CN101166847A - Material for plating and use thereof - Google Patents

Abstract

Disclosed is a material for plating having a resin layer which contains a polyimide resin of a specific structure. An electroless plating is performed on this resin layer. This material for plating is excellent in adhesion with an electroless-plated coating film formed on the resin surface even when the surface roughness of the resin layer is low, while exhibiting excellent solder heat resistance. Consequently, this material for plating can be suitably used for production of printed wiring boards or the like.

Description

Material for plating and application thereof

Technical field

The present invention relates to material for plating and application thereof, relate in particular to a kind ofly, can improve adhesive material for plating and application thereof between electroless plating cover film and substrate surface by implementing to be applied to various substrate surfaces when electroless plating covers.

Background technology

It is on metal or nonmetallic surface that electroless plating covers, and under the situation of no current by (not using electric energy), utilizes the reductive action of reductive agent to come a kind of plating treatment technology of precipitating metal.Such electroless plating covers and is widely used in the surface-functionalized of insulativity material such as various plastics, glass, pottery, timber etc.For example, implement on ABS resin or acrylic resin that electroless plating covers, the function plating of plating etc. as the decoration plating of the parts such as handle class of automobile grid or sign class, household appliances or in as through-holes of printed circuit boards.

But in most of the cases, above-mentioned electroless plating covers and intends implementing poor adherence between the various material surfaces of plating.Especially, electroless plating is covered handle when being applied to the manufacturing of above-mentioned printed circuit board (PCB) technical task with the poor adherence between electroless plating cover film and the insulating material.

In order to solve above-mentioned problem, use various methods, make the surface roughening of the insulative resin material that is applied to printed circuit board (PCB), by so-called anchoring effect obtain and electroless plating cover film between tackiness (for example referring to Patent Document 1).But this method is difficult to satisfy the requirement aspect fine wiring formation property in recent years.In other words, big when using this method to form fine wiring through the concave-convex surface on the surface of roughening, so produce wiring problem such as tilt, collapse.From this point as can be known, in order to satisfy the requirement that forms fine wiring, need on the resin face of surface smoothing, form the technology of metal deposition securely.

Therefore, developing the technology that on the resin face of surface smoothing, forms metal deposition securely.For example, patent documentation 2 discloses the tinsel of the tape tree fat of stacked metal plating after coating polyimide silxoane precursors on the heat-resistant resin film.But, in patent documentation 2 described technology,, put down in writing chromium sputtering method etc. side by side and covered method with electroless plating with regard to the formation method of metal level.This just, expression not have to consider and insulating material between poor adherence the Coated adhesion strength of electroless plating and intend relation between the surfaceness on the surface that the formation electroless plating covers.Do not put down in writing any content of confirming through reality yet.Even, do not put down in writing key property that printed circuit board (PCB) etc. requires as the welding thermotolerance yet.If the welding thermotolerance is bad, especially when being applied to double-sided printed-circuit board etc., expose in the place that has covered material two-side with wiring diagram, and can have the problem of above local foaming.

In addition, in printed circuit board (PCB) manufacturing process, for can be durable in reparing process, also require metal deposition and the tackiness between the resin under the high temperature firm, so-called reparing process is meant that the exchange lift-launch is judged as the operation of underproof parts by inspection in the electronic unit of printed circuit board (PCB).Yet, in above-mentioned patent documentation 2, do not have fully to consider at high temperature metal deposition and the tackiness between the resin.Than tackiness under normal conditions, the tackiness that improve under this high temperature is very difficult.

Patent documentation 1: day disclosure special permission communique [spy opens the 2000-198907 communique] (on July 18th, 2000 is open)

Patent documentation 2: day disclosure special permission communique [spy opens the 2002-264255 communique] (on September 18th, 2002 is open)

Summary of the invention

Invent problem to be solved

As mentioned above, a kind of material does not also appear, that is, under the little situation of surfaceness, the tackiness height between resin material and the electroless plating cover film and have can be anti-in the stable on heating material of welding of the excellence of the manufacturing of printed circuit board (PCB).

The present invention proposes in view of the above problems, its purpose is to provide a kind of material for plating and application thereof, described material for plating is applied to intend implementing the various material surfaces that electroless plating covers, and can improve and the tackiness of electroless plating between covering, and can also improve the welding thermotolerance.

Be used to solve the method for problem

The inventor etc. are in order to solve above-mentioned problem, have carried out found that of further investigation, if use following material for plating, just can improve and the tackiness of electroless plating between covering, and the while also can be improved thermotolerance, has so far finished the present application.The present invention is based on described new discovery and finish, and the present invention comprises following invention.

1) a kind of material for plating, it has and is used to implement the resin layer that electroless plating covers, above-mentioned resin layer contains the polyimide resin that has siloxane structure at least, above-mentioned polyimide resin is to make the reaction of acid dianhydride composition and two amine components and the polyimide resin that obtains, and described two amine components contain the diamines of following general formula (1) expression:

[Chemical formula 1]

(in the above-mentioned general formula (1), g represents the integer more than 1; In addition, R ¹¹And R ²²Can be identical or different, the expression carbonatoms is 1～6 alkylidene group or phenylene; R ³³, R ⁴⁴, R ⁵⁵And R ⁶⁶Each can be identical or different, and the expression carbonatoms is 1～6 following group, alkyl, phenyl, alkoxyl group or phenoxy group).

2) according to 1) described in material for plating, wherein, above-mentioned polyimide resin is that two amine components with the diamines that contains above-mentioned general formula (1) expression are the polyimide resin that raw material obtains, and the content of the diamines of this above-mentioned general formula (1) expression accounts for 1～49mol% of total diamines.

3) according to 1) described in material for plating, wherein, above-mentioned resin layer further contains the Thermocurable composition.

4) according to 3) described in material for plating, wherein, above-mentioned Thermocurable composition contains the Resins, epoxy composition, described Resins, epoxy composition contains epoxy compounds and solidifying agent.

5) according to 1) described in material for plating, wherein, the second-order transition temperature of above-mentioned polyimide resin is 100～200 ℃ scope.

6) according to 5) described in material for plating, wherein, above-mentioned polyimide resin contains the diamines of above-mentioned general formula (1) expression, its content accounts for 10～75mol% of total diamines.

7) according to 1) described in material for plating, wherein, the weight-average molecular weight Mw of the above-mentioned polyimide resin of being obtained by gel permeation chromatography is 30000～150000.

8) according to 1) described in material for plating, wherein, above-mentioned polyimide resin has the protected group that forms of functional group and/or this functional group.

9) according to 8) described in material for plating, wherein, above-mentioned functional group is more than one the group that is selected from hydroxyl, amino, carboxyl, amide group, sulfydryl, the sulfonic group.

10) according to 1)～9) in any described material for plating, wherein, above-mentioned electroless plating covers and is electroless plating copper.

11) according to 1)～10) in any described material for plating, wherein, except that being used to implement resin layer that above-mentioned electroless plating covers, also have other layer, as all, constitute by the layer more than 2 layers at least.

12) according to 11) described in material for plating, wherein, above-mentioned other layer is the macromolecule membrane layer, at least one surface of this macromolecule membrane layer, is formed with and is used to implement the resin layer that electroless plating covers.

13) according to 11) described in material for plating, wherein, above-mentioned other layer is macromolecule membrane layer and adhesive layer, on at least one surface of this macromolecule membrane layer, be formed with and be used to implement the resin layer that electroless plating covers, and on the another side of above-mentioned macromolecule membrane layer, be formed with above-mentioned adhesive layer.

14) according to 12) or 13) described in material for plating, wherein, above-mentioned macromolecule membrane layer is non-thermoplastically Kapton.

15) a kind of single-layer sheet, it has used above-mentioned 1)～10) in any described material for plating, and this single-layer sheet only is made of above-mentioned resin layer.

16) a kind of insulating trip, it has above-mentioned 11)～14) in any described material for plating.

17) a kind of multilayer body, it is above-mentioned 1)～14) in any described material for plating, 15) described single-layer sheet or 16) resin layer surface in the described insulating trip, lamination the electroless plating coating form.

18) a kind of printed circuit board (PCB), it has above-mentioned 1)～14) in any described material for plating, 15) described single-layer sheet or 16) described insulating trip.

19) according to 18) described in printed circuit board (PCB), wherein, the surfaceness of above-mentioned resin layer is during the arithmetic average roughness Ra less than 0.5 μ m that measures under cutoff 0.002mm, at 150 ℃, the adhesion strength between above-mentioned resin layer and coating layer is more than the 5N/cm.

20) a kind of solution, this solution is used to form implements the resin layer that electroless plating covers, wherein, contain the polyimide resin that has siloxane structure at least or the precursor polyamic acid of this polyimide resin, above-mentioned polyimide resin is to make the reaction of acid dianhydride composition and two amine components and the polyimide resin that obtains, and described two amine components contain the diamines of above-mentioned general formula (1) expression.

21) according to 20) described in solution, wherein, above-mentioned polyimide resin is that two amine components with the diamines that contains above-mentioned general formula (1) expression are the polyimide resin that raw material obtains, and the content of the diamines of this above-mentioned general formula (1) expression accounts for 1～49mol% of total diamines.

22) according to 20) described in solution, wherein, also contain the thermoset composition.

23) according to 22) described in solution, wherein, above-mentioned thermoset composition contains the Resins, epoxy composition, described Resins, epoxy composition contains epoxy compounds and solidifying agent.

24) according to 20) described in solution, wherein, the second-order transition temperature of above-mentioned polyimide resin is 100～200 ℃ scope.

25) according to 24) described in solution, wherein, above-mentioned polyimide resin contains the diamines of above-mentioned general formula (1) expression, its content accounts for 10～75mol% of total diamines.

26) according to 20) described in solution, wherein, be 30000～150000 by the weight-average molecular weight Mw of the above-mentioned polyimide resin of gel permeation chromatography.

27) according to 20) described in solution, wherein, above-mentioned polyimide resin has the protected group that forms of functional group and/or this functional group.

28) according to 27) described in solution, wherein, above-mentioned functional group is more than one the group that is selected from hydroxyl, amino, carboxyl, amide group, sulfydryl, the sulfonic group.

By record shown below other purpose of the present invention, feature and advantage as can be known.In addition, effect of the present invention can be with reference to accompanying drawing and explanation, and is clearer.

The invention effect

Because the present invention has and is used to implement the resin layer that electroless plating covers, and this resin layer has used the polyimide resin with ad hoc structure, so can reach following effect, promptly, by implementing to be applied to various material surfaces when electroless plating covers, can improve and the tackiness of electroless plating between covering, and then can improve the welding thermotolerance.

Embodiment

At first, ultimate principle of the present invention is described.Intending implementing the material surface that electroless plating covers, form the resin layer (surface) that contains polyimide resin earlier with above-mentioned particular silicone structure, then implement electroless plating again and cover.At this moment, the resin layer that has excellent tackiness with the electroless plating coating and contain the polyimide resin with siloxane structure plays the effect of interlaminar bonding agent.Therefore, electroless plating coating and formed adhesion securely between the material of resin layer.And then above-mentioned resin layer is compared with existing tackiness resin layer, and the welding thermotolerance is also excellent.In addition, because the tackiness excellence between above-mentioned resin layer and the electroless plating coating, so need not to increase the surfaceness that is used to implement plating.Therefore, has the excellent advantage of fine wiring processing.

Use above excellent character, technology of the present invention is applicable on various decoration plating purposes or the function plating purposes.Meanwhile, also have the welding thermotolerance, even and under the little situation of surfaceness, also can apply flexibly the advantage that forms the electroless plating coating securely, therefore can be used as the material for plating of use in printed circuit board etc. well.

With regard to embodiment of the present invention, following describing.In addition, the present invention is not limited to following record.In order to make provision against emergencies, explanation hereby.

＜1. material for plating 〉

The material for plating that the present invention relates to has and is used to implement the resin layer that electroless plating covers, above-mentioned resin layer contains the polyimide resin that has siloxane structure at least, above-mentioned polyimide resin so long as make the acid dianhydride composition and contain above-mentioned general formula (1) expression diamines the reaction of two amine components and the polyimide resin that obtains gets final product, other concrete structure is not particularly limited.

That is,, do not do qualification about other structure, material, form, shape, size etc. as long as above-mentioned material for plating has above-mentioned resin layer.For example, as the form of above-mentioned material for plating, can enumerate sheet (film like), have curved shape, tubular, case shape, other complicated three-dimensional shape of stratiform (tabular), the sheet material of thickness etc.In addition, also can be the individual layer material for plating that only is made of the above-mentioned resin layer of individual layer, also can be the lamination material for plating that is made of above-mentioned resin layer and other layer (for example being used for and opposed adhesive layer of formed circuit or macromolecule membrane layer etc.).

＜1-1. resin layer 〉

Above-mentioned resin layer is to be used for implementing in its surface the layer that electroless plating covers, as long as this resin layer contains the polyimide resin of the siloxane structure with above-mentioned general formula (1) expression, there is no particular limitation to other concrete structure.Below, by exemplifying a plurality of embodiments, describe the feature structure of the resin layer that is used for material for plating of the present invention in detail.

Resin layer under the blending ratio situation of two amine components of＜1-1-1. regulation preparation polyimide resin 〉

Discoveries such as the inventor, as the raw material of the polyimide resin with siloxane structure, the content with the diamines (diamino siloxanes) of specifying siloxane structure is relevant with the welding thermotolerance, therefore this diamino siloxanes has been carried out detailed research.Found that,, when accounting for 1～49mol% of total diamines, can improve the welding thermotolerance when ratio with diamines of the siloxane structure of structure shown in the above-mentioned general formula (1), and very excellent.

In order to solve this problem, the inventor etc. are conceived to have the content of the diamines of above-mentioned siloxane structure at first, be characterised in that when having found to use the polyimide resin of the above-mentioned diamino siloxanes that contains certain specified quantitative, can access tackiness and the stable on heating material of welding between satisfied simultaneously and the electroless plating cover film.

Particularly, above-mentioned polyimide resin preferably contains the polyimide resin by the two amine components formation of acid dianhydride composition and the diamines that contains above-mentioned general formula (1) expression.That is above-mentioned polyimide resin acid dianhydride composition and contain the two amine components reaction of diamines of above-mentioned general formula (1) expression and the resin that obtains preferably.Below, above-mentioned acid dianhydride composition is described.

As the acid dianhydride composition that uses among the present invention, can suitably use the acid dianhydride that in making present known polyimide resin, uses, to its concrete structure, be not particularly limited.For example can enumerate, pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-the sulfobenzide tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic acid dianhydride, 1,2,3,4-furans tetracarboxylic acid dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylprop acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, to aromatic tetracarboxylic acid's dianhydrides such as benzene diphthalic anhydrides, 4,4 '-hexafluoro isopropylidene diphthalic anhydrides, 4,4 '-the two Tetra hydro Phthalic anhydrides of oxo, 3,4 '-the two Tetra hydro Phthalic anhydrides of oxo, 3,3 '-the two Tetra hydro Phthalic anhydrides of oxo, 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, 4,4 '-quinhydrones two (Tetra hydro Phthalic anhydride), 2, two (4-hydroxy phenyl) the propane dibenzoates-3 of 2-, 3 ', 4,4 '-tetracarboxylic dianhydride, ethylene two (trimellitic acid monoesters acid anhydrides), to benzene two (trimellitic acid monoesters acid anhydrides) etc.Can use separately wherein a kind of, also can make up wherein 2 kinds with on use.For many conditions such as blending ratio of this moment, so long as those skilled in the art just can appropriate combination set.

Above-mentioned two amine components then are described.In the present invention, as above-mentioned two amine components, by using two amine components of general formula (1) expression, resulting polyimide resin has the feature of adhering securely with the electroless plating coating.

As the diamines of general formula (1) expression, for example can enumerate 1,1,3,3-tetramethyl--1, two (4-aminophenyl) sily oxide of 3-, 1,1,3,3-four phenoxy groups-1, two (4-amino-ethyl) sily oxide of 3-, 1,1,3,3,5, the 5-vegolysen, two (4-aminophenyl) trisiloxanes of 5-, 1,1,3,3-tetraphenyl-1,3-two (2-aminophenyl) sily oxide, 1,1,3,3-tetraphenyl-1, two (3-aminopropyl) sily oxide of 3-, 1,1,5,5-tetraphenyl-3,3-dimethyl-1, two (3-aminopropyl) trisiloxanes of 5-, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-two (the amino butyl of 3-) trisiloxanes, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-two (the amino amyl group of 3-) trisiloxanes, 1,1,3,3-tetramethyl--1, two (2-amino-ethyl) sily oxide of 3-, 1,1,3,3-tetramethyl--1, two (3-aminopropyl) sily oxide of 3-, 1,1,3,3-tetramethyl--1,3-two (the amino butyl of 4-) sily oxide, 1,3-dimethyl-1,3-dimethoxy-1,3-two (the amino butyl of 4-) sily oxide, 1,1,5,5-tetramethyl--3,3-dimethoxy-1, two (2-amino-ethyl) trisiloxanes of 5-, 1,1,5,5-tetramethyl--3,3-dimethoxy-1,5-two (the amino butyl of 4-) trisiloxanes, 1,1,5,5-tetramethyl--3,3-dimethoxy-1,5-two (the amino amyl group of 5-) trisiloxanes, 1,1,3,3,5, the 5-vegolysen, two (3-aminopropyl) trisiloxanes of 5-, 1,1,3,3,5,5-Hexaethyl-1, two (3-aminopropyl) trisiloxanes of 5-, 1,1,3,3,5,5-six propyl group-1, two (3-aminopropyl) trisiloxanes of 5-etc.In addition, as in two amine components of general formula (1) expression than the diamines that is easier to obtain, can enumerate KF-8010, X-22-161A, X-22-161B, X-22-1660B-3, KF-8008, KF-8012, the X-22-9362 of Shin-Etsu Chemial Co., Ltd's manufacturing etc.Above-mentioned two amine components can use separately, also can two or more mixing use.

In addition, in order to improve thermotolerance, wet fastness, in above-mentioned polyimide resin, can also be used in combination above-mentioned two amine components and other two amine component.As other two amine component, can use all diamines, for concrete structure, do not do special qualification.For example can enumerate; mphenylenediamine; O-Phenylene Diamine; Ursol D; between aminobenzyl amine; PAB amine; two (3-aminophenyl) thioether; (3-aminophenyl) (4-aminophenyl) thioether; two (4-aminophenyl) thioether; two (3-aminophenyl) sulfoxide; (3-aminophenyl) (4-aminophenyl) sulfoxide; two (3-aminophenyl) sulfone; (3-aminophenyl) (4-aminophenyl) sulfone; two (4-aminophenyl) sulfone; 3; 4 '-diaminobenzophenone; 4; 4 '-diaminobenzophenone; 3; 3 '-diaminodiphenyl-methane; 3; 4 '-diaminodiphenyl-methane; 4; 4 '-diaminodiphenyl-methane; 4; 4 '-diamino-diphenyl ether; 3; 3 '-diamino-diphenyl ether; 3; 4 '-diamino-diphenyl ether; two [4-(3-amino-benzene oxygen) phenyl] sulfoxide; two [4-(amino-benzene oxygen) phenyl] sulfoxide; 4; 4 '-diamino-diphenyl ether; 3; 4 '-diamino-diphenyl ether; 3; 3 '-diamino-diphenyl ether; 4; 4 '-the diamino-diphenyl thioether; 3; 4 '-the diamino-diphenyl thioether; 3; 3 '-the diamino-diphenyl thioether; 3; 3 '-diaminodiphenyl-methane; 3; 4 '-diaminodiphenyl-methane; 4; 4 '-diaminodiphenyl-methane; 4; 4 '-diamino diphenyl sulfone; 3; 4 '-diamino diphenyl sulfone; 3; 3 '-diamino diphenyl sulfone; 4; 4 '-the diaminobenzene formylaniline; 3; 4 '-the diaminobenzene formylaniline; 3; 3 '-the diaminobenzene formylaniline; 4; 4 '-diaminobenzophenone; 3; 4 '-diaminobenzophenone; 3; 3 '-diaminobenzophenone; two [4-(3-amino-benzene oxygen) phenyl] methane; two [4-(4-amino-benzene oxygen) phenyl] methane; 1; two [4-(3-amino-benzene oxygen) phenyl] ethane of 1-; 1; two [4-(4-amino-benzene oxygen) phenyl] ethane of 1-; 1; two [4-(3-amino-benzene oxygen) phenyl] ethane of 2-; 1; two [4-(4-amino-benzene oxygen) phenyl] ethane of 2-; 2; two [4-(3-amino-benzene oxygen) phenyl] propane of 2-; 2; two [4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2; two [4-(3-amino-benzene oxygen) phenyl] butane of 2-; 2; two [3-(3-amino-benzene oxygen) phenyl]-1 of 2-; 1,1,3; 3; the 3-HFC-236fa; 2, two [4-(4-amino-benzene oxygen) phenyl]-1,1 of 2-; 1; 3,3, the 3-HFC-236fa; 1; two (3-amino-benzene oxygen) benzene of 3-; 1; two (3-amino-benzene oxygen) benzene of 4-; 1,4 '-two (4-amino-benzene oxygen) benzene; 4,4 '-two (4-amino-benzene oxygen) biphenyl; two [4-(3-amino-benzene oxygen) phenyl] ketone; two [4-(4-amino-benzene oxygen) phenyl] ketone; two [4-(3-amino-benzene oxygen) phenyl] thioether; two [4-(4-amino-benzene oxygen) phenyl] thioether; two [4-(3-amino-benzene oxygen) phenyl] sulfone; two [4-(4-amino-benzene oxygen) phenyl] sulfone; two [4-(3-amino-benzene oxygen) phenyl] ether; two [4-(4-amino-benzene oxygen) phenyl] ether; 1; two [4-(3-amino-benzene oxygen) benzoyl] benzene of 4-; 1; two [4-(3-amino-benzene oxygen) benzoyl] benzene of 3-; 4,4 '-two [3-(4-amino-benzene oxygen) benzoyl] diphenyl ether; 4,4 '-two [3-(3-amino-benzene oxygen) benzoyl] diphenyl ether; 4; 4 '-two [4-(4-amino-α; α-Er Jiajibianji) phenoxy group] benzophenone; 4,4 '-two [4-(4-amino-α, α-Er Jiajibianji) phenoxy group] sulfobenzide; two [4-{4-(4-amino-benzene oxygen) phenoxy group } phenyl] sulfone; 1; two [the 4-(4-amino-benzene oxygen)-α of 4-; α-Er Jiajibianji] benzene; 1, two [4-(4-amino-benzene oxygen)-α, the α-Er Jiajibianji] benzene of 3-; 3; 3 '-dihydroxyl-4,4 '-benzidine etc.

Here, the diamino siloxanes of above-mentioned general formula (1) expression is preferably 1～49mol% with respect to total two amine components, more preferably 3～45mol%, further preferred 5～40mol%.When diamino siloxanes during with respect to the not enough 1mol% of total two amine components, the resin layer that contains polyimide resin reduces with the adhesion strength between the electroless plating cover film, when content surpasses 49mol%, and the reduction of welding thermotolerance.

Above-mentioned polyimide resin is, the polyamic acid polymer dehydration closed-loop by correspondence makes.The precursor polyamic acid polymkeric substance is above-mentioned acid dianhydride composition and two amine components are reacted with moles such as reality and to obtain.The manufacture method of above-mentioned polyimide resin, as long as have above-mentioned acid dianhydride composition and two amine components,, can carry out in the same manner with the manufacture method of present known polyimide resin as for other many conditions etc., to its concrete operation etc., do not do special qualification.Below explanation prepares the exemplary steps of polyamic acid polymer solution.

As the exemplary of polymerization process, can exemplify method as described below.That is,

1) aromatic diamine compound is dissolved in the organic polar solvent, makes itself and equimolar aromatic tetracarboxylic acid's two anhydride reactants of essence and the polymeric method.

2) in organic polar solvent, aromatic tetracarboxylic acid's dianhydride and aromatic diamine compound are reacted, obtain the prepolymer that two ends have anhydride group, here, aromatic diamine compound is few molar weight with respect to aromatic tetracarboxylic acid's dianhydride.Then, become the equimolar mode of essence, use aromatic diamine compound to carry out single phase or multistage polymerization process with aromatic tetracarboxylic acid's dianhydride and the aromatic diamine compound that in whole operation, uses.

3) in organic polar solvent, make the reaction of aromatic tetracarboxylic acid's dianhydride and aromatic diamine compound, obtain two ends and have amino prepolymer, here, aromatic diamine compound is an excess molar amounts with respect to aromatic tetracarboxylic acid's dianhydride.Then, after it replenishes the interpolation aromatic diamine compound, become the equimolar mode of essence with aromatic tetracarboxylic acid's dianhydride and the aromatic diamine compound that in whole operation, uses, use aromatic tetracarboxylic acid's dianhydride to carry out single phase or multistage polymerization process.

4) with after the dissolving of aromatic tetracarboxylic acid's dianhydride and/or being dispersed in the organic polar solvent, use aromatic diamine to carry out the polymeric method in the equimolar mode of essence.

5) in organic polar solvent, the mixture of equimolar aromatic tetracarboxylic acid's dianhydride of essence and aromatic diamine is reacted and the polymeric method.

These methods can be used separately, also can partly be used in combination.

" dissolving " described in this specification sheets be meant, desolventize outside the situation of dissolving solute fully, also comprises the solute homodisperse or be dispersed in the solvent and become situation with dissolving essence equal state.In addition, the reaction times during the preparation polyamic acid polymer, temperature of reaction are carried out after can suitably selecting according to ordinary method, do not do special qualification.

The organic polar solvent that uses in the polyreaction of polyamic acid can suitably select organic polar solvent to use according to above-mentioned two amine components and acid dianhydride composition in the solvent that use from the preparation of present known polyamic acid, do not do special qualification.For example can enumerate sulfoxide series solvents such as methyl-sulphoxide, ethyl-sulfoxide; N, dinethylformamide, N, the methane amide series solvent of N-diethylformamide etc.; N,N-dimethylacetamide, N, the ethanamide series solvent of N-diethyl acetamide etc.; N-methyl-2-pyridine alkane ketone, N-vinyl-pyridine alkane ketone series solvents such as 2-pyridine alkane ketone; The phenol series solvent of phenol, o-, m-or p-cresols, xylenol, halogenated phenol, pyrocatechol etc.; Perhaps hexamethylphosphoramide, gamma-butyrolactone etc.Further also can be used in combination the aromatic hydrocarbons of organic polar solvent and dimethylbenzene or toluene etc. as required.

