic necessary to general electric and electronic, also require in high temperature High adhesion can also be maintained between metal level and resin base material under environment oil attachment environment.

Therefore, even if the purpose of the present invention is a kind of use environment in high temperature and oil component is exposed to repeatedly of offer Under, also it is difficult to the resin raw material that declines with the adhesion strength of metal level.

If as described above, the circuit substrate such as FPC be positioned over repeatedly hot environment and oil attachment environment in, wiring layer with The adhesion strength of resin base material declines.The mechanism that the adhesion strength declines is investigated, results presumption reason is in oil contained Sulphur composition.Specifically, the sulphur compound from oil immerses the interface of such as copper wiring and polyimide base material, therefore copper Reacted with sulphur compound and form fragile copper sulfide layer.Cohesion destruction, therefore copper and polyimides are produced in the fragile layer Adhesion strength between base material declines.Decline (decline of oil resistivity) to the adhesion strength produced due to this mechanism further to grind Study carefully, as a result estimate, the principal degrading factor compound for declining oil resistivity is the reaction with copper in contained sulphur compound in oil Property very high mercaptan compound.Therefore, in the present invention, found to suppress the reaction of mercaptan compound and copper：By The acyclic compound for playing mercaptan compound the function as acceptor is added in polyimides, (block) can be blocked poly- The mercaptan compound moved in acid imide, to improve oil resistivity.In addition, especially being pushed away in the case of using copper foil as metal foil Survey following possibility：If there is cobalt element in copper foil surface by antirust treatment, the reactive high cobalt with sulphur compound Trigger (trigger) as copper sulfide layer formation.It has further been found that being present in the cobalt member of copper foil surface by control The amount of element, can improve the oil resistivity of copper-clad laminate and circuit substrate.

That is, polyamic acid composition of the invention includes following compositions (A) and composition (B)：

(A) polyamic acid of the weight average molecular weight in the range of 10,000~150,000 and

(B) acyclic compound, and

Contain (B) in the range of the parts by weight of 0.1 parts by weight~60 relative to the parts by weight of (A) composition 100 Composition.In the polyamic acid composition of the present invention, free-radical polymerised unsaturation present in every 1g weight of (A) composition The amount of key is below 3mmol, and the value of [quantity/molecular weight of (methyl) acryloyl group in 1 molecule] of (B) composition is More than 0.001.

In the polyamic acid composition of the present invention, (B) composition [quantity of (methyl) acryloyl group in 1 molecule/ Molecular weight] value can be more than 0.003.

The polyimide compositions of the present invention are by being heat-treated to the polyamic acid composition, by described in (A) Composition carries out imidizate and obtained.

The layered product of the present invention is the layered product for including metal level and the insulating barrier being formed on the metal level, and The insulating barrier includes the resin bed of the polyimide compositions.

The layered product of the present invention is preferably that the resin bed of the polyimide compositions is contacted and is laminated with the metal level Form.

The circuit substrate of the present invention is the circuit substrate for including insulating barrier and the wiring layer being formed on the insulating barrier, And the insulating barrier includes the resin bed of the polyimide compositions.

The circuit substrate of the present invention is preferably that the resin bed of the polyimide compositions and the wiring layer are contacted and layer Pressure is formed.

The application method of the circuit substrate of the present invention uses the circuit base in the oil containing organic compounds containing sulfur Plate.

The manufacture method of the layered product of the present invention is to be formed with base material and be formed with the substrate comprising polyimides The manufacture method of the layered product of the insulating barrier of the resin bed of composition, and the manufacture method of the layered product includes：Described The step of resin solution containing the polyamic acid composition being coated with base material and forms coated film；And by being applied to described Cloth film is heat-treated, the step of (A) composition carries out imidizate and forms the resin bed of polyimide compositions by described in.

The present invention circuit substrate manufacture method be include the resin bed comprising polyimide compositions insulating barrier and The manufacture method of the circuit substrate for the wiring layer being formed on the insulating barrier, and the manufacture method bag of the circuit substrate Include：The step of being coated with the resin solution containing the polyamic acid composition on metal foil and form coated film；By to institute Coated film is stated to be heat-treated, will described in (A) composition carry out imidizate and form the step of the resin bed of polyimide compositions Suddenly；And the step of the metallic foil pattern is formed into the wiring layer.

In addition, the layered product of the present invention can be：The metal level be copper foil, and be attached in the copper foil with it is described The amount of cobalt element on the face of insulating barrier contact is 2mg/dm²Below.

In addition, the circuit substrate of the present invention can be：The wiring layer is copper wiring layer, and

The amount for the cobalt element being attached on the face contacted with the insulating barrier in the copper wiring layer is 2mg/dm²With Under.

[The effect of invention]

According to the present invention, it is positioned over repeatedly in hot environment and oil attachment environment even if can be formed, metal level and tree The layered product that the adhesion strength of lipid layer does not also decline.In addition, the reliability of the electronic components such as circuit substrate can be improved by the present invention.

Embodiment

Hereinafter, embodiments of the present invention are described in detail.

[polyamic acid composition]

The polyamic acid composition of present embodiment contains following compositions (A) and composition (B)：

(A) polyamic acid of the weight average molecular weight in the range of 10,000~150,000 and

(B) acyclic compound.

<(A) composition：Polyamic acid>

In present embodiment, the polyamic acid of (A) composition is the predecessor of polyimides.Therefore, to being used as predecessor Polyimides after polyamic acid and imidizate carries out conclusion explanation.

In present embodiment, polyimides can for example be enumerated：Comprising aromatic polyimide, aliphatic polyimide, gather There is acid imide in the structures such as amide imide, polybenzimidazoles, polyester-imides, PEI, polysiloxane acid imide The heat-resistant resin of the polymer of base.

In the case where for example being applied as the base material of circuit substrate, polyimides can be suitably poly- using low heat expansion Acid imide.Specifically coefficient of linear thermal expansion (Coefficient OfThermal Expansion, CTE) be 1 × 10-6~ In the range of 30 × 10-6 (1/K), be preferably 1 × 10-6~25 × 10-6 (1/K) in the range of, more preferably 15 × 10-6~ Low heat expansion polyimides in the range of 25 × 10-6 (1/K).If the base material of this polyimides as circuit substrate is come Using, then it can suppress the warpage as circuit substrate, therefore favorably.But, more than the polyimides of the coefficient of linear thermal expansion It can also use, in this case can improve the adhesion with metal level.

The low heat expansion polyimides is preferably the polyimides with the construction unit represented by formula (1).It is logical In formula (1), 4 valency aromatic series bases represented by Ar1 expressions (2) or formula (3), Ar2 expressions (4) or formula (5) are represented Divalent aromatic series base, R1 independently represents the 1 valency alkyl or alkoxy of carbon number 1~6, X and Y independently represent singly-bound or Divalent base in divalent alkyl, O, S, CO, SO, SO2 or CONH selected from carbon number 1~15, n1 independently represents 0~4 integer, Q represents the presence mol ratio of Component units, the value for being 0.1~1.0.

The construction unit may be present in homopolymer, can also exist as the construction unit of copolymer.With In the case of the copolymer of multiple construction units, can exist as block copolymer, can also be deposited as random copolymer .In polyimides with this construction unit, the polyimides that can suitably utilize is non-thermal plasticity polyimides.

Polyimides is typically to make diamines with anhydride reaction to manufacture, therefore is managed by being illustrated to diamines and acid anhydrides The imido concrete example of depolymerization.In the formula (1), Ar₂The residue of diamines, Ar can be referred to₁The residue of acid anhydrides can be referred to, Therefore preferred polyimides is illustrated by diamines and acid anhydrides.But, non-thermal plasticity polyimides is not limited to By diamines and acid anhydrides described herein are come winner.

Acid anhydrides is preferably to illustrate：Pyromellitic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl Sulfone tetracarboxylic dianhydride, 4, the double phthalic anhydrides of 4 '-oxygen.In addition, acid anhydrides is also preferably to illustrate：2,2 ', 3,3 '-, 2,3,3 ', 4 '-or 3,3 ', 4,4 '-diphenylketone tetracarboxylic dianhydride, 2,3 ', 3,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl four Carboxylic acid dianhydride, 2,3 ', 3,4 '-diphenyl ether tetracarboxylic dianhydride, double (2,3- dicarboxyphenyi) ether dianhydrides etc..And then, acid anhydrides Preferably illustrate：3,3 ", 4,4 "-, 2,3,3 ", 4 "-or 2,2 ", 3,3 "-para-terpheny tetracarboxylic dianhydride, 2,2- double (2,3- Or 3,4- dicarboxyphenyi)-propane dianhydride, double (2,3- or 3.4- dicarboxyphenyis) methane dianhydrides, it is double (2,3- or 3, 4- dicarboxyphenyis) sulfone dianhydride, double (2,3- or 3,4- dicarboxyphenyi) the ethane dianhydrides of 1,1- etc..

