CN101134857B - Primer, conductor foil with resin, laminate and process for producing the laminate - Google Patents

Abstract

A resin primer capable of bonding with satisfactory strength an insulator layer to a conductor foil whose surface is relatively not roughened; a conductor foil with resin; a laminate; and a process for producing the laminate. The resin primer comprises a resin with film forming capability whose rupture energy is 0.15 J or more. The conductor foil with resin comprises a conductor foil and a resin layer consisting of the resin primer. The laminate comprises a conductor foil, an insulating layer disposed opposite to the conductor foil, and a resin layer consisting of the resin primer which is interposed between the conductor foil and the insulating layer so as to be in contact therewith. This laminate can be produced by applying heat and pressure to a laminate comprised of the conductor foil with resin and, superimposed on the resin, a prepreg.

Description

The manufacture method of priming paint, the conductor foil that has resin, plywood and plywood

Technical field

The present invention relates to the manufacture method of priming paint (primer), the conductor foil that has resin, plywood and plywood.

Background technology

In recent years, along with the miniaturization and the lightweight of information terminals such as Personal Computer and Cell phone, require to be installed in the densification that printing distributing board on these machines reaches miniaturization more and distribution.In order to adapt to these requirements, need make the distribution width become narrower, make the interval of each wiring closet become tight.In addition, in order to adapt to the high speed that electronic machine is handled, also require to increase the input and output quantity of the equipment on the electronic machine that is installed in.

In order to be adapted to these requirements, the element installation form on the printing distributing board is gradually by pin insert type GO TO table surface installation type, and then to the BGA (Ball Grid Array) that the uses plastic base area array type development as representative.In the substrate as the direct installation nude film of BGA and so on, the connection of chip generally is to use the terminal conjunction method by hot ultrasonic wave crimping to carry out.Yet, want to adapt to aforesaid requirement, increase the number of terminals that connects with terminal conjunction method with regard to needing, perhaps make this terminal narrowed width.

In the past, normally usedly as the substrate of these printing distributing boards be, by will being to be heated the plywood that pressurization obtains its integrated back behind the semicure impregnation material overlapping regulation numbers such as (prepreg) of matrix with resin with electrical insulating property.As resin, use heat-curing resins such as resol, Resins, epoxy, polyimide resin, bismaleimides-cyanate resin usually with electrical insulating property.In addition, also use thermoplastic resins such as fluorine resin or polyphenylene oxide resin etc. sometimes.

Method as form conductor circuit on printing distributing board is extensive use of the metal covering etch.In the method, use makes its incorporate conductor tectum lamination by heating and pressurizing behind conductor foils such as the last stacked tinsel in the surface (one side or two sides) of above-mentioned duplexer.Afterwards, by the conductor foil in this conductor tectum lamination is removed with etching method, can form circuit pattern.

In conductor tectum lamination, in order to prevent peeling off of circuit pattern etc., wish conductor foil and the insulator layer be made up of the duplexer of semicure impregnation material are closely engaged.Therefore, in the past, (electronic material editorial office compiles as open flat 4-No. 211941 communiques and " high-density printed wiring plate technique " the spy, census of manufacturing meeting, clear and on May 20th, 61, p149-157) puts down in writing in, by carry out asperitiesization in the surface to conductor foil, can show tackify (fixing) effect of the resin in itself and the insulator layer, thereby improve the engaging force of conductor foil and insulator layer.

But present inventors find after deliberation, when wanting to remove conductor foil a part of with etching method, have improved with above-mentioned method in the past in the conductor tectum lamination of engaging force, and the segment conductor paper tinsel that need remove is easy to residual.This may be because etching solution is difficult to enter the recess by the conductor foil surface of asperitiesization, thereby is difficult to carry out fully removing of this segment conductor paper tinsel.If it is residual that the segment conductor paper tinsel that so need remove has, then might cause short circuit etc., so little desirable.

In addition, as use the surface by the printing distributing board that the conductor foil of alligatoring obtains, also have cause because of skin effect, transmission signal is difficult to the problem of high frequencyization.Wherein, so-called " skin effect " is meant that the frequency of the signal that flows through conductor is high more, the interference of the magnetic line of force that produces at its conductor centre portions becomes big more, thus its conductor centre portions electrorheological must be difficult to by, the mobile electric current increases near conductive surface on the other hand.If the surface of conductor foil is by asperitiesization when producing this skin effect, then also can increase at this near surface resistance, thus the trend that exists electric current to be difficult to pass through.Like this, make the surface of conductor foil become coarse more, can hinder the high frequencyization of signal more.

In addition, if the distribution in the aforesaid printing distributing board is carried out densification, perhaps, increase the number of terminals be installed in the element on this wiring board, the terminal width carry out narrow and smallization, then the contact area of circuit pattern and body material can diminish.If like this, along with the minimizing of this contact area, the connectivity of circuit pattern and body material can descend, thereby exists conductor foil to be easy to the trend of peeling off from body material.Therefore, when being suitable for above-mentioned conventional art, be difficult to obtain fully to meet the printing distributing board of requirement of the densification of miniaturization and distribution.

Summary of the invention

Therefore, the present invention In view of the foregoing proposes, and purpose provides and can engage insulator layer and surface ratio more not resin primer, the conductor foil that has resin, plywood and the manufacture method thereof of the conductor foil of asperitiesization with sufficiently high intensity.

To achieve these goals, resin primer of the present invention is characterised in that and contains resin, and this resin has film forming ability, and energy to fracture is more than the 0.15J.

Wherein, the what is called of resin " energy to fracture " defines as described below and measures.At first, making resin formation is the rectangle film of wide 10mm, thick 50 μ m.Then, this rectangle film is stretched up to fracture with 5mm/ minute speed along its length.At this moment, giving the tensile stress of this rectangle film and the relation of this deformation of thin membrane (extensibility) can represent with stress-deformation curve as shown in Figure 1.The integrated value of the tensile stress of (up to breaking point) before the part of the oblique line among this Fig. 1, i.e. this rectangle film fracture is defined as " energy to fracture ".

Present inventors find that priming paint of the present invention has the as above resin of characteristic by containing, and can improve the engaging force of conductor foil and insulator layer.Its detailed reason is not clear now, but present inventors are presumed as follows.

Promptly, peel off the form of conductor foil from the plywood that between conductor foil and insulator layer, has the resin that obtains by this resin primer, the cohesion destruction that (1) cause by resin is arranged and the situation that conductor foil is peeled off from insulator layer, and (2) produce situation about peeling off between conductor foil and resin.But, consider resin to cohesion destructive patience height, so be difficult to cause peeling off when using this resin as above-mentioned (1) with characteristic as mentioned above.

In addition, can think to have in the resin of such characteristic, the stress of portion's generation within it can be dispersed to the scope of broad by being stretched.Therefore, when using this resin, even apply the power that will peel off conductor foil and since with the contact area of conductor foil on the mean force that is subjected to diminish, so as peeling off also of above-mentioned (2) can suppress fully.

In addition, another kind of resin primer of the present invention is the priming paint that contains resin, when being membranaceous with this ester moulding, if 10 mean roughness on this film (symbol 2 among Fig. 2) surface are adjusted into below the 0.1 μ m, and under room temperature environment on this film surface the drippage methane amide liquid (1 among Fig. 2), then this methane amide liquid phase is below 60 ° for the contact angle (θ among Fig. 2) on film surface, and this resin can use the present invention's various resins described later.

Present inventors find to contain the resin with such characteristic, and priming paint of the present invention also can improve the engaging force of conductor foil and insulator layer.Its detailed reason is not clear now, but present inventors are presumed as follows.That is, having as mentioned above, the shaping thing of the resin of characteristic may have high surface free energy.Therefore, when this resin was engaged with conductor foil, it is big that the interaction at the interface between this resin and the conductor foil (gravitation) becomes.Its result, the engaging force between conductor foil and the insulator layer uprises.

The resin molding that is obtained by these priming paint can suppress conductor foil fully and peel off from plywood.Therefore, these priming paint be can use, more high-density and the better printing distributing board of high frequency characteristic made.Especially use when containing the priming paint of the resin that has these two characteristics simultaneously, compare, can further improve the engaging force between conductor foil and the insulator layer with priming paint with single characteristic.

The priming paint of the invention described above preferably is made up of more than one the resin of key that is selected from imide bond, amino-formate bond and aromatic carboxylic acid ester bond that contains more than the 6 quality % according to quality standard in the resin contained in this priming paint.By using such priming paint, can make the engaging force between conductor foil and the insulator layer become higher.

In addition, another kind of resin primer of the present invention is the priming paint that contains resin, contain the polyamidoimide that on main chain, has siloxane structure as this resin, the content of all amide group that contain in this resin is defined as A weight %, when the content of all Siliciumatoms that contain in the above-mentioned resin is defined as C weight %, satisfy with following formula (a) and (b):

3≤A≤11?…(a)

1≤C≤16?…(b)。

Contain the polyamidoimide that on main chain, has siloxane structure, and the resin primer that satisfies above-mentioned condition also can show outstanding connectivity with respect to the tinsel with smoother surface.

As this resin primer, can be to contain above-mentioned resin and this resin to have that film forms ability, energy to fracture is the above priming paint of 0.15J, and/or when 10 mean roughness of formation when being film below the 0.1 μ m methane amide under the room temperature be priming paint below 60 ° with respect to the contact angle on this film surface.

In addition, another kind of resin primer of the present invention is the priming paint that contains resin, this resin contains the polyamidoimide that has siloxane structure on main chain, with have functional group that can react and the reactive compounds that can have amide group and/or Siliciumatom with the amide group that this polyamidoimide has, reactive compounds in the resin is being defined as the content of the amide group in the polyamidoimide Pa weight % with respect to the weight part B of polyamidoimide 100 weight parts, the content of the amide group in the reactive compounds is defined as Ea weight %, the content of the Siliciumatom in the polymeric amide is defined as Pc weight %, when the content of the Siliciumatom in the reactive compounds is defined as Ec weight %, can satisfy following formula (I) and (II):

3≤(Pa×100+Ea×B)/(100+B)≤11?…(I)

1≤(Pc×100+Ec×B)/(100+B)≤16?…(II)。

By containing the polyamidoimide that on main chain, has siloxane structure, also further contain aforesaid reactive compounds, except can further improving the connectivity of the resin layer of forming by resin primer, can also improve thermotolerance.In addition, if adjust the combined amount of this reactive compounds as described above, then the content of the content of the amide group that contains in the resin and Siliciumatom is easy to become above-mentioned suitable scope.Its result, the resin primer of the better connectivity that can obtain to volatilize.

Resin primer as this form, can be to contain above-mentioned resin and this resin to have that film forms ability, energy to fracture is the above priming paint of 0.15J, and/or when 10 mean roughness of formation when being film below the 0.1 μ m methane amide under the room temperature be priming paint below 60 ° with respect to the contact angle on this film surface.