By heat or chemical process, the solution dehydrates closed loop of the polyamic acid polymer that will obtain by aforesaid method, thus obtain polyimide resin.When making the solution dehydrates closed loop of polyamic acid polymer, carry out after also can suitably selecting according to conventional methods, for concrete grammar, do not do special qualification.For example can use by the use of thermal means that the thermal treatment polyamic acid solution realizes dewatering, use in the chemical process that dewatering agent realizes dewatering any one.In addition, can also use under decompression state by heating the method that realizes imidization.Below, each method is described.

As hot dehydration closed-loop method, can enumerate by the above-mentioned polyamic acid solution of heat treated and carry out imidization reaction, simultaneously the method for evaporating solvent.By this method, can obtain the solid polyimide resin.There is no particular limitation for heating condition, but preferred under the temperature below 200 ℃, carries out in 1 second～200 minutes the time range.

In addition, can enumerate, in above-mentioned polyamic acid solution, add dewatering agent and catalyzer more than the stoichiometry, carry out dehydration reaction thus, the method for evaporating organic solvent simultaneously as the chemical dehydration closed-loop policy.Can access the solid polyimide resin thus.As dewatering agent, for example can enumerate the aromatic anhydride etc. of the aliphatic anhydride, st-yrax acid anhydrides etc. of diacetyl oxide etc.In addition, as catalyzer, can exemplify the heterocycle tertiary amines etc. of the aromatic tertiary amine, pyridine, α-Jia Jibiding, beta-picoline, γ-picoline, isoquinoline 99.9 etc. of the aliphatic tertiary amine class, xylidine etc. of triethylamine etc.Condition optimization during the chemical dehydration closed loop is under the temperature below 100 ℃, and evaporation preferably under 200 ℃ of following temperature, is carried out in 5～120 minutes time range during organic solvent.

In addition, be used to prepare other method of polyimide resin, the method for not carrying out the evaporation of solvent in the dehydration closed-loop method of above-mentioned heat or chemistry is also arranged.Particularly, at first, will carry out that hot-imide is handled or chemical imidization is handled and the polyimide solution that obtains joins in the poor solvent, separate out polyimide resin.Then, remove unreacted monomer, make with extra care, drying, obtain the solid polyimide resin.Preferably select to have and to mix well with solvent as poor solvent, but be difficult to dissolve the solvent of the character of polyimide resin.Can exemplify acetone, methyl alcohol, ethanol, Virahol, benzene, methylcyclohexane, methylethylketone etc., but be not limited to this, can use present known all kinds of SOLVENTS with above-mentioned character.

Then the method that polyamic acid polymer solution carries out imidization is under reduced pressure heated in explanation.According to this imidization method, can will be rejected to outside the system by the water that imidization generates energetically, so can suppress the hydrolysis of polyamic acid, can access the high-molecular weight polyimide.In addition, according to this method, be present in one-sided or both sides ring-opening product closed loop again in the raw material acid dianhydride as impurity, so can expect further to improve the effect of molecular weight.

Decompression adds in the method for hot-imide down, and its heating condition is preferably at 80～400 ℃, and is more preferably more than 100 ℃, can carry out imidization better and can remove better and anhydrate, further preferred more than 120 ℃.Top temperature preferably below the heat decomposition temperature of purpose polyimide resin, is suitable for the end temp of general imidization usually, that is, and and about 250～350 ℃.

Although the pressure condition of decompression is the smaller the better, particularly, is 9 * 10 ⁴～1 * 10 ²Pa, preferred 8 * 10 ⁴～1 * 10 ²Pa, more preferably 7 * 10 ⁴～1 * 10 ²Pa.This is because decompression pressure hour, reduces the efficient of removing of the water that generated by imidization, causes the inadequate situation of imidization, situations such as the polyimide molecule amount reduction that perhaps obtains.

Polyimide resin more than has been described, but, in can be used in the resin of resin layer of the present invention, the example of the polyimide resin that contains siloxane structure that obtains easily can be enumerated X-22-8917, X-22-8904, X-22-8951, X-22-8956, X-22-8984, X-22-8985 etc. that Shin-Etsu Chemial Co., Ltd makes as a comparison.In addition, these materials are commercially available with the form of polyimide solution.

In addition, in order to improve the various characteristicses such as Young's modulus under thermotolerance, wet fastness, the high temperature, in above-mentioned resin layer, except that above-mentioned polyimide resin, can also use other thermoplastic resin or heat-curing resin.As this thermoplastic resin, for example can enumerate, polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, phenoxy resin, (not having siloxane structure) thermoplastically polyimide resin etc. can use or be used in combination more than 2 kinds above-mentioned resin separately.

In addition, as heat-curing resin, can enumerate bimaleimide resin, diallyl Na Dike acid imide resin (PVC ス ア リ Le Na ジ イ ミ De), resol, cyanate ester resin, Resins, epoxy, acrylic resin, methacrylic resin, cyanate resin, hydrogenation silyl cured resin, allyl group cured resin, unsaturated polyester resin etc., can use separately or appropriate combination is used above-mentioned resin.In addition, except that above-mentioned heat-curing resin, can also use side chain or terminal side chain reactive group type Thermocurable polymer with reactive group of epoxide group, allyl group, vinyl, alkoxysilyl, hydrogenation silyl etc. at macromolecular chain.

And, for the tackiness of further raising, various additives can be added in the resin layer or with various additives to being coated on methods such as resin layer surface with above-mentioned electroless plating coating, it is present in the resin layer.Above-mentioned various additive in reaching the scope of above-mentioned purpose, can suitably use present known composition, does not do special qualification.Specifically can exemplify organic mercaptan compound etc.

Except that mentioned component, can be as required, in above-mentioned resin layer, add present known additive, for example, antioxidant, photostabilizer, fire retardant, static inhibitor, thermo-stabilizer, UV light absorber, electroconductibility weighting agent (various organic fillers, mineral filler), inorganic earthfill rockfill concrete riprap RCC or various tougheners etc.These additives can carry out appropriate selection according to the kind of polyimide resin, to its classification, do not do special qualification.In addition, these additives can use separately, also can a plurality ofly be used in combination.In addition, the electroconductibility weighting agent generally is meant by all substrate material that is covered of the conductive material with carbon, graphite, metallics, tin indium oxide etc. and has given the material of electroconductibility.By adding various organic fillers, mineral filler, make it the surfaceness that reaches certain, can either not damage the formation of fine wiring, also can improve and the Coated tackiness of electroless plating.

But above-mentioned various other compositions that add in the resin layer preferably carry out in the scope of not violating the object of the invention.That is, add various other compositions in the resin layer to, be preferably limited to the surfaceness that does not make resin layer and become greater to adding on the dysgenic degree of fine wiring formation generation.In addition, add various other compositions in the resin layer to, preferably in the adhesive scope that does not reduce resin layer and electroless plating coating, make up.

In addition, the thickness of above-mentioned resin layer is preferably more than 10 .

In addition, above-mentioned material for plating can be sheet (a perhaps film like).When material for plating is sheet, also can be the lamination sheet material for plating that constitutes by resin layer and other layer, perhaps also can be the individual layer sheet material for plating that only constitutes by above-mentioned resin layer.When material for plating is the lamination sheet, as long as on the face (also can be two-sided) of at least one side of sheet, be formed with above-mentioned resin layer.When material for plating was the individual layer sheet, used on this flaky two-sided surface that is used to form the electroless plating coating that all can be used as.

In addition, when material for plating is sheet (perhaps film like), some lining papers (screening glass) are set on above-mentioned preferably.As such lining paper, for example apply, when dry resin solution prepares, above-mentioned supporter can be used as lining paper by curtain coating on supporter when above-mentioned.That is, above-mentioned sheet material for plating is integrated together with the supporter lamination, peels off this supporter then, supporter can be used as lining paper thus.As above-mentioned supporter, can suitably use tinsels such as the various resin films of PET etc. or aluminium foil, Copper Foil.In addition,, also can peel the sheet material for plating, teflon (teflon) resin sheets such as (registered trademarks) is used for this sheet material for plating as new lining paper from above-mentioned supporter as other method.In addition, in either event, preferred lining paper can be peeled off from resin layer, and forms such concavo-convex or defective in order to make resin layer surface not produce the fine wiring of damage, and preferred lining paper is enough level and smooth.

In addition, above-mentioned resin layer have and the electroless plating coating between the high advantage of adhesion strength, even if under the little situation of surfaceness, also be so.Here, the surfaceness that the present invention relates to is used in the arithmetic average roughness Ra that measures under the cutoff 0.002mm and represents.In JIS B 0601 (put down into and corrected version on February 1st, 6), defined arithmetic average roughness Ra.Especially, the numeric representation of arithmetic average roughness Ra of the present invention uses light interference type surface structure analysis device to observe the surface and the numerical value that obtains.Cutoff of the present invention is record to some extent in above-mentioned JIS B 0601, the wavelength that its expression is set when obtaining roughness curve by sectional curve (actual measurement data).That is, the value Ra that measures under cutoff 0.002mm has the arithmetic average roughness of calculating greater than the concavo-convex roughness curve of the wavelength of 0.002mm by removing from actual measurement data.

The arithmetic average roughness Ra less than 0.5 μ m that the surfaceness of above-mentioned resin layer is preferably measured under cutoff 0.002mm.Satisfying under the situation of this condition, when especially material for plating being used for the printed circuit board (PCB) purposes, having good fine wiring formation property.In order to reach state, preferably do not implement the physical surface roughening of sandblast etc. etc. with this surface.

According to the structure of aforesaid resin layer, also high even do not implement surface roughening with the adhesion strength of electroless plating coating, and the tackiness of material for plating of the present invention and other various materials is also excellent.Therefore,, at first form material for plating of the present invention, and then implement electroless plating and cover, then have the advantage that material for plating of the present invention and electroless plating coating are firmly adhered intend implementing the material surface that electroless plating covers.In addition, material for plating of the present invention can become the material of welding excellent heat resistance, so can be applicable to the manufacturing of various printed circuit board (PCB)s by containing the polyimide resin of specified quantitative, ad hoc structure.And then, even do not implement under the situation of surface roughening, and the adhesion strength between the electroless plating coating is also high, therefore and have the stable on heating advantage of sufficient welding, can be applicable in the manufacturing etc. of the printed circuit board (PCB)s such as flexible printed circuit board, printed circuit board, multi-layer flexible printed circuit board or combination (PVC Le De ア Star プ (built-up)) circuit card that require to form fine wiring.

＜1-1-2. contains the resin layer of polyimide resin and Thermocurable composition 〉

In addition, other embodiment of the present invention is described.That is, above-mentioned resin layer is to be used for implementing the layer that electroless plating covers on its surface, preferably contains the polyimide resin of the siloxane structure with above-mentioned general formula (1) expression and the material of Thermocurable composition, does not do special qualification for other concrete structure.

In the explanation to above-mentioned polyimide resin, with above-mentioned＜1-1-1〉the identical part of explanation in the hurdle omits, and distinct portions only is described.Distinct portions only is in two amine components,, has the blending ratio difference of diamines of the siloxane structure of above-mentioned general formula (1) that is.Particularly, here, the diamines of above-mentioned general formula (1) expression is 5～98mol%, more preferably 8～95mol% with respect to total two amine components preferably.This is because when the diamines of above-mentioned general formula (1) expression was less than 5mol% with respect to total two amine components, resulting polyimide resin may reduce with the tackiness of copper plate.In addition, the diamines of representing when general formula (1) contains sometimes to exceed the 98mol% ratio with respect to total two amine components, and the tackiness of resulting polyimide resin is too high, can be detrimental to operability.Like this, when polyimide resin had tackiness, foreign matter such as dust adhered to, produce the plating condition of poor by foreign matter when copper facing forms, so the unfavorable condition of having because have sometimes.For above-mentioned reasons, preferably contain the diamines of above-mentioned general formula (1) expression with the ratio of 5～98mol%, more preferably contain resulting polyimide resin with the ratio of 8～95mol% with respect to total two amine components with respect to total two amine components.

With above-mentioned＜1-1-1〉explanation in the hurdle different be except that polyimide resin, also to contain the Thermocurable composition on the resin layer.Except that this point, can quote above-mentioned＜1-1-1〉explanation on hurdle.

Then, the Thermocurable composition that is used for above-mentioned resin layer is described.Above-mentioned Thermocurable composition can suitably utilize known resin with Thermocurable at present, as its concrete structure, does not do special qualification.As the resin that constitutes above-mentioned Thermocurable composition, can enumerate, bimaleimide resin, diallyl Na Dike acid imide resin, resol, cyanate ester resin, Resins, epoxy, acrylic resin, methacrylic resin, cyanate resin, hydrogenation silyl cured resin, allyl group cured resin, unsaturated polyester resin etc. can use separately or appropriate combination is used above-mentioned resin.

In addition, except that above-mentioned Thermocurable composition, for example can also use side chain or terminal side chain reactive group type Thermocurable polymer with reactive group of epoxide group, allyl group, vinyl, alkoxysilyl, hydrogenation silyl, hydroxyl etc. at macromolecular chain.To these Thermocurable compositions, in order to improve thermotolerance, tackiness etc., can be as required, suitably add normally used epoxy hardener, crosslinking coagent, various couplants etc. such as the free radical reaction initiator, reaction promotor, triallyl cyanurate, triallyl isocyanurate etc. of organo-peroxide etc. or acid dianhydride system, amine system, imidazoles.

In these Thermocurable compositions, the preferred material that contains the Resins, epoxy composition that uses, this Resins, epoxy composition comprises epoxy compounds and solidifying agent.This is because Resins, epoxy is excellent on its processibility, electrical characteristic etc.Below, as the Thermocurable composition among the present invention, describe in detail by the material that uses Resins, epoxy, but the present invention is not limited to following formation.

The Resins, epoxy of Shi Yonging is so long as intramolecularly has the compound of the reactive epoxy groups more than 2 gets final product in the present invention, particularly, can enumerate for example bisphenol-type epoxy resin, bisphenol-A phenolic varnish type Resins, epoxy, biphenyl type epoxy resin, phenol novolak type epoxy resin, the alkylphenol phenolic resin varnish type epoxy resin, polyglycol type Resins, epoxy, cyclic aliphatic epoxy resin, o-cresol phenolic epoxy varnish, glycidyl amine type epoxy resin, naphthalene type Resins, epoxy, polyurethane modified epoxy resin, rubber modified epoxy resin, epoxy resins such as epoxy-modified polysiloxane; Their halogenated epoxy resin; Has the crystallinity Resins, epoxy of fusing point etc.These Resins, epoxy can only use a kind of, also can be used in combination by arbitrary proportion more than 2 kinds.

In these Resins, epoxy, preferably use Resins, epoxy, biphenyl type epoxy resin, the naphthalene type Resins, epoxy that has an aromatic nucleus and/or aliphatics ring in the molecular chain at least, crystallinity Resins, epoxy with fusing point with naphthalene skeleton with biphenyl backbone.In addition, these Resins, epoxy obtain easily, and the intermiscibility excellence, can give excellent thermotolerance and insulativity to the resin after solidifying.

In above-mentioned each Resins, epoxy, can further preferably use crystallinity Resins, epoxy or have the Resins, epoxy of representing among the formula group as follows (Chemical formula 2).

[Chemical formula 2]

(in the formula, q, r, s represent arbitrary integer respectively independently).

If use these Resins, epoxy, when then can give characteristic such as thermotolerance, can also form the well balanced material of many characteristics to material for plating of the present invention.

Above-mentioned crystallinity Resins, epoxy is so long as contain the Resins, epoxy of the crystalline texture with fusing point and get final product, just there is no particular limitation, particularly, for example preferred commodity in use name: YX4000H (manufacturing of japan epoxy resin Co., Ltd., biphenyl type epoxy resin), trade(brand)name: EXA7337 (manufacturing of big Japanese ink Industrial Co., Ltd, xanthene type Resins, epoxy) etc.

In addition, the Resins, epoxy that uses among the present invention can be above-mentioned any one Resins, epoxy, but preferred highly purified Resins, epoxy.The material for plating of the present invention that obtains thus can be realized the electrical insulating property that reliability is high.In the present invention, above-mentioned highly purified standard is halogen and the alkali-metal concentration that contains that contains in the Resins, epoxy.Particularly, halogen that contains in the Resins, epoxy and the alkali-metal concentration that contains are below the 25ppm during extraction under 120 ℃, 2 atmospheric pressure preferably, more preferably below the 15ppm.This be because, when halogen and the alkali-metal concentration that contains are higher than 25ppm, the resin after curing then, the reliability of its electrical insulating property is impaired.

In addition, contain the polyimide resin (thermoplastically polyimide) with siloxane structure of the present invention and the resin layer of Thermocurable composition, the mole number of epoxide group that contains in the resin combination 100g that forms this resin layer and the hydroxyl that generated by its ring-opening reaction is preferably in 0.01 mole～0.2 mole scope.The Resins, epoxy that uses in the Thermocurable composition of the present invention is particularly preferably on the basis of having considered its oxirane value (also being epoxy equivalent (weight)), determines and has the combined amount of the polyimide resin composition of siloxane structure.

Promptly, when using the big Resins, epoxy of epoxy equivalent (weight), than using epoxy equivalent (weight) circlet epoxy resins, even the combined amount of Resins, epoxy is many, also can satisfy the epoxide group that contains among the resin combination 100g that is used to form above-mentioned resin layer and the mole number of the hydroxyl that produces by its ring-opening reaction in the scope below 0.2 mole.

Mix excessive Resins, epoxy, then the combined amount of polyimide resin tails off.At this moment, have dielectric characteristics as the advantageous feature of polyimide resin, electrical insulating property and and the electroless plating coating between the tendency of tackiness variation.

Promptly, for the tackiness that makes material for plating of the present invention, thermotolerance, electrical insulating property etc. reach balance, the mole number of the hydroxyl that is necessary to make the epoxide group that contains among the resin combination 100g that forms above-mentioned resin layer and is generated by its ring-opening reaction is below 0.2 mole, further, in order to determine each combined amount, preferred Resins, epoxy of selecting to have suitable epoxy equivalent (weight).

On the one hand, if the combined amount of Resins, epoxy is very few, the tendency that then has the welding thermotolerance to reduce.Therefore, in forming the resin combination 100g of above-mentioned resin layer, preferably contain the epoxide group more than 0.01 mole and the mole number of the hydroxyl that generates by its ring-opening reaction.

In view of the foregoing, the epoxy equivalent (weight) of preferred employed Resins, epoxy is more than 150, more preferably more than 170, more preferably more than 190.In addition, the higher limit of the oxirane value of above-mentioned Resins, epoxy is preferably below 700, more preferably below 500, more preferably below 300.Therefore, the oxirane value of preferred above-mentioned Resins, epoxy is in 150～700 scope.

If the epoxy equivalent (weight) less than 150 of above-mentioned curable epoxy resin composition, then satisfy scope below 0.2 mole for the mole number of the hydroxyl that makes the epoxide group that contains among the resin combination 100g that contains polyimide resin and Thermocurable composition and generate by its ring-opening reaction, have to reduce the combined amount of Resins, epoxy, so the welding thermotolerance of material for plating of the present invention also reduces.On the one hand, if oxirane value surpasses 700, then the cross-linking density in the cured resin reduces, so have the situation that the welding thermotolerance reduces.

The Resins, epoxy that uses in the Thermocurable composition of material for plating of the present invention preferably uses suitable solidifying agent, curing catalyst.

Above-mentioned curing agent for epoxy resin is not particularly limited so long as to have the compound of activation hydrogen more than 2 in molecule just passable.As the activation hydrogen source, can enumerate amino, carboxyl, phenol hydroxyl, alcohol hydroxyl group, thiol group or the like functional group, can suitably use compound with these functional groups.In these compounds, the preferred use has amino amine epoxy hardener and the poly-phenols epoxy hardener with phenol hydroxyl.If use above-mentioned epoxy hardener, then can access the material for plating of balance of properties excellence.

As above-mentioned poly-phenols epoxy hardener, for example can enumerate phenol phenolic varnish (phenolnovolac), xylylene phenolic varnish, bisphenol-A phenolic varnish, tritane phenolic varnish, xenol Novolac, Dicyclopentadiene (DCPD) phenol phenolic varnish etc., there is no particular limitation for its concrete structure.In addition, in order to give excellent dielectric characteristics, preferably use the big material of hydroxyl equivalent, preferred hydroxyl equivalent is more than the 100g/eq, more preferably more than the 150g/eq, more than the further preferred 200g/eq.

In addition, above-mentioned amine epoxy hardener composition can use present known amine epoxy hardener composition so long as contain the material of at least a amine compound and get final product.For example can enumerate monoamines such as aniline, benzylamine, amido hexane; Various two amines that exemplify at two amine components that are used for making above-mentioned polyamic acid; Polyamines classes such as Diethylenetriaminee (DETA), tetraethylenepentamine, pentaethylene hexamine etc.

In addition, in above-mentioned amine, preferably use aromatic diamine, preferably contain the aromatic diamine of molecular weight more than 300, more preferably contain the aromatic diamine of molecular weight in 300～600 scope.By using above-mentioned aromatic diamine, can give good thermotolerance and dielectric characteristics to the cured resin after solidifying.In addition, if the molecular weight less than 300 of above-mentioned aromatic diamine, the polar group that contains in the structure of the cured resin after then solidifying becomes many, so damage dielectric characteristics sometimes.That is, the specific inductivity of cured resin or dielectric loss tangent uprise sometimes.On the one hand, if molecular weight surpasses 600, then the cross-linking density in the cured resin reduces, and therefore thermotolerance is impaired sometimes.

As above-mentioned aromatic diamine; can use present known aromatic diamine; do not do special qualification; but particularly; for example can enumerate; 1; the 4-diaminobenzene; 1; the 3-diaminobenzene; 2; 5-dimethyl-1; the 4-diaminobenzene; 1; the 2-diaminobenzene; p-diaminodiphenyl; 3; 3 '-dichlorobenzidine; 3; 3 '-tolidine; 3; 3 '-dimethoxy benzidine; 3; 3 '-dihydroxybiphenyl amine; 3,3 ', 5; 5 '-tetramethyl benzidine; 2; 2 '-dimethyl-4,4 '-benzidine; 2,2 '-two (trifluoromethyl)-4; 4 '-benzidine; 3; 3 '-diaminodiphenylmethane; 3,4 '-diaminodiphenylmethane; 4,4 '-diaminodiphenylmethane; 4; 4 '-the diamino diphenyl propane; 4; 4 '-the diamino-diphenyl HFC-236fa; 4,4 '-diamino-diphenyl silane; 4,4 '-the diamino-diphenyl diethylsilane; 4; 4 '-diamino-diphenyl ethyl phosphine oxide; 4; 4 '-diamino-diphenyl N-methylamine; 4,4 '-diamino-diphenyl N-aniline; 3,3 '-diaminodiphenyl oxide; 3; 4 '-diaminodiphenyl oxide; 4; 4 '-diaminodiphenyl oxide; 3,3 '-diaminodiphenyl sulfide; 3,4 '-diaminodiphenyl sulfide; 4; 4 '-diaminodiphenyl sulfide; 3; 3 '-diaminodiphenylsulfone(DDS); 3,4 '-diaminodiphenylsulfone(DDS); 4,4; 3; 3 '-the diaminobenzene formylaniline; 3; 4 '-the diaminobenzene formylaniline; 4,4 '-the diaminobenzene formylaniline; 3,3 '-diaminobenzophenone; 3; 4 '-diaminobenzophenone; 4; 4 '-diaminobenzophenone; 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-; two [4-(3-amino-benzene oxygen) phenyl] methane; two [4-(4-amino-benzene oxygen) phenyl] methane; 1, two [4-(3-amino-benzene oxygen) phenyl] ethane of 1-; 1, two [4-(4-amino-benzene oxygen) phenyl] ethane of 1-; 1; two [4-(3-amino-benzene oxygen) phenyl] ethane of 2-; 1; two [4-(4-amino-benzene oxygen) phenyl] ethane of 2-; 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-; 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2; two [4-(3-amino-benzene oxygen) phenyl] butane of 2-; 2; two [4-(4-amino-benzene oxygen) phenyl] butane of 2-; 2, two [4-(3-amino-benzene oxygen) phenyl]-1,1 of 2-; 1; 3,3, the 3-HFC-236fa; 2; two [4-(4-amino-benzene oxygen) phenyl]-1 of 2-; 1,1,3; 3; the 3-HFC-236fa; 4,4 '-two (3-amino-benzene oxygen) biphenyl; 4,4 '-two (4-amino-benzene oxygen) biphenyl; two [4-(3-amino-benzene oxygen) phenyl] ketone; two [4-(4-amino-benzene oxygen) phenyl] ketone; two [4-(3-amino-benzene oxygen) phenyl] thioether; two [4-(4-amino-benzene oxygen) phenyl] thioether; two [4-(3-amino-benzene oxygen) phenyl] sulfone; two [4-(4-amino-benzene oxygen) phenyl] sulfone; two [4-(3-amino-benzene oxygen) phenyl] ether; two [4-(4-amino-benzene oxygen) phenyl] ether; 1; two [4-(3-amino-benzene oxygen) benzoyl] benzene of 4-; 1; two [4-(3-amino-benzene oxygen) benzoyl] benzene of 3-; 4,4 '-two [3-(4-amino-benzene oxygen) benzoyl] phenyl ether; 4,4 '-two [3-(3-amino-benzene oxygen) benzoyl] phenyl ether; 4; 4 '-two [4-(4-amino-α; α-Er Jiajibianji) phenoxy group] benzophenone; 4,4 '-two [4-(4-amino-α, α-Er Jiajibianji) phenoxy group] sulfobenzide; two [4-{4-(4-amino-benzene oxygen) phenoxy group } phenyl] sulfone; 1; two [the 4-(4-amino-benzene oxygen)-α of 4-; α-Er Jiajibianji] benzene; 1, two [4-(4-amino-benzene oxygen)-α, the α-Er Jiajibianji] benzene of 3-; 1; the 5-diaminonaphthalene; 9,9 '-two (4-aminophenyl) fluorenes etc.These diamines can only use a kind of, also can be used in combination by arbitrary proportion more than 2 kinds.