Other acid anhydrides can for example be enumerated：1,2,7,8-, 1,2,6,7- or 1,2,9,10- phenanthrene-tetracarboxylic dianhydride, 2,3, 6,7- anthracene tetracarboxylic dianhydrides, 2,2- double (3,4- dicarboxyphenyi) tetrafluoropropane dianhydride, 2,3,5,6- hexamethylene dianhydrides, 2,3,6, 7- naphthalene tetracarboxylic acids dianhydride, 1,2,5,6- naphthalene tetracarboxylic acid dianhydrides, Isosorbide-5-Nitrae, 5,8- naphthalene tetracarboxylic acid dianhydrides, 4,8- dimethyl -1,2,3,5, 6,7- hexahydro naphthalenes -1,2,5,6- tetracarboxylic dianhydrides, 2,6- or 2,7- dichloronaphtalene-Isosorbide-5-Nitrae, 5,8- tetracarboxylic dianhydrides, 2,3,6,7- (or Isosorbide-5-Nitrae, 5,8-) Tetrachloronaphthalene-Isosorbide-5-Nitrae, 5,8- (or 2,3,6,7-) tetracarboxylic dianhydrides, 2,3,8,9-, 3,4,9,10-, 4,5, 10,11- or 5,6,11,12- perylenes-tetracarboxylic dianhydride, pentamethylene -1,2,3,4- tetracarboxylic dianhydrides, pyrazine -2,3,5,6- tetracarboxylic acids Acid dianhydride, pyrrolidines -2,3,4,5- tetracarboxylic dianhydrides, thiophene -2,3,4,5- tetracarboxylic dianhydrides, 4,4 '-bis- (2,3- dicarboxyl benzene Epoxide) diphenyl methane dianhydride etc..

Diamines is preferably to illustrate：4,4 '-diamino-diphenyl ether, 2 '-methoxyl group -4,4 '-diaminobenzene formailide, 1, Double (4- amino-benzene oxygens) benzene of 4-, 1,3- double (4- amino-benzene oxygens) benzene, 2,2 '-bis- [4- (4- amino-benzene oxygens) phenyl] third Alkane, 2,2 '-dimethyl -4,4 '-benzidine, 3,3 '-dihydroxy -4,4 '-benzidine, 4,4 '-diaminobenzene formyl Aniline etc..In addition, diamines is preferably to illustrate：2,2- double-[4- (3- amino-benzene oxygens) phenyl] propane, double [4- (4- aminobenzene oxygen Base) phenyl] sulfone, double [4- (3- amino-benzene oxygens) phenyl] sulfones, double [4- (4- amino-benzene oxygens)] biphenyl, double [4- (3- aminobenzenes Epoxide) biphenyl, double [1- (4- amino-benzene oxygens)] biphenyl, double [1- (3- amino-benzene oxygens)] biphenyl, double [4- (4- aminobenzene oxygen Base) phenyl] methane, double [4- (3- amino-benzene oxygens) phenyl] methane, double [4- (4- amino-benzene oxygens) phenyl] ethers, double [4- (3- amino-benzene oxygens) phenyl] ether, double [4- (4- amino-benzene oxygens)] diphenylketones, double [4- (3- amino-benzene oxygens)] diphenyl Ketone, double [4,4 '-(4- amino-benzene oxygens)] benzanilides, double [4,4 '-(3- amino-benzene oxygens)] benzanilides, 9,9- are double Double [4- (3- amino-benzene oxygens) phenyl] fluorenes of [4- (4- amino-benzene oxygens) phenyl] fluorenes, 9,9- etc..

Other diamines can for example be enumerated：2,2- pairs-[4- (4- amino-benzene oxygens) phenyl] HFC-236fas, 2,2- pairs-[4- (3- amino-benzene oxygens) phenyl] HFC-236fa, 4,4 '-methylene, two-ortho-aminotoluene, 4,4 '-methylene two -2,6- dimethyl benzenes Amine, 4,4 '-methylene -2,6- diethylaniline, 4,4 '-diamino-diphenyl propane, 3,3 '-diamino-diphenyl propane, 4, 4 '-diamino-diphenyl ethane, 3,3 '-diamino-diphenyl ethane, 4,4 '-diaminodiphenyl-methane, 3,3 '-diaminourea two Phenylmethane, 4,4 '-diamino diphenyl sulfide, 3,3 '-diamino diphenyl sulfide, 4,4 '-diamino diphenyl sulfone, 3, 3 '-diamino diphenyl sulfone, 4,4 '-diamino-diphenyl ether, 3,3- diamino-diphenyls ether, 3,4 '-diamino-diphenyl ether, Benzidine, 3,3 '-benzidine, 3,3 '-dimethyl -4,4 '-benzidine, 3,3 '-dimethoxy benzidine, 4,4 " - Diaminourea-para-terpheny, 3,3 "-diaminourea-para-terpheny, m-phenylenediamine, P- pHENYLENE dI AMINE, 2,6- diaminourea pyrroles Pyridine, Isosorbide-5-Nitrae-bis- (4- amino-benzene oxygens) benzene, double (4- amino-benzene oxygens) benzene of 1,3-, 4,4 '-[double (the 1- methyl Asias of Isosorbide-5-Nitrae-phenylene Ethyl)] it is dianil, 4,4 '-[1,3- phenylene double (1- methyl ethylidene)] dianils, bis(p-aminocyclohexyl)methane, double (to beta-amino-tert-butyl-phenyl) ether, double (to Beta-methyl-δ-Aminopentyl) benzene, to double (2- methyl -4- Aminopentyls) benzene, It is double (beta-amino-tert-butyl group) to double (1,1- dimethyl -5- Aminopentyls) benzene, 1,5-diaminonaphthalene, 2,6- diaminonaphthalenes, 2,4- Toluene, 2,4- diaminotoluenes, meta-xylene -2,5- diamines, paraxylene -2,5- diamines, m-xylene diamine, terephthaldehyde Amine, DAP, 2,5- diamino-pyridines, 2,5- diaminostilbenes, 3,4- oxadiazoles, piperazine etc..

Acid anhydrides and diamines can be used only its a kind respectively, or can also be two kinds or more to use.In addition, also may be used It is used together with other acid anhydrides or diamines for not included the formula (1) with described acid anhydrides or diamines, the situation Under, the acid anhydrides or the use ratio of diamines that the formula (1) is not included preferably are set to 90 moles of below %, preferably 50 rubbed You are below %.It is respective in the case of by selecting the species of acid anhydrides or diamines or using acid anhydrides of more than two kinds or diamines Mol ratio, can control thermal expansivity, adherence, glass transition temperature (Tg) etc..

Polyimides can also use TPI.TPI can be for example as circuit substrate Adhesion coating between wiring layer and insulating barrier is suitably utilized in the case of applying.Used in the predecessor of TPI Polyamic acid be preferably the polyamic acid with the construction unit represented by formula (6).In formula (6), Ar₃Expression (7), 2 valency aromatic series bases represented by formula (8) or formula (9), Ar₄4 valency aromatic series represented by expression (10) or formula (11) Base, R₂Independently represent the 1 valency alkyl or alkoxy of carbon number 1~6, V and W independently represent singly-bound or selected from carbon number 1~ 15 divalent alkyl, O, S, CO, SO₂Or the divalent base in CONH, m₁Independently represent 0~4 integer, p represents Component units There is mol ratio, the value for being 0.1~1.0.

In the formula (6), Ar3 can refer to the residue of diamines, and Ar4 can refer to the residue of acid anhydrides, therefore pass through two Amine and acid anhydrides are illustrated to preferred TPI.But, TPI is not limited to thus locate What illustrated diamines and acid anhydrides was obtained.

Being suitable for being formed the diamines of TPI can for example enumerate：4,4 '-diamino-diphenyl ether, 2 '-first Epoxide -4,4 '-diaminobenzene formailide, Isosorbide-5-Nitrae-bis- (4- amino-benzene oxygens) benzene, 1,3- double (4- amino-benzene oxygens) benzene, 2,2- Double [4- (4- amino-benzene oxygens) phenyl] propane, 2,2 '-dimethyl -4,4 '-benzidine, 3,3 '-dihydroxy -4,4 '-two Aminobphenyl, 4,4 '-diaminobenzene formailide etc..In addition, in the explanation that the non-thermal plasticity polyimides can be enumerated Cited diamines.

Being suitable for being formed the acid anhydrides of TPI can for example enumerate：Pyromellitic dianhydride, 3,3 ', 4,4 '-connection Benzene tertacarbonic acid's dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 4, the double phthalic anhydrides of 4 '-oxygen.In addition, may be used Enumerate acid anhydrides cited in the explanation of the non-thermal plasticity polyimides.