More specifically, as the aforesaid polyamidoimide that on main chain, has siloxane structure, preferably by the imide dicarboxylic acid mixture with the material that the reaction of the aromatic diisocyanate of following general formula (3) expression obtains, contain the imide dicarboxylic acid of the following general formula of usefulness (1) expression that makes aromatic diamine and trimellitic acid anhydride reactant and obtain among the described imide dicarboxylic acid mixture and make siloxane diamine and trimellitic acid anhydride reactant and imide dicarboxylic acid that the following general formula of usefulness (2) that obtains is represented.

[in the formula, R ¹The divalent group that expression is represented with following general formula (4a) or following general formula (4b), R ²¹Expression alkyl, phenyl or substituted-phenyl, R ²²The organic group of expression divalence, R ³Expression has the divalent organic group of at least one aromatic nucleus, and n represents 1-50 integer.

Wherein, in the formula (4a), R ⁴Be the alkylidene group of carbonatoms 1-3, halogenation alkylidene group, alkylsulfonyl, ether, carbonyl or the singly-bound of carbonatoms 1-3.Also has the R of a plurality of existence ²¹And R ²²Can be the same or different each other, in addition, the aromatic nucleus in each compound also can have other substituting group in addition.]

In addition, this polyamidoimide is the material that the aromatic diisocyanate reaction of 1.0-1.5 times of molar weights obtains by making integral molar quantity with respect to the imide dicarboxylic acid mixture preferably, at this moment, the imide dicarboxylic acid mixture is the material by two amine mixt that contain aromatic diamine and siloxane diamine and trimellitic acid anhydride reactant are obtained, and, in this two amine mixt, aromatic diamine/siloxane diamine amount is preferably 0/100-99.9/0.1 with molar ratio computing.

In addition, another kind of resin primer of the present invention is characterised in that and contains resin, and contains polyamidoimide as this resin, and this polyamidoimide has the structural unit of being made up of stable hydrocarbon.Wherein, as the structural unit of forming by stable hydrocarbon, preferably use the structure of following chemical formula (5) expression.

In such resin primer, above-mentioned resin also can be to have that film forms ability, energy to fracture is the above priming paint of 0.15J, and/or when 10 mean roughness of formation when being film below the 0.1 μ m methane amide under the room temperature be priming paint below 60 ° with respect to the contact angle on this film surface.

As the polyamidoimide that contains in the resin in the resin primer of this form, it is the material that the reaction by imide dicarboxylic acid and vulcabond obtains, described imide dicarboxylic acid obtains by making diamine compound and trimellitic acid anhydride reactant, as diamine compound, the preferred use with following general formula (6a), (6b) or the compound (6c) represented.

[in the formula, R ⁶¹Expression hydrogen atom, cyano group, methoxyl group, methyl or halogenation methyl, R ⁶²Expression is with following general formula (7a), (7b), (7c) with the base of any one expression (7d), the alkylidene group of carbonatoms 1-3, halogenation alkylidene group, alkylsulfonyl, ether, carbonyl or the singly-bound of carbonatoms 1-3, R ⁶³The alkylidene group of expression carbonatoms 1-3, halogenation alkylidene group, alkylsulfonyl, ether or the carbonyl of carbonatoms 1-3.

Wherein, in the formula (7a), R ⁷The alkylidene group of expression carbonatoms 1-3, halogenation alkylidene group, alkylsulfonyl, ether, carbonyl or the singly-bound of carbonatoms 1-3.Also has the R of a plurality of existence ⁶¹Can be the same or different each other.]

In addition, as this polyamidoimide, more preferably also contain the material that obtains with the compound of following general formula (8) expression as above-mentioned diamine compound.

[in the formula, R ⁸¹Expression methylene radical, alkylsulfonyl, ether, carbonyl or singly-bound, R ⁸²And R ⁸³Represent hydrogen atom, alkyl, phenyl or substituted-phenyl independently of one another, m represents 1-50 integer.]

In addition, as the vulcabond that in this polyamidoimide, uses, the preferred fragrance (cyclo) aliphatic diisocyanates.

In addition, if the resin in the resin primer of this form contains the reactive compounds that has with the aitiogenic functional group of amide group of polyamidoimide, then more preferably.

Resin primer of the present invention is the priming paint that contains aforesaid resin, except this resin, also can contain rubber constituent, and the content of this rubber constituent is that standard meter is preferably more than the 40 quality % with the quality of resin.Utilization contains the resin primer of this rubber constituent, can further improve the connectivity of conductor foil and insulator layer.

The conductor foil that has resin of the present invention is characterised in that, the resin layer that has conductor foil and on this conductor foil, be provided with, 10 mean roughness on conductor foil surface are below the 3 μ m, and resin layer is to form by the resin primer that is coated with the invention described above.In addition, as the conductor foil that has resin of the present invention, its feature also can be the resin layer that has conductor foil and be provided with on this conductor foil, and conductor foil is a tinsel, and resin layer is made up of the resin primer of the invention described above.

These have the conductor foil of resin owing to have the resin layer of being made up of the resin primer of the invention described above, so though the surface of conductor foil is also enough level and smooth, the engaging force between conductor foil and insulator layer is enough high.Therefore, this conductor foil that has resin is fit to make the high-density printing distributing board.And, because the surface smoothing of conductor foil, so when using this conductor foil that has resin, the electric current of the near surface that is produced by aforesaid skin effect increases less, therefore can make the printing distributing board that can also fully adapt to the high frequencyization of transmission signal.

In addition, the present invention also provides the substrate that can be used as printing distributing board to use, and the plywood that uses above-mentioned resin primer to obtain.Promptly, plywood of the present invention is characterised in that, by duplexer heating and pressurization are obtained, wherein said duplexer has the conductor foil that has resin of the invention described above and is layered in semicure impregnation material (prepreg) on the resin layer in this conductor foil that has resin.

That is the duplexer that obtains the like this resin layer that has conductor foil, form with the insulation layer that contains resin of this conductor foil subtend setting and the resin primer that between this conductor foil and insulation layer, is provided with, by the invention described above in the mode that contacts with these.Therefore, in this duplexer, as conductor foil, preferred 10 mean roughness that are suitable for the face that is connected with resin layer at least are the material below the 3 μ m.

Have the duplexer of these structures can be suitably by following duplexer heating and pressurization are made, wherein said duplexer has the conductor foil that has resin of the invention described above and has the coating resin priming paint in the conductor foil of resin and stacked semicure impregnation material on the layer that forms at this.

Description of drawings

Fig. 1 is the figure of the stress-deformation curve of expression resin.

Fig. 2 is the figure of the methane amide liquid contact angle on the expression resin surface.

Fig. 3 is the mode chart of the cross section structure of the expression conductor foil that has resin in the embodiment.

Fig. 4 is the mode chart of the cross section structure of conductor tectum lamination (duplexer) in the expression embodiment.

Fig. 5 is to use the FIB processing sectional view in the two sides copper plating film plywood that the resin primer of embodiment 7 obtains.

Fig. 6 is the FIB processing sectional view in the commercially available two sides copper plating film plywood.

Fig. 7 is the curve of expression transmission loss with respect to the value of signal frequency.

Embodiment

Below, the preferred embodiment of the present invention is elaborated.

[resin primer]

At first, resin primer of the present invention is described.Resin primer of the present invention is the priming paint that contains resin.As this resin, at first, can enumerate the resin that has film formation ability, has the above energy to fracture of 0.15J.

Wherein, the method for " energy to fracture " of measurement resin is as follows.At first, making resin formation is the rectangle film of wide 10mm, thick 50 μ m.Specifically, at first will go up and carry out drying, so that dried thickness reaches 50 μ m by the glossy surface (Rz=2 μ m) that resin solution a kind of or that form more than two kinds is coated on Copper Foil.

Then, this have resin Copper Foil, also do not contact a stacked again Copper Foil on the resin face of a side with Copper Foil, make this moment resin and glossy surface face-to-face, and exert pressure from the face that does not contact of this Copper Foil with resin layer.Then, remove the Copper Foil on this resin layer two sides, be cut into the rectangle film of width with 10mm with etching method.At this moment, the length of film preferably is longer than the distance between the preceding anchor clamps of this film that stretches, i.e. 60mm.

Then, two anchor clamps are disposed every 60mm along its length, and clamp film.Then, make two anchor clamps mobile in the opposite direction according to 5mm/ minute speed along the length direction of this film, thus oriented film.Be stretched to the film fracture always.

At this moment, the relation that gives the tensile stress of rectangle film and the distortion of this film (extensibility) can be represented with stress-deformation curve as shown in fig. 1.Obtain oblique line part among this Fig. 1, be the integrated value of the tensile stress of (up to breaking point) before the fracture of rectangle film, be this value defined " energy to fracture (unit: J) ".

This measuring method for example can use that オ-ト グ ラ Off AG-100C (society of Shimadzu Seisakusho Ltd. system, trade(brand)name) carries out, and can calculate energy to fracture from the stress-deformation curve that obtains as its result.

In addition, as resin, the resin that also preferably meets the following conditions, promptly, when being membranaceous with this ester moulding, if 10 mean roughness (Rz) that this resin molding (symbol 2 among Fig. 2) is surperficial are adjusted into below the 0.1 μ m and are dripping methane amide liquid (1 among Fig. 2) under the room temperature environment on this surface resin film, then this methane amide liquid phase is below 60 ° for the contact angle (θ among Fig. 2) (following only be called " methane amide contact angle ") of surface resin film.

This methane amide contact angle can be measured with method in the past, and for example can using, contact angle time meter CA-DT (consonance interface science Co., Ltd. system, trade(brand)name) measures.

Wherein, " 10 mean roughness " of above-mentioned surface resin film can use for example commercially available contact pin type surface finish measurement device etc. to derive according to the method for masurement of JIS B0601-1994.

As the resin that in the resin primer of embodiment, contains, can be suitable for resin with aforesaid any characteristic with being not particularly limited.Particularly, can enumerate for example heat-curing resins such as resol, Resins, epoxy, polyimide resin and bismaleimides-cyanate resin.In addition, also can enumerate thermoplastic resins such as fluorine resin and polyhenylene resin.These can be used alone or be used in combination more than two kinds.

In addition, as resin, suitable is with the quality of this resin is that standard meter contains more than one the resin of key that is selected from imide bond, amino-formate bond and aromatic carboxylic acid ester bond more than the 6 quality %.Also have, among the present invention, so-called " quality % " or " mass parts " is same as weight basis value (" weight % " or " weight part ") (following identical) in fact.