Wherein, especially can preferably use 2, two [4-(3-amino-benzene oxygen) phenyl] propane, 2 of 2-, two [4-(4-amino-benzene oxygen) phenyl] propane, 2 of 2-, two [3-(3-amino-benzene oxygen) phenyl]-1 of 2-, 1,1,3,3,3-HFC-236fa, 2, two [4-(4-amino-benzene oxygen) phenyl]-1,1 of 2-, 1,3,3,3-HFC-236fa, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] ether, two [4-(4-amino-benzene oxygen) phenyl] ether.These compounds not only from the operability that easily is dissolved in solvent etc. and easily aspect consideration such as acquisitions be excellent, also be by in amine component, containing these compounds, can make the resin after the curing become all excellent resin of many characteristics such as thermotolerance (second-order transition temperature is high), dielectric characteristics.

The combined amount of polyimide resin and Thermocurable composition, preferably with respect to the polyimide resin of 100 weight parts, the Thermocurable composition is 1～100 weight part, more preferably 3～70 weight parts especially are preferably 5～50 weight parts.In addition, the cured resin in cure component and the combined amount of solidifying agent according to the kind of employed cured resin and solidifying agent and different, are decided so can't summarize.As long as use suitable combined amount.

In addition, in the present invention, preferably use curing catalyst, it is used to promote the curing reaction of above-mentioned Resins, epoxy.

As the curing catalyst that uses among the present invention, can use present known curing catalyst, to its concrete structure, do not do special qualification.Particularly, for example can enumerate phosphine based compounds such as imidazolium compounds class, triphenylphosphine; Aminated compoundss such as tertiary amine system, trimethanolamine, trolamine, tetrem hydramine; 1,8-diaza-dicyclo [5,4,0]-11 carbon-borate-based compounds such as 7-alkene-tetraphenyl borate etc.These curing catalysts can only use a kind of, also can be used in combination by arbitrary proportion more than 2 kinds.

Wherein preferred imidazolium compounds class.Particularly, for example can enumerate imidazoles, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazoles, 2 isopropyl imidazole, 2, imidazoles such as 4-methylimidazole, 2-phenyl-4-methylimidazole; Glyoxal ethyline quinoline, 2-ethyl imidazol(e) quinoline, 2 isopropyl imidazole quinoline, 2-benzylimidazoline, 2-undecyl imidazole quinoline, 2,4-methylimidazole quinoline, 2-phenyl-imidazolines such as 4-methylimidazole quinoline; 2,4-diamino-6-[2 '-methylimidazolyl-(1 ')]-ethyl-s-triazine, 2,4-diamino-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine, 2,4-diamino-6-[2 '-ethyl-4 '-methylimidazolyl-(1 ')]-ethyl-piperazines such as s-triazine are imidazoles etc.These imidazoles can only use wherein a kind of, also can be used in combination by two or more arbitrary proportions.

There is no particular limitation to the usage quantity (ratio of mixture) of these curing catalysts, be the amount that can promote to react between Resins, epoxy composition and the epoxy hardener, and in the scope of the dielectric characteristics of not damaging cured resin, get final product, generally, when if the amount of total epoxy composition is 100 weight parts, curing catalyst preferably uses in the scope of 0.01～10 weight part, more preferably 0.1～5 weight part.

In addition, as above-mentioned curing catalyst, from excellent viewpoint such as the property obtained, solvent solubility, preferably use 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-diamino-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine].

Have on the surface of above-mentioned material for plating and to be used to implement the resin layer that electroless plating covers.This resin layer contains and the good polyimide resin of the Coated tackiness of electroless plating and the Thermocurable composition of excellent heat resistance, and this polyimide resin has siloxane structure.Therefore, according to above-mentioned material for plating or lamination material for plating, even do not carry out surface roughening, and the adhesion strength between the electroless plating cover film is also high, and the welding excellent heat resistance.Even adhesion strength at high temperature also uprises.

In addition, the character of the above-mentioned excellence of above-mentioned material for plating flexible Application can be applied on the various printed circuit board (PCB)s.For example can enumerate flexible printed circuit board, printed circuit board, multi-layer flexible printed circuit board, multilayer rigid circuit board or the combination circuit plate etc. that require to form fine wiring as various printed circuit board (PCB)s.

That is, intending implementing the material surface that electroless plating covers, form the resin layer (surface) that contains polyimide resin and Thermocurable composition, this polyimide resin has above-mentioned siloxane structure, implements electroless plating then and covers.At this moment, contain and the electroless plating coating between have the polyimide resin of good adhesion and a Thermocurable composition resin layer play the effect of interlayer tackiness agent, this polyimide resin has siloxane structure.Therefore, the advantage that has electroless plating coating and the firm adhesion of the storeroom that has formed resin layer.Further, because above-mentioned resin layer also contains the Thermocurable composition, so than tackiness resin layer in the past, the welding excellent heat resistance.In addition, because the tackiness of above-mentioned resin layer and electroless plating coating is good, need not to strengthen the surfaceness that is used to implement plating.Therefore, also has the excellent advantage of fine wiring processing.

The above excellent character of flexible Application, the technology of the present invention can be applicable in various decoration plating purposes or the function plating purposes.Wherein, also have thermotolerance simultaneously, even and to apply flexibly surfaceness little, also can form the advantage of electroless plating coating securely, so can effectively utilize as use in printed circuit board material for plating etc.

The characteristic resin layer of the second-order transition temperature of＜1-1-3. polyimide resin 〉

Other embodiment of resin layer of the present invention is described in addition.That is, above-mentioned resin layer preferably contains the siloxane structure with above-mentioned general formula (1) expression, and second-order transition temperature is the polyimide resins in 100～200 ℃ of scopes, and other concrete structure is not done special qualification.

In addition, the polyimide resin with above-mentioned siloxane structure is preferably the polyimide resin that accounts for 10～75mol% of total diamines with acid dianhydride composition and two amine components that contain the diamines of above-mentioned general formula (1) expression as the diamines of raw material and general formula (1) expression.According to above-mentioned composition, can access polyimide resin a in the adhesion strength excellence under normality and the high temperature and between the copper facing.

In addition, the identical part of explanation described in other embodiment with above-mentioned resin layer is omitted in the explanation of above-mentioned polyimide resin, and distinct portions only is described.

The inventor etc. find by the layer that contains the polyimide resin with siloxane structure, even if its surface smoothing, electroless plating covers also and can adhere securely, and characteristic to employed polyimide resin, especially the adhesive relation under second-order transition temperature and welding thermotolerance or the high temperature is discovered, second-order transition temperature is in 100～200 ℃ scope the time, and is extremely important to satisfying simultaneously with the tackiness and the welding thermotolerance of electroless plating coating.In addition, if second-order transition temperature in 100～200 ℃ scope, then not only can improve the tackiness under the normality, can also improve the tackiness under the high temperature.In order not only to make the tackiness that overlays under the normality with electroless plating good, also make tackiness at high temperature good, and realize the welding thermotolerance simultaneously, the inventor etc. are conceived to have the second-order transition temperature of the polyimide resin of above-mentioned siloxane structure first and study.

Layer of the present invention is meant the layer with the above thickness of 1nm.This thickness can be uniformly, also can be uneven.

In addition, as mentioned above, above-mentioned resin layer is characterised in that and contains the polyimide resin of second-order transition temperature in 100～200 ℃ of scopes.Here, second-order transition temperature of the present invention is the film that is made of above-mentioned polyimide resin by making, and uses this film, measures dynamic viscoelastic and try to achieve under condition determination shown below.

That is, can be with the TD direction of above-mentioned film as measuring direction, with DMS6100 (manufacturing of SII Nanotec Solution), from room temperature to 300 ℃, with 3 ℃/minute determination of heating rate dynamic viscoelastic, resulting tan δ peak temperature is a second-order transition temperature.In addition, exemplify an example of making above-mentioned film, the solution that will contain polyimide resin with siloxane structure, curtain coating is coated in rolled copper foil, and (a day Mining マ テ リ ア Le ズ company makes, BHY-22B-T) on the light face, 60 ℃, 80 ℃ each 1 minute down, 100 ℃ following 3 minutes, 120 ℃, 140 ℃ each 1 minute down, 150 ℃ following 3 minutes, under 180 ℃ of following conditions of 30 minutes, carry out drying, rolled copper foil is removed in etching, obtains in dry 30 minutes down at 60 ℃.There is no particular limitation for thickness, more than the preferred 10 μ m.

The second-order transition temperature of above-mentioned polyimide resin with siloxane structure is preferably in 100～200 ℃ scope, more preferably in 105～195 ℃ scope.When second-order transition temperature is lower than 100 ℃, have the tendency that resulting material for plating adhesion strength at high temperature reduces, when being higher than 200 ℃, have the tendency that the adhesion strength of resulting material for plating under normality and high temperature reduces.

In addition, polyimide resin with above-mentioned siloxane structure is the polyimide resin that the diamines of raw material and general formula (1) expression accounts for 10～75mol% of total diamines with acid dianhydride composition and two amine components that contain the diamines of above-mentioned general formula (1) expression preferably, can access especially at high temperature the polyimide resin with copper-plated adhesion strength excellence thus.

Above-mentioned polyimide resin is by using the diamines of general formula (1) expression, is in surfaceness hour, also with the Coated adhesion strength height of electroless plating.In addition, obtain the kind that the polyimide resin of second-order transition temperature in 100～200 ℃ of scopes depends on employed acid dianhydride and diamines, so be difficult to lump together, but, when by the diamine contents of general formula (1) expression with respect to total diamines more for a long time, it has the tendency that second-order transition temperature reduces.

In addition, if use aftermentioned to have flexible diamines, then has the tendency that second-order transition temperature reduces.The diamines of general formula (1) expression preferably accounts in the scope of 10～75mol% of total diamines, more preferably 13～60mol%, more preferably 15～49mol%.When the diamines of general formula (1) expression drops on above-mentioned scope, can access tackiness and the material for plating that welds excellent heat resistance under normality and the high temperature.

In addition, as acid dianhydride composition and two amine components, can use the material that in other embodiment of above-mentioned resin layer, illustrates.In addition, above-mentioned polyimide resin can also be used in combination two amine components and other two amine component of above-mentioned general formula (1) expression.Can use all diamines as other two amine component, this diamines also can use the material that illustrates in other embodiment of above-mentioned resin layer.

As mentioned above, the second-order transition temperature of polyimide resin depends on the kind of employed acid dianhydride and diamines, therefore, plan obtains the polyimide resin of second-order transition temperature in 100～200 ℃ of scopes and is difficult to lump together, but, when the diamines of general formula (1) expression with respect to the content of total diamines more for a long time, have the tendency that second-order transition temperature reduces.

In addition, if use has flexible diamines more for a long time, then has the tendency that second-order transition temperature reduces.Having flexible diamines is the diamines with flexibility structures such as ether, sulfuryl, ketone group, thioether groups, the material of preferred following general formula (3) expression.

[chemical formula 3]

[chemical formula 4]

(R in the formula ₄Be to be selected from by chemical formula 4

A kind of group in the divalent organic group of expression, the R in the formula ₅Can be identical or different, be to be selected from H-, CH ₃-,-OH ,-CF ₃,-SO ₄,-COOH ,-CO-NH ₂, Cl-, Br-, F-and CH ₃A kind of group among the O-.)

In addition, the diamines of above-mentioned general formula (1) expression preferably accounts in the scope of 10～75mol% of total diamines, more preferably accounts for 13～60mol%, further preferably accounts for 15～49mol%.

The preparation method of polyimide is identical with the explanation of other embodiment of above-mentioned resin layer.

In addition, be purpose to improve thermotolerance, reduction tackiness etc., also can in polyimide resin, contain other composition.Can use resins such as thermoplastic resin, heat-curing resin as other composition.

As thermoplastic resin, can enumerate polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, phenoxy resin, thermoplastically polyimide resin etc., these can be separately or appropriate combination use.In addition, as heat-curing resin, for example can enumerate bimaleimide resin, diallyl Na Dike acid imide resin, resol, cyanate ester resin, Resins, epoxy, acrylic resin, methacrylic resin, cyanate resin, hydrogenation silyl cured resin, allyl group cured resin, unsaturated polyester resin etc., can use separately or appropriate combination is used above-mentioned resin.In addition, except that above-mentioned heat-curing resin, can also use side chain or terminal side chain reactive group type Thermocurable polymer with epoxide group, allyl group, vinyl, alkoxysilyl, hydrogenation silyl isoreactivity group at macromolecular chain.

In addition, can also add the various additives identical in the resin layer with other embodiment.In addition, the content of the polyimide resin in the above-mentioned resin layer, preferably with respect to the polyimide resin of 100 weight parts, other composition is below 100 weight parts.

In addition, above-mentioned resin layer is identical with other embodiment, though have the little situation of surfaceness, with the also high advantage of adhesion strength of electroless plating coating.The preferred less than 0.5 μ m of the arithmetic average roughness Ra that the surfaceness of above-mentioned resin layer is measured under cutoff 0.002mm.When satisfying this condition, when especially material for plating of the present invention being used in the printed circuit board (PCB) purposes, has good fine wiring formation property.In order to form state, preferably do not implement physics tunicle roughenings such as sandblast etc. with this surface.

As mentioned above, the structure and the second-order transition temperature of the polyimide resin by being given for above-mentioned resin layer especially can make the electroless plating coating be firmly stuck to level and smooth surface.And then make not only tackiness excellence with other various storerooms, and the also material of excellence of welding thermotolerance and high temperature adhesion strength down.Therefore, can be suitable in the manufacturing of various printed circuit board (PCB)s.Further, by the following advantage of flexible Application, although promptly be smooth-flat-surface, but and the adhesion strength between the electroless plating coating is also high, and have the adhesion strength under sufficient welding thermotolerance, the high temperature, can be applicable in the manufacturing etc. of printed circuit board (PCB) of flexible printed circuit board, printed circuit board, multi-layer flexible printed circuit board or the combination circuit plate etc. that require to form fine wiring.

The characteristic resin layer of the weight-average molecular weight of＜1-1-4. polyimide resin 〉

Other embodiment of resin layer of the present invention is described in addition.That is, above-mentioned resin layer preferably contains the weight-average molecular weight Mw that has above-mentioned general formula (1) expression siloxane structure and obtained by gel permeation chromatography at 30000～150000 polyimide resin.

In addition, polyimide resin with above-mentioned siloxane structure further preferably is raw material and uses with respect to 1 mole of two amine component with acid dianhydride composition and two amine components that contain the diamines of above-mentioned general formula (1) expression, addition in 0.95～1.05 molar range the acid dianhydride composition and the polyimide resin that obtains.This be for obtain and electroless plating copper between the polyimide resin of adhesion strength excellence.

Discoveries such as the inventor are by containing the layer of polyimide resin with above-mentioned siloxane structure, even in the occasion of its surface smoothing, electroless plating covers also and can firmly adhere.Further the molecular weight of research polyimide resin and the stable on heating relation of welding are found, as polyimide resin, molecular weight is in specified range the time, can realize and significant tackiness and the welding thermotolerance of electroless plating between covering.The weight-average molecular weight Mw that promptly finds to have above-mentioned siloxane structure and obtained by gel permeation chromatography is at 30000～150000 polyimide resin, to the tackiness between realizing simultaneously covering with electroless plating and to weld thermotolerance very important.Not only can realize and the tackiness of electroless plating between covering, can also realize welding stable on heating characteristics, the inventor etc. are conceived at first and have a relation between the molecular weight of polyimide resin of siloxane structure.

Material for plating of the present invention preferably has at least and is used to implement the resin layer that electroless plating covers, but preferred the use intending implementing the material surface that electroless plating covers at first forms material for plating of the present invention, implements the method that electroless plating covers then.Thus, can apply flexibly the effect that material for plating of the present invention plays the interlayer tackiness agent, electroless plating covers the advantage of firmly adhering with storeroom, is applicable to various decoration plating purposes or function plating purposes.Wherein,, also can form the electroless plating coating securely, satisfy the stable on heating advantage of welding simultaneously, as the material for plating use of use in printed circuit board even can apply flexibly the little situation of surfaceness.

In addition, above-mentioned resin layer contains and has above-mentioned siloxane structure and be 30000～150000 polyimide resin by the weight-average molecular weight Mw that gel permeation chromatography is obtained.According to above-mentioned formation, when covering the tackiness excellence intermembranous with electroless plating, the welding thermotolerance is also good.

The weight-average molecular weight Mw of the polyimide resin that uses in the above-mentioned resin layer is preferably 35000～140000, and more preferably 40000～130000.Here, when Mw is lower than 30000, can't be welded thermotolerance fully, in addition, when being higher than 150000, the solvability of polyimide resin is impaired, have or not the manufactured polyimide resin solution sometimes, perhaps can't obtain the situation of sufficient Resin Flow.

Above-mentioned weight-average molecular weight Mw can obtain by carrying out following mensuration, promptly, as determinator, the HLC-8220GPC that uses eastern ソ one to make, the GPC-8020 that east ソ one makes, use the post of the TSK gel Super AWM-H that has connected two eastern ソ one manufacturings as post, use the TSK guardcolumn Super AW-H of eastern ソ one manufacturing as ガ one De カ ラ system, use contains 0.02M phosphoric acid as moving phase, 0.03M the N of lithiumbromide, dinethylformamide, polyimide resin a is dissolved in the sample for preparing concentration 0.1 weight % in the solvent identical with above-mentioned moving phase, and with 40 ℃ of column temperature, flow velocity 0.6ml/ minute the above-mentioned sample of gel permeation chromatography.

Above-mentioned polyimide resin, preferably two amine components with acid dianhydride composition and the diamines that contains above-mentioned general formula (1) expression are that raw material makes.In addition, preferred described polyimide resin is, with respect to 1 mole of two amine component, adds the acid dianhydride composition in 0.95～1.05 mole the scope and the polyimide resin that obtains.

Here, " addition of acid dianhydride composition " described in this specification sheets is meant, the purity of supposing two amine components and acid dianhydride composition respectively is 100% o'clock scope.Therefore, when the purity of two amine components and acid dianhydride composition is lower than 100%, be necessary to consider its purity, at this moment, above-mentioned scope changes to some extent.For example, when two amine components are made of 1 part of diamines 1 (purity A%), when forming, the preferred addition scope of acid dianhydride 2 is (0.95 * A/B) mole～(1.05 * A/B) moles to the acid dianhydride composition by 1 part of acid dianhydride 2 (purity B).For example, when the purity of two amine components is 100%, the purity of acid dianhydride is 98% o'clock, and with respect to 1 mole of two amine component, acid dianhydride composition addition is in 0.969～1.071 mole the scope.

Sometimes represent acid dianhydride composition or two amine components by functional group's equivalent, at this moment, decide addition to get final product as long as calculate molecular weight from this functional group's equivalent.

Can suitably use the material identical for above-mentioned acid dianhydride composition with above-mentioned embodiment.In addition, by using two amine components of above-mentioned general formula (1) expression, the resin layer that contains the gained polyimide resin has the feature of adhering securely with the electroless plating coating.

In addition, above-mentioned polyimide resin can be used in combination above-mentioned two amine components and other two amine component.As other two amine component, can use all diamines, can use two amine components identical with above-mentioned embodiment.

Here, the diamines of above-mentioned general formula (1) expression preferably accounts for 1～75mol% of total diamines, more preferably accounts for 3～60mol%, further preferably accounts for 5～49mol%.When the diamines of general formula (1) expression is lower than 1mol% or is higher than 75mol%, all can't fully obtain and the cover situation of intermembranous adhesion strength of electroless plating.

The preparation method of polyimide also can carry out in the same manner with above-mentioned embodiment.

Prepare above-mentioned weight-average molecular weight Mw and be the method for 30000～150000 polyimide resin, can enumerate and be used alone or in combination following method and realize, (i) purity of consideration acid dianhydride and two amine components, control the ratio of acid dianhydride and two amine components, wherein acid dianhydride and two amine components are as the raw material of the polyamic acid of the precursor of preparation polyimide resin, (ii) polymerization temperature, the polymerization time during controlled polymerization, (iii) control the viscosity of polyamic acid, (iv) control the methods such as condition of imidization.

(i) illustrate that consideration is used as the raw material acid dianhydride of preparation polyamic acid and the purity factor of two amine components, control the ratio of acid dianhydride and two amine components, wherein polyamic acid is the precursor of polyimide resin.In order to obtain weight-average molecular weight Mw is 30000～150000 polyimide resin, preferably with respect to 1 mole of two amine component, uses the acid dianhydride composition of 0.95～1.05 molar range and obtains.

The (ii) polymerization temperature during controlled polymerization, the situation of polymerization time, when polymerization temperature was high, molecular weight had the tendency of reduction, and when polymerization time was long, molecular weight had the tendency of reduction.If polymerization time is too short, then can't obtain sufficient molecular weight.Therefore, the preferable range of polymerization temperature and polymerization time is at 0～45 ℃, 30～200 minutes.

(iii) control the situation of the viscosity of polyamic acid, the viscosity of the polyamic acid before the preferred imidization is at 6～3000poise.

(iv) to the explanation of condition of control imidization.

When polyamic acid carried out imidization, the decomposition and the imidization of polyamic acid carried out with vying each other.The molecular weight of polyimide depends on the composition of polyamic acid self, but high temperature, its easy more decomposition, and therefore high temperature, its molecular weight is more little.In addition, when utilizing chemical imidization method, the usage quantity of dewatering agent is many more, promotes the decomposition of polyamic acid.On the other hand, the type of heating during as imidization, heat-up rate are fast more, promote imidization more, and when utilizing chemical imidization method, the usage quantity of catalyzer is many more, promotes imidization more.Therefore, according to these tendencies as mentioned above, the amount of the temperature when suitably selecting imidization, heat-up rate, dewatering agent, the amount of catalyzer obtain the polyimide of molecules of interest amount.

More than, polyimide resin has been described, but, also can in above-mentioned resin layer, have contained other composition in order to improve thermotolerance, to reduce tackiness etc.As other composition, can suitably use resin, various additives etc. such as the various thermoplastic resins that illustrate in the above-mentioned embodiment, heat-curing resin.

Certainly, as above-mentioned other composition, it focuses on, though strengthen the surfaceness of resin layer, but be unlikely to bring on the degree of bad influence to fine wiring formation property, make up in the scope that the intermembranous tackiness of resin layer and electroless plating cover is reduced, this point will be noted.In addition, the content of the polyimide resin in the resin layer is preferably with respect to 100 weight part polyimide resins, and other composition is below 100 weight parts.

In addition, resin layer have and the electroless plating coating between the high advantage of adhesion strength, even if under the little situation of surfaceness, also be so.Here, the arithmetic average roughness Ra less than 0.5 μ m that preferably under cutoff 0.002mm, measures of the surfaceness of above-mentioned resin layer.When satisfying this condition, when especially material for plating of the present invention being used for printed circuit board (PCB), has good fine wiring formation property.

The formation of resin layer as mentioned above, by structure and the weight-average molecular weight Mw that stipulates used polyimide resin, the electroless plating coating of especially can on smooth-flat-surface, adhering securely.This material not only with the tackiness excellence of other various storerooms, and the welding thermotolerance is also excellent.Therefore, can be applicable in the manufacturing of various printed circuit board (PCB)s.And then, utilize following advantage, that is, on smooth-flat-surface, and the tackiness height between the electroless plating coating, and have sufficient welding thermotolerance, can be applicable in the manufacturing of the flexible printed circuit board that requires to form fine wiring etc.

＜1-1-5. polyimide resin has the resin layer that functional group is a feature 〉

In addition, other embodiment to resin layer of the present invention describes.That is, above-mentioned resin layer preferably contains and has above-mentioned general formula (1) expression siloxane structure and have functional group and/or the polyimide resin of this protected group of functional group.Below, sometimes " the protected group of functional group and/or this functional group " is also referred to as functional group etc.

Here, the functional group that the present invention relates to is meant and is imbued with chemically reactive atomic group.Functional group does not have special restriction, but from satisfying the tackiness between covering with electroless plating simultaneously and welding stable on heating viewpoint, is preferably selected from more than one the group in hydroxyl, amino, carboxyl, amide group, sulfydryl, the sulfonic group.In addition, by using these functional groups, can become the material good with the tackiness of various storerooms.In addition, above-mentioned polyimide resin is a raw material with acid dianhydride composition and two amine components that contain the diamines of above-mentioned general formula (1) expression and have a diamines of functional group and/or this protected group of functional group preferably.

Discoveries such as the inventor are by containing the layer of polyimide resin with above-mentioned siloxane structure, though the situation of its surface smoothing, the electroless plating coating of also can adhering securely.And then, find first, by in employed polyimide resin, importing functional group etc., can realize tackiness and welding thermotolerance simultaneously with the electroless plating coating.The inventor etc. carry out following research at first, that is, and and by in having the polyimide resin of siloxane structure, importing functional group, with the tackiness and the welding thermotolerance of normality between realization and electroless plating coating.

In addition, above-mentioned resin layer contain have above-mentioned siloxane structure, the polyimide resin of functional group and/or this protected group of functional group.Above-mentioned functional group can produce chemical interaction with various resin materials, therefore can improve the adhesion strength with various storerooms.

In addition, this functional group also can be the protected group that forms of functional group.Here, " the protected group that forms of functional group " that the present invention relates to be meant, the group that makes functional group and generate during with the compound reaction of this functional group reactions.For example can exemplify, when functional group is the situation of hydroxyl, amino or amide group, reaction such as this functional group and diacetyl oxide and acetylizad group.On the other hand, when functional group is sulfydryl, can the group that generate with the unsaturated polyester compound reaction be shown example.

The protected group that forms of functional group can not reduce the tackiness with electroless plating cover film or interlaminar resin, so can directly use.Even, also can pass through elimination reaction, the cancellation blocking group uses after getting back to original functional group's state.In addition, functional group coexists as with the group of protecting functional group to form and also can.