Can be used only respectively by being suitable for being formed the diamines and acid anhydrides of TPI by its a kind, can also be by 2 kinds Above and for using.Diamines and acid anhydrides beyond described in alternatively, it is also possible to and with.

In polyamic acid as the predecessor of TPI, the construction unit represented by formula (6) may be present in In homopolymer, can also exist as the construction unit of copolymer.In the case of the copolymer with multiple construction units, Can exist as block copolymer, can also exist as random copolymer.Construction unit represented by formula (6) is many Kind, can be a kind or two or more.Advantageously using the construction unit represented by formula (6) as principal component, preferably wrap Predecessor containing the construction unit represented by preferably 60 moles more than %, more preferably 80 moles of more than % formula (6).

Polyimides can be by forming using imidizate (hardening) is carried out as the polyamic acid of its predecessor.Low-heat is swollen The predecessor of swollen property or TPI is that the synthesis of polyamic acid can be by making the acid anhydrides and diamines in a solvent Reacted to carry out.Used solvent can for example be enumerated：DMA (N, N-dimethyl Acetamide, DMAc), positive methyl pyrrolidone, 2- butanone, diethylene glycol dimethyl ether (diglyme), dimethylbenzene etc., can also By a kind of these solvents or two or more and for using.The synthesis of polyamic acid is preferably by the mol ratio of acid anhydrides and diamines (molal quantity of molal quantity/diamines of acid anhydrides) is set to be more than 1.By putting into superfluous acid anhydrides, polyamic acid can be set to and do not had The structure of amine end, can suppress the reactivity with acyclic compound.

(A) polyamic acid of composition is used as polyamic acid solution.Generally, it is advantageous to as reaction dissolvent solution, but can Optionally concentrated, diluted or be replaced into other organic solvents.In addition, the polyamic acid of (A) composition be typically due to it is molten Agent solubility is excellent, so also easily mixed with acyclic compound.

In addition, the polyamic acid of (A) composition is in order to suppress the reaction with acyclic compound, and preferably described polyamide Poor polyamide without free-radical polymerised unsaturated bond or free-radical polymerised unsaturated bond in the molecular skeleton of acid Acid.Specifically, the amount of free-radical polymerised unsaturated bond present in every 1g weight of polyamic acid be preferably 3mmol with Under, more preferably below 2.5mmol.As described above, by by free-radical polymerised unsaturated bond contained in polyamic acid Amount is suppressed to low value, can suppress acyclic compound and react and be consumed with polyamic acid, therefore can make acyclic compound For sulphur compound capture means and function in a effective manner.Herein, the functional group with free-radical polymerised unsaturated bond To have 1 valency organic group of (methyl) acrylic, vinyl or pi-allyl etc. in end or side chain.

In addition, in polyamic acid, for the amount of free-radical polymerised unsaturated bond present in every 1g weight to be suppressed The combination of below 3mmo1 acid anhydrides and diamines is not particularly limited, if enumerating concrete example, and preferred acid anhydrides can for example be enumerated： Pyromellitic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 2,2 ', 3, 3 '-, 2,3,3 ', 4 '-or 3,3 ', 4,4 '-diphenylketone tetracarboxylic dianhydride, diamines preferably can be enumerated：2,2 '-bis- [4- (4- Amino-benzene oxygen) phenyl] propane, 4,4 '-diamino-diphenyl ether.

As polyamic acid solution, commercially available product can also be used suitably, for example, can enumerate：Ube Industries The non-thermal plasticity polyamide acid varnish of manufacture is U- varnish-A (trade name), non-thermal plasticity polyamide acid varnish U- varnish-S (business The name of an article), the polyamide thermoplastic acid varnish SPI-200N (trade name) of aurification limited company manufacture, thermoplastic are lived by Nippon Steel Property polyamide acid varnish SPI-300N (trade name), polyamide thermoplastic acid varnish SPI-1000G (trade name), east it is beautiful (Toray) Trenyce#3000 (trade name) of limited company's manufacture etc..

Suppress the viewpoint with the reaction of acyclic compound with regard to reducing the amine end that can be played a role as nucleophilic reagent For, the weight average molecular weight of the polyamic acid of (A) composition is preferably 10, more than 000, more preferably 10,000~150, In the range of 000.In addition, by the way that weight average molecular weight is set into 10, more than 000, can also expect to make the motion of strand Property decline, the effect for declining the nucleophilicity of amine end.

<(B) composition：Acyclic compound>

In present embodiment, methacrylic compound is included in acyclic compound.Acyclic compound is preferably not With the compound containing sulfenyl for making metal vulcanize (oxidation).More specifically, for example it is preferably not include to make such as mercapto Play a role the functional group of (vulcanization) for oxidant to metal.Wherein, what is existed in main chain such as-SO2- contains sulfenyl due to not With the function as oxidant, so can be used, and it is without prejudice.

Acyclic compound is for example preferably that the value of [quantity/molecular weight of (methyl) acryloyl group in 1 molecule] is More than 0.001, preferably more than 0.003 acyclic compound.If described value is less than 0.001, in order to show invention Effect and required acrylic acid addition increase, and there is a possibility that the decline of the specialities such as the heat resistance of polyimides inherently. For this viewpoint, acyclic compound is preferably that intramolecular has the multifunctional propylene acidifying of multiple (methyl) acryloyl groups Compound.

The concrete example of acyclic compound for example can be used：2-EHA, acrylic acid 2- hydroxy methacrylates, propylene Sour 2- hydroxy propyl esters, acryloyl group phosphoric acid 2- hydroxy methacrylates, acrylic acid 2- methoxyethoxyethyl acrylates, acrylic acid 2- ethyoxyl second Epoxide ethyl ester, tetrahydrofurfuryl acrylate, acrylate, isodecyl acrylate, stearyl acrylate ester, lauryl Ester, glycidyl acrylate, allyl acrylate, ethoxy acrylate, methoxy acrylate, acrylic acid N, N '-two Methylamino ethyl ester, benzyl acrylate, acrylic acid bicyclopentadiene base ester, bicyclopentadiene ethoxy acrylate etc. are single Acrylate；Or dicyclopentenyl acrylate, dicyclopentenyl epoxide ethyl propylene acid esters, 1,3-BDO diacrylate, BDO diacrylate, 1,6- butanediol diacrylates, diethylene glycol diacrylate, neopentyl glycol diacrylate Ester, polyethylene glycol 200 diacrylate, polyethylene glycol 400 diacrylate, Macrogol 600 diacrylate, diethylene glycol Diacrylate, neopentylglycol diacrylate, 3-hydroxypivalic acid ester neopentylglycol diacrylate, triethylene glycol diacrylate Ester, double (acryloyloxyethoxy) bisphenol-As, double (acryloyloxyethoxy) tetrabromobisphenol As, tripropylene glycol diacrylate Ester, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, isocyanic acid three (2- hydroxyethyls) ester, pentaerythrite Polyfunctional acrylic esters such as tetraacrylate, dipentaerythritol acrylate, dipentaerythritol monohydroxypentaacryande etc.. In the acyclic compound of the illustration, acyclic compounds more than preferably 2 functions can for example be enumerated：Tripropylene glycol two Acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, isocyanic acid three (2- hydroxyethyls) ester, season Penta tetra-acrylate, dipentaerythritol acrylate, dipentaerythritol monohydroxypentaacryande.

Acyclic compound preferably uses commercially available product.Commercially available product can for example be enumerated：NIPPON PHARMACEUTICAL CO., LTD's system KAYARAD D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, the DN- made 2475、SR-295、SR-355、SR-399E、SR-494、SR-9041、SR-368、SR-415、SR-444、SR-454、SR-492、 SR-499、SR-502、SR-9020、SR-9035、SR-111、SR-212、SR-213、SR-230、SR-259、SR-268、SR- 272、SR-344、SR-349、SR-601、SR-602、SR-610、SR-9003、PET-30、T-1420、GPO-303、TC-120S、 HDDA、NPGDA、TPGDA、PEG400DA、MANDA、HX-220、HX-620、R-551、R-712、R-167、R-526、R-551、 R-712、R-604、R-684、TMPTA、THE-330、TPA-320、TPA-330、KS-HDDA、KS-TPGDA、KS-TMPTA；East Aronix M-400, M-404, M-408, M-450, M-305, M-309, M-310, M- of Asia synthesis limited company manufacture 315、M-320、M-350、M-360、M-208、M-210、M-215、M-220、M-225、M-233、M-240、M-245、M-260、 M-270、M-1100、M-1200、M-1210、M-1310、M-1600、M-221、M-203、TO-924、TO—1270、TO-1231、 TO-595、TO-756、TO—1343、TO-902、TO-904、TO-905、TO-1330；Chemistry limited company of common prosperity society system Iight acrylate PE-4A, DPE-6A, the DTMP-4A made；The manufacture of Osaka Organic Chemical Industry limited company PhSEA, Viscoat#802 etc..