Here, the content to above-mentioned each key describes.So-called " imide bond " is the key of being made up of a nitrogen-atoms and two ketonic linkages (C=O), so-called " amino-formate bond " is the key of being made up of a nitrogen-atoms and an ester bond (COO), and so-called " aromatic carboxylic acid ester bond " is the key of being made up of an ester bond (COO).

The quality of each key can multiply each other by the nucleidic mass summation with the mole number of this key and the atom that constitutes each key and calculate.From the above, the nucleidic mass summation that constitutes the atom of each key is 70 for imide bond, is 58 for amino-formate bond, is 44 for the aromatic carboxylic acid ester bond.Each key was calculated by the proportioning of resin with respect to ratio (quality %) expression of resin solid composition total mass when the content of each key (quality %) usable resins reaction (condensation reaction or polycondensation etc.) finished.Also have, solvent and the weighting agent with the resinous principle reaction is not included in this resin solid composition.

Compound (resin) with this key has the character that above-mentioned methane amide contact angle is reduced.As this resin, can enumerate polyimide, polyetherimide, polyamidoimide, urethane, polyarylester particularly and resin that these modifications are obtained etc.These resins can be the resins that himself has the above energy to fracture of 0.15J, also can be the resins with methane amide contact angle below 60 °.

In addition, as the resin that contains in resin primer, the 1st resin shown below and the 2nd resin and other resin also are fit to.Wherein, also preferably contain resin just like the polyamidoimide of the 1st resin and the 2nd resin and so on.If these resins have the characteristic of above-mentioned energy to fracture and/or the characteristic of methane amide contact angle simultaneously, then more preferably.In addition, resin can contain resin shown below respectively separately, also can multiple combination contain.

Below, the 1st resin, the 2nd resin and other resin that are suitable as the resin that contains in the resin primer of embodiment and other composition except resin are described.

(the 1st resin)

At first, the 1st resin is described.The 1st resin is the resin that contains the polyamidoimide that has siloxane bond in main chain.As this resin, preferably, when the content of all Siliciumatoms that contain in the resin is defined as C weight %, satisfy above-mentioned formula (a) and resin (b) when the content of all amide group that contain in the resin is defined as A weight %.

Wherein, when the content of amide group and Siliciumatom does not satisfy above-mentioned scope, except the bond strength of the conductor tectum lamination that uses these acquisitions descends, also there is the inadequate trend of thermotolerance.The preferable range of above-mentioned A is more than 6 below 9, and the preferable range of above-mentioned C is more than 5 below 12.

If the 1st resin so not only contains the polyamidoimide that has siloxane structure in main chain, but also contain reactive compounds, then more preferably with the functional group that can react with the amide group of this polyamidoimide.

When also containing reactive compounds, the content of this reactive compounds preferably satisfies condition shown below.Promptly, reactive compounds is with respect to the weight part B of polyamidoimide 100 weight parts, the content of the amide group in the polyamidoimide is being defined as Pa weight %, the content of the amide group in the acid amides reactive compounds is defined as Ea weight %, the content of the Siliciumatom in the polyamidoimide is defined as Pc weight %, when the content of the Siliciumatom in the reactive compounds is defined as Ec weight %, satisfy above-mentioned formula (I) and (II).

When the combined amount of each composition of resin meets above-mentioned formula (I) and (II) time, all acid amides base unit weights and all silicon amounts will be comprised in above-mentioned formula (a) and the scope (b), the conductor foil in can improving the conductor tectum lamination that uses this resin acquisition more and the bond strength of insulation layer, also can make thermotolerance become outstanding.On the other hand, if the combined amount of each composition does not satisfy above-mentioned formula (I) and (II), then there is these characteristics insufficient trend that becomes.From improving the viewpoint of this characteristic more, in the above-mentioned formula (I) (lower limit of Pa * 100+Ea * B)/(100+B) is preferably 6, and the upper limit is preferably 9.In addition, from same viewpoint, in the above-mentioned formula (II) (Pc * 100+Ec * B)/(100+B) lower limit is preferably 5, and the upper limit is preferably 12.

The resin primer that contains the resin that satisfies this condition not only has outstanding connectivity with tinsel, and has outstanding thermotolerance.This mainly is because introduced the polyamidoimide of siloxane structure in the high polyamidoimide of thermotolerance.The polyamidoimide of this structure not only has high connectivity with tinsel etc., and has under the temperature that does not make resin solidification and can be easily to become component to be reduced to characteristic below the 5 weight % with being contained in remaining organic solvent in this resin.So remaining organic solvent amount in the resin is reduced to 5 weight % when following,, also extremely is difficult for producing bubble that the volatilization because of organic solvent causes etc. even at high temperature expose knitting layer to the open air in the operations such as scolding tin afterwards.

The so-called polyamidoimide that has siloxane structure in main chain is meant the material that has siloxane structure, amido linkage and imide bond in its main chain.Wherein, so-called siloxane structure is meant in its structure and has-structure of SiO-key.In addition, as siloxane structure, preferably on Siliciumatom, be combined with the structure of two any monovalent organic radical groups.

As such polyamidoimide, preferably by imide dicarboxylic acid mixture and the material that obtains with the reaction of the aromatic diisocyanate of following above-mentioned general formula (3) expression, wherein said imide dicarboxylic acid mixture is contained the imide dicarboxylic acid (hereinafter referred to as " the 1st imide dicarboxylic acid ") of the above-mentioned general formula of usefulness (1) expression that makes aromatic diamine and trimellitic acid anhydride reactant and obtain, the imide dicarboxylic acid (hereinafter referred to as " the 2nd imide dicarboxylic acid ") of the above-mentioned general formula of usefulness (2) expression that obtains with making siloxane diamine and trimellitic acid anhydride reactant.

Wherein, as the 1st imide dicarboxylic acid, preferably in above-mentioned general formula (1), use R ¹The functional group of expression is the material with the divalent group of above-mentioned formula (4a) expression.At this moment, as using R in the above-mentioned formula (4a) ⁴The functional group of expression is preferably usefulness-C (CH ₃) ₂The group of-expression or with-C (CF ₃) ₂The group of-expression.

As the aromatic diamine that is used to form the 1st such imide dicarboxylic acid, for example can enumerate 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP), two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, two [4-(4-amino-benzene oxygen) phenyl] methane, 4,4 '-two (4-amino-benzene oxygen) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] ether, two [4-(4-amino-benzene oxygen) phenyl] ketone, 1,3-two (4-amino-benzene oxygen) benzene, 1,4-two (amino-benzene oxygen) benzene.Wherein, also preferred especially BAPP.

In addition, as the 2nd imide dicarboxylic acid, can be set forth in the above-mentioned formula (2) R ²¹Be preferably the alkyl of carbonatoms 1-6, more preferably the alkyl of carbonatoms 1-3 material,, R ²²Be preferably the alkylidene group of carbonatoms 1-6, the material of the alkylidene group of carbonatoms 1-3 more preferably.

As the siloxane diamine that is used to form these the 2nd imide dicarboxylic acid, preferred dimethyl silica methane series two terminal amine.This compound can be bought from the market as amino-modified silicone oil X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1500) (more than be chemical industry society of SHIN-ETSU HANTOTAI system), BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200) (more than be eastern beautiful ダ ウ コ-two Application グ シ リ コ-Application society system) etc.Also have, these can separately or be used in combination.

Contain the imide dicarboxylic acid mixture of these the 1st and the 2nd imide dicarboxylic acid can (A) by behind the synthetic various imide dicarboxylic acid in advance, both are mixed modulate, in addition, also can (B) aromatic diamine by will being used to form each imide dicarboxylic acid and siloxane diamine mix form two amine mixt after, trimellitic acid 1,2-anhydride and this mixture reaction are modulated.

When adopting the method for (B), preferably manage to make the combined amount of aromatic diamine, siloxane diamine and trimellitic acid 1,2-anhydride to meet the following conditions.That is, when the mole number aromatic diamine is defined as D, the mole number of siloxane diamine is defined as E, the value that when mole number of trimellitic acid 1,2-anhydride is defined as F, preferably makes (D+E)/F is in the scope of 1.0/2.0-1.0/2.2.

At this moment, the mixture ratio D/E of D and E preferably according to the amine equivalent decision of E, is generally 99.9/0.1-0/100.Particularly, for example, when the amine equivalent of siloxane diamine is 400-500, D/E is preferably 99.9/0.1-0/100, and when amine equivalent was 800-1000, D/E was preferably 99.9/0.1-60/40, when amine equivalent was 1500-1600, D/E was preferably 99.9/0.1-60/40.By making D, E and F in such scope, can make the composition ratio of the 1st and the 2nd imide dicarboxylic acid among the imide dicarboxylic acid mixture become good, make the amide group in the polyamidoimide and the content of Siliciumatom be easy to possess above-mentioned formula (a) and condition (b).

In (B) method, can obtain the imide dicarboxylic acid mixture by making trimellitic acid 1,2-anhydride and above-mentioned diamines mixture reaction.For example, this reaction can make it after reaction under 50-90 ℃ by managing to make both dissolve or be scattered in non-proton property polar solvent, in reacted solution, add can with water azeotropic aromatic hydrocarbons, under 120-180 ℃, make its reaction again and dehydration closed-loop takes place react and implement.

Wherein, as non-proton property polar solvent, can enumerate N,N-DIMETHYLACETAMIDE, dimethyl formamide, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone, 4-butyrolactone, tetramethylene sulfone etc.Wherein, also particularly suitable is N-methyl-2-pyrrolidone.

In addition, as can with water azeotropic aromatic hydrocarbons, can enumerate toluene, benzene, dimethylbenzene, ethylbenzene etc., preferred toluene.This aromatic hydrocarbons preferably adds 0.1-0.5 amount by weight with respect to non-proton property polar solvent.In addition, after the reaction of this dehydration closed-loop finishes, before the reaction of carrying out with aromatic diisocyanate described later, preferably rise to about 190 ℃ by the temperature that makes solution, remove in advance can with water azeotropic aromatic hydrocarbons.

The polyamidoimide that has siloxane structure on main chain can react synthetic with the imide dicarboxylic acid mixture who obtains as described above by making the aromatic diisocyanate with above-mentioned general formula (3) expression.As such aromatic diisocyanate, can enumerate 4,4 '-diphenylmethanediisocyanate (MDI), 2,4-toluene support vulcabond, 2,6-toluene support vulcabond, naphthalene-1,5-vulcabond, 2,4-toluene support dipolymer etc.

As the polyamidoimide of such acquisition, can enumerate compound with repeating unit of representing with the repeating unit of following general formula (9a) expression with following general formula (9b).These repeating units can the block combination, also can random combination.In addition, the R in the formula ¹, R ², R ²², R ³With n and above-mentioned synonym.