Above-mentioned polyimide resin can A) to contain the acid dianhydride composition of acid dianhydride with the protected group that forms of siloxane structure and functional group and/or this functional group; and two amine component be raw material; B) to contain acid dianhydride with siloxane structure; acid dianhydride composition with acid dianhydride of the protected group that forms of functional group and/or this functional group; and two amine component be raw material; C) with the acid dianhydride composition; and two amine components that contain the diamines with the protected group that forms of siloxane structure and functional group and/or this functional group are raw material, D) with the acid dianhydride composition; and contain diamines with siloxane structure; two amine components of the diamines of the group that functional group and/or this protective group are formed are method manufacturings such as raw material.Wherein, from raw material easily viewpoint such as acquisition consider preferred D) with the acid dianhydride composition and two amine components that contain the diamines of diamines with siloxane structure, the protected group that forms of functional group and/or this functional group be raw material.Further preferred polyimide resin with the acid dianhydride composition and two amine components that contain diamines and have a diamines of the protected group that forms of functional group and/or this functional group with above-mentioned general formula (1) expression be raw material.Can use the material that illustrates in above-mentioned other embodiment for above-mentioned acid dianhydride composition.

Then, two amine components preferably use two amine components of above-mentioned general formula (1) expression.Thus, the resulting resin layer that contains polyimide resin has the feature of firmly adhering with the electroless plating coating.Concrete material by two amine components of above-mentioned general formula (1) expression can use the material that illustrates in other embodiment.

In addition, as two amine components, preferably contain diamines with functional group and/or this protected group of functional group.Especially preferably contain and have the diamines that is selected from more than one functional groups in hydroxyl, amino, carboxyl, amide group, sulfydryl, the sulfonic group.As such diamines, can enumerate 3,3 '-dihydroxyl-4,4 '-benzidine, 4,3 '-dihydroxybiphenyl base-3,4 '-diamines, 3,3 '-benzidine base-4,4 '-glycol, 3,3 '-the diamino benzhydrol, 2,2 '-the diamino dihydroxyphenyl propane, 1,3-diamino-2-propyl alcohol, 1,4-diamino-2-butylene, 4, the 6-diamino resorcin, 2,6-diamino Resorcinol, 5,5 '-methylene radical-two (anthranilic acids), 3,5-diamino M-nitro benzoic acid, 3,4-diamino M-nitro benzoic acid, 4,4 '-diamino-N-benzanilide, 3,4 '-diamino-N-benzanilide, 3,3 '-diamino-N-benzanilide, 2,5-diaminobenzene-1,4-two mercaptan, 4,4 '-diamino-3,3 '-two sulfanilyl-biphenyl, 3,3 '-dimethyl-4,4 '-benzidine-6,6 '-disulfonic acid, 4,4 '-diamino hexichol-2,2 '-disulfonic acid etc.Above-mentioned diamines can use separately, also can two or more mixing use.In addition, the functional group of above-mentioned diamines is that the protected group that forms also can.

In addition, above-mentioned polyimide resin can be used in combination above-mentioned two amine components and other two amine component, as other two amine component, can use all diamines.Particularly, can use the diamines that exemplifies in above-mentioned other embodiment.

Here, the diamines of preferred formula (1) expression accounts in the scope of 1～75mol% of total diamines, more preferably 3～60mol%, more preferably 5～49mol%.When the diamines of general formula (1) expression is lower than 1mol% or during more than 75mol%, all have fully to obtain and cover intermembranous adhesion strength and weld stable on heating situation of electroless plating.

In addition, the diamines that preferably has a protected group that forms of functional group and/or this functional group accounts in the scope of 1～99mol% of total diamines, more preferably in the scope of 3～99mol%.When the diamines with functional group is lower than 1mol%, has and fully to obtain and cover intermembranous adhesion strength and weld stable on heating situation of electroless plating.The tendency that also has the adhesion strength with various interlaminar resins to reduce in addition.

The preparation method of polyimide also can utilize above-mentioned method, has no particular limits.

More than, polyimide resin has been described, be purpose still to improve thermotolerance, reduction tackiness etc., also can in resin layer, contain other composition.As other composition, can suitably use resin, various additives etc. such as the various thermoplastic resins that illustrate in the above-mentioned embodiment, heat-curing resin.

Certainly, as above-mentioned other composition, it focuses on strengthening the surfaceness of resin layer, but is unlikely to bring on the degree of bad influence to fine wiring formation, perhaps can not reduce in the intermembranous adhesive scope of resin layer and electroless plating cover and make up, this point will be noted.In addition, the content of the polyimide resin in the resin layer is preferably with respect to 100 weight part polyimide resins, and other composition is below 100 weight parts.

In addition, resin layer have and the electroless plating coating between the high advantage of adhesion strength, even if under the little situation of surfaceness, also be so.Here, the arithmetic average roughness Ra less than 0.5 μ m that preferably under cutoff 0.002mm, measures of the surfaceness of above-mentioned resin layer.When satisfying this condition, when especially material for plating of the present invention being used for the printed circuit board (PCB) purposes, has good fine wiring formation property.

Above-mentioned resin layer is to use has above-mentioned particular silicone structure, and the polyimide resin with the protected group that forms of functional group and/or this functional group constitutes, therefore, and the electroless plating coating of especially can on smooth-flat-surface, adhering securely.And then, when becoming the tackiness excellence with other various storerooms, and the also excellent material of welding thermotolerance.Therefore, can be applicable in the manufacturing of various printed circuit board (PCB)s.And then, utilize following advantage, that is, on smooth-flat-surface, and the tackiness height between the electroless plating coating, and have sufficient welding thermotolerance, can be applicable in the manufacturing of the flexible printed circuit board that requires to form fine wiring etc.

＜1-2. electroless plating coating 〉

The electroless plating coating that forms on the resin layer of material for plating of the present invention can use present known electroless plating coating, concrete structure is not done special the qualification.For example can enumerate electroless plating copper, electroless plating nickel, electroless plating gold, electroless plating silver, electroless plating tin etc., the applicable all electroless plating coating of the present invention.In the above-mentioned various electroless plating coating,, be preferably electroless plating copper, electroless plating nickel,, be preferably electroless plating copper especially as the printed circuit board (PCB) purposes from electrical characteristic viewpoints such as industrial point, anti-ion transport.

In addition, the plating liquid of the above-mentioned electroless plating copper layer that is used to be shaped can use present known material, and there is no particular limitation to its concrete structure, can use to form conventional plating liquid that any one electroless plating copper uses etc.In addition, in the purposes of multilayer printed circuit board etc., in order to ensure being used for the through hole that interlayer connects, the decontamination of the glue slag (ス ミ ア) that produces when implementing to be used to remove perforate such as laser is usually earlier handled, and carries out plating again and handles.

In addition, above-mentioned electroless plating can be only to cover the metal plating that constitutes by electroless plating, also can be to form electro deposition again after covering at the formation electroless plating, to reach the metal plating of expectation thickness.In addition, the thickness of coating can form the form that can use in present known printed circuit board (PCB) etc., there is no particular limitation, but if consider fine wiring formation property etc., then its thickness is preferably below the 25 μ m, more preferably below the 20 μ m, more preferably below the 15 μ m.

Material for plating involved in the present invention as long as have above-mentioned resin layer, and for other structure, is not done special qualification.In addition, when for example material for plating of the present invention being applicable to the printed circuit board of printed circuit board (PCB), especially combination circuit plate etc., can be the material for plating that only constitutes, promptly so-called single-layer sheet by above-mentioned resin layer.

In addition, also can be the material for plating that constitutes by above-mentioned resin layer and other layer (for example, being used for and the opposed adhesive layer C of circuit that forms).As above-mentioned layer C, for example can enumerate bond layer, can enumerate the resin layer that contains thermoplastically polyimide resin and Thermocurable composition more specifically.

That is, material for plating of the present invention further has other layer except the resin layer that is used to implement above-mentioned electroless plating and covers, can be the material that is made of the layer more than 2 layers at least.In addition, other layer beyond the above-mentioned resin layer can form the structure more than 2 layers.For example, can be the lamination material for plating that constitutes by resin layer A/ macromolecule membrane layer B, also can be the lamination material for plating that constitutes by resin layer A/ macromolecule membrane layer B/ layer C.Below, as an application examples of lamination material for plating of the present invention, illustrate as other layer use macromolecule membrane layer, on this macromolecule membrane layer, form the structure of the lamination material for plating of above-mentioned resin layer.Below explanation is by layer material for plating that constitutes more than 2 layers.

＜2. by the two-layer above layer material for plating that constitutes 〉

＜2-1. embodiment 1 〉

Lamination material for plating involved in the present invention, be at least one surface of macromolecule membrane layer, to be formed with to be used to implement the resin layer that electroless plating covers, above-mentioned resin layer so long as＜the 1-1. resin layer described in resin layer get final product, other concrete structure is not done special qualification.Above-mentioned lamination material for plating for example can be applicable on printed circuit board (PCB), the especially flexible printed circuit board.

The above-mentioned material for plating that is made of two-layer above layer can be by the material for plating that above-mentioned resin layer/the macromolecule membrane layer constitutes, and also can be the material by resin layer/macromolecule membrane layer/resin layer constitutes.

In addition, the above-mentioned material for plating that is made of two-layer above layer preferably is formed with on a face of macromolecule membrane layer and is used to implement the resin layer that electroless plating covers, above-mentioned resin layer is＜the 1-1. resin layer〉described in resin layer, on the another side of above-mentioned macromolecule membrane layer, form above-mentioned adhering agent layer.That is, above-mentioned lamination material for plating can be that described adhesive layer is mutually opposed with circuit by the material that resin layer/macromolecule membrane layer/adhering agent layer constitutes.

In addition,, can use above-mentioned＜1 to above-mentioned resin layer and electroless plating coating〉material that illustrates in the hurdle, therefore omit its explanation here.Below describe macromolecule membrane layer and adhering agent layer in detail.

＜2-1-1. macromolecule membrane layer 〉

The macromolecule membrane that uses in the lamination material for plating of the present invention is, for the low thermal coefficient of expansion and the high tenacity that realize the lamination material for plating are used.In addition, when using above-mentioned lamination material for plating, be expected to obtain dimensional stability as flexible printed circuit board.Therefore, preferably use the macromolecule membrane of thermal expansivity below 20ppm.Further, for fear of the viscous deformation that causes owing to heating, by the defectives such as expansion that volatile component causes, preferably use the macromolecule membrane of high heat resistance, low water absorbable.

In addition, in order to form the through hole of path, the thickness of preferred above-mentioned macromolecule membrane layer is below the 50 μ m, more preferably below the 35 μ m, further below the preferred 25 μ m.In addition, the lower value of thickness is preferably more than the 1 μ m, more preferably more than the 2 μ m.In other words, preferred thickness is thin as almost can to neglect, and can guarantee the macromolecule membrane of sufficient electrical insulating property.

Such macromolecule membrane layer can be single layer structure, also can be structure more than 2 layers.For example, when it is single layer structure, can use polyolefine such as polyethylene, polypropylene, polybutene; Ethylene-vinyl alcohol copolymer, polystyrene, polyethylene terephthalate, polybutylene terephthalate, 2, polyester such as 6-(ethylene naphthalate); Further, nylon 6, Ni Long11, aromatic polyamide, polyamide-imide resin, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyketone are that resin, polysulfones are films such as resin, polyphenylene sulfide, polyetherimide resin, fluoro-resin, polyarylester, liquid crystal polymer resin, polyphenylene oxide resin, non-thermoplastically polyimide resin.

In addition, for and above-mentioned resin layer between have excellent adherence, at the single face of above-mentioned individual layer macromolecule membrane layer or two-sided, heat-curing resin and/or thermoplastic resin can be set, perhaps handle with various organism such as organic monomer, couplants.Especially as above-mentioned macromolecule membrane layer, when using non-thermoplastically polyimide resin, and the adherence between above-mentioned resin layer is more excellent, and is therefore preferred.Further, also can use lamination macromolecule membrane layer, this lamination macromolecule membrane layer is as above to state the individual layer macromolecule membrane by the tackiness agent lamination to form.

As the macromolecule membrane layer that satisfies above-mentioned many characteristics, can use non-thermoplastically Kapton.Below, the example when using non-thermoplastically Kapton as above-mentioned macromolecule membrane layer is described, but the present invention being not limited to this embodiment, this is self-evident.

As the non-thermoplastically Kapton that above-mentioned macromolecule membrane layer uses, can use present known method preparation, the concrete grammar of its preparation method is not done qualification.For example, can by with the polyamic acid curtain coating, be coated on the supporter, carry out chemistry or hot-imide and obtain.Wherein, with viewpoints such as toughness, breaking tenacity and production efficiency from film, preferably in the polyamic acid organic solvent solution, make with acid anhydrides such as diacetyl oxides and be the chemical converting agent (dewatering agent) of representative and be the interactional method of catalyzer of representative with tertiary amines of isoquinoline 99.9, beta-picoline, pyridine etc. etc., that is chemical imidization method.In addition, further preferred and with the method for chemical imidization method and thermal curing method.

As above-mentioned polyamic acid, can use known all polyamic acids at present basically, have no particular limits.For example can prepare by the following method, at least a aromatic acid dianhydride and at least a diamines that are the essence equimolar amount are dissolved in the organic solvent, under the temperature condition of control, stir resulting polyamic acid organic solvent solution, till the polymerization of above-mentioned acid dianhydride and diamines finishes.

As the acid dianhydride that can be used for making non-thermoplastically polyimide of the present invention, comprise pyromellitic acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, the two O-phthalic acid dianhydrides of oxo, two (2,3-dicarboxyl phenyl) methane dicarboxylic anhydride, two (3,4-dicarboxyl phenyl) methane dicarboxylic anhydride, 1, two (2,3-dicarboxyl phenyl) the ethane dicarboxylic anhydrides of 1-, 1,1-two (3,4-dicarboxyl phenyl) ethane dicarboxylic anhydride, 1, two (3,4-dicarboxyl phenyl) the ethane dicarboxylic anhydrides of 2-, 2,2-two (3,4-dicarboxyl phenyl) propane dicarboxylic anhydride, 1, two (3,4-dicarboxyl phenyl) the propane dicarboxylic anhydrides of 3-, 4,4 '-hexafluoro isopropylidene-Tetra hydro Phthalic anhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, to penylene two (trimellitic acid monoesters acid anhydrides), ethylene two (trimellitic acid monoesters acid anhydrides), dihydroxyphenyl propane two (trimellitic acid monoesters acid anhydrides), 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, to aromatic series O-phthalic acid dianhydride and analogues thereof such as phenylene diphthalic anhydrides.These can use separately, also can mix use by two or more arbitrary proportions.

In the above-mentioned acid dianhydride, preferably use the two O-phthalic acid dianhydrides, 3,3 of pyromellitic acid anhydride, oxo ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, to penylene two (trimellitic acid monoesters acid anhydrides).These acid dianhydride ratios are easier to obtain, and can obtain the film that characteristics such as suitable Young's modulus, linear expansivity, water-intake rate average out easily, so preferred.

In addition; the diamines that uses as being used for synthetic non-thermoplastically polyimide of the present invention contains 1; 4-diaminobenzene (to inferior phenylenediamine); 1; the 3-diaminobenzene; 1; the 2-diaminobenzene; 3; 3 '-dichlorobenzidine; 3; 3 '-tolidine; 3; 3 '-dimethoxy benzidine; 3; 3 '-dihydroxybiphenyl amine; 3; 3 '; 5; 5 '-tetramethyl benzidine; 4; 4 '-diamino-diphenyl propane; 4; 4 '-diamino hexichol HFC-236fa; 1; the 5-diaminonaphthalene; 4; 4 '-diamino hexichol diethylsilane; 4; 4 '-diamino-diphenyl silane; 4; 4 '-diamino two styroyl phosphine oxides; 4; 4 '-diamino-diphenyl N-methylamine; 4; 4 '-diamino-diphenyl N-aniline; 4; 4 '-diaminodiphenyl oxide; 3; 4 '-diaminodiphenyl oxide; 3; 3 '-diaminodiphenyl oxide; 4; 4 '-diaminodiphenyl sulfide; 3; 4 '-diaminodiphenyl sulfide; 3; 3 '-diaminodiphenyl sulfide; 3; 3 '-diaminodiphenylmethane; 3,4 '-diaminodiphenylmethane; 4,4 '-diaminodiphenylmethane; 4; 4 '-diaminodiphenylsulfone(DDS); 3; 4 '-diaminodiphenylsulfone(DDS); 3,3 '-diaminodiphenylsulfone(DDS); 4,4 '-the diaminobenzene formylaniline; 3; 4 '-the diaminobenzene formylaniline; 3; 3 '-the diaminobenzene formylaniline; 4,4 '-diaminobenzophenone; 3,4 '-diaminobenzophenone; 3; 3 '-diaminobenzophenone; two [4-(3-amino-benzene oxygen) phenyl] methane; two [4-(4-amino-benzene oxygen) phenyl] methane; 1; two [4-(3-amino-benzene oxygen) phenyl] ethane of 1-; 1, two [4-(4-amino-benzene oxygen) phenyl] ethane of 1-; 1, two [4-(3-amino-benzene oxygen) phenyl] ethane of 2-; 1; two [4-(4-amino-benzene oxygen) phenyl] ethane of 2-; 2; two [4-(3-amino-benzene oxygen) phenyl] propane of 2-; 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2, two [4-(3-amino-benzene oxygen) phenyl] butane of 2-; 2; two [3-(3-amino-benzene oxygen) phenyl]-1 of 2-; 1,1,3; 3; the 3-HFC-236fa; 2, two [4-(4-amino-benzene oxygen) phenyl]-1,1 of 2-; 1; 3,3, the 3-HFC-236fa; 1; two (3-amino-benzene oxygen) benzene of 3-; 1; two (3-amino-benzene oxygen) benzene of 4-; 1,4 '-two (4-amino-benzene oxygen) benzene; 4,4 '-two (4-amino-benzene oxygen) biphenyl; 4; 4 '-two (3-amino-benzene oxygen) biphenyl; two [4-(3-amino-benzene oxygen) phenyl] ketone; two [4-(4-amino-benzene oxygen) phenyl] ketone; two [4-(3-amino-benzene oxygen) phenyl] thioether; two [4-(4-amino-benzene oxygen) phenyl] thioether; two [4-(3-amino-benzene oxygen) phenyl] sulfone; two [4-(4-amino-benzene oxygen) phenyl] sulfone; two [4-(3-amino-benzene oxygen) phenyl] ether; two [4-(4-amino-benzene oxygen) phenyl] ether; 1; two [4-(3-amino-benzene oxygen) benzoyl] benzene of 4-; 1, two [4-(3-amino-benzene oxygen) benzoyl] benzene of 3-; 4,4 '-two [3-(4-amino-benzene oxygen) benzoyl] phenyl ether; 4; 4 '-two [3-(3-amino-benzene oxygen) benzoyl] phenyl ether; 4; 4 '-two [4-(4-amino-α, α-Er Jiajibianji) phenoxy group] benzophenone; 4,4 '-two [4-(4-amino-α; α-Er Jiajibianji) phenoxy group] sulfobenzide; two [4-{4-(4-amino-benzene oxygen) phenoxy group } phenyl] sulfone; 1; two [4-(4-amino-benzene oxygen)-α, the α-Er Jiajibianji] benzene of 4-; 1, the two [4-(4-amino-benzene oxygen)-α of 3-; α-Er Jiajibianji] benzene; 4,4 '-diamino-diphenyl ethyl phosphine oxide etc. and analogue thereof.These can use separately, also can be used in combination by two or more arbitrary proportions.

In the above-mentioned diamines, preferably use 2,2 '-two [4-(3-amino-benzene oxygen) phenyl] propane, 4,4,4 '-diaminobenzene formylaniline and Ursol D.These diamines ratios are easier to obtain, and can access the film that characteristics such as suitable Young's modulus, linear expansivity, water-intake rate average out, so preferred.

In addition, in the present invention, the preferably combination of acid dianhydride and two amines is, pyromellitic acid anhydride and 4,4 '-combination of diaminodiphenyl oxide, pyromellitic acid anhydride and 4,4 '-combination of diaminodiphenyl oxide and Ursol D, pyromellitic acid anhydride, TOPOT 2,2 (trimellitic acid monoesters acid anhydrides) and 4,4 '-combination of diaminodiphenyl oxide and Ursol D, pyromellitic acid anhydride, TOPOT 2,2 (trimellitic acid monoesters acid anhydrides), 3,3 ', 4,4 '-combination of biphenyl tetracarboxylic dianhydride and 4 and Ursol D, pyromellitic acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and 4, Ursol D and 2, the combination of two [4-(3-amino-benzene oxygen) phenyl] propane of 2-.Make up these monomers and the non-thermoplastically polyimide of synthetic shows the excellent specific property of suitable Young's modulus, dimensional stability, low water absorption etc., can be applicable to material for plating of the present invention.

The preferred organic solvent that is used for synthesizing polyamides acid is the acid amides series solvent, i.e. N, and dinethylformamide, N,N-dimethylacetamide, N-methyl-2-pyridine alkane ketone etc. preferably use N, dinethylformamide.

In addition; by method of chemical treatment (ケ ミ カ Le キ ユ ア) when carrying out imidization; as the chemical imidization transforming agent that adds in the polyamic acid composition; for example can use aliphatic anhydride, aromatic anhydride, N, N '-dialkyl group carbodiimide, lower aliphatic halogenide, halogenated lower aliphatics halogenide, halogenated lower fatty acid anhydride, aryl phosphoric acids dihalide, sulfinyl halogenide or two or more their mixture.Wherein, especially preferably use the independent a kind of or two or more mixtures of aliphatic anhydride such as diacetyl oxide, propionic anhydride, butyryl oxide.

These chemical imidization transforming agents preferably add 1～10 times of amount with respect to the mole number at the polyamic acid position in the polyamic acid solution, more preferably add 1～7 times of amount, 1～5 times of amount of further preferred interpolation.In addition, in order to carry out imidization effectively, use catalyzer when preferably using chemical converting agent.Can use aliphatic tertiary amine, aromatic nitrile base, heterocycle tertiary amine etc. as catalyzer.Wherein especially preferably use the heterocycle tertiary amine.Particularly, preferably use quinoline, isoquinoline 99.9, beta-picoline, pyridine etc.These catalyzer preferably add 1/20～10 times of amount with respect to the mole number of chemical converting agent, more preferably add 1/15～5 times of amount, 1/10～2 times of amount of further preferred interpolation.If the amount of these chemical converting agents and catalyzer is few, then can't effectively carry out imidization, on the contrary,, be difficult to control if too much, then imidization is fast.

In addition, the non-thermoplastically Kapton that obtains by above-mentioned myriad of well known method also can add plasticizer or antioxidants inorganic or organism filler, organic phosphine compound etc. by known method, on at least one face of this non-thermoplastically Kapton, implement chemical surface treatment such as known physical surface treatment such as Corona discharge Treatment, plasma discharge processings, ionic valve processing or prime treatment, can give further good characteristic.

The thickness of non-thermoplastically Kapton is preferably in the scope of 2 μ m～125 μ m, more preferably in the scope of 5 μ m～75 μ m.If thinner than this scope, the rigidity deficiency of lamination material for plating not only then, also becoming difficulty of operation.On the one hand, if film is blocked up, then when making printed circuit board (PCB), from the viewpoint of controlling resistance, be necessary to enlarge circuit width, therefore miniaturization, the densification with printed circuit board (PCB) requires to disagree.

In addition, be used for the non-thermoplastically Kapton of above-mentioned macromolecule membrane layer, be preferably low linear expansion coefficient.For example, can be the Kapton of 10～20ppm even can the production line coefficient of expansion be the Kapton of 10～20ppm by the production line coefficient of expansion, therefore obtain, can effectively utilize than being easier to industrial.Make up rigid structure monomer and flexible structure monomer methods in the proper ratio in order to control the linear expansivity of non-thermoplastically Kapton, can to enumerate.In addition except that this method, acid anhydrides composition in the time of also can be by the synthesizing polyamides acid solution and the interpolation of two amine components order, chemical imidization and the selection of hot-imide, the temperature condition when polyamic acid is converted into polyimide etc. are controlled the linear expansivity of the non-thermoplastically Kapton of gained.

The modulus in tension of non-thermoplastically Kapton is measured based on ASTM D882-81.If Young's modulus is low, then the rigidity of film reduces, and it is difficult that operation becomes.On the one hand, if too high, then the flexibility of film is impaired, produces spool (ROLL-TO-ROLL) the processing difficulty that becomes, perhaps film unfavorable condition such as become fragile.For example, the Kapton of Young's modulus 3～10GPa, the Kapton of further 4～7GPa can carry out industrial production, and obtain than being easier to, and can use their commercially available prod.

When the control stretching Young's modulus, identical with linear expansivity, can be by making up rigid structure monomer and flexible structure monomer in the proper ratio, the acid anhydrides composition when perhaps controlling the synthesizing polyamides acid solution and the interpolation of two amine components realize in proper order.Further, also can wait and control by the selection of chemical imidization and hot-imide, temperature condition when polyamic acid is converted into polyimide.

＜2-1-2. adhering agent layer 〉

As above-mentioned adhering agent layer, can use present known tackiness agent.There is no particular limitation to its concrete formation.The tackiness agent that uses when for example, above-mentioned adhering agent layer is preferably lamination material for plating and other base material (for example having the base material of circuit formation face etc.) lamination.This adhering agent layer preferably has excellent processibility, makes when circuit formation face carries out lamination, and this tackiness agent flows between circuit and can bury circuit.

Generally, hot curing resin composition has aforesaid excellent in workability, so above-mentioned adhering agent layer preferably contains hot curing resin composition.For example can use heat-curing resins such as Resins, epoxy, resol, thermohardening type polyimide resin, cyanate ester resin, hydrogenation silyl cured resin, bimaleimide resin, diallyl Na Dike acid imide resin, acrylic resin, methacrylic resin, allylic resin, unsaturated polyester resin as this hot curing resin composition; The side chain of macromolecular chain or terminal side chain reactive group type Thermocurable polymer and suitable thermal curing agents, the hot curing resin composition that curing catalysts makes up with allyl group, vinyl, alkoxysilyl, hydrogenation silyl isoreactivity group.