<Allocate ratio>

The polyamic acid composition of present embodiment relative to (A) composition the parts by weight of polyamic acid 100 and 0.1 Contain the acyclic compound of (B) composition in the range of the parts by weight of parts by weight~60, the parts by weight of more preferably 1 parts by weight~20 In the range of, in the range of the parts by weight of most preferably 1 parts by weight~10.If relative to the parts by weight of polyamic acid 100, acrylic acid chemical combination The allotment ratio of thing is less than 0.1 parts by weight, then can not fully obtain the effect of capture sulphur compound.If the tune of acyclic compound Proportion then easily produces the mutual polymerisation of acyclic compound more than 60 parts by weight, there is capture and derives from oil component Sulphur compound effect decline situation.

<Solvent>

In addition, the polyamic acid composition of present embodiment and then can also contain solvent.Solvent can for example be enumerated：N, N- Dimethyl acetamide (DMAc), positive methyl pyrrolidone, 2- butanone, diethylene glycol dimethyl ether, dimethylbenzene etc., can also be by these 1 kind of solvent or two or more and for using.

<The preparation of polyamic acid composition>

Polyamic acid composition is by with the polyamic acid and (B) composition of (A) composition described in the allotment ratio input Acyclic compound, mixed to prepare.It is preferably optionally to use solvent when preparing polyamic acid composition.

[polyimide compositions]

The polyimide compositions of present embodiment are by being heat-treated to polyamic acid composition, by (A) composition Polyamic acid carry out imidizate and obtain.There is no particular restriction for the method for imidizate, such as suitably using being heat-treated, i.e., Heated under temperature conditionss in the range of 80 DEG C~400 DEG C in the time range of 1 minute~60 minutes.

In the polyimide compositions of present embodiment, it is believed that acyclic compound be present under non-bond state it is poly- In acid imide.Herein, so-called " non-bond state ", refers to that the functional group of acyclic compound is not formed between polyimides Key, acyclic compound maintains state during allotment.Wherein, in the total amount for the acyclic compound being mixed in polyamic acid, Can also exist need not maintain non-bond state in polyimides, but the propylene of key is formed between polyimides Acid compound.For this viewpoint, for example (A) composition polyamic acid in its molecular skeleton without free-radical polymerised In the case of unsaturated bond, the amount of (methyl) acryloyl group, propylene present in every 1g weight as polyamic acid composition The amount of acid compound is preferably set to more than 0.096mmol, below 3.0mmol, is more preferably set to more than 0.15mmol, 2.5mmol Below.If the amount per (methyl) acryloyl group present in 1g weight is less than 0.096mmol, existing fully to be captured The situation of the effect of sulphur compound, if more than 3.0mmol, existing and using polyimide compositions as the lamination of resin bed The misgivings that the oil resistivity of body or circuit substrate declines.

[layered product and circuit substrate]

The layered product of present embodiment is that the resin bed for being laminated the polyimide compositions on metal foil is formed.Lamination The concrete example of body metal-coating lamination body such as can enumerate copper-clad laminate (CCL).In addition, the circuit substrate of present embodiment is Circuit substrate including insulating barrier, the wiring layer being formed on insulating barrier, and insulating barrier includes the polyimide compositions Resin bed.In the layered product and circuit substrate of present embodiment, the resin beds of polyimide compositions be preferably with gold The state of category layer (including wiring layer) contact is laminated to use.

There is no particular restriction for the material of metal foil or wiring layer in the layered product and circuit substrate of present embodiment, example It can such as enumerate：Copper, stainless steel, iron, nickel, beryllium, aluminium, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium, lead, magnesium, manganese and their alloy Deng.Wherein, particularly preferably copper or copper alloy.

The layered product and circuit substrate of present embodiment shown in embodiment, are impregnated in containing sulfur-bearing organic compound as be described hereinafter In the oil of 150 DEG C of thing, such as after more than 250 hours, high adhesion strength can be also maintained between metal level and resin bed. In present embodiment, acyclic compound plays a role as the capture means of organic compounds containing sulfur are caught.

[copper-clad laminate and circuit substrate]

Then, as the preferred embodiment of present embodiment, to the copper-clad laminate and circuit that metal foil is copper foil Substrate is illustrated.The copper-clad laminate of present embodiment includes insulating barrier and is laminated at least side of the insulating barrier Copper foil on face, and used in the oil containing organic compounds containing sulfur.In addition, the circuit substrate of present embodiment is included absolutely Edge layer and the copper wiring layer being formed on the insulating barrier, and used in the oil containing organic compounds containing sulfur.

[copper foil, copper wiring layer]

In the copper-clad laminate and circuit substrate of present embodiment, copper foil and copper wiring layer are attached to and insulating barrier The amount of cobalt element on the face of contact is preferably below 2mg/dm2, more preferably below 1mg/dm2, especially preferably 0.5mg/ Below dm2.The amount of cobalt element in the surface of copper foil and copper wiring layer is more few better, is most preferably substantially free of cobalt member Element.If the amount of cobalt element is more than 2mg/dm2, the reactivity of cobalt and sulphur compound is high, thus touching as copper sulfide layer formation Send out device and turn into and cause the factor that the adhesion strength of copper foil and insulating barrier declines.In addition, copper alloy can also be used in copper foil.

The amount of the cobalt element on surface is for example available for below 2mg/dm2 copper foil：Furukawa circuit paillon foil (Furukawa Circuit Foil) company's manufacture electrolytic copper foil F1-WS, F2-WS, the city such as the electrolytic copper foil HLB of Japanese electrolysis company manufacture Sell product.

The copper foil used in the copper-clad laminate and circuit substrate of present embodiment can also be through implementing antirust treatment Copper foil.Antirust treatment can for example be carried out：Nickel processing, chromic acid salt treatment, zinc or the formation of kirsite film are handled, these are handled Combination etc..In addition, organic rust preventing processing can for example carry out the processing using BTA or derivatives thereof.Herein, nickel or chromium by It is reactive low with sulphur compound in the dense oxidation film for being formed at metal surface, but the reactivity of cobalt or zinc and sulphur compound It is high.For this viewpoint, the total amount of cobalt element and Zn-ef ficiency is preferably below 2mg/dm2, more preferably 1mg/dm2 with Under, especially preferably below 0.5mg/dm2.

The thickness of the copper foil used in the copper-clad laminate and circuit substrate of present embodiment is not particularly limited, for example It can be set in the range of 8 μm~200 μm.

[insulating barrier]

The resin such as polyimides, epoxy resin can be used in insulating barrier.In these resins, it is however preferred to have superior heat resistance The polyimides of property.In addition, in present embodiment, polyimides is preferably using the function with capture organic compounds containing sulfur Polyimides.Therefore, to the polyimides of the function with capture organic compounds containing sulfur, 2 preferred embodiments are illustrated To illustrate.

(the 1st embodiment)

1st embodiment of the polyimides of the function with capture organic compounds containing sulfur can be used following polyamides sub- Amine composition, it is by being heat-treated to following polyamic acid composition, making its imidizate and obtain, the polyamides Amino acid composition includes following compositions (A) and composition (B)：

(A) polyamic acid of the weight average molecular weight in the range of 10,000~150,000 and

(B) acyclic compound, and

Contain (B) in the range of the parts by weight of 0.1 parts by weight~60 relative to the parts by weight of (A) composition 100 Composition.In 1st embodiment, the chemical combination can be used in the polyamic acid of (A) composition and the acyclic compound of (B) composition Thing.

(the 2nd embodiment)

The TPI of 2nd embodiment is by utilizing aromatic diamine and aromatic tetracarboxylic acid's dianhydride The polyamic acid for reacting and obtaining is heat-treated, the TPI for making its imidizate and obtaining.Herein, aromatic series Diamines contains the aromatic diamine of the free-radical polymerised unsaturated bond in the range of with carbon number 2~6, relative to polyamic acid Every 1g, in the range of the amount of free-radical polymerised unsaturated bond is 0.096mmol~3mmol.

The metal-coating lamination body and circuit substrate made using the TPI of the 2nd embodiment is impregnated in In 150 DEG C of the oil containing sulphur compound, after more than 1000 hours, the height between metal level and resin bed is also able to maintain that Adhesion strength.As described above, in the 2nd embodiment, the free-radical polymerised unsaturated bond in TPI is used as seizure The capture means of sulphur compound play a role.

Constituting the polyimides of the TPI of the 2nd embodiment can for example enumerate：Include polyimides, polyamides The heat resistance of polymer with imide in the structures such as amine acid imide, polybenzimidazoles, polyester-imides, PEI Resin.