The reaction of imide dicarboxylic acid mixture and aromatic diisocyanate under the situation of the solution heating that will contain the imide dicarboxylic acid as described above in order to remove aromatic hydrocarbons, preferably will be carried out after the reacted solution elder generation cool to room temperature.After in the solution that is cooled like this, adding aromatic diisocyanate, make temperature rise to about 190 ℃, it was reacted about 2 hours, can obtain polyamidoimide.

In this reaction, aromatic diisocyanate is preferably 1.0-1.5 times of molar weights with respect to the add-on of imide dicarboxylic acid mixture integral molar quantity, more preferably 1.1-1.3 times of molar weights.If then there is the flexible downward trend of the resin layer of being made up of resin primer in 1.0 times of molar weights of the add-on deficiency of aromatic diisocyanate, when surpassing 1.5 times of molar weights in addition, there is the flexible downward trend of resin layer equally.

In addition, as the reactive compounds that in the 1st resin, contains, can enumerate heat-curing resin with the functional group that can react with the amide group of above-mentioned polyamidoimide.This reactive compounds also can be the compound that has amide group and/or Siliciumatom in molecule.

As such heat-curing resin, can enumerate multi-functional epoxy compound, polyimide resin, unsaturated polyester resin, urethane resin, bimaleimide resin, triazine-bimaleimide resin, resol etc.Wherein, also preferred multi-functional epoxy compound.If use the multi-functional epoxy compound as reactive compounds, then the resin layer that is formed by the resin primer that contains these is except can improving the connectivity with conductor foil, and thermotolerance, mechanical characteristics and electrical characteristic are also outstanding.As the multi-functional epoxy compound that such multi-functional epoxy compound preferably has two above epoxy group(ing), the multi-functional epoxy compound who more preferably has three above epoxy group(ing).

As multi-functional epoxy compound, can enumerate the Resins, epoxy that the reaction of polyphenol such as for example making dihydroxyphenyl propane, phenolic varnish type resol, ortho-cresol phenolic varnish type resol and Epicholorohydrin forms with two above epoxy group(ing); The Resins, epoxy that the reaction of polyvalent alcohol such as 1,4-butyleneglycol and Epicholorohydrin is formed; The poly glycidyl ester that the reaction of polyprotonic acid such as phthalandione, six hydrogen phthalandiones and Epicholorohydrin is formed; Amine, acid amides or have the N-Racemic glycidol radical derivative of the compound of hetero ring type nitrogen salt base; Alicyclic epoxy resin etc.

In addition, as multi-functional epoxy compound, can suitably use ZX-1548-2 (Dongdu changes into society's system), the DER-331L that can buy from the market (ダ ウ ケ ミ カ Le society system bisphenol A type epoxy resin), YDCN-195 (Dongdu changes into society's system cresols phenolic resin varnish type epoxy resin) etc. with three above glycidyls.

Contain that the combined amount of the above-mentioned reactive compounds in the resin of polyamidoimide preferably has according to this compound, with the quantity decision of the aitiogenic functional group of amide group.Promptly, reactive compounds is with respect to the weight part B of polyamidoimide 100 weight parts, the content of the amide group in the polyamidoimide is being defined as Pa weight %, the content of the amide group in the reactive compounds is defined as Ea weight %, the content of the Siliciumatom in the polyamidoimide is defined as Pc weight %, when the content of the Siliciumatom in the reactive compounds is defined as Ec weight %, be defined as satisfying above-mentioned formula (I) and value (II).

Like this, when in making resin, containing the multi-functional epoxy compound, preferably add this multi-functional epoxy compound's solidifying agent or curing catalyst again as reactive compounds.As solidifying agent and curing catalyst, can suitably use known.For example, as solidifying agent, can enumerate amines such as Dyhard RU 100, diaminodiphenyl-methane, guanylurea; Imidazoles; Multifunctional phenols such as quinhydrones, Resorcinol, dihydroxyphenyl propane and these halogenide, phenolic varnish type resol, soluble phenolic resin type resol; Anhydride phthalic acid, benzophenone tetracarboxylic dianhydride, methyl nadic acid anhydrides such as (acid of Ha イ ミ Star Network).In addition, as curing catalyst, can enumerate imidazoles such as alkyl substituted imidazole, benzoglyoxaline.

The combined amount of solidifying agent can determine according to the epoxy equivalent (weight) among the multi-functional epoxy compound.For example, when adding amine compound as solidifying agent, its combined amount is preferably the amount that the Ahew that makes amine and multi-functional epoxy compound's epoxy equivalent (weight) equates.In addition, when solidifying agent was multifunctional phenols or anhydrides, it was 0.6-1.2 equivalents with respect to multi-functional epoxy compound's 1 equivalent that its combined amount preferably manages to make phenol hydroxyl or carboxyl.In addition, the combined amount of curing catalyst is 0.001-10 weight parts with respect to multi-functional epoxy compound's 100 weight parts preferably.

If the combined amount of these solidifying agent or curing catalyst is less than above-mentioned scope, then multi-functional epoxy compound's curing becomes insufficient, thereby has the glass transition temp downward trend of the resin layer that is obtained by the resin primer that contains resin.On the other hand, if greater than above-mentioned scope, then because there is the electrical characteristic downward trend by the resin layer of resin primer acquisition in residual solidifying agent or curing catalyst.

In addition, the resin that contains polyamidoimide also can contain other compositions such as weighting agent, coupler, fire retardant except containing above-mentioned polyamidoimide, reactive compounds, solidifying agent etc.

(the 2nd resin)

Below, the 2nd resin is described.Contain material as polyamidoimide in the 2nd resin with structural unit of forming by stable hydrocarbon.As such structural unit, preferably have the unit of ring alkylidene group, more preferably have the unit of one or two cyclohexylidene, further the unit of preferably representing with above-mentioned chemical formula (5).Use contains the resin primer of this polyamidoimide, and it is outstanding but also Tg is high, wet fastness and the outstanding resin layer of thermotolerance then can to form not only connectivity with conductor foil.

As the polyamidoimide that in the 2nd resin, contains, preferably the reaction by imide dicarboxylic acid and vulcabond obtains, and wherein said imide dicarboxylic acid can obtain by making the diamine compound and the trimellitic acid anhydride reactant that have aforesaid structural unit between two amino.

As such diamine compound, the compound of preferably using above-mentioned general formula (6a), (6b) or (6c) representing.Particularly; for example can enumerate 2; 2-two [4-(4-amino cyclohexyloxy) cyclohexyl] propane; two [4-(3-amino cyclohexyloxy) cyclohexyl] sulfone; two [4-(4-amino cyclohexyloxy) cyclohexyl] sulfone; 2; 2-two [4-(4-amino cyclohexyloxy) cyclohexyl] HFC-236fa; two [4-(4-amino cyclohexyloxy) cyclohexyl] methane; 4; 4 '-two [4-amino cyclohexyloxy] dicyclohexyl; two [4-(4-amino cyclohexyloxy) cyclohexyl] ether; two [4-(4-amino cyclohexyloxy) cyclohexyl] ketone; 1; 3-two (4-amino cyclohexyloxy) benzene; 1; 4-two (4-amino cyclohexyloxy) benzene; 2; 2-dimethyl dicyclohexyl-4; 4 '-diamines; 2; 2-two (trifluoromethyl) dicyclohexyls-4; 4 '-diamines; 2; 6; 2 '; 6 '-tetramethyl--4; 4 '-diamines; 5; 5 '-dimethyl-2; 2 '-alkylsulfonyl-dicyclohexyl-4; 4 '-diamines; 3; 3 '-dihydroxyl dicyclohexyl-4; 4 '-diamines; (4; 4 '-diamino) dicyclohexyl methyl hydride; (4; 4 '-diamino) two hexamethylene ethers; (4; 4 '-diamino) two hexamethylene sulfones; (4; 4 '-diamino) two pimelinketone; (3,3 '-diamino) two hexamethylene ethers; 2,2-two (4-amino cyclohexyloxy) propane etc.Wherein, also preferred (4,4 '-diamino) dicyclohexyl methyl hydride.These diamine compounds may be used alone, can also be used in combination.

Polyamidoimide in the 2nd resin is preferably the compound that also uses the diamine compound acquisition of representing with above-mentioned general formula (8) as diamine compound except above-mentioned compound.In diamine compound, as R with above-mentioned general formula (8) expression ⁸²And R ⁸³, preferably be alkyl, phenyl or the substituted-phenyl of hydrogen atom, carbonatoms 1-3 independently of one another.As the substituting group in this substituted-phenyl, can enumerate the alkyl and the halogen atom of carbonatoms 1-3.

As diamine compound, especially preferably use R with above-mentioned general formula (8) expression ⁸¹The base of expression is the compound of ether.By containing this diamine compound, the resin primer that can make polyamidoimide and contain it has low elasticity rate and high Tg.As such diamine compound, ジ エ Off ア-ミ Application D-400, ジ worker 7 ア-ミ Application D-2000 that suitable use can be bought from the market (more than be サ Application テ Network ノ ケ ミ カ Le society system) etc.

Polyamidoimide in the 2nd resin is preferably, and also further contains the compound that aromatic diamine or siloxane diamine etc. obtain as diamine compound except above-mentioned compound.At this moment, aromatic diamine and siloxane diamine have no particular limits, and can enumerate the synthetic compound of the polyamidoimide that for example is used for above-mentioned the 1st resin.By adding aromatic diamine, the Tg of polyamidoimide and resin primer is uprised, thereby improve thermotolerance.In addition, by adding siloxane diamine, can make the resin primer low elasticity rateization that becomes.

Polyamidoimide in the 2nd resin for example can be synthetic by method as follows.That is, at first, above-mentioned diamine compound and trimellitic acid 1,2-anhydride are reacted in non-protonic solvent down at 70-100 ℃.Wherein,, can enumerate and the identical solvent of polyamidoimide synthetic that is used for above-mentioned the 1st resin preferred NMP as non-protonic solvent.

Wherein, the content of non-proton property polar solvent preferably is made as gross weight solids component weight with respect to solution and reaches 10-70 weight %, the amount of 20-60 weight % more preferably.When the solids component in the solution surpasses 70 weight %, there is the decreased solubility of solids component and reacts inadequate trend.On the other hand, when less than 10 weight %, the solvent usage quantity becomes too much, is unfavorable for cost control.

After the above-mentioned reaction, synthetic identical with the polyamidoimide of above-mentioned the 1st resin, in the solution that obtains, add and can heat down, thereby obtain the imide dicarboxylic acid by making it that dehydration closed-loop reaction take place with water azeotropic aromatic hydrocarbons and at 150-200 ℃.At this moment, owing to also distillating the problem that causes not enough aequum at the effusive while aromatic hydrocarbons of water sometimes, so, manage to make the concentration of aromatic hydrocarbons in the solution to keep constant for example preferably by making solvent turn back to reaction soln etc. again except that after anhydrating from effusive liquid.In addition, after the dehydration closed-loop reaction finishes, preferably wait and heat up in a steamer aromatic hydrocarbons by heated solution.