In above-mentioned adhering agent layer, can in these hot curing resin compositions, further add the thermoplastically polymer.Particularly, for example can enumerate the hot curing resin composition that contains Resins, epoxy and phenoxy resin, contain the hot curing resin composition of Resins, epoxy and thermoplastically polyimide resin and contain cyanate ester resin and the hot curing resin composition of thermoplastically polyimide resin etc.Wherein, used the lamination material for plating of the hot curing resin composition that contains Resins, epoxy and thermoplastically polyimide resin, satisfied balance, therefore most preferably as many characteristics of lamination material for plating.In addition, in order to realize low heat expansion property, also can on above-mentioned adhering agent layer, add various fillers.

In addition, also can use the complex body of fiber and resin as adhering agent layer.At this moment, the complex body of fiber and resin is B stage condition (semi-cured state).

The complex body of above-mentioned fiber and resin is described.There is no particular limitation to be used for the fiber of this complex body, is preferably selected from least a fiber of paper, woven fiber glass, glass non-woven, aramid fiber cloth, aramid nonwoven cloth, tetrafluoroethylene.As paper, can use with by the system paper of raw material preparing such as timber, bark, cotton, fiber crops, synthetic resins with paper pulp, dissolving with the paper of paper pulp such as paper pulp, synthetic paper-pulp as raw material.As woven fiber glass, glass non-woven, woven fiber glass, the glass non-woven that can use E glass or D glass and other glass to constitute.As aramid fiber cloth, aramid nonwoven cloth, can use the aramid fiber cloth, the aramid nonwoven cloth that constitute by aromatic polyamide or aromatic polyamide imide.Here, aromatic polyamide is present known ortho position type aromatic polyamide or paratype aromatic polyamide or their copolymerization aromatic polyamide etc.Preferably use the tetrafluoroethylene that has carried out stretch process and had fine continuous poriferous matter structure as tetrafluoroethylene.

There is no particular limitation to can be used in the resin of above-mentioned complex body, but, be preferably selected from Resins, epoxy from viewpoints such as thermotolerances, the thermohardening type polyimide resin, cyanate ester resin, hydrogenation silyl cured resin, bimaleimide resin, diallyl Na Dike acid imide resin, acrylic resin, methacrylic resin, allylic resin, unsaturated polyester resin, polysulfone resin, polyethersulfone resin, the thermoplastically polyimide resin, polyphenylene oxide resin, polyolefin resin, polycarbonate resin, at least a resin in the vibrin.

For example can exemplify as the complex body of above-mentioned fiber and resin layer of prepreg (プ リ プ レ グ (prepreg) is shown ).

＜2-2. embodiment 2 〉

As mentioned above, as long as this material for plating has above-mentioned resin layer, even then the material that is formed by arbitrary structures, form also can.For example, can be by above-mentioned resin layer and material in order to constitute with the opposed adhesive layer C of formed circuit.

＜2-3. embodiment 3 〉

This material for plating also can be the material that is made of the material that above-mentioned resin layer and the complex body C stageization that makes above-mentioned fiber and resin form, and also can be the material that constitutes the resin layer/fiber of C stage state and the complex body/resin layer of resin.

＜3. be used to form the solution of resin layer 〉

In order to make above-mentioned material for plating, the preferred solution that contains above-mentioned polyimide resin that uses.Promptly, solution of the present invention is to be used to form the enforcement electroless plating to cover the solution of using resin layer, be preferably the solution of the precursor polyamic acid that contains polyimide resin with siloxane structure or this polyimide resin at least, above-mentioned polyimide resin is preferably the acid dianhydride composition and contains the two amine components reaction of diamines of above-mentioned general formula (1) expression and the polyimide resin that obtains.In this manual, above-mentioned solution is called " basic solution ".

Above-mentioned basic solution is so long as form above-mentioned＜1〉resin layer that illustrates in the hurdle gets final product with solution, particularly, gets final product so long as contain the solution of the polyimide resin with above-mentioned siloxane structure.Above-mentioned basic solution is as above-mentioned＜1〉illustrate in the hurdle, except that polyimide resin, in the object of the invention scope, can also contain various other compositions, in addition, can also use all solvents that can dissolve these resinous principles.Here said " dissolving " is meant the amount with respect to solvent, and dissolved resinous principle amount perhaps is dispersed in the situation in the solution more than 1 weight %.

Above-mentioned basic solution can be on the expectation material by apply with present known method such as dipping, spraying, spin coating, drying forms resin layer.

In addition, as above-mentioned basic solution, in order to make above-mentioned material for plating, the preferred solution that uses the polyamic acid of the precursor that contains polyimide resin.That is, the present invention includes, form the solution of resin layer on above-mentioned material for plating, this solution contains the polyamic acid with above-mentioned siloxane structure.Described solution also is an example in the basic solution.

Above-mentioned basic solution particularly, gets final product so long as contain the solution of the polyamic acid with above-mentioned siloxane structure so long as be used to form the solution of above-mentioned resin layer and get final product.Above-mentioned basic solution as mentioned above, except that polyamic acid solution and Thermocurable composition, can also contain other composition, can use all solvents of these resinous principles of dissolving in addition.

On the expectation material, the coating, the imidization that carry out above-mentioned basic solution by known methods such as dipping, spraying, spin coatings form above-mentioned resin layer.In addition, as mentioned above, imidization can adopt the by the use of thermal means that dewaters by the thermal treatment polyamic acid solution, use in the chemical process that dewatering agent dewaters any one.In addition, can also use heating under reduced pressure to carry out the method for imidization.Wherein, simple from handling, as to make excellent in efficiency viewpoint, the preferred use by heat-treating the by the use of thermal means that dewaters carried out the method for imidization.

Further, in above-mentioned basic solution, it is the polyimide resin that raw material obtains that above-mentioned polyimide resin is preferably 1～49mol%, two amine components that content with the diamines of above-mentioned general formula (1) expression accounts for total diamines.

Further, in above-mentioned basic solution, preferably contain the Thermocurable composition.

In addition, in above-mentioned basic solution, above-mentioned Thermocurable composition is preferably the material that contains the Resins, epoxy composition, and this Resins, epoxy composition comprises epoxy compounds and solidifying agent.

In addition, in above-mentioned basic solution, the second-order transition temperature of preferred above-mentioned polyimide resin is in 100～200 ℃ scope.Further, in this solution, above-mentioned polyimide resin is preferably to account for 10～75mol% of total diamines at the diamines by general formula (1) expression.

In addition, in above-mentioned basic solution, the weight-average molecular weight Mw that above-mentioned polyimide resin is preferably obtained by gel permeation chromatography is 30000～150000.Further, in this solution, above-mentioned polyimide resin is preferably, and with respect to 1 mole of two amine component that contain the diamines of above-mentioned general formula (1) expression, adds the acid dianhydride composition in 0.95～1.05 molar range and the material that obtains.

In addition, in above-mentioned basic solution, above-mentioned polyimide resin is preferably the material with the protected group that forms of functional group and/or this functional group.Further, in this solution, above-mentioned functional group is preferably more than one the group that is selected from hydroxyl, amino, carboxyl, amide group, sulfydryl, the sulfonic group.

＜4. the manufacture method of material for plating 〉

The manufacture method of above-mentioned material for plating for example can be used above-mentioned＜3〉solution that illustrates in the hurdle, there is no particular limitation to other operation, condition, equipment etc.

For example, for example can enumerate and to contain the solution of above-mentioned polyimide resin at least as the manufacture method of above-mentioned material for plating, by dipping, spraying, spin coating, roller coat, rod be coated with, known method such as intaglio plate coating, on the material of expectations such as inner layer circuit board or macromolecule membrane layer, implement coating, drying, form the method for resin layer.

Other example as the manufacture method of above-mentioned material for plating, can enumerate the above-mentioned polyamic acid solution of preparation, with this solution by dipping, spraying cloth, spin coating, roller coat, rod be coated with, known method such as intaglio plate coating, on the material of expectations such as inner layer circuit board or macromolecule membrane layer, implement coating, imidization, form the method for resin layer.Here, on the material of expectations such as inner layer circuit board or macromolecule membrane layer, implement coating, when imidization forms resin layer, in order to carry out imidization, be necessary to form high temperature, might produce thermal degradation when, the dimensional change of material, the problems such as generation of unrelieved stress.Therefore, in the manufacture method of material for plating of the present invention, more preferably use the method for polyimide resin solution.

In addition, as mentioned above, above-mentioned material for plating can be the sheet monolayer material (single-layer sheet) that only is made of above-mentioned resin layer.At this moment, for example be used to form the solution of implementing the resin layer that electroless plating covers, curtain coating is coated on any supporter, carries out drying then, can make the flaky material that is made of resin layer thus.In addition, on the material that this flaky material is laminated to expectations such as inner layer circuit board or macromolecule membrane layer, can easily form the lamination material for plating.

In addition, by on insulating material, forming above-mentioned resin layer, can be used as insulating trip and use.

＜5. multilayer body, printed circuit board (PCB) etc. 〉

In addition, the present invention comprises multilayer body, and this multilayer body is that lamination electroless plating coating forms on the resin layer surface of above-mentioned material for plating, single-layer sheet, insulating trip etc.

And above-mentioned material for plating is preferred on the purposes such as printed circuit board (PCB).That is, the present invention includes the printed circuit board (PCB) that is provided with above-mentioned material for plating, single-layer sheet or insulating trip.Above-mentioned printed circuit board (PCB) is so long as the circuit card that has used above-mentioned material for plating etc. to form gets final product, and there is no particular limitation about other concrete structure.

In addition, above-mentioned printed circuit board (PCB) has electroless plating coating and resin layer, and this resin layer contains the polyimide resin with above-mentioned siloxane structure, and above-mentioned electroless plating coating can be formed on the above-mentioned resin layer.

In addition, above-mentioned material for plating can be suitable on the present known printed circuit board (PCB), and there is no particular limitation to concrete purposes.For example, can enumerate printed circuit board (PCB)s such as flexible printed circuit board, printed circuit board, multi-layer flexible printed circuit board, multilayer printed circuit board, combination circuit plate.

In addition, manufacture method as above-mentioned printed circuit board (PCB), get final product so long as be included in the method that forms the operation of resin layer on any substrate and on above-mentioned resin layer, form the operation of electroless plating coating, described resin layer contains the polyimide resin with above-mentioned siloxane structure, and there is no particular limitation for other concrete operation, condition, producing apparatus etc.Below, the manufacture method of the above-mentioned printed circuit board (PCB) of explanation that gives some instances.

At first, the situation of using the sheet material for plating to make printed circuit board (PCB) is described.In addition, used on the resin layer of sheet material for plating, be formed with the material of above-mentioned lining paper (screening glass).Earlier on above-mentioned resin layer successively lamination have lining paper the sheet material for plating, formed the internal substrate of circuit pattern.Then, can on the resin layer surface that exposes by release backing paper, implement electroless plating and cover processing, form the circuit pattern metal level, obtain printed circuit board (PCB) thus.

In addition, in above-mentioned operation, when using flexible printed circuit board, can make multi-layer flexible circuit board as internal substrate.In addition, when the printed circuit board (PCB) that has used glass-epoxy base material etc. is used as internal substrate, can make multilayer rigid circuit board or combination circuit plate.

In addition, in order to realize electrical connection in vertical direction, be necessary on multilayer printed circuit board, to form through hole, can pass through known methods such as laser, machine drilling, punching or chemical milling, form through hole on printed circuit board (PCB) of the present invention, available electroless plating such as covers at known method implements conductionization.

In addition, when lamination material for plating and internal substrate, can utilize hot pressings such as hot-pressing processing, vacuum pressed processing, lamination treatment (heat lamination processing), vacuum lamination processing, hot-roll lamination processing, the processing of vacuum hot-roll lamination to handle.Wherein,, promptly handle, can bury between circuit better seamlessly, can realize better by vacuum pressed processing, vacuum lamination processing, vacuum hot-roll lamination by the processing under vacuum.

In addition, also can be after above-mentioned resin layer surface forms the electroless plating coating, perhaps by etching etc. after forming circuit pattern on this electroless plating coating, on resin layer, implement heat treated.At this moment, can further improve the tackiness between electroless plating coating and resin layer, so preferred.

As mentioned above, by on the base material that is used to implement the electroless plating coating (material) surface, use and contain the resin layer of polyimide resin, even specially do not implement surface roughening with ad hoc structure, also and the adhesion strength height between the electroless plating coating, and can improve thermotolerance.

In addition, the surfaceness of material for plating of the present invention, multilayer body, printed circuit board (PCB) etc., though very little, under hot environment, the tackiness between coating and resin layer is good.

Particularly, for example, when above-mentioned resin layer contains above-mentioned polyimide resin and Thermocurable composition, shown in following embodiment, be used to implement the surfaceness of the resin layer of coating, be preferably below the 0.5 μ m at the arithmetic average roughness Ra that measures under the cutoff 0.002mm, when more preferably 0.1 μ m was following, the adhesion strength that reaches under 150 ℃ between above-mentioned coating and resin layer was the above beneficial effect of 5N/cm.

In addition, the polyimide resin that in above-mentioned resin layer, contains, when on its second-order transition temperature, having feature, shown in following embodiment, be used to implement the surfaceness of the resin layer of coating, be preferably below the 0.5 μ m at the arithmetic average roughness Ra that measures under the cutoff 0.002mm, when more preferably 0.1 μ m is following, the adhesion strength under 120 ℃ that reaches between above-mentioned coating and resin layer is more than the 5N/cm, is more preferably the above beneficial effect of 8N/cm.

Further, above-mentioned resin layer has under normal conditions the character of adhering well with coating.The tackiness of this coating and resin layer can be represented with " normality adhesion strength " and " adhesion strength behind the PCT ".

Particularly, in material for plating of the present invention, multilayer body or the printed circuit board (PCB), when above-mentioned resin layer contains above-mentioned polyimide resin and Thermocurable composition, about the tackiness of above-mentioned resin layer and coating, in preferred " normality adhesion strength " scope more than 5N/cm.And/or, about the tackiness of the copper plate of above-mentioned resin layer character, in preferred " adhesion strength behind the PCT " scope more than 3N/cm.

In addition, in material for plating of the present invention, multilayer body or the printed circuit board (PCB), when the second-order transition temperature of the polyimide resin that contains in the above-mentioned resin layer has feature, the tackiness that is related to above-mentioned resin layer and copper plate, preferably " normality adhesion strength " more than 6N/cm, the more preferably scope more than 9N/cm.And/or, the character of above-mentioned resin layer is for the tackiness of copper plate, preferred " adhesion strength behind the PCT " more than 3N/cm, the more preferably scope more than 6N/cm.

In addition, in material for plating of the present invention, multilayer body or the printed circuit board (PCB), when the weight-average molecular weight of the polyimide resin that contains in the above-mentioned resin layer has feature, the tackiness of above-mentioned resin layer and copper plate, preferably " normality adhesion strength " more than 6N/cm, the more preferably scope more than 9N/cm.And/or, the character of above-mentioned resin layer is for the tackiness of copper plate, preferred " adhesion strength behind the PCT " more than 3N/cm, the more preferably scope more than 5N/cm.

In addition, in material for plating of the present invention, multilayer body or the printed circuit board (PCB), when the polyimide resin that contains in the above-mentioned resin layer has functional group, the tackiness of above-mentioned resin layer and copper plate, preferably " normality adhesion strength " more than 5N/cm, the more preferably scope more than 11N/cm.And/or, the character of above-mentioned resin layer is for the tackiness of copper plate, preferred " adhesion strength behind the PCT " more than 3N/cm, the more preferably scope more than 6N/cm.

Here, " arithmetic average roughness Ra " definition to some extent in JIS B 0601 (put down into and corrected version on February 1st, 6).The numeric representation of described especially in this manual " arithmetic average roughness Ra " is observed surperficial and numerical value that try to achieve with light interference type surface structure analysis device.Describe concrete measuring method in the following embodiments in detail.The wavelength that " cutoff " expression among the present invention is set when obtaining roughness curve by cross section curve (measured data), and be documented among the above-mentioned JIS B 0601.That is, so-called " the arithmetic average roughness value Ra that measures under cutoff 0.002mm " be meant, removes from measured data to have the concavo-convex of the wavelength longer than 0.002mm and arithmetic average roughness that roughness curve that obtain calculates.In addition, " normality adhesion strength ", " adhesion strength behind the PCT " and above-mentioned resin layer under hot environment and the adhesive evaluation between coating can be undertaken by the method for estimating " the plating adherence under the normality ", " the plating tackiness behind the PCT " shown in the following embodiment, " the plating tackinesss under 120 ℃ ", " the plating tackinesss under 150 ℃ ".

In addition, utilize the following advantage of material for plating of the present invention, for example specially do not implement surface roughening, also and the high advantage of the adhesion strength between the electroless plating coating, can be applicable in the manufacturing etc. of the printed circuit board (PCB)s such as flexible printed circuit board, printed circuit board, multi-layer flexible printed circuit board, multilayer rigid circuit board or combination circuit plate that require to form fine wiring.

In addition, by single face or the above-mentioned material for plating of two-sided combination at the macromolecule membrane layer of non-thermoplastically polyimide etc., when the intensity that improved material, toughness, Young's modulus can be provided, linear expansivity reduces, dimensional stability improves, the plating multilayer body that the operability of while material also improves.In addition, especially by on the single face of non-thermoplastically Kapton, being formed for implementing that electroless plating covers, as to use above-mentioned material for plating resin layer, form the adhering agent layer that contains thermoplastically polyimide resin and Thermocurable composition simultaneously overleaf, can make assembled substrate that has improved dimensional stability or the assembled substrate that does not have core pattern.

Below exemplify embodiment, further describe embodiment of the present invention.Certainly, the present invention is not limited to following examples, and trickle part can adopt various modes, and this is self-evident.

In addition, the embodiment or the embodiment that in the project of the best mode that enforcement the present invention uses, use, just be used for clearly illustrating technology contents of the present invention, be not be used for limiting of the present invention, in the claim scope of purpose of the present invention and following record, can carry out various changes and realize.That is, in not departing from the scope of the present invention, those skilled in the art can carry out various variations, modification and change.

Embodiment

(embodiment A)

In the present embodiment, form the characteristic of property, carry out evaluation as follows as material for plating to weld thermotolerance and fine wiring.In addition, the resin layer that electroless plating to be formed in its surface covers is a layer A, with the opposed layer of the circuit that forms be a layer B.

[welding thermotolerance]

Make copper-coated laminated board (CCL-HL950K TypeSK, aerochemistry company of Mitsubishi makes) and to have layer B of material for plating of supporter opposed, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, after the heating and pressurizing 6 minutes, peel off supporter, in hot-air oven, drying is 60 minutes under 180 ℃, to obtain multilayer body.Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after having carried out decontamination processing and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and implement on electroless plating copper.After the processing of 180 ℃, 30 minutes heat drying of above-mentioned multilayer body enforcement, cut off with the size of 15mm, 30mm, under the condition of 30 ℃ of temperature, humidity 70%, placed 200 hours, make test film.Be set in top temperature under 260 ℃ the condition, above-mentioned test film is put into IR reflow stove, weld thermal test.The reflow stove FT-04 that IR reflow stove uses CIS company to make.In addition, repeat 3 these tests, no expansible is expressed as zero, have expansible be expressed as *.In addition, decontamination processing and electroless plating copper are to implement with the operation of record in the following table 1～2.

[fine wiring formation]

The layer B of the material for plating that has supporter and the circuit of the circuit card with the circuit that forms high 18 μ m, line/space (L/S)=50 μ m/50 μ m are formed in the face of putting, this circuit card is by processing copper-coated laminated board (CCL-HL950K TypeSK, aerochemistry company of Mitsubishi makes) and get, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, carry out heating and pressurizing after 6 minutes, peel off supporter, in hot-air oven, drying is 60 minutes under 180 ℃, with the multilayer body that obtains being made of material for plating/BT substrate.Then, by UV-YAG laser, the internal diameter of offering until this electrode directly over the electrode of inner layer B T substrate is the through hole of 30 μ m, then, and after implementing electroless plating on the whole base plate face and covering, 180 ℃ of heat treated of implementing 30 minutes down.Then, on the copper plate that forms, form corrosion-resisting pattern, after enforcement thickness is the copper electroplating of 10 μ m, peel off corrosion-resisting pattern, be that etching reagent is removed the copper facing of exposing further, prepare the printed circuit board (PCB) of circuit with L/S=10 μ m/10 μ m with sulfuric acid/hydrogen peroxide.With the circuit of this printed circuit board (PCB) do not have broken string or shape defect, the information slip that prepared well is shown qualified (zero), has the information slip of broken string or shape defect to be shown defective (*) generation, estimate.

Table 1

Operation	Liquid is formed		Treatment temp	Treatment time
					Expand	Infiltration Securiganth P sodium hydroxide expands	500ml/l 3g/l	60℃	5 minutes
Washing
					Microetch	Concentrate compact CP sodium hydroxide	550ml/l 40g/l	80℃	5 minutes
Washing
					Neutralization	Reducing solution Securiganth P500 sulfuric acid	50ml/l 70ml/l	40℃	5 minutes

Table 2

The operation title	Liquid is formed	Treatment temp	Treatment time
				The sanitising agent conditioning agent	Sanitising agent Securiganth902 40ml/l sanitising agent Additive 902 3ml/l sodium hydroxide 20g/l	60℃	5 minutes
Washing
				Preimpregnation	Preimpregnation Neoganth-B 20ml/l sulfuric acid 1ml/l	Room temperature	1 minute
Add catalyzer	Promoting agent Neoganth 834 conc 40ml/l sodium hydroxide 4g/l boric acid 5g/l	40℃	5 minutes
				Washing
Sensitization	Reductive agent Neoganth 1g/l sodium hydroxide 5g/l	Room temperature	2 minutes
				Washing
Plated by electroless plating	Base soln Printoganth MSKDK 80ml/l copper solutions Printoganth MSK 40ml/l reductive agent Cu 14ml/l stablizer Printoganth MSKDK 3ml/l	32℃	15 minutes

[synthesis example 1 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 24g (0.12mol) 4 that 24g (0.03mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide and N, dinethylformamide (hereinafter referred to as DMF) stirs and dissolving, adds 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin 1.

[synthesis example 2 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 21g (0.105mol) 4 that 37g (0.045mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide and N, dinethylformamide (hereinafter referred to as DMF) stirs and dissolving, adds 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin 2.

[synthesis example 3 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 18g (0.09mol) 4 that 49g (0.06mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide and N, dinethylformamide (hereinafter referred to as DMF) stirs and dissolving, adds 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin 3.

[synthesis example 4 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 31g (0.105mol) 1 that 37g (0.045mol) Shin-Etsu Chemial Co., Ltd makes, two (3-amino-benzene oxygen) benzene and the N of 3-, dinethylformamide (hereinafter referred to as DMF) stirs and dissolving, adds 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin 4.

[synthesis example 5 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 12g (0.06mol) 4 that 73g (0.09mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide and N, dinethylformamide (hereinafter referred to as DMF) stirs and dissolving, adds 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin 5.

[synthesis example 6 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 6g (0.03mol) 4 that 97g (0.12mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide and N, dinethylformamide (hereinafter referred to as DMF) stirs and dissolving, adds 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin 6.

[synthesis example 7 of polyimide resin]

In the glass flask of 2000ml capacity, add 41g (0.143mol) 1, two (3-amino-benzene oxygen) benzene of 3-, 1.6g (0.007mol) 3,3 '-dihydroxyl-4,4 '-benzidine and DMF, stir and dissolving, interpolation 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 180 minutes, 665Pa, obtains polyimide resin 7.

[preparation example 1 of the solution of form layers A]

Polyimide resin 1 is dissolved in the dioxolane, obtains the solution (A-a) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 2 of the solution of form layers A]

Polyimide resin 2 is dissolved in the dioxolane, obtains the solution (A-b) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 3 of the solution of form layers A]

Polyimide resin 3 is dissolved in the dioxolane, obtains the solution (A-c) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 4 of the solution of form layers A]

Polyimide resin 4 is dissolved in the dioxolane, obtains the solution (A-d) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 5 of the solution of form layers A]

Polyimide resin 5 is dissolved in the dioxolane, obtains the solution (A-e) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 6 of the solution of form layers A]

Polyimide resin 6 is dissolved in the dioxolane, obtains the solution (A-f) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 1 of the solution of form layers B]

Polyimide resin 7 is dissolved in the dioxolane, obtains the solution (A-g) that solid component concentration reaches 25 weight %.On the one hand, refine two [4-(3-amino-benzene oxygen) phenyl] sulfones of the diamines that industry (strain) company makes, the four countries of 0.2g of biphenyl type epoxy resin YX4000H, the 17.9g Wakayama that 32.1g japan epoxy resin (strain) company is made change into the epoxy hardener 2 that industry (strain) company makes, 4-diamino-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine is dissolved in the dioxolane, obtains the solution (A-h) of solid component concentration 50%.Mix 50g solution (A-g) and 50g solution (A-h), obtain the solution (A-i) of form layers B.

[embodiment 1]

Solution (A-a) curtain coating of form layers A is coated on the surface of the polyethylene terephthalate's film (trade(brand)name セ ラ ピ one Le HP, Japan メ ラ イ ジ Application グ corporate system) that constitutes supporter.Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ supporter of 2 μ m with 60 ℃ temperature.Further, on the layer A surface of the material that constitutes by above-mentioned layer A/ supporter, the solution of curtain coating coating form layers B carries out drying with 60 ℃, 100 ℃, 120 ℃, 150 ℃ temperature, obtains the material for plating that has supporter that is made of the thick thick layer A/ supporter of layer B/2 μ m of 38 μ m.Use this material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 3.

[embodiment 2～4]

According to the solution of the A of form layers shown in the table 3, the order with identical with embodiment 1 obtains the material for plating that has supporter that is made of layer B/ layer A/ supporter.Use the resulting material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 3.