The predecessor used in the TPI of 2nd embodiment is preferably to have the formula (6) represented Construction unit polyamic acid.In especially the 2nd embodiment, the 1 of carbon number 1~6 is independently represented using R2 in formula (6) At least one in valency alkyl or alkoxy, and R2 has the chemical combination of the free-radical polymerised unsaturated bond in the range of carbon number 2~6 Thing.

The TPI of 2nd embodiment changes aromatic diamine by being used in the diamines of raw material, and is formed Polyimides with excellent heat resistance.For the radical polymerization imported in TPI in the range of carbon number 2~6 Property unsaturated bond, diamines is preferably that can illustrate the aromatic diamine represented by following formulas (12).

(in formula, X1 is represented to be selected from singly-bound, CH2, C (CH3) any one of 2 and SO2, and R3, R4 are represented with carbon number 2 1 valency organic group of the free-radical polymerised unsaturated bond in the range of~6.)

In formula (12), R3, R4 represent the 1 valency organic group with free-radical polymerised unsaturated bond, be preferably in end or There is the 1 valency organic group of (methyl) acrylic, vinyl or pi-allyl, represented by more preferably CH=CH-R5- on person's side chain Group.Herein, R5 represents straight key, the alkylidene in the range of carbon number 1~4, and for the aspect of reactivity, preferably R5 is straight Key (that is, R3, R4 in formula (12) are vinyl).The concrete example of the compound of the formula (12) can enumerate 2, and 2 '-divinyl- 4,4 '-diaminourea-biphenyl etc..

In addition, the aromatic diamine example beyond the diamines with the free-radical polymerised unsaturated bond in the range of carbon number 2~6 It can such as enumerate：4,4 '-diamino-diphenyl ether, 2 '-methoxyl group -4,4 '-diaminobenzene formailide, Isosorbide-5-Nitrae-bis- (4- aminobenzenes Epoxide) benzene, double (4- amino-benzene oxygens) benzene of 1,3-, 2,2- double [4- (4- amino-benzene oxygens) phenyl] propane, 2,2 '-dimethyl- 4,4 '-benzidine, 3,3 '-dihydroxy -4,4 '-benzidine, 4,4 '-diaminobenzene formailide etc..

Being suitable for being formed the acid anhydrides of TPI can for example enumerate：Pyromellitic dianhydride, 3,3 ', 4,4 '-connection Benzene tertacarbonic acid's dianhydride, 3,3 ', 4,4 '-diphenyl sulfone tetracarboxylic dianhydride, 4, the double phthalic anhydrides of 4 '-oxygen.

Its a kind can be used only respectively for the diamines and acid anhydrides, can also be two kinds or more to use.In addition, Can be used together it is described beyond diamines and acid anhydrides.

In addition, the amount of the free-radical polymerised unsaturated bond of carbon number 2~6 present in every 1g weight of polyamic acid is preferred In the range of 0.096mmol~3mmol, in the range of more preferably 0.15mmol~2mmol.If every 1g weights of polyamic acid The amount of the free-radical polymerised unsaturated bond of carbon number 2~6 present in amount is less than 0.096mmol, then existing fully to obtain The situation of the effect of sulphur compound is captured, if more than 3mmol, existing and easily producing the mutual polymerization of the unsaturated bond instead Should, the situation that capture declines from the effect of the sulphur compound of oil component.

The synthesis of polyamic acid can react by making the acid anhydrides to carry out in a solvent with diamines.Used solvent example It can such as enumerate：DMA (DMAc), positive methyl pyrrolidone, 2- butanone, diethylene glycol dimethyl ether, dimethylbenzene Deng, can also by a kind of these solvents or two or more and for using.The synthesis of polyamic acid is preferably by acid anhydrides and two The mol ratio (molal quantity of molal quantity/diamines of acid anhydrides) of amine is set to be more than 1.By putting into superfluous acid anhydrides, polyamides can be set to Amino acid does not have the structure of amine end, can suppress the reactivity with the free-radical polymerised unsaturated bond in the range of carbon number 2~6.

Synthesized polyamic acid is used as polyamic acid solution.It is frequently advantageous that as reaction dissolvent solution, visually needs Concentrated, diluted or be replaced into other organic solvents.In addition, being generally easily formed as the polyamic acid of predecessor The excellent solution of solvent soluble.

TPI is prepared by the way that polyamic acid is carried out into imidizate (hardening).The method of imidizate is simultaneously It is not particularly limited, such as suitably using the time model under the temperature conditionss in the range of 80 DEG C~400 DEG C at 1 minute~60 minutes Enclose the interior heat treatment heated.

Suppress anti-with free-radical polymerised unsaturated bond with regard to reducing the amine end that can be played a role as nucleophilic reagent For the viewpoint answered, the predecessor of TPI be polyamic acid weight average molecular weight be preferably 10,000 with On, in the range of more preferably 50,000~300,000, in the range of most preferably 50,000~150,000.In addition, passing through Weight average molecular weight is set to 10, more than 000, can also expect to make the motility of strand to decline, make the nucleophilic of amine end Property decline effect.

The polyamic acid composition of 2nd embodiment be with carbon number 2~6 in the range of free-radical polymerised unsaturated bond Polyamic acid and solvent mixture.Herein, solvent can for example be enumerated：DMA (DMAc), positive methyl pyrrole Pyrrolidone, 2- butanone, diethylene glycol dimethyl ether, dimethylbenzene etc., can also by a kind of these solvents or two or more and be used for Use.

In the layered product and circuit substrate of present embodiment, the resin beds of polyimide compositions be preferably with copper foil The state of (including wiring layer) contact is laminated to use.The layered product and circuit substrate of present embodiment are implemented as be described hereinafter Shown in example, be impregnated in oil of 150 DEG C containing organic compounds containing sulfur, such as, also can be in copper after more than 250 hours High adhesion strength is maintained between paper tinsel and resin bed.

The thickness of insulating barrier in the copper-clad laminate and circuit substrate of present embodiment is not particularly limited, and for example may be used It is set in the range of 3 μm~100 μm.

[application method of circuit substrate]

The application method of the circuit substrate of present embodiment is containing organic compounds containing sulfur by the circuit substrate Used in oil.Herein, the oil containing organic compounds containing sulfur is such as can enumerate engine oil, transmission oil.In addition, sulfur-bearing is organic Compound mercaptan compound such as can enumerate benzothiazole.The temperature in use of the circuit substrate of present embodiment in the oil For example, normal temperature is to 200 DEG C or so.

[manufacture method of layered product and circuit substrate]

In present embodiment, the method for circuit substrate is made and unrestricted.For example, it may be preparing to include polyimides The layered product of resin bed and metal level, the etching metal layer is formed the method (subtractive process (subtractive of distribution method)).Alternatively, it is also possible to be by the resin bed of polyimides formed Seed Layer after, resist is formed into pattern, And then metal is carried out pattern plating to form the method (semi-additive process (semi-additive method)) of distribution.

The layered product used in subtractive process is for example ready for including the resin film of polyimides, is sputtered on the resin film Metal and formed after Seed Layer, metal level is for example formed using plating to prepare layered product.Alternatively, it is also possible to prepare comprising poly- Imido resin film, using methods such as thermo-compression bonding, lamination (lamination) metal foil carrys out forming layer on the resin film Laminate.And then, it can also be dried by the coating fluid containing polyamic acid and acyclic compound of casting on metal foil And formed after coated film, it is heat-treated and makes its imidizate, so as to forms the resin bed of polyimides to prepare layered product.

Hereinafter, in case of the combination for typically enumerating casting method and subtractive process, to the circuit base of present embodiment The manufacture method of plate is specifically described.

First, the manufacture of layered product may include：

(1) step that coated film is formed containing the resin solution of polyamic acid composition is coated with the base materials such as metal foil Suddenly；And

(2) by being heat-treated to coated film, the polyamic acid of (A) composition is subjected to imidizate and polyamides Asia is formed The step of resin bed of amine composition.

In addition, in addition to the manufacture of circuit substrate is the step of including (1), (2), can so that including：

(3) the step of metallic foil pattern of layered product being formed into wiring layer.

(1) step that coated film is formed containing the resin solution of polyamic acid composition is coated with the base materials such as metal foil Suddenly：

It can be made as the metal foil of base material with the shape such as sliced, web-like person or endless belt (endless belt) shape With.It is efficient to be set to web-like or endless belt-shaped form in order to obtain productivity, and be set to can quantity-produced shape Formula.And then, for more greatly showing the viewpoint of improvement of the Wiring pattern precision in circuit substrate, copper foil is excellent Elect the web-like for being formed as strip as.

The method for forming coated film can be by the way that the solution of polyamic acid composition be directly coated in metal foil, or is applied It is dried and is formed after being distributed on the polyimide layer supported by metal foil.There is no particular restriction for the method being coated with, for example It is coated with using coating machines such as comma formula (comma), die type (die), blade type (knife), lip formulas (lip).