As the imide dicarboxylic acid of such acquisition, can enumerate compound with following general formula (10a) expression, when being used in combination the diamine compound of representing with above-mentioned general formula (8), also can generate compound simultaneously with following general formula (10b) expression.In addition, in the following formula, R ¹⁰Expression from above-mentioned general formula (6a), (6b) or (6c) compound of expression remove the divalent group that the back that deaminizes forms, R ⁸¹, R ⁸², R ⁸³With m and above-mentioned synonym.

Polyamidoimide can obtain by making the imide dicarboxylic acid and the di-isocyanate reaction that obtain as described above.When such synthesizing polyamides imide, the combined amount of diamine compound, trimellitic acid 1,2-anhydride and vulcabond preferably manages to make diamine compound: trimellitic acid 1,2-anhydride: vulcabond is 1:2-2.2:1-1.5 according to molar ratio computing, is preferably 1:2-2.2:1-1.3.If like this, will finish the building-up reactions of imide dicarboxylic acid and polyamidoimide expeditiously, can obtain more high molecular and the outstanding polyamidoimide of film formation property.

As vulcabond, can suitably use aromatic diisocyanate and aliphatic diisocyanate the two.What for example, be fit to is the material of representing with following general formula (11).In the following formula, as R ¹¹, can enumerate usefulness-Ph-CH ₂The group of-Ph-expression, toluene support base, naphthylidene, hexa-methylene or isophorone base.

OCN—R ¹¹—NCO?…(11)

As aromatic diisocyanate, suitable is and the identical material of polyamidoimide synthetic that is used for above-mentioned the 1st resin, wherein, and also preferred MDI.By making it contain MDI,, can also improve the flexible of the resin layer formed by this priming paint except the film that can improve resin primer forms the property.In addition, as aliphatic diisocyanate, can enumerate hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, isophorone diisocyanate etc.

As vulcabond, can use any in aromatic diisocyanate and the aliphatic diisocyanate separately, also can be used in combination, but preferably contain aromatic diisocyanate at least, more preferably and use both.

When both and time spent, it is about 5-10 moles of % with respect to the content of aromatic diisocyanate that its ratio of mixture preferably manages to make aliphatic diisocyanate.With aromatic diisocyanate and aliphatic diisocyanate, can further improve the thermotolerance of polyamidoimide and resin primer by so also.

The reaction of imide dicarboxylic acid and these vulcabond preferably adds vulcabond in the above-mentioned reacted solution that contains the imide dicarboxylic acid carries out, and its temperature of reaction is preferably 130-200 ℃.

If this reaction is carried out in the presence of basic catalyst more preferably, at this moment, temperature of reaction can be 70-180 ℃, preferred 120-150 ℃.Thus, the negative reactions such as reaction with regard to suppressing to be produced each other by vulcabond obtain more high-molecular weight polyamidoimide.

As basic catalyst, can enumerate trialkylamines such as Trimethylamine 99, triethylamine, tripropyl amine, three (2-ethyl is own) amine, trioctylamine.Wherein, triethylamine is also removed after the reaction easily owing to can suitably promote reaction, so preferred.

The polyamidoimide of Huo Deing for example has the repeating unit with following general formula (12a) expression in molecule like this, under situation about being fit to, can have the repeating unit with following general formula (12b) expression simultaneously.In addition, in the following formula, R ¹⁰, R ¹¹, R ⁸¹, R ⁸², R ⁸³With m and above-mentioned synonym.

As the polyamidoimide in the 2nd resin of such acquisition, preferably its weight-average molecular weight is 20000-300000, more preferably 30000-200000, further preferred 40000-150000.In addition, wherein so-called weight-average molecular weight is to measure the value that is converted and obtained by the typical curve that uses polystyrene standard to make in the back with gel permeation chromatography.

The 2nd resin is also identical with above-mentioned the 1st resin, if except polyamidoimide also contain have with this polyamidoimide in amide group have the reactive compounds of reactive functional group, then more preferably.As such reactive compounds, can suitably use the material that is suitable in above-mentioned the 1st resin, its combined amount is 5-25 weight % with respect to the total amount of resin primer preferably.

If the combined amount deficiency of reactive compounds 5 weight % then contain film formation property decline of the resin primer of the 2nd resin sometimes.On the other hand, if surpass 25 weight %, then except the resin layer of being made up of resin primer becomes fragile, also there is connectivity downward trend with conductor foil.In addition, when making it contain this reactive compounds, if also contain solidifying agent and/or curing catalyst in the same manner, then more preferably with above-mentioned the 1st resin.

In addition, in the 2nd resin,, also can contain weighting agent, coupler, fire retardant etc. as other composition.

(other resin)

As the resin of the resin primer that is contained in embodiment, except the above-mentioned the 1st or the 2nd resin, can also suitably use other resin shown below.As other resin, at first, can enumerate by making the resin and the isocyanates that in structure, contain hydroxyl react the carbamate that obtains.Wherein,, can enumerate phenylcarbimide, ethyl isocyanate, propyl isocyanate, butyl isocyanate, isocyanic acid fluoro phenyl ester, isocyanic acid chloro phenyl ester, isocyanic acid bromo phenyl ester etc., but and be limited to these as isocyanates.

In addition, as other resin, also can enumerate aromatic carboxylic acid esters by the resin that has hydroxyl in structure and aromatic carboxylic acid or its derivatives reaction are obtained.As this reaction, can enumerate for example is the direct esterification of the aromatic carboxylic acid and the hydroxyl of catalyzer with the mineral acid.

As the aromatic derivant carboxylate, can enumerate Benzoyl chloride, benzoyl bromide, methyl benzoyl chloride, toluyl bromine, ethylamino benzonitrile acyl chlorides, ethylamino benzonitrile acylbromide, propylbenzene formyl chloride, propyl group benzoyl bromide, butylbenzene formyl chloride, butyl benzoyl bromide etc., but be not limited to these.

In aromatic carboxylic acid esters synthetic,, except above-mentioned, also can enumerate the method for tolysulfonyl (ト シ Le) change through perhydroxyl radical as the method that forms the aromatic dicarboxylic acid ester bond.For example, can be by making the reaction of hydroxyl and Tosyl chloride, additional p-toluenesulfonyl (tosic acid ion) in structure.This p-toluenesulfonyl is outstanding leavings group, can be converted to the carboxylic acid ion at an easy rate.

(other composition)

As mentioned above, the resin primer in the embodiment can contain above-mentioned various resin, but except these resins, can also contain other composition in addition.As other composition, at first can enumerate rubber constituent.If resin primer also contains rubber constituent, will improve the resin layer formed by resin primer connectivity more with respect to tinsel.

Wherein so-called " rubber constituent " is meant the polymer substance with rubber-like elasticity.As rubber constituent, can enumerate for example acrylic rubber, natural rubber, synthetic polyisoprene, divinyl rubber, chloroprene rubber, paracril, silicone rubber, chemglaze etc., but be not limited to these.If this rubber contains in resin more than the 40 quality %, then more preferably.

In addition, as other composition,, can also contain engineering plastics such as nylon, polycarbonate, polyarylester etc. except rubber constituent.The resin that has added these materials will have bigger energy to fracture, and thus obtained resin layer will have the stronger connectivity with respect to tinsel.

[conductor foil that has resin]

Below, the conductor foil that has resin in is preferred embodiment described.The conductor foil that has resin is the above-mentioned resin primer of coating and the material that forms on conductor foil.Fig. 3 is the mode chart of the cross section structure of the expression conductor foil that has resin in the embodiment.The resin layer 14 that the illustrated conductor foil 10 that has resin has conductor foil 12 and forms thereon, be made up of the resin primer of above-mentioned embodiment.

Wherein, as conductor foil 12, preferred 10 mean roughness (Rz) of coating resin priming paint side surface at least are the following materials of 3 μ m, more preferably the following material of 2 μ m.

In addition, the Rz on conductor foil 12 surfaces is identical with " 10 mean roughness " of surface resin film, can use according to the method for masurement of JIS B0601-1994 and derive, and for example can use commercially available contact pin type surface finish measurement device etc. to measure.

In conductor, can produce magnetic line of force near the mobile electric current because the interference of the centre portions magnetic line of force of conductor is big more, so current concentration in around and turning (comer).This effect is called skin effect, and frequency is high more, and this trend is strong more.In contrast, the conductor circuit that is obtained by above-mentioned conductor foil 12 is below the 3 μ m owing to its Rz, and is very smooth, thus may be able to suppress increase by the resistance of above-mentioned skin effect generation, thus help the transmission of radio-frequency signal.

As conductor foil 12, as long as have aforesaid characteristic, just can use, but from the good viewpoint of electroconductibility, the preferable alloy paper tinsel is if Copper Foil then more preferably with being not particularly limited.As Copper Foil, can use electrolytic copper foil and rolled copper foil etc., preferably do not form concavo-convex Copper Foil from the teeth outwards by asperities processing etc.

The glossy surface of common electrolytic copper foil satisfies these conditions, when using such Copper Foil, can make its glossy surface directly be used as the coated face of resin primer.As the Copper Foil that satisfies this condition, can enumerate F0-WS (Rz=1.2), F1-WS, F2-WS (Rz=3.0), GTS, GTS-MP, GTS-FLP, GY, GY-MP, TSTO, DT-GL, DT-GLD (more than be Furukawa サ-キ Star ト Off オ イ Le society system), 3EC-VLP (society of Mitsui Metal Co., Ltd. system, Rz=3.0), SLP, YGP (Japanese electrolysis society system) etc.The glossy surface of the Copper Foil that these are commercially available has the Rz of 1.5-2.0 μ m, and especially as the little Copper Foil of surfaceness, FO-WS (Furukawa サ-キ Star ト Off オ イ Le society system, Rz=1.2 μ m) can buy from the market.The thickness of these Copper Foils is preferably about 9-18 μ m.

In addition, can also use peelable (ピ-ラ Block Le) Copper Foil that stacked Copper Foil as thin as a wafer formed after the surface of carrier copper foil carried out the demoulding and handle thereon, the Copper Foil as this moment can use 3 μ m or 5 μ m thick.As this Copper Foil, for example, MTS (society of Mitsui Metal Co., Ltd. system), NAP (Japanese electrolysis society system), FCF (Furukawa サ-キ Star ト Off オ イ Le society system) etc. can buy from the market and obtain.

In addition, Copper Foil can use as required and to have suitable thickness.Commercially available Copper Foil has the thickness of about 10-150 mu m ranges, but uses the Copper Foil with 18 μ m and 35 μ m thickness usually as the circuit substrate purposes.But,, more preferably use among the present invention to have 12 μ m or the thick relatively thinner Copper Foils such as Copper Foil of 9 μ m from forming the viewpoint of finer circuit pattern.