[embodiment 5]

Solution (A-b) curtain coating of form layers A is coated on the surface of 25 μ m Kaptons (j) (trade(brand)name ア ピ カ Le NPI, (strain) カ ネ カ system).Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ macromolecule membrane of 2 μ m with 60 ℃ temperature.Further, on the macromolecule membrane surface of the material that constitutes by above-mentioned layer A/ macromolecule membrane, the solution of curtain coating coating form layers B carries out drying with 60 ℃, 100 ℃, 120 ℃, 150 ℃ temperature, obtains the material for plating that is made of the thick thick layer A of layer B/ macromolecule membrane/2 μ m of 38 μ m.Use this material for plating, estimate according to the evaluation order of aforementioned various assessment items.In addition, the lining paper during as lamination uses polyethylene terephthalate's film (trade(brand)name セ ラ ピ one Le HP, Japan メ ラ イ ジ Application グ corporate system).Evaluation result is shown in table 3.

[embodiment 6]

By spinner, solution (A-b) curtain coating of form layers A is coated on the surface of copper-coated laminated board (CCL-HL950K TypeSK, Mitsubishi's aerochemistry corporate system).Then, use hot-air oven, carry out drying, obtain the material for plating that constitutes by the thick layer A/ copper-coated laminated board of 2 μ m with 60 ℃, 150 ℃, 180 ℃ temperature.Decontamination processing, electroless plating cover, further the multilayer body of copper electroplating is supplied with in the welding thermal test this material for plating has been implemented.

In addition, to the material for plating that constitutes by layer A/ copper-coated laminated board, directly over the electrode of inner layer B T substrate until this electrode, become the through hole of internal diameter 30 μ m by the UV-YAG laser beam drilling, after then whole base plate being implemented electroless plating copper, under 180 ℃, implement 30 minutes heat treated.Then, on the copper plate that forms, form corrosion-resisting pattern, after implementing the copper electroplating of thickness 10 μ m, peel off corrosion-resisting pattern, further, with sulfuric acid/hydrogen peroxide is that etching reagent is removed the copper facing of exposing, and prepares the printed circuit board (PCB) of the circuit with L/S=10 μ m/10 μ m, estimates fine wiring formation property.Evaluation result is shown in table 3.

[embodiment 7]

Except using solid component concentration with preparation example 2 to be adjusted into the solution (A-k) of 10 form layers A, the thickness of layer A is beyond the 5 μ m, to obtain material for plating in the same manner with embodiment 6, estimates welding thermotolerance and fine wiring and forms property.Evaluation result is shown in table 3.

As shown in Table 3, in embodiment 1～7, use the sample that on material for plating of the present invention two-sided, has covered copper to weld thermal test, even but such situation also demonstrates sufficient welding thermotolerance.

[comparative example 1]

Except the solution (A-e) that uses form layers A, carry out in the same manner with embodiment 1, obtain the material for plating that has supporter that layer B/ layer A/ supporter constitutes.Use the resulting material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 4.

[comparative example 2]

Except the solution (A-f) that uses form layers A, carry out in the same manner with embodiment 1, obtain the material for plating that has supporter that layer B/ layer A/ supporter constitutes.Use the resulting material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 4.

As shown in Table 4, in comparative example 1,2, can form electroless plating cover film securely at smooth-flat-surface, thus fine wiring formation property excellence, but weld poor heat resistance.

Table 3

	Embodiment	Embodiment	Embodiment	Embodiment	Embodiment	Embodiment	Embodiment
									1	2	3	4	5	6	7
The solution of form layers A	(A-a)	(A-b)	(A-c)	(A-d)	(A-b)	(A-b)	(A-k)
								The solution of form layers B	(A-i)	(A-i)	(A-i)	(A-i)	(A-i)	-	-
Macromolecule membrane	-	-	-	-	(j)	-	-
								The welding thermotolerance	○	○	○	○	○	○	○
Fine wiring formation property L/S=10 μ m/10 μ m	○	○	○	○	○	○	○

Table 4

	Comparative example	Comparative example
				1	2
The solution of form layers A	(A-e)	(A-f)
			The solution of form layers B	(A-i)	(A-i)
The welding thermotolerance	×	×
			Fine wiring formation property L/S=10 μ m/10 μ m	○	○

[Embodiment B]

(be used to form and implement the synthesis example that electroless plating covers the solution of using resin layer: A-1)

At N, in the dinethylformamide (hereinafter referred to as DMF), with the KF-8010 and 4 of mol ratio ground adding in 1: 1 as Shin-Etsu Chemial Co., Ltd's manufacturing of two amine components, 4 '-diaminodiphenyl oxide, after stirring and the dissolving, add 78g and be about equimolar 4 with respect to two amine components, 4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin.

Polyimide solution and epoxy compounds solution are mixed with 9: 1 ratio of weight ratio, the weight ratio that has prepared polyimide resin composition with siloxane structure and Resins, epoxy composition is that the resin layer that 9: 1 enforcement electroless plating covers forms with solution (A-1), wherein, above-mentioned polyimide solution be with resulting polyimide resin with siloxane structure with solid component concentration 10 weight % be dissolved in the polyimide solution of dioxolane; Above-mentioned epoxy compounds solution is that refine two [4-(3-amino-benzene oxygen) phenyl] sulfones of the diamines that industry (strain) company makes, the four countries of 1.3 weight parts of the Wakayama of biphenyl type epoxy resin YX4000H that japan epoxy resin (strain) company of 196 weight parts is made, 108 weight parts change into the curable epoxide promotor 2 that industry (strain) company makes, 4-diamino-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine is dissolved in the dioxolane, reaches the epoxy compounds solution of solid component concentration 10%.

In addition, with 121 ℃, 24 hours condition, the chippy YX4000H of extraction in pure water was with ionic impurity (Cl-, Br-, the SO in this extraction water of ion chromatography measurement ₄ ^2-, Na ⁺) content be 3ppm.

(be used to form and implement the synthesis example that electroless plating covers the solution of using resin layer: A-2)

Except mix polyimide solution and epoxy compounds solution at 7: 3 with weight ratio, according to the identical method of synthesis example (A-1), the weight ratio of having synthesized polyimide resin composition with siloxane structure and Resins, epoxy composition be 7: 3, implement the resin layer that electroless plating covers and form with solution (A-2).

(be used to form and implement the synthesis example that electroless plating covers the solution of using resin layer: A-3)

Except the KF-8010 and 4 that makes with 1: 2 ratio of mol ratio dissolving Shin-Etsu Chemial Co., Ltd, 4 '-diaminodiphenyl oxide is used as beyond two amine components, according to the identical method of synthesis example (A-1), the weight ratio of having synthesized polyimide resin composition with siloxane structure and Resins, epoxy composition be 9: 1, implement the resin layer that electroless plating covers and form with solution (A-3).

(be used to form and implement the synthesis example that electroless plating covers the solution of using resin layer: A-4)

Except epoxy compounds solution is following composition, according to the identical method of synthesis example (A-1), the weight ratio of having synthesized polyimide resin composition with siloxane structure and Resins, epoxy composition is 9: 1, implement the resin layer formation solution (A-4) that electroless plating covers, wherein, epoxy compounds solution is the Resins, epoxy [NC-3000H] with Nippon Kayaku K. K's manufacturing of 290 weight parts, the resol [NC-30] that the flourish chemical industry of group (strain) of 126 weight parts is made, 1.3 the four countries of weight part change into the curable epoxide promotor 2 that industry (strain) company makes, 4-diamino-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine is dissolved in the epoxy compounds solution that reaches solid component concentration 10% in the dioxolane.

(be used to form and implement the synthesis example that electroless plating covers the solution of using resin layer: A-5)

Not hybrid epoxidized compound solution only uses the polyimide solution that obtains in synthesis example (A-1), prepare do not contain the Resins, epoxy composition, be used to implement the resin layer that electroless plating covers and form with solution (A-5).

(be used to form and implement the synthesis example that electroless plating covers the solution of using resin layer: A-6)

With 1 of 41g, two (3-amino-benzene oxygen) benzene of 3-are dissolved among the DMF while stirring, add equimolar 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 180 minutes, 665Pa, obtains polyimide resin.Except use with resulting polyimide resin with solid component concentration be 10 weight % be dissolved in the polyimide solution of dioxolane, according to the identical method of synthesis example (A-1), the weight ratio of having synthesized the polyimide resin composition that do not contain siloxane structure and Resins, epoxy composition be 9: 1, be used to implement the resin layer that electroless plating covers and form with solution (A-6).

(adhering agent layer forms the synthesis example with solution: C-1)

With 1 of 41g, two (3-amino-benzene oxygen) benzene of 3-are dissolved among the DMF while stirring, add equimolar 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 180 minutes, 665Pa, obtains polyimide resin.Above-mentioned polyimide solution and epoxy compounds are mixed with 2: 1 ratio of weight ratio, the weight ratio of having synthesized thermoplastically polyimide resin composition and Resins, epoxy composition is 1: 1 a solution (C), wherein, above-mentioned polyimide solution be with resulting polyimide resin with solid component concentration 20 weight % be dissolved in polyimide solution in the dioxolane; Above-mentioned epoxy compounds solution is that refine two [4-(3-amino-benzene oxygen) phenyl] sulfones of the diamines that industry (strain) company makes, the four countries of 1.2 weight parts of the Wakayama of biphenyl type epoxy resin YX4000H that japan epoxy resin (strain) company of 196 weight parts is made, 108 weight parts change into the epoxy hardener 2 that industry (strain) company makes, 4-diamino-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine is dissolved in the dioxolane, reaches the epoxy compounds solution of solid component concentration 40%.

(embodiment 8)

The resin layer formation that the enforcement electroless plating that obtains in the synthesis example (A-1) is covered is coated on the surface of the polyethylene terephthalate's film (trade(brand)name セ ラ ピ one Le HP, Japan メ ラ イ ジ Application グ corporate system) that constitutes supporter with solution (A-1) curtain coating.Then, use hot-air oven, respectively carry out 1 minute drying, obtain having the material for plating of the thick resin layer of 25 μ m with 60 ℃, 100 ℃, 150 ℃ temperature.

Make resulting material for plating mutually opposed with glass epoxide copper-coated laminated board [リ シ ヨ one ラ イ ト CS-3665] (Toshimasa Kogyo Co., Ltd. makes: copper thickness 18 μ m, thickness of slab 0.6mm), after carrying out 6 minutes heating and pressurizing under 170 ℃ of temperature, 1MPa pressure, the vacuum condition, peel off polyethylene terephthalate's film of supporter, and respectively 130 ℃ of down heating 10 minutes, 150 ℃ of heating 10 minutes down, 180 ℃ of heating 30 minutes down, obtain the multilayer body that constitutes by material for plating/copper-coated laminated board with resin layer.

On the exposing surface of the resin layer of gained multilayer body, under following table 5 and table 6 condition, by decontamination, electroless plating cover, electrolytic coating, form copper plate (thickness 8 μ m).Then, 180 ℃ of following heat dryings 30 minutes, the preparation plated substrate.To resulting plated substrate,, measure behind normality and the pressure cooking test (PCT) and the plating adherence under 150 ℃ according to JPCA-BU01-1998 (the Japanese printed wiring industry of Corporation can be issued).In addition, measure " normality plating adherence ", " plating adherence behind the PCT ", " the plating adherences under 150 ℃ " under the following conditions.

Normality: under 23 ℃, 50% atmosphere, place the adhesion strength of measuring after 24 hours

Behind the PCT: under 121 ℃, 100% atmosphere, place the adhesion strength of measuring after 96 hours

150 ℃: the adhesion strength under 150 ℃ of environment

Table 5

Operation	Liquid is formed		Treatment temp	Treatment time
					Expand	Infiltration Securiganth P sodium hydroxide expands	500ml/l 3g/l	60℃	5 minutes
Washing
					Microetch	Concentrate compact CP sodium hydroxide	550ml/l 40g/l	80℃	5 minutes
Washing
					Neutralization	Reducing solution Securiganth P500 sulfuric acid	50ml/l 70ml/l	40℃	5 minutes

Table 6

The operation title	Liquid is formed		Treatment temp	Treatment time
					The sanitising agent conditioning agent	Sanitising agent Securiganth 902 sanitising agent Additive 902 sodium hydroxide	40ml/l 3ml/l 20g/l	60℃	5 minutes
Washing
					Preimpregnation	Preimpregnation Neoganth B sulfuric acid	20ml/l 1ml/l	Room temperature	1 minute
Add catalyzer	Promoting agent Neoganth 834 conc sodium hydroxide boric acid	20ml/l 4g/l 5g/l	40℃	5 minutes
					Washing
Sensitization	Reductive agent Neoganth sodium hydroxide	1g/l 5g/l	Room temperature	2 minutes
					Washing
Plated by electroless plating	Base soln Printoganth MSKDK copper solutions Printoganth MSK reductive agent Cu stablizer Printoganth	80ml/l 40ml/l 14ml/l 3ml/l	32℃	15 minutes
					Washing
Acid activity	98％H 2SO 4	100ml/l	Room temperature	0.5 minute
					Copper electroplating	CuSO 4·5H 2O 98％H 2SO 4 NaCl top LUCINA 81 H L top LUCINA MAKE-UP	70g/l 200g/l 80g/l 2.5ml/l 10ml/l	RT 2A/dm 2	20 minutes

In addition,, block plated substrate with wide 15mm, long 30mm, under 30 ℃, 60%RH condition, carry out 192 hours damping after, carried out 3 Reflow Soldering tests of 260 ℃, find the expansion of plating.The Reflow Soldering test is carried out in such a way.

Make copper-coated laminated board (CCL-HL950K TypeSK, aerochemistry company of Mitsubishi make) and have layer B of material for plating of supporter opposed, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, after the heating and pressurizing 6 minutes, peel off supporter, use hot-air oven, descend dry 60 minutes to obtain multilayer body at 180 ℃.Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer be carried out decontamination and electroless plating coated with after, cover on the copper at electroless plating that the copper electroplating layer that forms thick 18 μ m carries out.To above-mentioned multilayer body, under 180 ℃, implement heat drying and handle after 30 minutes, cut into the size of 15mm, 30mm, under 30 ℃ of temperature, humidity 70% condition, placed 200 hours and make test film.Be set in top temperature under 260 ℃ the condition, above-mentioned test film is dropped in the IR reflow stove, weld thermal test.The reflow stove FT-04 that IR reflow stove uses CIS company to make.In addition, repeat 3 these tests, do not have expansible to be expressed as zero, have expansible be expressed as *.In addition, decontamination and electroless plating copper are to implement by the operation of record in the following table 1～2.

Measure in the item in above-mentioned tackiness, use the sample that has proceeded to the decontamination operation by the sample making order, measure the surface roughness Ra of resin layer surface.Measure and use optical interference formula surfaceness meter (the NewView5030 system that ZYGO company makes), under the condition of table 7, measured the arithmetic average roughness Ra of resin layer surface.

Table 7

Condition determination	Object lens	50 times of speculums
			Image zooming	2
	FDA Res	Conventional
			Analysis condition	Remove	Post
Strainer	High pressure
		Filter Low Waven		0.002mm

The resulting table 8 that the results are shown in.

Table 8

	Embodiment 8	Comparative example 3
			In the resin of layer A, the mol ratio of siloxane diamine in total diamines	50％	50％
The kind of Thermocurable composition	YX4000H/BAPS-M	-
			The amount of Thermocurable composition	10％	Do not have
Constitute	Single-layer sheet	Single-layer sheet
			Adhesion strength (normality) N/cm	10	11
Adhesion strength (behind the PCT) N/cm	6	7
			Adhesion strength (150 ℃) N/cm	6	4
Anti-levelling property again	Carry out 3 levelling tests again, do not expand	Carry out 1 anti-test of levelling again, just produce and expand
			Arithmetic average roughness Ra	0.1μm	0.1μm

YX4000H: the biphenyl type epoxy resin (trade(brand)name) that japan epoxy resin (strain) company makes

BAPS-M: refine two [4-(3-amino-benzene oxygen) phenyl] sulfones of the diamines that industry (strain) company makes of Wakayama

NC3000H: Nippon Kayaku K. K's system Resins, epoxy (trade(brand)name)

NC-30: the flourish chemical industry of group (strain) is made resol (trade(brand)name)

(comparative example 3)

Except use the solution that does not contain the Thermocurable composition (A-5) obtain in above-mentioned synthesis example (A-5), the method according to identical with embodiment 1 obtains the multilayer body that is made of material for plating/copper-coated laminated board.Plating adherence (behind normality, the PCT, 150 ℃), Reflow Soldering test, the Ra of gained multilayer body have been measured.Gained the results are shown in table 8.

(embodiment 9)

Being used to of obtaining in the synthesis example (A-1) implemented the resin layer that electroless plating covers form the surface that is coated on polyethylene terephthalate's film (trade(brand)name セ ラ ピ one Le HP, Japan メ ラ イ ジ Application グ corporate system) of formation supporter with solution (A-1) curtain coating.Then, use hot-air oven, under 60 ℃, 100 ℃, 150 ℃ temperature, respectively carry out 30 seconds heat drying, obtain having the material for plating A-1 of the resin layer of thick 2 μ m.Further, in material for plating A-1, on the face that has formed resin layer, the solution (C) of synthetic thermoplastically polyimide resin composition and Resins, epoxy composition in the coating synthesis example (C), use hot-air oven, under 80 ℃, 100 ℃, 120 ℃, 150 ℃ temperature, respectively carry out 1 minute heat drying, obtain having supporter/the thick resin layer A/38 of 2 μ m μ m thick the layer C material for plating.

Peel off resulting material for plating from the PET film of supporter, make layer C and glass epoxide copper-coated laminated board in opposed mode, promptly opposed with glass epoxide copper-coated laminated board [リ シ ヨ one ラ イ ト CS-3665] (Toshimasa Kogyo Co., Ltd. makes: copper thickness 18 μ m, thickness of slab 0.6mm), after 60 minutes, obtain the multilayer body that constitutes by material for plating/copper-coated laminated board in 170 ℃ of temperature, 3MPa pressure, the descending heating and pressurizing of vacuum condition with resin layer.

Plating adherence (behind normality, the PCT, 150 ℃), levelling test again, the Ra of the multilayer body that gained is made of material for plating/copper-coated laminated board have been measured.Gained the results are shown in table 9.

Table 9

	Embodiment 9	Embodiment 10	Comparative example 4
				In the resin of layer A, the mol ratio of siloxane diamine in total diamines	50％	50％	Do not have
The kind of Thermocurable composition	YX4000H/BAPS -M	YX4000H/BAPS- M	YX4000H/BAPS- M
				The amount of Thermocurable composition	10％	30％	10％
Constitute	Layer A/ layer C	Layer A/ layer C	Layer A/ layer C
				Adhesion strength (normality) N/cm	10	9	3
Adhesion strength (behind the PCT) N/cm	6	6	1
				Adhesion strength (150 ℃) N/cm	6	7	1
Anti-levelling property again	Carry out 3 levelling tests again, do not expand	Carry out 3 levelling tests again, do not expand	Carry out 3 levelling tests again, do not expand
				Arithmetic average roughness Ra	0.1μm	0.1μm	0.1μm

(embodiment 10)

Being used to of obtaining in using synthesis example (A-2) implements the resin layer that electroless plating covers and forms with the solution (A-2), and the method according to identical with embodiment 9 obtains the multilayer body that is made of the material for plating/copper-coated laminated board with resin layer.

Plating adherence (behind normality, the PCT, 150 ℃), levelling test again, the Ra of the multilayer body that gained is made of material for plating/copper-coated laminated board have been measured.Gained the results are shown in table 9.

(comparative example 4)

Being used to of obtaining in using synthesis example (A-6) implements the resin layer that electroless plating covers and forms with the solution (A-6), and the method according to identical with embodiment 9 obtains the multilayer body that is made of the material for plating/copper-coated laminated board with resin layer.

Plating adherence (behind normality, the PCT, 150 ℃), levelling test again, the Ra of the multilayer body that gained is made of material for plating/copper-coated laminated board have been measured.Gained the results are shown in table 9.

(embodiment 11)

Being used to of obtaining in the synthesis example (A-1) implemented the resin layer that electroless plating covers form the surface that is coated on the non-thermoplastically Kapton (trade(brand)name ア ピ カ Le NPI, Bell Yuan chemical industry Co., Ltd. system) of thickness 12.5 μ m with solution (A-1) curtain coating.Then, use hot-air oven, carry out heat drying, obtain having the Kapton of the thick resin layer of 2 μ m with 60 ℃ of temperature.

Then, with the non-thermoplastically Kapton face of formed resin layer opposition side on, the solution (C) that obtains in the curtain coating coating synthesis example (C), use hot-air oven, with 80 ℃, 100 ℃, 120 ℃, 150 ℃ temperature, respectively carry out 30 seconds heat drying, obtain the material for plating that the layer C by the non-thermoplastically polyimide film layer B/10 μ m of the resin layer A/12.5 μ m of 2 μ m constitutes.

Make gained material for plating and glass epoxide copper-coated laminated board [リ シ ヨ one ラ イ ト CS-3665] (Toshimasa Kogyo Co., Ltd. makes: copper thickness 18 μ m, thickness of slab 0.6mm) opposed, and make resin layer be exposed at the surface, under 170 ℃ of temperature, 3MPa pressure, vacuum condition, carry out 60 minutes heating and pressurizing, obtain the multilayer body that constitutes by material for plating/copper-coated laminated board with resin layer.

Plating adherence (behind normality, the PCT, 150 ℃), levelling test again, the Ra of the multilayer body that gained is made of material for plating/copper-coated laminated board have been measured.Gained the results are shown in table 10.

Table 10

	Embodiment 11	Embodiment 12	Embodiment 13	Comparative example 5
					In the resin of layer A, the mol ratio of siloxane diamine in total diamines	50％	33％	50％	50％
The kind of Thermocurable composition	YX4000H/BAPS-M	YX4000H/BAPS-M	NC3000H/NC30	-
					The amount of Thermocurable composition	10％	10％	10％	Do not have
Constitute	Layer A/ layer B/ layer C	Layer A/ layer B/ layer C	Layer A/ layer B/ layer C	Layer A/ layer B/ layer C
					Adhesion strength (normality) N/cm	10	9	10	11
Adhesion strength (behind the PCT) N/cm	6	6	6	7
					Adhesion strength (150 ℃) N/cm	6	7	6	4
Anti-levelling property again	Carry out 3 levelling tests again, do not expand	Carry out 3 levelling tests again, do not expand	Carry out 3 levelling tests again, do not expand	Carry out 1 levelling test again, just produce and expand
					Arithmetic average roughness Ra	0.1μm	0.1μm	0.1μm	0.1μm

(embodiment 12)

Form with the solution (A-3) except using being used to of in synthesis example (A-3), obtaining to implement the resin layer that electroless plating covers, obtain the multilayer body that constitutes by material for plating/copper-coated laminated board in the same manner with resin layer with embodiment 11.

Plating adherence (behind normality, the PCT, 150 ℃), levelling test again, the Ra of the multilayer body that gained is made of material for plating/copper-coated laminated board have been measured.Gained the results are shown in table 10.

(embodiment 13)

Form with the solution (A-4) except using being used to of in synthesis example (A-4), obtaining to implement the resin layer that electroless plating covers, obtain the multilayer body that constitutes by material for plating/copper-coated laminated board in the same manner with resin layer with embodiment 11.

Plating adherence (behind normality, the PCT, 150 ℃), levelling test again, the Ra of the multilayer body that gained is made of material for plating/copper-coated laminated board have been measured.Gained the results are shown in table 10.

(comparative example 5)

Form with the solution (A-5) except using being used to of in synthesis example (A-5), obtaining to implement the resin layer that electroless plating covers, obtain the multilayer body that constitutes by material for plating/copper-coated laminated board in the same manner with resin layer with embodiment 11.

Plating adherence (behind normality, the PCT, 150 ℃), levelling test again, the Ra of the multilayer body that gained is made of material for plating/copper-coated laminated board have been measured.Gained the results are shown in table 10.

(embodiment 14)

Being used to of to obtaining in synthesis example (A-1) implements the resin layer that electroless plating covers and forms with solution (A-1), and curtain coating is coated on the surface of non-thermoplastically Kapton (trade(brand)name ア ピ カ Le NPI, Bell Yuan chemical industry Co., Ltd. system) of thickness 25 μ m.Then, use hot-air oven, carry out heat drying, obtain the material for plating that constitutes by thick resin layer A of 2 μ m and non-thermoplastically polyimide film layer B with 60 ℃ of temperature.

Measured gained by the plating adherence of material for plating (behind normality, the PCT, 150 ℃), levelling test again, Ra.Gained the results are shown in table 11.

Table 11

	Embodiment 14	Embodiment 15	Embodiment 16	Embodiment 17	Comparative example 6
						The mol ratio of resin siloxane diamine in whole diamines of layer A	50％	50％	33％	50％	Do not have
The kind of Thermocurable composition	YX4000H /BAPS-M	YX4000H /BAPS-M	YX4000H /BAPS-M	NC3000/NC30	YX4000H /BAPS-M
						The amount of Thermocurable composition	10％	30％	10％	10％	10％
Constitute	Layer A/ layer B	Layer A/ layer B	Layer A/ layer B	Layer A/ layer B	Layer A/ layer B
						Adhesion strength (normality) N/cm	10	9	9	10	3
Adhesion strength (behind the PCT) N/cm	6	6	6	6	1
						Adhesion strength (150 ℃) N/cm	6	7	7	6	1
Anti-levelling property again	Carry out 3 levelling tests again, do not expand	Carry out 3 levelling tests again, do not expand	Carry out 3 levelling tests again, do not expand	Carry out 3 levelling tests again, do not expand	Carry out 3 levelling tests again, do not expand
						Arithmetic average roughness Ra	0.1μm	0.1μm	0.1μm	0.1μm	0.1μm

(embodiment 15)

Being used to of obtaining in the synthesis example (A-2) implemented the resin layer that electroless plating covers form the surface that is coated on the non-thermoplastically Kapton (trade(brand)name ア ピ カ Le NPI, Bell Yuan chemical industry Co., Ltd. system) of thickness 25 μ m with solution (A-2) curtain coating.Then, use hot-air oven, carry out heat drying, obtain the material for plating that constitutes by thick resin layer A of 2 μ m and non-thermoplastically polyimide film layer B with 60 ℃ of temperature.

The plating adherence (behind normality, the PCT, 150 ℃) of gained material for plating, levelling test again, Ra have been measured.Gained the results are shown in table 11.