The resin bed of polyimide compositions can be individual layer, can also include multilayer.Polyimide layer is being set to many In the case of layer, other predecessors can be coated with successively on the layer of the predecessor comprising differently composed composition to be formed.In forerunner The layer of thing is included in the case of more than 3 layers, can be used the predecessor of same composition more than 2 times.In addition, the thickness of the layer of predecessor Degree (after drying) is preferably in the range of 3 μm~100 μm, is preferably in the range of 3 μm~50 μm.It is coated with polyamic acid group In the method for the present embodiment of the solution of compound, the thickness of coated film can be freely adjusted.

It is preferably the polyamides to be contacted with metal level in the case where the resin bed of polyimide compositions is set into multilayer The mode of resin bed of the resin bed of imines composition as TPI forms the layer of predecessor.By using thermoplastic Property polyimides, can improve the adhesion with metal level.This TPI is preferably that glass transition temperature (Tg) is Less than 350 DEG C persons, more preferably 200 DEG C~320 DEG C.

Alternatively, it is also possible to which the temporary transient imidizate of the layer of individual layer or the predecessor of multilayer to be made to individual layer or multilayer After polyimide layer, so on the polyimide layer formed predecessor layer.

(2) by being heat-treated to coated film, the polyamic acid of (A) composition is subjected to imidizate and polyamides Asia is formed The step of resin bed of amine composition：

There is no particular restriction for the method for imidizate, for example the suitable temperature conditionss using in the range of 80 DEG C~400 DEG C Under the heat treatment heated in the time range of 1 minute~60 minutes.In order to suppress the oxidation of metal foil, preferably hypoxemia Heat treatment under environment, is preferably under the inert gas environment such as nitrogen or rare gas, the reducing gas ring such as hydrogen specifically Carried out under border or in vacuum.By heat treatment, the polyamic acid in coated film carries out imidizate and forms polyimides. Now think, the major part of the acyclic compound of contained (B) composition is not reacted with polyamic acid in coated film, And divided a word with a hyphen at the end of a line with non-bond state in polyimides, form polyimide compositions.In this way, it can manufacture sub- including polyamides The resin bed (individual layer or multilayer) and the layered product of metal foil of amine composition.

(3) the step of metallic foil pattern of gained layered product being formed into wiring layer：

In this step, pattern is formed by the way that metal foil is etched into regulation shape, wiring layer is processed into.Etching can be with Carried out using any means such as photoetching technique.

In addition, in described above, the characteristic step only to the manufacture method of the circuit substrate of present embodiment is carried out Explanation.That is, when manufacturing circuit substrate, generally carry out it is described beyond the step of, such as through hole processing or rear step in preceding step The steps such as rapid terminal plating, sharp processing can be carried out according to well-established law.

As previously discussed, using the polyimide compositions of present embodiment, high temperature ring is positioned over repeatedly even if can be formed In border and oil attachment environment, the layered product that the adhesion strength of metal foil and resin bed will not also decline.In addition, by using this reality The polyimides of mode is applied, the reliability of circuit substrate can be improved.The circuit substrate of present embodiment for example can drawing in automobile Hold up, inlet manifold, alternating current generator, radiator or gear-box, speed changer etc. are used under the hot environment of easy attaching oil Preferably by the machine used under non-cohesive oily environment can also be applied in machine, in the purposes such as FPC.

[embodiment]

Hereinafter, the present invention is specifically described using embodiment, but the present invention is not by any limit of these embodiments It is fixed.In addition, in following examples, it is as long as no special instructions, then various to determine, evaluate as described below.

[measure of adhesion strength]

Adhesion strength is the evaluation sample to being cut into wide 10mm, long 100mm, uses cupping machine (Toyo Seiki stock The manufacture of part Co., Ltd, Strograph-M1), with the speed of 50mm/ minutes by between copper foil and polyimides on 180 ° of directions Peel off, be adhesion strength by masterpiece when peeling off.

[measure of sulphur concentration]

Sulphur concentration (hereinafter sometimes referred to as " S concentration ") be by will evaluate sample copper and polyimides between peel off after, it is right The release surface of copper foil side carries out the analysis of energy dispersion type fluorescent x-ray analyzer (EDX) to obtain.

The abbreviation used in the present embodiment represents following compound.

BAPP：2,2- double (4- aminophenoxy phenyls) propane

VAB：2,2 '-divinyl -4,4 '-benzidine

m-TB：2,2 '-dimethyl -4,4 '-benzidine

TPE-R：1,3 '-bis- amino-benzene oxygen benzene

PMDA：Pyromellitic acid anhydride

BPDA：3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride

DMAc：DMA

1~synthesis example of synthesis example 2：

For synthesizing polyamides acid A, polyamic acid B, and make the diamines shown in table 1 under nitrogen flowing while 200ml's Stirring is while be dissolved in solvent DMAc in separable flask.Then, the tetracarboxylic dianhydride shown in addition table 1.Then, by solution Continue to stir 5 hours at room temperature to carry out polymerisation, keep diel.Confirm to obtain sticky polyamic acid solution, it is raw Into the polyamic acid of high polymerization degree.By the polyamic acid A of gained, polyamic acid B solution (hereinafter referred to as polyamic acid solution A, Polyamic acid solution B) solid constituent and solution viscosity be shown in Table 1.

[table 1]

Synthesis example	1	2
			Polyamic acid	A	B
BAPP	8.11g	-
			m-TB	-	6.32g
TPE-R	-	0.97g
			PMDA	4.10g	5.77g
BPDA	0.29g	1.95g

DMAc	87.5g	85g
			Solid constituent	12.5%	15%
Viscosity	1,300cP	29,000cP

Embodiment 1

Relative to the parts by weight of solid constituent 100 of the amic acid solution A obtained in synthesis example 1, mix equivalent to 5 parts by weight (NIPPON PHARMACEUTICAL CO., LTD manufactures the 0.63g acyclic compounds of (acryloyl group is 0.56mmol/g), trade name： KAYARAD PET-30), it is stirred at room temperature 2 hours, prepares polyamic acid composition 1.In copper foil A (Co amounts：2.68mg/ dm², Zn amounts：0.13mg/dm², Cr amounts：0.08mg/dm², Ni amounts：0.76mg/dm²) on turn into 2 μm with the thickness after hardening Mode is coated with polyamic acid composition 1, the heat drying at 130 DEG C and after removing solvent, thereon with the thickness after hardening into The amic acid solution B obtained in synthesis example 2, the heat drying at 125 DEG C are coated with for 21 μm of modes and solvent is removed.And then, Thereon by the thickness after hardening turn into 2 μm in the way of be coated with polyamic acid solution A, the heat drying at 125 DEG C and remove molten Agent.Then, each rank for carrying out 1 minute~15 minutes at 130 DEG C, 145 DEG C, 160 DEG C, 210 DEG C, 280 DEG C, 320 DEG C, 360 DEG C Section property heat treatment, being produced on copper foil includes the wiring substrate layered product 1 of 3 strata imide layers.Polyimides on copper foil The thickness of layer is followed successively by 2 μm/21 μm/2 μm from copper foil side.Wiring substrate layered product 1 is cut into after 10cm × 3cm, with The mode that copper foil turns into 9cm × 2cm etches copper foil, and 10cm × 3cm coating (coverlay) (new day is thermally compressed in copper foil side Iron lives the manufacture of aurification limited company, trade name：Espanex SPC) evaluate sample 1 to make.Evaluate the copper foil of sample 1 Adhesion strength (adhesion strength 1) between polyimides is 1.3kN/m.In addition, polyamic acid A is carried out into imidizate and obtained Polyimides be thermoplasticity, polyamic acid B is subjected to imidizate and the polyimides that obtains is non-thermal plasticity.

Then to evaluating sample 1, the automatic transmission fluid (trade name manufactured using baking oven in matsuda company：ATF M- III 150 DEG C, 250 hours are carried out in) to be heat-treated.Determine the copper foil after heat treatment and the adhesion strength between polyimides (is adhered strong 2) degree, is as a result 0.82kN/m.The S concentration of the release surface of copper foil side now is 0.4%.Then, determine and 150 are carried out in oil DEG C, 1,000 hour heat treatment after copper foil and the adhesion strength (adhesion strength 3) between polyimides, be as a result 0.18kN/m.Will As a result it is shown in Table 2.