As the tinsel beyond the Copper Foil, can enumerate the aluminium foil of thick 5-200 μ m, between the copper foil layer of the copper foil layer of thick 0.5-15 μ m and thick 10-300 μ m, be provided with the composite foil of three-decker in the middle layer of forming by nickel, nickel-phosphorus, nickel-tin alloy, Ni-Fe alloy, lead, lead-tin alloy etc. and the composite foil of double-layer structure that aluminium and Copper Foil are compounded to form etc.Also preferred its surfaceness of these tinsels satisfies above-mentioned condition.

On these conductor foils 12, can implement with known method during coating resin priming paint, for example can enumerate with comma coating, dip-coating, touch the method for coating and natural curtain coating coating etc.This coating is to carry out under 0.1-10%, preferred 2-6% the varnish state in the concentration of resin primer by making the resin primer dissolving or being scattered in back in the organic solvent etc. preferably.

As the organic solvent that is used for varnish, can enumerate N,N-DIMETHYLACETAMIDE, dimethyl formamide, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone, γ-butyrolactone, tetramethylene sulfone, pimelinketone etc.In addition, when coating resin priming paint under the varnish state, be preferably in coating back and do not produce under the solidified degree at resin primer and organic solvent is volatilized by heating to wait.

(conductor tectum lamination)

Fig. 4 is the mode chart of the cross section structure of conductor tectum lamination (duplexer) in the expression embodiment.Conductor tectum lamination 20 has and possesses insulator layer 26 successively, the structure of knitting layer 24 and conductor foil 22.

As insulator layer 26,, just can be suitable for so long as be generally used for conductor tectum lamination with being not particularly limited.Promptly, as insulator layer 26, can enumerate the material that constitutes by following semicure impregnation material, described semicure impregnation material serve as reasons semicure impregnation material that the curable resin of B level state with reinforcing fiber forms and the semicure impregnation material of forming by the curable resin of B level state with reinforcing fiber.Wherein, if the material that the semicure impregnation material that utilization is made up of the curable resin of the B level state with reinforcing fiber is formed is then preferred.

The semicure impregnation material that the former curable resin by the B level state that does not have reinforcing fiber is formed can make semi-cured state (B level) and obtain after curable resin is configured as film like.In addition, the semicure impregnation material that the latter's the curable resin by the B level state with reinforcing fiber is formed can curable resin is contained be dipped in the reinforcing fiber after, obtain by making this resin become semi-cured state (B level) by impregnation.

Curable resin can be identical with the resin that constitutes resin primer, also can be different.As curable resin, preferred epoxy, polyimide resin, resol etc. particularly.

In addition, as reinforcing fiber, can enumerate the glass fibre of forming by E glass, D glass, S glass, Q glass etc.; The organic fibre of forming by polyimide, polyester, tetrafluoroethylene etc.; And with these fibers that mix to form.These fibers can as have for example yarn fabric, non-woven fabrics, rove, prescind the precursor mat, surfacing is with the reinforcing fiber of shapes such as (surfacing) seat.

Ratio of mixture with curable resin and reinforcing fiber in the semicure impregnation material of reinforcing fiber is by mass ratio preferred consolidation resin/reinforcing fiber=20/80-80/20, and more preferably 40/60-60/40.

As this semicure impregnation material, can also use commercially available semicure impregnation material.For example, can enumerate semicure impregnation material (GEA-67, GEA-679, the GEA-679F that the heat-curing resin that will with Resins, epoxy be principal constituent contains the woven fiber glass (Network ロ ス) that is dipped in as glasscloth; Hitachi Chemical Co., Ltd.'s system), be impregnated with the high-frequency semicure impregnation of the adaptation material (GEA-LX-67 of the resin of low-k; Hitachi Chemical Co., Ltd.'s system), will be mixed in the resin that polyimide forms to the thermofixation composition and contain the semicure impregnation material (GEA-I-671 that is dipped in the woven fiber glass; Hitachi Chemical Co., Ltd.'s system).In addition, insulator layer 26 can be the material that only uses these semicure impregnation materials of one deck to form, also can be overlapping multilayer and material.

The layer that knitting layer 24 is made up of the resin primer of the invention described above.Specifically, be preferably the layer that above-mentioned resin primer drying is formed.In addition, as conductor foil 22, the preferred use at the above-mentioned conductor foil that uses in the conductor foil 10 of resin that has is conductor foil below the 3 μ m with the Rz on the junction surface of knitting layer 24 more preferably.

This conductor tectum lamination 20 can be made as followsly.That is, at first, after above-mentioned overlapping individual layer of semicure impregnation material or multilayer, obtain duplexers by the stacked above-mentioned conductor foil that has a resin 10 thereon, this moment, conductor foil contacted with this resin layer 14.At this moment, the thickness that has the resin layer 14 in the conductor foil 10 of resin, from printing distributing board and the slimming of machine of this printing distributing board and the viewpoint that shortens time of drying are set, protuberance with the conductor foil surface is a benchmark, be preferably below the 5 μ m, more preferably below the 4 μ m, be preferably especially below the 3 μ m.

Then, this duplexer is heated under prescribed condition and/or pressurize and obtain conductor tectum lamination 20.Thus, make the resin in the semicure impregnation material and the resin layer 14 that has in the duplexer 10 of resin solidifies, form insulator layer 26 and knitting layer 24 respectively.Heating is preferably carried out under 160-250 ℃ temperature, and pressurization is preferably at the pressure of 0.1-8.0MPa, particularly carry out under vacuum.Heating and the preferred use of pressurization vacuum pressed machine etc. carry out simultaneously.At this moment, can carry out these handle more than 10 minutes, preferred more than 30 minutes, more preferably more than 60 minutes, make the outstanding conductor tectum lamination 20 of connectivity of conductor foil 22 and insulator layer 26 (semicure impregnation material).

In addition, conductor tectum lamination of the present invention also can have conductor foil by knitting layer on two faces of insulation layer.This conductor tectum lamination can be managed the stacked above-mentioned conductor foil that has resin and be made on two faces of semicure impregnation material or its duplexer.

In having the conductor tectum lamination of this structure, conductor foil engages with the cured article (insulator layer) of semicure impregnation material by the knitting layer be made up of the cured article of resin primer of the present invention, and the cured article that forms insulation layer and knitting layer is by being solidified into the state of one.Therefore, the conductor foil in the conductor tectum lamination can engage securely with insulation layer.

Therefore, even using this conductor tectum lamination to form under the situation of printing distributing board, also seldom peel off from body material by the circuit pattern that the conductor foil of firm engagement forms with fine circuits pattern.In addition, the cured article of knitting layer is owing to being to be formed by the resin primer that contains aforesaid resin, so also have high thermotolerance.Therefore, when conductor tectum lamination is exposed in operations such as plating under the pyritous situation, this knitting layer also seldom produces bubble etc.

Embodiment

Below, by embodiment the present invention is described in further detail, but the present invention is not limited to these embodiment.

The modulation of＜resin primer 〉

(embodiment 1-3)

Each raw material shown in the table 1 is mixed, make its dissolving, thereby obtain the resin primer of embodiment 1-3 by stirring.In addition, in the table 1, use DER-331L (epoxy equivalent (weight)=184, ダ ウ ケ ミ カ Le society system, trade(brand)name) as bisphenol A type epoxy resin, use HP-850N (hydroxyl equivalent=106, Hitachi Chemical Co., Ltd.'s system, trade(brand)name), use W-248DR (Xin Zhong village chemical industry Co., Ltd. system, trade(brand)name) as acrylic rubber as phenolic varnish type resol.

(table 1)

?	Embodiment 1	Embodiment 2	Embodiment 3
				Resin (g) bisphenol A type epoxy resin phenolic varnish type resol acrylic rubber	510.6	521.2	531.7
DBU(g)	0.01	0.02	0.03
				MEK(g)	9.9	12.2	14.6

(embodiment 4)

Add phenoxy resin (YP-50, hydroxyl equivalent=284, Toto Kasei KK's system, trade(brand)name) 100g and pimelinketone 330g in 1 liter of removable flask with reflux exchanger, thermometer, agitator, heated and stirred makes its dissolving.Then, add phenylcarbimide 41.9g, triethylamine 0.3g and under 130 ℃, make its reaction 3 hours.Then, in ethanol, behind the redeposition, make its drying, thus the phenoxy resin of phenyl carbamate that obtained addition.Then, make this resin dissolves in dimethyl formamide (DMF), its concentration is 30 quality %, thereby obtains the resin primer of embodiment 4.

(embodiment 5)

Make commercially available joint fastener AS-3000E (Hitachi changes into Co., Ltd.'s system) be dissolved in methylethylketone (MEK), make its concentration reach 30 quality %, thereby obtain the resin primer of embodiment 5.

(comparative example 1-3)

Each raw material shown in the table 2 is mixed, make its dissolving, thereby obtain resin primer by stirring.In addition, in the table 2, as bisphenol A type epoxy resin, phenolic varnish type resol and acrylic rubber, adopt with embodiment 1-3 in the identical material of use.

(table 2)

?	Comparative example 1	Comparative example 2	Comparative example 3
				Resin (g) bisphenol A type epoxy resin phenolic varnish type resol acrylic rubber	552.9	57.54.3	5105.8
DBU(g)	0.05	0.075	0.1
				MEK(g)	19.4	25.2	31.6

(comparative example 4)

Make polysulfone resin (コ-デ Le P-1700, ア モ コ society system, trade(brand)name) be dissolved in DMF, making its concentration is 30 quality %, thereby obtains resin primer.

(comparative example 5)

Make polyethersulfone resin (5003P, Sumitomo Chemical Company Ltd's system, trade(brand)name) be dissolved in DMF, make its concentration reach 30 quality %, thereby obtain resin primer.

The measurement of＜energy to fracture 〉

The measurement of energy to fracture is to use オ-ト グ ラ Off AG-100C (Shimadzu Seisakusho Ltd.'s system, trade(brand)name) to carry out.

For the resin primer that obtains by embodiment 1-3 and comparative example 1-3, at first, resin primer is coated on Copper Foil (GTS-18, Furukawa サ-キ Star ト Off オ イ Le society system, trade(brand)name) on the glossy surface (Rz=2 μ m), in being heated to 120 ℃ warm braw circular form drying machine dry 10 minutes, dried thickness was 50 μ m.Then be arranged at knitting layer on the Copper Foil, also not with the surface of Copper Foil engage side on, stacked again another Copper Foil, and make glossy surface and above-mentioned surface face-to-face, from Copper Foil not with the knitting layer contact side, under 170 ℃, the condition of 3.0MPa, carry out pressurization in 1 hour.Then, remove the Copper Foil on two sides with etching method.Thus, obtain to measure with test film (resin film) relevant for the energy to fracture of embodiment 1-3 and comparative example 1-3.