(embodiment 16)

Being used to of obtaining in the synthesis example (A-3) implemented the resin layer that electroless plating covers form the surface that is coated on the non-thermoplastically Kapton (trade(brand)name ア ピ カ Le NPI, Bell Yuan chemical industry Co., Ltd. system) of thickness 25 μ m with solution (A-3) curtain coating.Then, use hot-air oven, carry out heat drying, obtain the material for plating that constitutes by thick resin layer A of 2 μ m and non-thermoplastically polyimide film layer B with 60 ℃ of temperature.

The plating adherence (behind normality, the PCT, 150 ℃) of gained material for plating, levelling test again, Ra have been measured.Gained the results are shown in table 11.

(embodiment 17)

Being used to of obtaining in the synthesis example (A-4) implemented the resin layer that electroless plating covers form the surface that is coated on the non-thermoplastically Kapton (trade(brand)name ア ピ カ Le NPI, Bell Yuan chemical industry Co., Ltd. system) of thickness 25 μ m with solution (A-4) curtain coating.Then, use hot-air oven, carry out heat drying, obtain the material for plating that constitutes by thick resin layer A of 2 μ m and non-thermoplastically polyimide film layer B with 60 ℃ of temperature.

The plating adherence (behind normality, the PCT, 150 ℃) of gained material for plating, levelling test again, Ra have been measured.Gained the results are shown in table 11.

(comparative example 6)

Being used to of obtaining in the synthesis example (A-6) implemented the resin layer that electroless plating covers form the surface that is coated on the non-thermoplastically Kapton (trade(brand)name ア ピ カ Le NPI, Bell Yuan chemical industry Co., Ltd. system) of thickness 25 μ m with solution (A-6) curtain coating.Then, use hot-air oven, carry out heat drying, obtain the material for plating that constitutes by thick resin layer A of 2 μ m and non-thermoplastically polyimide film layer B with 60 ℃ of temperature.

The plating adherence (behind normality, the PCT, 150 ℃) of gained material for plating, levelling test again, Ra have been measured.Gained the results are shown in table 11.

At first, by the result of embodiment 8～17 as can be known, have the polyimide resin of siloxane structure if use, even then be used to form the surfaceness hour of the resin layer of electroless plating coating, the adhesion strength behind normality and the PCT is also good.On the one hand, by the result of comparative example 4,6 as can be known,, then be used to form the surfaceness hour of the resin layer of electroless plating coating, can't obtain adhesion strength behind sufficient normality adhesion strength and the PCT if do not use polyimide resin with siloxane structure.

In addition, by the result of embodiment 8～17 as can be known, when being used to implement contain the thermofixation composition on the resin layer of electroless plating coating, the welding thermotolerance is good.Adhesion strength under hot environment is also good as can be known.On the one hand, by the result of comparative example 3～6 as can be known, when the resin layer that is used for implementing the electroless plating coating does not contain the thermofixation composition, perhaps if the amount of cure component after a little while, the adhesion strength under the hot environment is insufficient.

By above result as can be known, material for plating of the present invention, it contains polyimide resin and the Thermocurable composition with siloxane structure, this material for plating surface smoothing, and plating adherence and anti-levelling property again are good.Therefore, material for plating of the present invention etc. is applicable in the manufacturing that requires fine wiring and stable on heating printed circuit board (PCB).

(Embodiment C)

In the present embodiment, as the characteristic of material for plating, the second-order transition temperature of polyimide resin, tackiness, welding thermotolerance are estimated according to shown below.In addition, the layer that electroless plating to be formed in its surface covers is a layer A, with the opposed layer of the circuit that forms be a layer B.

[second-order transition temperature of polyimide resin]

The gained polyimide resin is dissolved in the dioxolane, and the preparation solid component concentration is the polyimide resin solution of 20 weight %.This solution casting is coated on the light face of rolled copper foil (trade(brand)name BHY-22B-T, day Mining マ テ リ ア Le ズ company make), 60 ℃, 80 ℃ dry one minute down respectively, 100 ℃ dry 3 minutes down, 120,140 ℃ down respectively dry one minute, 150 ℃ dry three minutes down, 180 ℃ dry 30 minutes down, rolled copper foil is removed in etching, obtains the film of thickness 25 μ m 60 ℃ of dryings of carrying out 30 minutes.Use the film that obtains like this,, carry out Measurement of Dynamic Viscoelasticity, obtain second-order transition temperature according to following condition determination.

(condition determination)

Measure machine: DMS6100 (manufacturing of SII Nanotec Solution)

Measure temperature range: room temperature～300 ℃

Heat-up rate: 3 ℃/minute

Second-order transition temperature: tan δ peak temperature is a second-order transition temperature.

Sample: with the TD direction serves as to measure direction.

[tackiness]

Layer B and the copper-coated laminated board (CCL-HL950KTypeSK, aerochemistry company of Mitsubishi make) that will have the material for plating of supporter are opposed, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, after the heating and pressurizing 6 minutes, peel off supporter, in hot-air oven, drying is 60 minutes under 180 ℃, obtains multilayer body.Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and form on electroless plating copper.Then, 180 ℃ of following drying treatment after 30 minutes,, measure the adhesion strength behind normality and the pressure cooking test (PCT) according to JPCA-BU01-1998 (the printed wiring industry of Corporation Japan can distribution).In addition, according to the adhesion strength under the following condition mensuration high temperature.In addition, carry out decontamination and electroless plating copper according to the operation of record in table 1～table 2 of the foregoing description A.

Normality adhesion strength: under the atmosphere of 25 ℃ of temperature, humidity 50%, place the adhesion strength of measuring after 24 hours.

Adhesion strength behind the PCT: under the atmosphere of 121 ℃ of temperature, humidity 100%, place the adhesion strength of measuring after 96 hours.

Adhesion strength under the high temperature: under 25 ℃ of temperature, humidity 50% atmosphere, place after 24 hours the adhesion strength of under 120 ℃ of atmosphere of temperature, measuring.

[welding thermotolerance]

Make the layer B and the copper-coated laminated board (CCL-HL950KTypeSk of the material for plating that has supporter, aerochemistry company of Mitsubishi makes) opposed, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, after the heating and pressurizing 6 minutes, peel off supporter, in hot-air oven, 180 ℃ of dryings 60 minutes obtain multilayer body.Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after having carried out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and form on electroless plating copper.After the heat drying of implementing on the above-mentioned multilayer body 180 ℃, 30 minutes is handled, cut into the size of 15mm, 30mm, under the condition of 30 ℃ of temperature, humidity 70%, placed 200 hours, be used as test film.Be set in top temperature under 260 ℃ the condition, above-mentioned test film is dropped in the IR reflow stove, weld thermal test.The reflow stove FT-04 that IR reflow stove uses CIS company to make.In addition, repeating 3 these tests, do not have expansible to be expressed as zero, expansible is expressed as *.In addition, implement decontamination and electroless plating copper according to the operation of record in the following table 1～2.

[synthesis example 8 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 21g (0.105mol) 4 that 37g (0.045mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide and N, dinethylformamide (hereinafter referred to as DMF) stirs and dissolving, adds 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin 8.

[synthesis example 9 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 15.4g (0.077mol) 4 that 60.6g (0.073mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide and N, dinethylformamide (hereinafter referred to as DMF) stirs and dissolving, adds 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin 9.

[synthesis example 10 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 6g (0.03mol) 4 that 99.6g (0.12mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide and N, dinethylformamide (hereinafter referred to as DMF) stirs and dissolving, adds 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin 10.

[synthesis example 11 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 28.5g (0.1425mol) 4 that 6.2g (0.0075mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide and N, dinethylformamide (hereinafter referred to as DMF) stirs and dissolving, adds 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin 11.

[synthesis example 12 of polyimide resin]

In the glass flask of 2000ml capacity, add 41g (0.143mol) 1, two (3-amino-benzene oxygen) benzene of 3-, 1.6g (0.007mol) 3,3 '-dihydroxyl-4,4 '-benzidine and DMF, stir and dissolving, interpolation 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 180 minutes, 665Pa, obtains polyimide resin 12.

[preparation example 7 of the solution of form layers A]

Polyimide resin 1 is dissolved in the dioxolane, obtains the solution (C-a) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 8 of the solution of form layers A]

Polyimide resin 2 is dissolved in the dioxolane, obtains the solution (C-b) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 9 of the solution of form layers A]

Polyimide resin 3 is dissolved in the dioxolane, obtains the solution (C-c) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 10 of the solution of form layers A]

Polyimide resin 4 is dissolved in the dioxolane, obtains the solution (C-d) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 11 of the solution of form layers A]

Refine two [4-(3-amino-benzene oxygen) phenyl] sulfones, the 0.02g four countries of the diamines that industry (strain) company makes of biphenyl type epoxy resin YX4000H, the 1.79g Wakayama that 3.21g japan epoxy resin (strain) company is made change into the epoxy hardener 2 that industry (strain) company makes, 4-diamino-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine is dissolved in the dioxolane, obtains the solution (C-e) of solid component concentration 5%.45g solution (C-a) and 5g solution (C-e) are mixed, obtain the solution (C-f) of form layers B.

[preparation example 2 of the solution of form layers B]

Polyimide resin 5 is dissolved in the dioxolane, obtains the solution (C-g) of form layers A.Solid component concentration reaches 25 weight %.

On the one hand, refine two [4-(3-amino-benzene oxygen) phenyl] sulfones, the 0.2g four countries of the diamines that industry (strain) company makes of biphenyl type epoxy resin YX4000H, the 17.9g Wakayama that 32.1g japan epoxy resin (strain) company is made change into the epoxy hardener 2 that industry (strain) company makes, 4-diamino-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine is dissolved in the dioxolane, obtains the solution (C-h) of solid component concentration 50%.Mix 40g solution (C-g) and 20g solution (C-h), obtain the solution (C-i) of form layers B.

[embodiment 18]

Solution (C-a) curtain coating of form layers A is coated on the surface of the resin film (trade(brand)name SG-1, パ Na Star Network corporate system) that constitutes supporter.Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ supporter of 2 μ m with 60 ℃ temperature.Further, on the layer A surface of the material that constitutes by above-mentioned layer A/ supporter, the solution (C-i) of curtain coating coating form layers B, under 60 ℃, 100 ℃, 120 ℃, 150 ℃ temperature, carry out drying respectively, obtain the material for plating that has supporter that constitutes by the thick thick layer A/ supporter of layer B/2 μ m of 38 μ m.Use this material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 12.

[embodiment 19～20]

According to the solution of the A of form layers shown in the table 12, the order with identical with embodiment 18 obtains the material for plating that has supporter that is made of layer B/ layer A/ supporter.Use the resulting material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 12.

[embodiment 21]

Solution (C-a) curtain coating of form layers A is coated on the surface of the 25 μ m Kaptons of preparing as layer C (j) (trade(brand)name ア ピ カ Le NPI, (strain) カ ネ カ system).Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ layer C (Kapton) of 2 μ m with 60 ℃ temperature.Further, on the layer C surface of the material that constitutes by above-mentioned layer A/ layer C, the solution of curtain coating coating form layers A, after 60 ℃ of temperature were carried out drying, drying was 60 minutes under 180 ℃, obtained the material for plating that is made of the thick thick layer A of layer A/ layer C/2 μ m of 2 μ m.Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and carry out on electroless plating copper.After 30 minutes, measure various tackinesss in the same manner 180 ℃ of following drying treatment with above-mentioned tackiness evaluation.In addition, the part of this print is cut into the size of 15mm, 30mm, estimate the welding thermotolerance in the same manner with the evaluation of above-mentioned welding thermotolerance.Evaluation result is shown in table 12.

[embodiment 22]

Solution (C-a) curtain coating of form layers A is coated on the surface of the 25 μ m Kaptons of preparing as layer C (j) (trade(brand)name ア ピ カ Le NPI, (strain) カ ネ カ system).Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ layer C (Kapton) of 2 μ m 60 ℃ of temperature.Further, on the layer C surface of the material that constitutes by above-mentioned layer A/ layer C, the solution of curtain coating coating form layers B after carrying out drying under 60 ℃, 100 ℃, 120 ℃, the 150 ℃ temperature, obtains the material for plating that is made of the thick thick layer A of layer B/ layer C/2 μ m of 38 μ m.

Make the layer B and the copper-coated laminated board (CCL-HL950K TypeSk, aerochemistry company of Mitsubishi makes) of material for plating opposed, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, after the heating and pressurizing 6 minutes, in hot-air oven, 180 ℃ of dryings 60 minutes obtain multilayer body.In addition, the lining paper as multilayer body uses resin film (trade(brand)name SG-1, パ Na Star Network corporate system).Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and finish on electroless plating copper.Then, after the heat drying of implementing 180 ℃, 30 minutes is handled, measure various tackinesss in the same manner with above-mentioned tackiness evaluation.In addition, the part of sample is cut into the size of 15mm, 30mm, estimate the welding thermotolerance in the same manner with the evaluation of above-mentioned welding thermotolerance.Evaluation result is shown in table 12.

[embodiment 23]

Solution (C-a) curtain coating of form layers A is coated on the surface of the resin film (trade(brand)name ア Off レ Star Network ス, Asahi Glass Co., Ltd's system) that constitutes supporter.Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ supporter of 2 μ m 60 ℃ of temperature.To become the mode of supporter/layer A/ prepreg/layer A/ supporter, overlapping this material and the prepreg (k) (trade(brand)name ES-3306S, sharp prosperous industry (strain) are made) for preparing as layer C, at 170 ℃, 4MPa, 2 hours condition, after lamination is integrated, peel off two-sided supporter, under 180 ℃, used hot-air oven dry 30 minutes, obtain the multilayer body that constitutes by the thick layer C/ layer A of layer A/70 μ m.

Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and finish on electroless plating copper.Then, implement 180 ℃, 30 minutes drying treatment after, measure various tackinesss in the same manner with above-mentioned tackiness evaluation.

In addition, the part of this sample is cut into the size of 15mm, 30mm, estimate the welding thermotolerance in the same manner with the evaluation of above-mentioned welding thermotolerance.Evaluation result is shown in table 12.

[comparative example 7]

Except the solution (C-c) that uses form layers A, carry out in the same manner with embodiment 18, obtain the material for plating that has supporter that layer B/ layer A/ supporter constitutes.Use the resulting material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 13.

As shown in Table 13, in comparative example 7, although used polyimide resin, because second-order transition temperature is low, so tackiness under the high temperature or welding poor heat resistance with siloxane structure.

[comparative example 8]

Except the solution (C-d) that uses form layers A, carry out in the same manner with embodiment 18, obtain the material for plating that has supporter that layer B/ layer A/ supporter constitutes.Use the resulting material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 13.

As shown in Table 13, in comparative example 8, although used polyimide resin with siloxane structure, the second-order transition temperature height, so various adhesion strength is low, the welding poor heat resistance.

Table 12

		Embodiment	Embodiment	Embodiment	Embodiment	Embodiment	Embodiment
										18	19	20	21	22	23
The solution of form layers A		(C-a)	(C-b)	(C-f)	(C-a)	(C-a)	(C-a)
								The solution of form layers B		(C-i)	(C-i)	(C-i)	-	(C-i)	-
Layer C		-	-	-	(j)	(j)	(k)
								Constitute		Layer A/ layer B	Layer A/ layer B	Layer A/ layer B	Layer A/ layer C/ layer A	Layer A/ layer C/ layer B	Layer A/ layer C/ layer A
The glass transformation temperature of polyimide resin (℃)		164	117	164	164	164	164
								Adhesion strength (N/cm)	Normality	11	11	8	10	10	10
Behind the PCT	6	8	6	6	6	6
							Under the high temperature		10	8	8	9	8	10
The welding thermotolerance		○	○	○	○	○									○

Table 13

		Comparative example	Comparative example
						7	8
The solution of form layers A		(C-c)	(C-d)
				The solution of form layers B		(C-i)	(C-i)
Layer C		-	-
				Constitute		Layer A/ layer B	Layer A/ layer B
Glass transformation temperature (℃)		45	220
				Adhesion strength (N/cm)	Normality	9	3
Behind the PCT	6	1
			Under the high temperature		3	2
The welding thermotolerance		×					×

[embodiment D]

In the present embodiment, as the characteristic of material for plating, the weight-average molecular weight Mw of polyamic acid, polyimide resin, tackiness, the welding thermotolerance is following estimates.In addition, the layer that electroless plating to be formed in its surface covers is a layer A, with the opposed layer of the circuit that forms be a layer B.

[the weight-average molecular weight Mw of polyimide resin]

Use the polyimide resin that has prepared, under the following conditions,, obtain the weight-average molecular weight Mw of polyimide resin by gel permeation chromatography.In addition, polyimide resin being dissolved in the solvent identical with following moving phase, is that the solution of 0.1 weight % uses as sample with preparation concentration.

(condition determination)

Determinator: the HLC-8220GPC that eastern ソ one makes;

Post: the TSK gel Super AWM-H that has connected two eastern ソ one manufacturings forms

Guard column: the TSK guardcolumn Super AW-H that eastern ソ one makes

Moving phase: contain the N of 0.02M phosphoric acid, 0.03M lithiumbromide, dinethylformamide

Column temperature: 40 ℃

Flow velocity: 0.6ml/ minute

[tackiness]

Make the layer B and the copper-coated laminated board (CCL-HL950KTypeSk of the material for plating that has supporter, aerochemistry company of Mitsubishi makes) opposed, after carrying out 6 minutes heating and pressurizing under 170 ℃ of temperature, 1MPa pressure, the vacuum condition, peel off supporter, use hot-air oven, 180 ℃ of dryings 60 minutes, obtain multilayer body.Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer be carry out decontamination and electroless plating coated with after, cover on the copper at electroless plating and to form the thick copper electroplating layer of thick 18 μ m and finish.Then, after the heat drying of implementing 180 ℃, 30 minutes is handled,, measure the adhesion strength behind normality and the pressure cooking test (PCT) according to JPCA-BU01-1998 (the printed wiring industry of Corporation Japan can distribution).In addition, decontamination and the electroless plating operation of covering record in table 1～2 according to the foregoing description A is implemented.

Normality adhesion strength: under the atmosphere of 25 ℃ of temperature, humidity 50%, place the adhesion strength of measuring after 24 hours

Adhesion strength behind the PCT: under the atmosphere of 121 ℃ of temperature, humidity 100%, place the adhesion strength of measuring after 96 hours

[welding thermotolerance]

Make the layer B and the copper-coated laminated board (CCL-HL950KTypeSk of the material for plating that has supporter, aerochemistry company of Mitsubishi makes) opposed, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, after the heating and pressurizing 6 minutes, peel off supporter, use hot-air oven, 180 ℃ of dryings 60 minutes obtain multilayer body.Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after having carried out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and finish on electroless plating copper.After the processing of 180 ℃, 30 minutes heat drying of above-mentioned multilayer body enforcement, cut into the size of 15mm, 30mm, under the condition of 30 ℃ of temperature, humidity 70%, placed 200 hours, make test film.Be set in top temperature under 260 ℃ the condition, above-mentioned test film is dropped in the IR reflow stove, weld thermal test.The reflow stove FT-04 that IR reflow stove uses CIS company to make.In addition, repeating 3 these tests, do not have expansible to be expressed as zero, expansible is expressed as *.In addition, decontamination and electroless plating copper are implemented according to the operation of record in the following table 1～2.

[synthesis example 13 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010 (functional group's equivalent 415), 21.08g (0.1053mol) 4 that 37.10g (0.0447mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide (purity 99%) and N, dinethylformamide (hereinafter referred to as DMF), stir and dissolving, add 78.34g (0.1505mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides (purity 99%), at room temperature stir about is 1 hour, obtains the DMF solution of the polyamic acid of solid component concentration 35%.This soltion viscosity is 340poise.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 120 minutes, 665Pa, obtains polyimide resin 13.

[synthesis example 14 of polyimide resin]

Add 3.2g beta-picoline, 3.5g diacetyl oxide in the polyamic acid solution that in 50g synthesis example 1, obtains, at room temperature stirred 10 hours, carry out imidization.Then, this solution is little by little added in the Virahol of high-speed stirring, obtain thread polyimide resin., pulverize after 30 minutes 50 ℃ of dryings,,, obtain thermoplastically polyimide resin 14 50 ℃ of dryings 2 hours with washed with isopropyl alcohol 2 times with pulverizer.

[synthesis example 15 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010 (functional group's equivalent 415), 21.08g (0.1053mol) 4 that 37.10g (0.0447mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide (purity 99%) and N, dinethylformamide (hereinafter referred to as DMF), stir and dissolving, add 75.99g (0.1460mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides (purity 99%), at room temperature stir about is 1 hour, obtains the DMF solution of the polyamic acid of solid component concentration 35%.The viscosity of this solution is 23poise.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 60 minutes, 665Pa, obtains polyimide resin 15.

[synthesis example 16 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010 (functional group's equivalent 415), 21.08g (0.1053mol) 4 that 37.10g (0.0447mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide (purity 99%) and N, dinethylformamide (hereinafter referred to as DMF), stir and dissolving, add 80.68g (0.1550mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides (purity 99%), stir about is 1 hour under the room temperature, obtains the DMF solution of the polyamic acid of solid component concentration 35%.The viscosity of this solution is 18poise.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 60 minutes, 665Pa, obtains polyimide resin 16.

[synthesis example 17 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010 (functional group's equivalent 415), 21.08g (0.1053mol) 4 that 37.10g (0.0447mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide (purity 99%) and N, dinethylformamide (hereinafter referred to as DMF), stir and dissolving, add 73.65g (0.1415mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides (purity 99%), stir about is 1 hour under the room temperature, obtains the DMF solution of the polyamic acid of solid component concentration 35%.This soltion viscosity is 5poise.In the above-mentioned polyamic acid solution of 50g, add 3.2g beta-picoline, 3.5g diacetyl oxide, at room temperature stirred 10 hours, carry out imidization.Then, this solution is little by little added in the Virahol of high-speed stirring, obtain thread polyimide resin., pulverize after 30 minutes 50 ℃ of dryings,,, obtain thermoplastically polyimide resin 17 50 ℃ of dryings 2 hours with washed with isopropyl alcohol 2 times with pulverizer.

[synthesis example 18 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010 (functional group's equivalent 415), 21.08g (0.1053mol) 4 that 37.10g (0.0447mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide (purity 99%) and N, dinethylformamide (hereinafter referred to as DMF), stir and dissolving, add 83.80g (0.1610mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides (purity 99%), stir about is 1 hour under the room temperature, obtains the DMF solution of the polyamic acid of solid component concentration 35%.This soltion viscosity is 4poise.In the above-mentioned polyamic acid solution of 50g, add 3.2g beta-picoline, 3.5g diacetyl oxide, at room temperature stirred 10 hours, carry out imidization.Then, this solution is little by little joined in the Virahol of high-speed stirring, obtain thread polyimide resin., pulverize after 30 minutes 50 ℃ of dryings,,, obtain thermoplastically polyimide resin 18 50 ℃ of dryings 2 hours with washed with isopropyl alcohol 2 times with pulverizer.

[synthesis example 19 of polyimide resin]

In the glass flask of 2000ml capacity, add 41.72g (0.1427mol) 1, two (3-amino-benzene oxygen) benzene (purity 98.1%) of 3-, 1.58g (0.0073mol) 3,3 '-dihydroxyl-4,4 '-benzidine (purity 99.6%) and DMF, stir and dissolving, interpolation 77.45g (0.1488mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides (purity 99.0%), stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 35%.The viscosity of this solution is 410poise.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 180 minutes, 665Pa, obtains polyimide resin 19.

[preparation example 12 of the solution of form layers A]

Polyimide resin 1 is dissolved in the dioxolane, obtains the solution (D-a) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 13 of the solution of form layers A]

Polyimide resin 2 is dissolved in the dioxolane, obtains the solution (D-b) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 14 of the solution of form layers A]

Polyimide resin 3 is dissolved in the dioxolane, obtains the solution (D-c) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 15 of the solution of form layers A]

Polyimide resin 4 is dissolved in the dioxolane, obtains the solution (D-d) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 16 of the solution of form layers A]

Polyimide resin 5 is dissolved in the dioxolane, obtains the solution (D-e) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 17 of the solution of form layers A]

Polyimide resin 6 is dissolved in the dioxolane, obtains the solution (D-f) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 3 of the solution of form layers B]

Polyimide resin 7 is dissolved in the dioxolane, obtains the solution (D-g) of form layers A.Make solid component concentration reach 25 weight %.On the one hand, refine two [4-(3-amino-benzene oxygen) phenyl] sulfones, the 0.2g four countries of the diamines that industry (strain) company makes of biphenyl type epoxy resin YX4000H, the 17.9g Wakayama that 32.1g japan epoxy resin (strain) company is made change into the epoxy hardener 2 that industry (strain) company makes, 4-diamino-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine is dissolved in the dioxolane, obtains the solution (D-h) of solid component concentration 50%.Mix 40g solution (D-g) and 20g solution (D-h), obtain the solution (D-i) of form layers B.

[embodiment 24]

Solution (D-a) curtain coating of form layers A is coated on the surface of the resin film (trade(brand)name SG-1, パ Na Star Network corporate system) that constitutes supporter.Then, use hot-air oven, carry out drying, obtain the insulating trip that constitutes by the thick layer A/ supporter of 2 μ m with 60 ℃ temperature.Further, on the layer A surface of the insulating trip that constitutes by above-mentioned layer A/ supporter, the solution (D-i) of curtain coating coating form layers B, under 60 ℃, 100 ℃, 120 ℃, 150 ℃ temperature, carry out drying, obtain the material for plating that has supporter that constitutes by the thick thick layer A/ supporter of layer B/2 μ m of 38 μ m.Use this material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 14.

[embodiment 25～27]

According to the solution of the A of form layers shown in the table 14, the order with identical with embodiment 24 obtains the insulating trip that has supporter that is made of layer B/ layer A/ supporter.Use the resulting insulating trip that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 14.