Embodiment 2

Except the parts by weight of solid constituent 100 relative to polyamic acid solution A, mix equivalent to 10 parts by weight (acryloyls Base is 1.17mmol/g) 1.25g acyclic compounds beyond, in the same manner as in Example 1 obtain polyamic acid combination After thing 2, wiring substrate layered product 2 is obtained, so as to obtain evaluation sample 2.It is viscous between the copper foil and polyimides of evaluation sample 2 Intensity (adhesion strength 1) for 1.3kN/m.In addition, automatic transmission fluid (the trade name manufactured in matsuda company：ATF M- III in), the copper foil after 150 DEG C of progress, heat treatment in 250 hours and the adhesion strength (adhesion strength 2) between polyimides are 0.56kN/m.The S concentration of the release surface of copper foil side now is 5%.Then, determine and 150 DEG C, 1,000 hour are carried out in oil Adhesion strength (adhesion strength 3) between copper foil and polyimides after heat treatment, is as a result 0.11kN/m.Show the result in table 2 In.

Embodiment 3

Except the parts by weight of solid constituent 100 relative to polyamic acid solution A, and mix equivalent to 20 parts by weight (propylene Acyl group is 2.34mmol/g) 2.50g acyclic compounds beyond, in the same manner as in Example 1 obtain polyamic acid group After compound 3, wiring substrate layered product 3 is obtained, so as to obtain evaluation sample 3.Between the copper foil and polyimides of evaluating sample 3 Adhesion strength (adhesion strength 1) is 1.3kN/m.In addition, automatic transmission fluid (the trade name manufactured in matsuda company：ATF M-III in), the copper foil after 150 DEG C of progress, heat treatment in 250 hours and the adhesion strength (adhesion strength 2) between polyimides are 0.5kN/m.The S concentration of the release surface of copper foil side now is 5%.Then, determine and 150 DEG C, 1,000 hour heat are carried out in oil Adhesion strength (adhesion strength 3) between copper foil and polyimides after processing, is as a result 0kN/m.Show the result in table 2.

Comparative example 1

Polyamic acid solution A is coated with the way of the thickness after hardening turns into 2 μm on copper foil, is heated at 130 DEG C dry It is dry and remove solvent.Then, it is coated with the amic acid obtained in synthesis example 2 in the way of the thickness after hardening turns into 21 μm thereon Solution B, the heat drying at 125 DEG C and remove solvent.And then, it is coated with thereon in the way of the thickness after hardening turns into 2 μm Polyamic acid solution A, the heat drying at 125 DEG C and remove solvent.Then, 130 DEG C, 145 DEG C, 160 DEG C, 210 DEG C, 280 DEG C, 320 DEG C, each interim heat treatment for carrying out 1 minute~15 minutes at 360 DEG C, being formed on copper foil includes 3 strata acid imides The wiring substrate layered product 4 of layer.Then, evaluation sample is obtained by wiring substrate layered product 4 in the same manner as example 1 Product 4.It is 1.3kN/m to evaluate the adhesion strength (adhesion strength 1) between the copper foil and polyimides of sample 4.In addition, in matsuda company Automatic transmission fluid (the trade name of manufacture：ATF M-III) in, the copper foil after 150 DEG C of progress, heat treatment in 250 hours is with gathering Adhesion strength (adhesion strength 2) between acid imide is 0.12kN/m.The S concentration of the release surface of copper foil side now is 7%.Connect , determine copper foil and the adhesion strength (adhesion strength between polyimides after 150 DEG C of progress, heat treatment in 1,000 hour in oil 3) it is as a result, 0kN/m.Show the result in table 2.

[table 2]

It is long-term resistance in 150 DEG C of oil in 1~embodiment of embodiment 3 using the polyamic acid composition of the present invention The result of oiliness test is, small impregnated of 250 in oil compared with the sample (comparative example 1) for being not added with acyclic compound When at the time of adhesion strength 2 be shown as about 4 times~7 times of 0.5kN/m~0.82kN/m.Moreover, 1~embodiment of embodiment 3 In, the sulphur component amount of the copper foil side of release surface is 0.4%~5%, also can more be reduced compared with the 7% of comparative example 1.And then, Adhesion strength (0kN/m), phase are lost in adhesion strength 3 after on impregnating 1,000 hour in 150 DEG C of oil, comparative example 1 For this, added with the parts by weight of acyclic compound 5~10 embodiments 1 of parts by weight, keep in embodiment 2 0.11kN/m~ 0.18kN/m adhesion strength, discovery improves oil resistivity by the addition of acyclic compound.

Reference example 1-1

In (the Co amounts of copper foil 1：0mg/dm², Zn amounts：0.04mg/dm², Cr amounts：0.10mg/dm², Ni amounts：0.22mg/dm²) On by the thickness after hardening turn into 2 μm in the way of be coated with polyamic acid solution A, the heat drying at 130 DEG C and remove solvent.After And, the amic acid solution B obtained in synthesis example 2 is coated with the way of the thickness after hardening turns into 21 μm thereon, at 125 DEG C Heat drying and remove solvent.And then, polyamic acid solution A is coated with the way of the thickness after hardening turns into 2 μm thereon, Heat drying at 125 DEG C and remove solvent.Then, at 130 DEG C, 145 DEG C, 160 DEG C, 210 DEG C, 280 DEG C, 320 DEG C, 360 DEG C Each interim heat treatment for carrying out 1 minute~15 minutes, is formed in the wiring substrate including 3 strata imide layers on copper foil and uses Layered product 1-4.Then, in the same manner as example 1, obtained by wiring substrate with layered product 1-4 and evaluate sample 1-4. The adhesion strength (adhesion strength 1) between the copper foil and polyimides of sample 1-4 is evaluated more than 2kN/m.In addition, in matsuda company Automatic transmission fluid (the trade name of manufacture：ATF M-III) in, the copper foil after 150 DEG C of progress, heat treatment in 250 hours is with gathering Adhesion strength (adhesion strength 2) between acid imide is more than 2kN/m.Then, determine in oil carry out 150 DEG C, 1,000 hour heat at Adhesion strength (adhesion strength 3) between copper foil and polyimides after reason, as a result for more than 2kN/m.Show the result in table 3.

Reference example 1-2

(the Co amounts 0mg/dm of copper foil 2 is used except replacing the copper foil 1 of reference example 1-1², Zn amounts：0.08mg/dm², Cr amounts： 0.10mg/dm², Ni amounts：0.13mg/dm²) beyond, so that wiring substrate layered product is made with the identical mode of reference example 1-1 1—5.Then, in the same manner as example 1, obtained by wiring substrate with layered product 1-5 and evaluate sample 1-5.Evaluate sample Adhesion strength (adhesion strength 1) between the copper foil and polyimides of product 1-5 is 1.4kN/m.In addition, manufactured in matsuda company Automatic transmission fluid (trade name：ATF M-III) in, copper foil and polyimides after 150 DEG C of progress, heat treatment in 250 hours Between adhesion strength (adhesion strength 2) be 1.4kN/m.The S concentration of the release surface of copper foil side now is 0%.Then, determine In oil carry out 150 DEG C, 1,000 hour heat treatment after copper foil and the adhesion strength (adhesion strength 3) between polyimides, as a result for 1.4kN/m.Show the result in table 3.

Reference example 1-3

(the Co amounts 0.42mg/dm of copper foil 3 is used except replacing the copper foil 1 of reference example 1-1², Zn amounts：0.10mg/dm², Cr Amount：0.05mg/dm², Ni amounts：0.43mg/dm²) beyond, so that wiring substrate lamination is made with the identical mode of reference example 1-1 Body 1-6.Then, in the same manner as example 1, obtained by wiring substrate with layered product 1-6 and evaluate sample 1-6.Evaluate Adhesion strength (adhesion strength 1) between the copper foil and polyimides of sample 1-6 is more than 2kN/m.In addition, in matsuda company system Automatic transmission fluid (the trade name made：ATF M-III) in, copper foil and polyamides after 150 DEG C of progress, heat treatment in 250 hours Adhesion strength (adhesion strength 2) between imines is more than 2kN/m.Then, determine in oil carry out 150 DEG C, 1,000 hour heat at Adhesion strength (adhesion strength 3) between copper foil and polyimides after reason, as a result for more than 2kN/m.Show the result in table 3.

Comparative example 2

In addition to replacing the copper foil 1 of reference example 1-1 and using copper foil A, with the identical mode system of reference example 1-1 Into wiring substrate layered product 1-7.Then, in the same manner as example 1, obtained by wiring substrate with layered product 1-7 Evaluate sample 1-7.It is 1.3kN/m to evaluate the adhesion strength (adhesion strength 1) between sample 1-7 copper foil and polyimides.Separately Outside, the automatic transmission fluid (trade name manufactured in matsuda company：ATF M-III) in, carry out 150 DEG C, 250 hours and be heat-treated Adhesion strength (adhesion strength 2) between copper foil and polyimides afterwards is 0.12kN/m.The S of the release surface of copper foil side now is dense Spend for 7%.Then, determine the copper foil in oil after 150 DEG C of progress, heat treatment in 1,000 hour and the adhesion between polyimides is strong Spend (adhesion strength 3), be as a result 0kN/m.Show the result in table 3.