Resin primer for embodiment 4 and comparative example 4,5, at first, resin primer is coated on the carrier thin film, by in being heated to 120 ℃ warm braw circular form drying machine dry 10 minutes, dried thickness is 50 μ m, measures with test film (resin film) thereby obtain energy to fracture.

In addition,, be cured, obtain energy to fracture and measure with test film (resin film) by making joint fastener AS-3000E for the resin primer of embodiment 5.

Then, two anchor clamps are clamped above-mentioned each test film every 60mm along its length.Then, make two anchor clamps mobile in the opposite direction according to 5mm/ minute speed, thereby stretch this test film along the length direction of this test film.At this moment, with above-mentioned measurement device distortion and tensile stress values.Finish this stretching in the moment of film fracture then.The integrated value of obtaining the tensile stress before the test film fracture in the stress-deformation curve of acquisition is as energy to fracture.The results are shown in the table 3.

(table 3)

?	Energy to fracture (J)	The methane amide contact angle (°)	Copper Foil stripping strength (kN/m)	The stripping strength of Copper Foil/resin boundary surface (kN/m)
					Embodiment 1	0.81	65	2.1	0.3
Embodiment 2	0.71	64	1.9	0.3
					Embodiment 3	0.32	64	1.1	0.4
Embodiment 4	0.058	55	0.4	0.9
					Embodiment 5	0.18	58	0.9	0.9
Comparative example 1	0.058	64	0.5	0.3
					Comparative example 2	0.012	63	0.4	0.3
Comparative example 3	0.0044	63	0.4	0.3
					Comparative example 4	0.054	72	0.01	0.2
Comparative example 5	0.081	69	0.05	0.3
					Comparative example 6	?	?	0.1	?

The measurement of＜methane amide contact angle 〉

The contact angle of methane amide is measured and can be used the contact angle time meter CA-DT of consonance interface science society system to carry out as described below.Resin primer for embodiment 1-3 and comparative example 1-3, this resin primer is coated on Copper Foil (GTS-18, Furukawa サ-キ Star ト 7 オ イ Le society systems, trade(brand)name) on the glossy surface (Rz=2 μ m), in being heated to 120 ℃ warm braw circular form drying machine dry 10 minutes, measure the lip-deep methane amide contact angle of resin film that after making it solidify 1 hour under 170 ℃ the environment, obtains then.

Resin primer for embodiment 4 and comparative example 4,5 is coated on this resin primer on the carrier thin film, measures the lip-deep methane amide contact angle of resin film by obtaining after dry 10 minutes in being heated to 120 ℃ warm braw circular form drying machine.

In addition, for the resin primer of embodiment 5, measure the lip-deep methane amide contact angle of resin film that obtains by joint fastener AS-3000E is solidified.The results are shown in the table 3.

The measurement of＜Copper Foil stripping strength 〉

Generally in the wiring board field, during the connectivity between resin and tinsel is estimated, adopt the stripping test of measuring the Copper Foil stripping strength usually.Therefore, in order to estimate resin that obtains by priming paint in the conductor tectum lamination of the present invention and the connectivity between the conductor foil, measured the Copper Foil stripping strength as described below.

At first, the embodiment 1-4 of acquisition as described above and the priming paint of comparative example 1-5 are coated on the glossy surface (Rz=2 μ m) of Copper Foil (GTS-18), in being heated to 120 ℃ warm braw circular form drying machine, make its dry 10 minutes, dried thickness is 5 μ m, thereby makes the Copper Foil that has resin.Then, by stacked 5 layers of low-k semicure impregnation material (GEA-LX-67, Hitachi Chemical Co., Ltd.'s system, trade(brand)name), on its both sides, the stacked above-mentioned Copper Foil that has resin makes resin (knitting layer) and semicure impregnation material face opposite this moment, pressurization is 90 minutes under 230 ℃, the condition of 3.0MPa, obtains two sides copper plate lamination.

In addition, priming paint for embodiment 5, at first, AS-3000E is dissolved in the methylethylketone (MEK), make its concentration reach 30 weight %, the resin solution that obtains is coated on the carrier thin film, in being heated to 120 ℃ warm braw circular form drying machine, carried out drying 10 minutes, dried thickness is 50 μ m, thereby makes the Copper Foil that has resin.Then, stacked 5 layers of low-k semicure impregnation material (GEA-LX-67, Hitachi Chemical Co., Ltd.'s system, trade(brand)name), on its both sides, the stacked above-mentioned Copper Foil that has resin makes resin (knitting layer) and semicure impregnation material face opposite this moment, pressurization is 90 minutes under 230 ℃, the condition of 3.0MPa, obtains two sides copper plate lamination.

In addition, as a comparative example 6, stacked 5 layers of low-k semicure impregnation material (GEA-LX-67, Hitachi Chemical Co., Ltd.'s system, trade(brand)name), laminated copper foil on its both sides (GES-18) makes glossy surface (Rz=2 μ m) and semicure impregnation material face opposite this moment, pressurization is 90 minutes under 230 ℃, the condition of 3.0MPa, obtains two sides copper plate lamination.

Then, Copper Foil that the 1cm on each two sides copper plate lamination is wide is peeled off according to 5cm/ minute speed and is measured the Copper Foil stripping strength.The results are shown in the table 3.

The measurement of the stripping strength of＜Copper Foil/resin boundary surface 〉

Because the resin and the joint interface between the conductor foil that are obtained by priming paint become level and smooth more, bonding area is few more, become important so not only constitute the resin rerum natura of priming paint, and the chemical interaction between this resin and the conductor foil also becomes important.Therefore,, estimate, use by the tinsel resin of pruning and measure the cutting system of engaging force, measured conductor foil and the stripping strength at the interface of the knitting layer formed by resin relevant for chemically interactive connectivity in order to eliminate the influence that produces by the resin rerum natura.

At first, will be used to measure the embodiment 1-5 of Copper Foil stripping strength and the Copper Foil identical materials that has resin of comparative example 1-5 is fixed on supporting substrate, and make the knitting layer formed by resin in the above, and it is set to measure uses sample.Use the ダ イ プ ラ ウ イ Application テ ス system サ イ カ ス CN-100 of Co., Ltd. type to measure the stripping strength of the Copper Foil/resin boundary surface of this Copper Foil that has resin.

Specifically, by under the speed of 0.5 μ m/ second of 10 μ m/ seconds of horizontal velocity, vertical speed, the blade of the wide 2mm of incision on knitting layer, the travel direction of blade is only become move, measured the stripping strength of Copper Foil/resin boundary surface thus to horizontal direction.The results are shown in the table 3.

Energy to fracture is the material among the above embodiment 1-3 and 5 of 0.15J, even under the situation of the level and smooth Copper Foil that 10 mean roughness of use are 2 μ m, also can obtain the above Copper Foil stripping strength of 0.9kN/m.The methane amide contact angle is the material among the embodiment 4,5 below 60 °, even under the situation of the level and smooth Copper Foil that to use 10 mean roughness be 2 μ m, the stripping strength at the interface between this Copper Foil and the resin has also reached 0.9kN/m.

On the other hand, the not enough 0.15J of energy to fracture, methane amide contact angle surpass the material in 60 ° the comparative example 1-5, and its Copper Foil stripping strength is below 0.5kN/m, and the stripping strength of Copper Foil/resin boundary surface is below the 0.3kN/m, has all shown lower value.In addition, with Copper Foil and semicure impregnation material directly the Copper Foil stripping strength of stacked comparative example 6 be 0.1kN/m, compare with embodiment 1-5 and shown lower value.

Synthesizing of＜polyamidoimide 〉

(synthesis example 1)

To water and basis weight susceptor with the 25mL that has the cock that is connected with reflux exchanger, thermometer, in the removable flask of the 1L of agitator, input is as 2 of aromatic diamine, 2-two [4-(4-amino-benzene oxygen) phenyl] propane (BAPP) 57.5g (0.14mol), reactive silicone oil KF8010 (chemical industry society of SHIN-ETSU HANTOTAI system as siloxane diamine, amine equivalent 421) 50.5g (0.06mol), trimellitic acid 1,2-anhydride (TMA) 80.7g (0.42mol), as N-methyl-2-pyrrolidone (NMP) 580g of non-proton property polar solvent, stirred 30 minutes down at 80 ℃.

After stir finishing, add as can with the toluene 100mL of water azeotropic aromatic hydrocarbons, make temperature rise to 160 ℃ and refluxed 2 hours.If in the water and basis weight susceptor, accumulate more than the about 7.2mL of water, and confirm not see that water distillates, and just remove the water in the water and basis weight susceptor, and meanwhile make temperature rise to 190 ℃, thus remove toluene.

After making the solution of flask turn back to room temperature, add 4,4 '-diphenylmethanediisocyanate (MDI) 60.1g (0.24mol) is as aromatic isocyanate, makes temperature rise to 190 ℃ and make its reaction 2 hours.After the reaction, with the solution cool to room temperature, thus the nmp solution of the polyamidoimide of acquisition amide group content 8.05 weight %, silicon atom content 8.68 weight %.

(synthesis example 2)

In the removable flask of the 1L of the water and basis weight susceptor with the 25mL that has the cock that is connected with reflux exchanger, thermometer, agitator, input, stirred 30 minutes down at 80 ℃ as reactive silicone oil KF8010, the TMA80.7g (0.42mol) of siloxane diamine, the 494g NMP as non-proton property polar solvent as BAPP41.1g (0.10mol), the 84.2g (0.10mol) of aromatic diamine.

After stir finishing, add as can with the toluene 100mL of water azeotropic aromatic hydrocarbons, make temperature rise to 160 ℃ and refluxed 2 hours.If in the water and basis weight susceptor, accumulate more than the about 7.2mL of water, and confirm not see that water distillates, and just remove the water in the water and basis weight susceptor, and meanwhile make temperature rise to 190 ℃, thus remove toluene.

After making the solution of flask turn back to room temperature, add MDI60.1g (0.24mol), make temperature rise to 190 ℃ and make its reaction 2 hours as aromatic isocyanate.After the reaction, with the solution cool to room temperature, thus the nmp solution of the polyamidoimide of acquisition amide group content 7.38 weight %, silicon atom content 13.26 weight %.

(synthesis example 3)

In the removable flask of the 1L of the water and basis weight susceptor with the 25mL that has the cock that is connected with reflux exchanger, thermometer, agitator, drop into 41.05g (0.10mol) as the BAPP of aromatic diamine, as dimethyl benzene fundamental mode reactive silicone oil X-22-9409 (chemical industry society of the SHIN-ETSU HANTOTAI system of siloxane diamine, amine equivalent 679) 135.8g (0.10mol), TMA80.7g (0.42mol), as the NMP590g of non-proton property polar solvent, stirred 30 minutes down at 80 ℃.