[embodiment 28]

Solution (D-a) curtain coating of form layers A is coated on the surface of the 25 μ m Kaptons of preparing as layer C (j) (trade(brand)name ア ピ カ Le NPI, (strain) カ ネ カ system).Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ layer C (Kapton) of 2 μ m with 60 ℃ temperature.Further, on the layer C surface of the material that constitutes by above-mentioned layer A/ layer C, the solution of curtain coating coating form layers A, carry out drying with 60 ℃ of temperature after, carry out 60 minutes dryings at 180 ℃, obtain the insulating trip that constitutes by the thick thick layer A of layer A/ layer C/2 μ m of 2 μ m.Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and finish on electroless plating copper.After 180 ℃, 30 minutes drying treatment of enforcement, similarly measure various tackinesss with above-mentioned tackiness evaluation.In addition, the part of this sample is cut into the size of 15mm, 30mm, estimate the welding thermotolerance in the same manner with the evaluation of above-mentioned welding thermotolerance.Table 14 that evaluation result is shown in.

[embodiment 29]

Solution (D-a) curtain coating of form layers A is coated on the surface of the 25 μ m Kaptons of preparing as layer C (j) (trade(brand)name ア ピ カ Le NPI, (strain) カ ネ カ system).Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ layer C (Kapton) of 2 μ m with 60 ℃ temperature.Further, on the layer C surface of the material that constitutes by above-mentioned layer A/ layer C, the solution (D-i) of curtain coating coating form layers B carries out drying under 60 ℃, 100 ℃, 120 ℃, 150 ℃ temperature, obtain the material for plating that is made of the thick thick layer A of layer B/ layer C/2 μ m of 38 μ m.

Make the layer B and the copper-coated laminated board (CCL-HL950K TypeSk, aerochemistry company of Mitsubishi makes) of above-mentioned material for plating opposed, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, after the heating and pressurizing 6 minutes, use hot-air oven, drying is 60 minutes under 180 ℃, obtains multilayer body.Lining paper during in addition, as lamination uses resin film (trade(brand)name SG-1, パ Na Star Network corporate system).Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and finish on electroless plating copper.Then, implement 180 ℃, 30 minutes drying treatment after, measure various tackinesss in the same manner with above-mentioned tackiness evaluation.For, the part of this sample is cut into the size of 15mm, 30mm, estimate the welding thermotolerance in the same manner with the evaluation of above-mentioned welding thermotolerance.Table 14 that evaluation result is shown in.

[embodiment 30]

Solution (D-a) curtain coating of form layers A is coated on the surface of the resin film (trade(brand)name ア Off レ Star Network ス, Asahi Glass Co., Ltd's system) that constitutes supporter.Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ supporter of 2 μ m with 60 ℃ temperature.To become the mode of supporter/layer A/ prepreg/layer A/ supporter, overlapping this material and the prepreg of preparing as layer C (k) (trade(brand)name ES-3306S, sharp prosperous industry (strain) are made), under 170 ℃, 4MPa, 2 hours condition, after lamination is integrated, peel off two-sided supporter, under 180 ℃, used hot-air oven dry 30 minutes, obtain the multilayer body that constitutes by the thick layer C/ layer A of layer A/70 μ m.

Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and finish on electroless plating copper.Then, after the heat drying of implementing 180 ℃, 30 minutes is handled, measure various tackinesss in the same manner with above-mentioned tackiness evaluation.In addition, the part of this sample is cut into the size of 15mm, 30mm, estimate the welding thermotolerance in the same manner with the evaluation of above-mentioned welding thermotolerance.Evaluation result is shown in table 14.

[comparative example 9]

Except the solution (D-e) that uses form layers A, carry out in the same manner with embodiment 24, obtain the material for plating that has supporter that layer B/ layer A/ supporter constitutes.Use the resulting material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 15.

[comparative example 10]

Except the solution (D-f) that uses form layers A, carry out in the same manner with embodiment 24, obtain the material for plating that has supporter that layer B/ layer A/ supporter constitutes.Use the resulting material for plating that has supporter, estimate according to aforementioned various assessment item purpose evaluation orders.Evaluation result is shown in table 15.

As shown in Table 15, in comparative example 9,10, although used the polyimide resin with siloxane structure, the weight-average molecular weight of polyimide resin is low, so adhesion strength and welding poor heat resistance.

Table 14

		Embodiment	Embodiment	Embodiment	Embodiment	Embodiment	Embodiment	Embodiment
											24	25	26	27	28	29	30
The solution of form layers A		(D-a)	(D-b)	(D-c)	(D-d)	(D-a)	(D-a)	(D-a)
									The solution of form layers B		(D-i)	(D-i)	(D-i)	(D-i)	-	(D-i)	-
Layer C		-	-	-	-	(j)	(j)	(k)
									Constitute		Layer A/ layer B	Layer A/ layer B	Layer A/ layer B	Layer A/ layer B	Layer A/ layer C/ layer A	Layer A/ layer C/ layer B	Layer A/ layer C/ layer A
The weight-average molecular weight Mw that is used for the polyimide of layer A		84000	52000	48000	45000	84000	84000	84000
									Adhesion strength (N/cm)	Normality	11	9	9	9	11	10	10
Behind the PCT	6	6	6	5	6	6	6
								The welding thermotolerance		○	○	○	○	○	○	○

Table 15

		Comparative example	Comparative example
						9	10
The solution of form layers A		(D-e)	(D-f)
				The solution of form layers B		(D-i)	(D-i)
Layer C		-	-
				Constitute		Layer A/ layer B	Layer A/ layer B
The weight-average molecular weight Mw that is used for the polyimide of layer A		24000	17000
				Adhesion strength (N/cm)	Normality	5	4
Behind the PCT	2	2
			The welding thermotolerance		×	×

[embodiment E]

In the present embodiment, as the characteristic of material for plating, tackiness, welding thermotolerance are estimated in the following way.In addition, the layer that electroless plating to be formed in its surface covers is a layer A, with the opposed layer of the circuit that forms be a layer B.

[tackiness]

Layer B and the copper-coated laminated board (CCL-HL950KTypeSK, aerochemistry company of Mitsubishi make) that will have the material for plating of supporter are opposed, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, after the heating and pressurizing 6 minutes, peel off supporter, in hot-air oven, 180 ℃ of dryings 60 minutes obtain multilayer body.Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and finish on electroless plating copper.Then, 180 ℃ of following drying treatment after 30 minutes,, measure the adhesion strength behind normality and the pressure cooking test (PCT) according to JPCA-BU01-1998 (the printed wiring industry of Corporation Japan can distribution).In addition, decontamination and electroless plating copper are implemented according to the operation of record in table 1～table 2 of the foregoing description A.

Normality adhesion strength: under the atmosphere of 25 ℃ of temperature, humidity 50%, place the adhesion strength of measuring after 24 hours.

Adhesion strength behind the PCT: under the atmosphere of 121 ℃ of temperature, humidity 100%, place the adhesion strength of measuring after 96 hours.

[welding thermotolerance]

Make the layer B and the copper-coated laminated board (CCL-HL950KTypeSk of the material for plating that has supporter, aerochemistry company of Mitsubishi makes) opposed, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, after the heating and pressurizing 6 minutes, peel off supporter, in hot-air oven, drying is 60 minutes under 180 ℃, obtains multilayer body.Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and finish on electroless plating copper.After the processing of 180 ℃, 30 minutes heat drying of above-mentioned multilayer body enforcement, cut into the size of 15mm, 30mm, under the condition of 30 ℃ of temperature, humidity 70%, placed 200 hours, be used as test film.Be set in top temperature under 260 ℃ the condition, above-mentioned test film is dropped in the IR reflow stove, weld thermal test.The reflow stove FT-04 that IR reflow stove uses CIS company to make.In addition, repeating 3 these tests, do not have expansible to be expressed as zero, expansible is expressed as *.In addition, decontamination and electroless plating copper are to implement according to the operation of record in the following table 1～2.

[synthesis example 20 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 19.52g (0.0975mol) 4 that 37g (0.045mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide, 1.62g (0.0075mol) 3,3 '-dihydroxyl-4,4 '-benzidine and N, dinethylformamide (hereinafter referred to as DMF), stir and dissolving, add 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 35%.In the above-mentioned polyamic acid solution of 50g, add 3.2g beta-picoline, 3.5g diacetyl oxide, at room temperature stirred 10 hours, carry out imidization.Then, this solution is little by little added in the Virahol of high-speed stirring, obtain thread polyimide resin., pulverize after 30 minutes 50 ℃ of dryings,,, obtain polyimide resin 20 50 ℃ of dryings 2 hours with washed with isopropyl alcohol 2 times with pulverizer.

[synthesis example 21 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 18g (0.09mol) 4 that 37g (0.045mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide, 3.24g (0.015mol) 3,3 '-dihydroxyl-4,4 '-benzidine and N, dinethylformamide (hereinafter referred to as DMF), stir and dissolving, add 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.In the above-mentioned polyamic acid solution of 50g, add 3.2g beta-picoline, 3.5g acid anhydrides, at room temperature stirred 10 hours, carry out imidization.Then, this solution is little by little added in the Virahol of high-speed stirring, obtain thread polyimide resin., pulverize after 30 minutes 50 ℃ of dryings,,, obtain polyimide resin 21 50 ℃ of dryings 2 hours with washed with isopropyl alcohol 2 times with pulverizer.

[synthesis example 22 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 19.52g (0.0975mol) 4 that 37g (0.045mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide, 2.15g (0.0075mol) 5,5 '-methylene radical-two (anthranilic acids) and N, dinethylformamide (hereinafter referred to as DMF), stir and dissolving, add 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 100 minutes, 665Pa, obtains polyimide resin 22.

[synthesis example 23 of polyimide resin]

In the glass flask of 2000ml capacity, add KF-8010, the 18g (0.09mol) 4 that 37g (0.045mol) Shin-Etsu Chemial Co., Ltd makes, 4 '-diaminodiphenyl oxide and 3.41g (0.015mol) 4,4 '-diaminobenzene formylaniline and N, dinethylformamide (hereinafter referred to as DMF), stir and dissolving, add 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 100 minutes, 665Pa, obtains polyimide resin 23.

[synthesis example 24 of polyimide resin]

In the glass flask of 2000ml capacity, add 41g (0.143mol) 1, two (3-amino-benzene oxygen) benzene of 3-, 1.6g (0.007mol) 3,3 '-dihydroxyl-4,4 '-benzidine and DMF, stir and dissolving, interpolation 78g (0.15mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two Tetra hydro Phthalic anhydrides, stir about 1 hour obtains the DMF solution of the polyamic acid of solid component concentration 30%.Above-mentioned polyamic acid solution packed into to be coated with in the vessel of teflon (registered trademark), in vacuum drying oven, with the heating of reducing pressure of 200 ℃, 180 minutes, 665Pa, obtains polyimide resin 24.

[preparation example 18 of the solution of form layers A]

Polyimide resin 1 is dissolved in the dioxolane, obtains the solution (E-a) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 19 of the solution of form layers A]

Polyimide resin 2 is dissolved in the dioxolane, obtains the solution (E-b) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 20 of the solution of form layers A]

Polyimide resin 3 is dissolved in the dioxolane, obtains the solution (E-c) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 21 of the solution of form layers A]

Polyimide resin 4 is dissolved in the dioxolane, obtains the solution (E-d) of form layers A.Make solid component concentration reach 5 weight %.

[preparation example 22 of the solution of form layers A]

Refine two [4-(3-amino-benzene oxygen) phenyl] sulfones, the 0.02g four countries of the diamines that industry (strain) company makes of biphenyl type epoxy resin YX4000H, the 1.79g Wakayama that 3.21g japan epoxy resin (strain) company is made change into the epoxy hardener 2 that industry (strain) company makes, 4-diamino-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine is dissolved in the dioxolane, obtains the solution (E-e) of solid component concentration 5%.20g solution (E-a) and 3g solution (E-e) are mixed, obtain solution (E-f).

[preparation example 23 of the solution of form layers A]

20g solution (E-d) and 8g solution (E-e) are mixed, obtain solution (E-g).

[preparation example 4 of the solution of form layers B]

Polyimide resin 5 is dissolved in the dioxolane, obtains polyimide resin solution (E-h).Solid component concentration reaches 25 weight %.

On the one hand, refine two [4-(3-amino-benzene oxygen) phenyl] sulfones, the 0.2g four countries of the diamines that industry (strain) company makes of biphenyl type epoxy resin YX4000H, the 17.9g Wakayama that 32.1g japan epoxy resin (strain) company is made change into the epoxy hardener 2 that industry (strain) company makes, 4-diamino-6-[2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine is dissolved in the dioxolane, obtains the solution (C-i) of solid component concentration 50%.Mix 40g solution (E-h) and 20g solution (E-i), obtain the solution (E-j) of form layers B.

[embodiment 31]

Solution (E-a) curtain coating of form layers A is coated on the surface of the resin film (trade(brand)name SG-1, パ Na Star Network corporate system) that becomes supporter.Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ supporter of 2 μ m with 60 ℃ temperature.Further, on the layer A surface of the material that constitutes by above-mentioned layer A/ supporter, the solution of curtain coating coating form layers B carries out drying with 60 ℃, 100 ℃, 120 ℃, 150 ℃ temperature, obtains the material for plating that has supporter that is made of the thick thick layer A/ supporter of layer B/2 μ m of 38 μ m.Use this material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 16.

[embodiment 32～36]

According to the solution of the A of form layers shown in the table 3, the order with identical with embodiment 1 obtains the material for plating that has supporter that is made of layer B/ layer A/ supporter.Use the resulting material for plating that has supporter, estimate according to the evaluation order of aforementioned various assessment items.Evaluation result is shown in table 16.

[embodiment 37]

Solution (E-a) curtain coating of form layers A is coated on the surface of the 25 μ m Kaptons of preparing as layer C (k) (trade(brand)name ア ピ カ Le NPI, (strain) カ ネ カ system).Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ layer C (Kapton) of 2 μ m with 60 ℃ temperature.Further, on the layer C surface of the material that is made of above-mentioned layer A/ layer C, the solution of curtain coating coating form layers A is after 60 ℃ of temperature are carried out drying, carry out 60 minutes dryings at 180 ℃, obtain the material for plating that constitutes by the thick thick layer A of layer A/ layer C/2 μ m of 2 μ m.Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and carry out on electroless plating copper.After implementing 180 ℃, 30 minutes drying treatment, measure various tackinesss in the same manner with above-mentioned tackiness evaluation.In addition, the part of this print is cut into the size of 15mm, 30mm, estimate the welding thermotolerance in the same manner with the evaluation of above-mentioned welding thermotolerance.Evaluation result is shown in table 16.

[embodiment 38]

Solution (E-a) curtain coating of form layers A is coated on the surface of the 25 μ m Kaptons of preparing as layer C (k) (trade(brand)name ア ピ カ Le NPI, (strain) カ ネ カ system).Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ layer C (Kapton) of 2 μ m 60 ℃ of temperature.Further, on the layer C surface of the material that constitutes by above-mentioned layer A/ layer C, the solution of curtain coating coating form layers B after 60 ℃, 100 ℃, 120 ℃, 150 ℃ temperature are carried out drying, obtains the material for plating that is made of the thick thick layer A of layer B/ layer C/2 μ m of 38 μ m.

Make the layer B and the copper-coated laminated board (CCL-HL950K TypeSk, aerochemistry company of Mitsubishi makes) of above-mentioned material for plating opposed, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, after the heating and pressurizing 6 minutes, in hot-air oven, 180 ℃ of dryings 60 minutes obtain multilayer body.Lining paper during in addition, as lamination uses resin film (trade(brand)name SG-1, パ Na Star Network corporate system).Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and finish on electroless plating copper.Then, implement 180 ℃, 30 minutes drying treatment after, measure various tackinesss in the same manner with above-mentioned tackiness evaluation.In addition, the part of this sample is cut into the size of 15mm, 30mm, estimate the welding thermotolerance in the same manner with the evaluation of above-mentioned welding thermotolerance.Evaluation result is shown in table 16.

[embodiment 39]

Solution (E-a) curtain coating of form layers A is coated on the surface of the resin film (trade(brand)name ア Off レ Star Network ス, Asahi Glass Co., Ltd's system) that constitutes supporter.Then, use hot-air oven, carry out drying, obtain the material that constitutes by the thick layer A/ supporter of 2 μ m 60 ℃ of temperature.To become the mode of supporter/layer A/ prepreg/layer A/ supporter, overlapping this material and the prepreg of preparing as layer C (1) (trade(brand)name ES-3306S, sharp prosperous industry (strain) are made), at 170 ℃, 4MPa, 2 hours condition, after lamination is integrated, peel off two-sided supporter, at 180 ℃, dry 30 minutes, obtain the multilayer body that constitutes by the thick layer C/ layer A of layer A/70 μ m with hot-air oven.

Then, on the layer A surface of exposing, form the copper layer.The formation of copper layer is after carrying out decontamination and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and finish on electroless plating copper.Then, after 30 minutes, measure various tackinesss in the same manner 180 ℃ of following drying treatment with above-mentioned tackiness evaluation.In addition, the part of this sample is cut into the size of 15mm, 30mm, estimate the welding thermotolerance in the same manner with the evaluation of above-mentioned welding thermotolerance.Evaluation result is shown in table 16.

[comparative example 11]

Solution (E-j) curtain coating of form layers B is coated on the surface of the resin film (trade(brand)name SG-1, パ Na Star Network corporate system) that constitutes supporter.Then, use hot-air oven, 60 ℃, 100 ℃, 120 ℃, 150 ℃ temperature is carried out drying, obtains the material for plating that has supporter that is made of the thick layer B/ supporter of 38 μ m.Make the layer B and copper-coated laminated board (the CCL-HL950K TypeSk of the material for plating that has supporter, aerochemistry company of Mitsubishi makes) opposed, under 170 ℃ of temperature, pressure 1MPa, vacuum condition, after the heating and pressurizing 6 minutes, peel off supporter, in hot-air oven, drying is 60 minutes under 180 ℃, obtains multilayer body.Then, on the layer B that exposes, form the copper layer.The formation of copper layer is after carrying out decontamination processing and electroless plating copper, forms the thick copper electroplating layer of 18 μ m and finish on electroless plating copper.After 30 minutes, measure various tackinesss in the same manner 180 ℃ of following drying treatment with above-mentioned tackiness evaluation.In addition, the part of this sample is cut into the size of 15mm, 30mm, estimate the welding thermotolerance in the same manner with the evaluation of above-mentioned welding thermotolerance.Evaluation result is shown in table 17.

Table 16

		Embodiment	Embodiment	Embodiment	Embodiment	Embodiment	Embodiment	Embodiment	Embodiment	Embodiment
													31	32	33	34	35	36	37	38	39
The solution of form layers A		(E-a)	(E-b)	(E-c)	(E-d)	(E-f)	(E-g)	(E-a)	(E-a)	(E-a)
											The solution of form layers B		(E-j)	(E-j)	(E-j)	(E-j)	(E-j)	(E-j)	-	(E-j)	-
Layer C		-	-	-	-	-	-	(k)	(k)	(1)
											Constitute		Layer A/ layer B	Layer A/ layer B	Layer A/ layer B	Layer A/ layer B	Layer A/ layer B	Layer A/ layer B	Layer A/ layer C/ layer A	Layer A/ layer C/ layer B	Layer A/ layer C/ layer A
Adhesion strength (N/cm)	Normality	12	12	11	12	12	12	11	11	12
											Behind the PCT	8	8	7	8	8	8	6	6	7
	The welding thermotolerance		○	○	○	○	○	○	○	○											○

Table 17

		Comparative example
					11
The solution of form layers A		-
			The solution of form layers B		(E-j)
Layer C		-
			Constitute		Layer B
Adhesion strength (N/cm)	Normality	3
			Behind the PCT	1
	The welding thermotolerance				×

Industrial applicibility

Material for plating of the present invention is not only high with the Coated adherence of electroless plating, and is high with the adherence of various resin materials. Further, even in surface roughness of the present invention hour, also and the adherence between electroless plating tunicle and various resin material high, and have excellent welding heat resistance. Therefore, especially can be applicable to require to form in the manufacturing etc. of printed circuit board (PCB) of fine wiring. Therefore, the present invention not only can be suitable for raw material processing industry or the various chemical industries such as resin combination or sticker, also can be applicable to the industrial field of various electronic units.

Particularly, such as the decoration plating of the parts such as handle class that can be applicable to the function plating such as various plastics, glass, pottery, timber, automobile grills or sign class, household appliances, especially can be applicable in the manufacturing etc. of various printed circuit board (PCB)s. Further, can be applicable to require to form in the printed circuit board (PCB) such as flexible printed circuit board, printed circuit board, multi-layer flexible printed circuit board, combination circuit plate of fine wiring.

Claims (28)

1. material for plating wherein, has and is used to implement the resin layer that electroless plating covers,

Above-mentioned resin layer contains the polyimide resin that has siloxane structure at least,

Above-mentioned polyimide resin is to make the reaction of acid dianhydride composition and two amine components and the polyimide resin that obtains, and described two amine components contain the diamines of following general formula (1) expression:

[Chemical formula 1]

(in the above-mentioned general formula (1), g represents the integer more than 1; In addition, R ¹¹And R ²²Can be identical or different, the expression carbonatoms is 1～6 alkylidene group or phenylene; R ³³, R ⁴⁴, R ⁵⁵And R ⁶⁶Can be identical or different, the expression carbonatoms is 1～6 following group, alkyl, phenyl, alkoxyl group or phenoxy group).

2. material for plating according to claim 1, wherein, above-mentioned polyimide resin is that two amine components with the diamines that contains above-mentioned general formula (1) expression are the polyimide resin that raw material obtains, and the content of the diamines of this above-mentioned general formula (1) expression accounts for 1～49mol% of total diamines.

3. material for plating according to claim 1, wherein, above-mentioned resin layer further contains the Thermocurable composition.

4. material for plating according to claim 3, wherein, above-mentioned Thermocurable composition contains the Resins, epoxy composition, and described Resins, epoxy composition contains epoxy compounds and solidifying agent.

5. material for plating according to claim 1, wherein, the second-order transition temperature of above-mentioned polyimide resin is 100～200 ℃ scope.

6. material for plating according to claim 5, wherein, above-mentioned polyimide resin contains the diamines of above-mentioned general formula (1) expression, and its content accounts for 10～75mol% of total diamines.

7. material for plating according to claim 1, wherein, the weight-average molecular weight Mw of the above-mentioned polyimide resin of being obtained by gel permeation chromatography is 30000～150000.

8. material for plating according to claim 1, wherein, above-mentioned polyimide resin has the protected group that forms of functional group and/or this functional group.

9. material for plating according to claim 8, wherein, above-mentioned functional group is more than one the group that is selected from hydroxyl, amino, carboxyl, amide group, sulfydryl, the sulfonic group.

10. according to any described material for plating in the claim 1～9, wherein, above-mentioned electroless plating covers and is electroless plating copper.

11. according to any described material for plating in the claim 1～10, wherein, except that being used to implement resin layer that above-mentioned electroless plating covers, further have other layers,, constitute by the layer more than 2 layers at least as all.

12. material for plating according to claim 11, wherein, above-mentioned other layers are the macromolecule membrane layer, at least one surface of this macromolecule membrane layer, are formed with and are used to implement the resin layer that electroless plating covers.

13. material for plating according to claim 11, wherein, above-mentioned other layers are macromolecule membrane layer and adhesive layer, on at least one surface of this macromolecule membrane layer, be formed with and be used to implement the resin layer that electroless plating covers, and on the another side of above-mentioned macromolecule membrane layer, be formed with above-mentioned adhesive layer.

14. according to claim 12 or 13 described material for plating, wherein, above-mentioned macromolecule membrane layer is non-thermoplastically Kapton.

15. a single-layer sheet wherein, used any described material for plating in the claim 1～10, and this single-layer sheet only is made of above-mentioned resin layer.

16. an insulating trip wherein, has any described material for plating in the claim 11～14.

17. a duplexer, wherein, the resin layer surface in claim 1～14 in any described material for plating, the described single-layer sheet of claim 15 or the described insulating trip of claim 16, lamination electroless plating coating forms.

18. a printed circuit board (PCB) wherein, has any described material for plating, the described single-layer sheet of claim 15 or the described insulating trip of claim 16 in the claim 1～14.

19. printed circuit board (PCB) according to claim 18, wherein, the surfaceness of above-mentioned resin layer is during the arithmetic average roughness Ra less than 0.5 μ m that measures under cutoff 0.002mm, at 150 ℃, the adhesion strength between above-mentioned resin layer and coating layer is more than the 5N/cm.

20. being used to form, a solution, this solution implements the resin layer that electroless plating covers, wherein,

Contain the polyimide resin that has siloxane structure at least or the precursor polyamic acid of this polyimide resin,

Above-mentioned polyimide resin is to make the reaction of acid dianhydride composition and two amine components and the polyimide resin that obtains, and described two amine components contain the diamines of following general formula (1) expression:

[Chemical formula 2]

(in the above-mentioned general formula (1), g represents the integer more than 1; In addition, R ¹¹And R ²²Can be identical or different, the expression carbonatoms is 1～6 alkylidene group or phenylene; R ³³, R ⁴⁴, R ⁵⁵And R ⁶⁶Can be identical or different, the expression carbonatoms is 1～6 following group, alkyl, phenyl, alkoxyl group or phenoxy group).

21. solution according to claim 20, wherein, above-mentioned polyimide resin is that two amine components with the diamines that contains above-mentioned general formula (1) expression are the polyimide resin that raw material obtains, and the content of the diamines of this above-mentioned general formula (1) expression accounts for 1～49mol% of total diamines.

22. solution according to claim 20 wherein, further contains the thermoset composition.

23. solution according to claim 22, wherein, above-mentioned thermoset composition contains the Resins, epoxy composition, and described Resins, epoxy composition contains epoxy compounds and solidifying agent.

24. solution according to claim 20, wherein, the second-order transition temperature of above-mentioned polyimide resin is 100～200 ℃ scope.

25. solution according to claim 24, wherein, above-mentioned polyimide resin contains the diamines of above-mentioned general formula (1) expression, and its content accounts for 10～75mol% of total diamines.

26. solution according to claim 20 wherein, is 30000～150000 by the weight-average molecular weight Mw of the above-mentioned polyimide resin of gel permeation chromatography.

27. solution according to claim 20, wherein, above-mentioned polyimide resin has the protected group that forms of functional group and/or this functional group.

28. solution according to claim 27, wherein, above-mentioned functional group is more than one the group that is selected from hydroxyl, amino, carboxyl, amide group, sulfydryl, the sulfonic group.