[table 3]

In reference example 1-1~reference example 1-3, by using the few 1~copper foil of copper foil 3 of Co amounts, with being exceeded using Co amounts 2mg/dm²Copper foil A comparative example 2 compare, the result for carrying out the long-term oil resistance experiment in 150 DEG C of oil is obvious confirmation To the raising of oil resistivity.

Synthesis example 2-1

Under nitrogen flowing, 15.67g BAPP (0.0382 mole), 0.47g are loaded into 300ml separable flask VAB (0.0020 mole), 100g DMAc with vinyl, are stirred at room temperature and dissolve it.Then add 8.27g's PMDA (0.0379 mole) and 0.59g BPDA (0.00199 mole), solution is continued at room temperature stirring 5 hours to enter Row polymerisation, obtains polyamic acid solution a.

Synthesis example 2-2~synthesis example 2-5

It is molten to prepare polyamic acid with the identical mode of synthesis example 2-1 in addition to the raw material composition being set to shown in table 4 Liquid b, polyamic acid solution c, polyamic acid solution d, polyamic acid solution e.

[table 4]

Reference example 2-1

The polyamic acid polymerizeing in synthesis example 2-1 is coated with the way of the thickness after hardening turns into 2 μm on copper foil A molten Liquid a, the heat drying at 130 DEG C and after removing solvent, be coated with synthesis in the way of the thickness after hardening turns into 21 μm thereon The acid amides acid solution e that obtains, the heat drying at 125 DEG C in example 2-5 and remove solvent.And then, thereon with the thickness after hardening Degree is coated with the polyamic acid solution d obtained in synthesis example 2-4, the heat drying at 125 DEG C and removed molten as 2 μm of mode Agent.Then, each rank for carrying out 1 minute~15 minutes at 130 DEG C, 145 DEG C, 160 DEG C, 210 DEG C, 280 DEG C, 320 DEG C, 360 DEG C Section property heat treatment, being produced on copper foil includes the wiring substrate layered product 2-1 of 3 strata imide layers.Polyamides on copper foil is sub- The thickness of amine layer is followed successively by 2 μm/21 μm/2 μm from copper foil side.Then, wiring substrate layered product 2-1 is cut into 10cm After × 3cm, copper foil is etched in the way of copper foil turns into 9cm × 2cm, 10cm × 3cm coating (new day is thermally compressed in copper foil side Iron lives the manufacture of aurification limited company, trade name：Espanex SPC), evaluate sample 2-1 to make.Evaluation sample 2- Adhesion strength (adhesion strength 1) between 1 copper foil and polyimides is 1.3kN/m.

Sequentially for evaluation sample 2-1, the automatic transmission fluid (trade name manufactured using baking oven in matsuda company： ATF M-III) in carry out 150 DEG C, 250 hours be heat-treated.Determine the copper foil after heat treatment and the adhesion strength between polyimides (adhesion strength 2), is as a result 0.30kN/m.The S concentration of the release surface of copper foil side now is 5%.Then, determine in oil Carry out 150 DEG C, 1,000 hour heat treatment after copper foil and the adhesion strength (adhesion strength 3) between polyimides, as a result for 0.05kN/m.Show the result in table 5.

Reference example 2-2

Except being coated with the polyamic acid polymerizeing in synthesis example 2-2 in the way of the thickness after hardening turns into 2 μm on copper foil A Beyond solution b, wiring substrate is obtained with after layered product 2-2 using with the identical of reference example 2-1 method, obtains and evaluates sample 2- 2.It is 1.3kN/m to evaluate the adhesion strength (adhesion strength 1) between sample 2-2 copper foil and polyimides.In addition, in matsuda company Automatic transmission fluid (the trade name of manufacture：ATF M-III) in, the copper foil after 150 DEG C of progress, heat treatment in 250 hours is with gathering Adhesion strength (adhesion strength 2) between acid imide is 0.76kN/m.The S concentration of the release surface of copper foil side now is 1%.Connect , determine copper foil and the adhesion strength (adhesion strength between polyimides after 150 DEG C of progress, heat treatment in 1,000 hour in oil 3) it is as a result, 0.18kN/m.Show the result in table 5.

Reference example 2-3

Except being coated with the polyamic acid polymerizeing in synthesis example 2-3 in the way of the thickness after hardening turns into 2 μm on copper foil A Beyond solution c, wiring substrate is obtained with after layered product 2-3 using with the identical of reference example 2-1 method, obtains and evaluates sample 2- 3.It is 1.3kN/m to evaluate the adhesion strength (adhesion strength 1) between the copper foil and polyimides of sample 2-3.In addition, public in matsuda Take charge of the automatic transmission fluid (trade name of manufacture：ATF M-III) in, carry out 150 DEG C, 250 hours heat treatment after copper foil with Adhesion strength (adhesion strength 2) between polyimides is 0.55kN/m.The S concentration of the release surface of copper foil side now is 5%.Connect , determine copper foil and the adhesion strength (adhesion strength between polyimides after 150 DEG C of progress, heat treatment in 1,000 hour in oil 3) it is as a result, 0.05kN/m.Show the result in table 5.

[table 5]

More than, embodiments of the present invention are described in detail with the purpose of illustration, but the present invention is not limited to The embodiment.For example, in the embodiment, the purposes of polyimides of the invention can enumerate the circuit substrates such as FPC Exemplified by base material, but it is also possible to for the purposes beyond described, such as cover the covering layer film of the wiring layer of circuit substrate Adhering agent layer, the coil type of (coverlay film) body or covering layer film engage (Tape Automated automatically Bonding, TAB), adhesion resin in chip size packages (ChipScale Package, CSP) etc. etc..

Claims (12)

1. a kind of polyamic acid composition, comprising following compositions (A) and composition (B), and not comprising photo-induced polymerization initiator：

(A) polyamic acid of the weight average molecular weight in the range of 10,000~150,000 and

(B) acyclic compound, and

Relative to the parts by weight of (A) composition 100, and contain described (B) composition in the range of the parts by weight of 1 parts by weight~20； And the polyamic acid composition is characterised by：

The amount of free-radical polymerised unsaturated bond present in every 1g weight of (A) composition is below 3mmol,

The value of [quantity/molecular weight of (methyl) acryloyl group in 1 molecule] of (B) composition is more than 0.001.

2. polyamic acid composition according to claim 1, it is characterised in that：[(the first in 1 molecule of (B) composition Base) acryloyl group quantity/molecular weight] value be more than 0.003.

3. a kind of polyimide compositions, it is characterised in that：By entering to polyamic acid composition according to claim 1 Row heat treatment, (A) composition carries out imidizate and obtained by described in.

4. a kind of layered product, it is characterised in that：Including metal level and the insulating barrier being formed on the metal level；And

The insulating barrier includes the resin bed of polyimide compositions according to claim 3.

5. layered product according to claim 4, it is characterised in that：The layered product is the tree of the polyimide compositions Lipid layer is contacted and is laminated with the metal level and forms.

6. the layered product according to claim 4 or 5, it is characterised in that：

The metal level is copper foil, and

The amount for the cobalt element being attached on the face contacted with the insulating barrier in the copper foil is 2mg/dm²Below.

7. a kind of circuit substrate, it is characterised in that：Including insulating barrier and the wiring layer being formed on the insulating barrier；And

The insulating barrier includes the resin bed of polyimide compositions according to claim 3.

8. circuit substrate according to claim 7, it is characterised in that：The layered product is the polyimide compositions Resin bed is contacted and is laminated with the wiring layer and forms.

9. the circuit substrate according to claim 7 or 8, it is characterised in that：

The wiring layer is copper wiring layer, and

The amount for the cobalt element being attached on the face contacted with the insulating barrier in the copper wiring layer is 2mg/dm²Below.

10. a kind of application method of circuit substrate, it is characterised in that：By the circuit substrate according to claim 7 or 8 containing Used in the oil for having organic compounds containing sulfur.

11. a kind of manufacture method of layered product, the layered product is formed with base material and is formed with the substrate including polyamides The insulating barrier of the resin bed of imines composition；And

The manufacture method of the layered product is characterised by including：

It is coated with the resin solution containing polyamic acid composition according to claim 1 on the substrate and forms coating The step of film；And

By being heat-treated to the coated film, (A) composition carries out imidizate and forms the polyimides group by described in The step of resin bed of compound.

12. a kind of manufacture method of circuit substrate, the circuit substrate includes the exhausted of the resin bed comprising polyimide compositions Edge layer and the wiring layer being formed on the insulating barrier；And the manufacture method of the circuit substrate is characterised by including：

It is coated with the resin solution containing polyamic acid composition according to claim 1 on metal foil and forms coated film The step of；

By being heat-treated to the coated film, (A) composition carries out imidizate and forms the polyimides group by described in The step of resin bed of compound；And

The step of metal foil is patterned and the wiring layer is formed.