After stir finishing, add as can with the toluene 100mL of water azeotropic aromatic hydrocarbons, make temperature rise to 160 ℃ and refluxed 2 hours.If in the water and basis weight susceptor, accumulate more than the about 7.2mL of water, and confirm not see that water distillates, and just remove the water in the water and basis weight susceptor, and meanwhile make temperature rise to 190 ℃, thus remove toluene.

After making the solution of flask turn back to room temperature, add MDI60.1g (0.24mol), make temperature rise to 190 ℃ and make its reaction 2 hours as aromatic isocyanate.After the reaction, with the solution cool to room temperature, thus the nmp solution of the polyamidoimide of acquisition amide group content 6.12 weight %, silicon atom content 10.99 weight %.

(relatively synthesis example 1)

In the removable flask of the 1L of the water and basis weight susceptor with the 25mL that has the cock that is connected with reflux exchanger, thermometer, agitator, input is as dimethyl benzene fundamental mode reactive silicone oil X-22-161A (chemical industry society of SHIN-ETSU HANTOTAI system of siloxane diamine, amine equivalent 805) 161.0g (0.10mol), TMA40.34g (0.21mol), as the NMP430g of non-proton property polar solvent, stirred 30 minutes down at 80 ℃.

After stir finishing, add as can with the toluene 100mL of water azeotropic aromatic hydrocarbons, make temperature rise to 160 ℃ and refluxed 2 hours.If in the water and basis weight susceptor, accumulate more than the about 3.6mL of water, and confirm not see that water distillates, and just remove the water in the water and basis weight susceptor, and meanwhile make temperature rise to 190 ℃, thus remove toluene.

After making the solution of flask turn back to room temperature, add MDI30.1g (0.12mol), drop into triethylamine 1.0g again, make temperature rise to 110 ℃ and make its reaction 4 hours as aromatic isocyanate.After the reaction, with the solution cool to room temperature, thus the nmp solution of the polyamidoimide of acquisition amide group content 4.07 weight %, silicon atom content 27.96 weight %.

The modulation of＜resin primer 〉

(embodiment 6)

The nmp solution 63.3g (solids component 30 weight %) of the polyamidoimide that will obtain by synthesis example 1, be DER331L (ダ ウ ケ ミ カ Le society system as the Resins, epoxy of reactive compounds, bisphenol A type epoxy resin) 2.0g (dimethylacetamide solutions of resin solid composition 50 weight %), 2-ethyl-4-Methylimidazole 0.02g mixes, and stir about 1 hour becomes even up to composition.Then, solid component concentration is adjusted into 5 weight %, at room temperature left standstill for deaeration 2 hours then by adding N,N-DIMETHYLACETAMIDE, thus the resin primer of acquisition amide group content 7.65 weight %, silicon atom content 8.25 weight %.

(embodiment 7)

The nmp solution 63.3g (solids component 30 weight %) of the polyamidoimide that will be obtained by synthesis example 2, be that DER331L2.0g (dimethylacetamide solutions of resin solid composition 50 weight %), 2-ethyl-4-Methylimidazole 0.02g mix as the Resins, epoxy of reactive compounds, stir about 1 hour becomes even up to composition.Then, solid component concentration is adjusted into 5 weight %, at room temperature left standstill for deaeration 2 hours then by adding N,N-DIMETHYLACETAMIDE, thus the resin primer of acquisition amide group content 7.38 weight %, silicon atom content 12.56 weight %.

(embodiment 8)

The nmp solution 60.0g (solids component 30 weight %) of the polyamidoimide that will obtain by synthesis example 3, be that (Dongdu changes into society's system to YDCN500-10 as the Resins, epoxy of reactive compounds, bisphenol A type epoxy resin) 4.0g (dimethylacetamide solutions of resin solid composition 50 weight %), 2-ethyl-4-Methylimidazole 0.04g mixes, and stir about 1 hour becomes even up to composition.Then, solid component concentration is adjusted into 5 weight %, at room temperature left standstill for deaeration 2 hours then by adding N,N-DIMETHYLACETAMIDE, thus the resin primer of acquisition amide group content 5.81 weight %, silicon atom content 10.44 weight %.

(embodiment 9)

The nmp solution 63.3g (solids component 30 weight %) of the polyamidoimide that will obtain by synthesis example 1, be NC3000H (Japanese chemical drug society system as the Resins, epoxy of reactive compounds, ザ イ ロ Star Network type Resins, epoxy) 2.0g (dimethylacetamide solutions of resin solid composition 50 weight %), 2-ethyl-4-Methylimidazole 0.02g mixes, and stir about 1 hour becomes even up to composition.Then, solid component concentration is adjusted into 5 weight %, at room temperature left standstill for deaeration 2 hours then by adding N,N-DIMETHYLACETAMIDE, thus the resin primer of acquisition amide group content 7.25 weight %, silicon atom content 7.81 weight %.

(embodiment 10)

By in the nmp solution 63.3g (solids component 30 weight %) of the polyamidoimide that obtains by synthesis example 2, adding N,N-DIMETHYLACETAMIDE solid component concentration is adjusted into 5 weight %, at room temperature left standstill for deaeration 2 hours then, thus the resin primer of acquisition amide group content 7.38 weight %, silicon atom content 13.26 weight %.

(comparative example 7)

The nmp solution 26.7g (solids component 30 weight %) of the polyamidoimide that will be obtained by synthesis example 2, be that DER331L24.0g (dimethylacetamide solutions of resin solid composition 50 weight %), 2-ethyl-4-Methylimidazole 0.24g mix as the Resins, epoxy of reactive compounds, stir about 1 hour becomes even up to composition.Then, solid component concentration is adjusted into 5 weight %, at room temperature left standstill for deaeration 2 hours then by adding N,N-DIMETHYLACETAMIDE, thus the resin primer of acquisition amide group content 2.95 weight %, silicon atom content 5.30 weight %.

(comparative example 8)

The nmp solution 60.0g (solids component 30 weight %) of the polyamidoimide that will be obtained by synthesis example 1 relatively, be that DER331L4.0g (dimethylacetamide solutions of resin solid composition 50 weight %), 2-ethyl-4-Methylimidazole 0.04g mix as the Resins, epoxy of reactive compounds, stir about 1 hour becomes even up to composition.Then, solid component concentration is adjusted into 5 weight %, at room temperature left standstill for deaeration 2 hours then by adding N,N-DIMETHYLACETAMIDE, thus the varnish of the gel-type resin of acquisition amide group content 3.66 weight %, silicon atom content 25.16 weight %.

The measurement of＜Copper Foil stripping strength 〉

The resin primer of embodiment 6-10 and comparative example 7-8 is coated on glossy surface (the Rz=1.5 μ m of electrolytic copper foil (thick 12 μ m) respectively by natural curtain coating; Rz is the surfaceness of measuring according to JIS B0601-1994) on, make it make the Copper Foil that has resin down in dry 20 minutes then at 130 ℃.The thickness of dried resin layer is 1-2 μ m.

Then, with low-k semicure impregnation material (Hitachi Chemical Co., Ltd.'s system, GEA-LX-67) body material (hereinafter referred to as " low-k is a body material ") that forms of overlapping regulation number or with imide series semicure impregnation material (Hitachi Chemical Co., Ltd.'s system, GEA-I-671) on two faces of the body material (hereinafter referred to as " imide series body material ") of overlapping regulation number formation, the overlapping above-mentioned Copper Foil that respectively has resin of mode that contacts with each resin (knitting layer) with this face, at 230 ℃, 3.0MPa, carry out crimping under 90 minutes the pressurized conditions, thereby make two sides copper plate lamination.

In addition, as a comparative example 9, the electrolytic copper foil that does not have resin (knitting layer) by crimping on the duplexer of the overlapping regulation number of above-mentioned semicure impregnation material is made two sides copper plate lamination.

By measuring the Copper Foil stripping strength (90 ° of stripping strengths are according to JIS C6481) when 90 degree directions are peeled off respectively in the two sides copper plate lamination that will obtain, carry out the measurement of Copper Foil stripping strength (kN/m).What obtain the results are shown in the table 4.

The stable on heating evaluation of＜scolding tin 〉

Above-mentioned each two sides copper plate lamination is cut into the size of 20mm * 20mm, makes scolding tin thermal test sample.This sample be impregnated in respectively in 260 ℃ the solder bath, confirm with the naked eye whether bubble and the tinsel on the joint interface of Copper Foil and body material is peeled off from body material, thereby carry out the stable on heating evaluation of scolding tin.Impregnated in after the solder bath through also observe bubble more than 180 seconds and peel off generation to be defined as the scolding tin thermotolerance outstanding and do not represent with zero, 180 seconds with interior generation bubble or peel off be defined as the also usefulness * expression of scolding tin poor heat resistance.What obtain the results are shown in the table 4

The shape evaluation of＜joint interface 〉

Carry out hole processing along the vertical direction (thickness direction) of above-mentioned each two sides copper plate lamination with FIB (focused ion light beam), observe scan ion images (by the secondary electron image of ion beam emission) from the 45 degree directions in the hole that forms.Fig. 5 is to use the FIB processing sectional view in the two sides copper plate lamination that the resin primer of embodiment 7 obtains, and Fig. 6 is the FIB processing sectional view in the commercially available two sides copper plate lamination.

(table 4)

As shown in Table 4, the Copper Foil bond strength of the two sides copper plate lamination of the resin primer acquisition of use embodiment 6-10 is all more than 0.8kN/m.In addition, in the scolding tin thermal test, do not produce bubble yet and peel off.Therefore, can judge to have good bond strength and scolding tin thermotolerance.

In addition, can judge by Fig. 5, in the copper plate lamination of embodiment, Copper Foil A and knitting layer B and body material C carried out the joint interface of the integrated duplexer that forms becomes very level and smooth with comparing as the joint interface of Copper Foil D among Fig. 6 of plywood in the past and body material E.In addition, the thickness of Copper Foil 1 in the copper plate lamination shown in Fig. 5 and the knitting layer 2 between the body material 3 is 1-2 μ m.

Thus, can judge resin primer, when use has the tinsel of smooth-flat-surface, also can obtain the extraordinary conductor tectum of the connectivity lamination of tinsel and body material according to embodiment 6-10.Therefore, can confirm to make printing distributing board with fine circuits pattern by using this conductor tectum lamination.

In addition, the conductor tectum lamination of embodiment is owing to have the cured article of the very high knitting layer of thermotolerance between tinsel and body material, so even be exposed under the high heat in scolding tin etc., the bubble of generation etc. are considerably less.Therefore, can confirm to have the wiring circuit of surface smoothing, so the high speed of operation that can realize the high frequencyization of transmission signal and use the electronic machine of this printing distributing board by the printing distributing board that the conductor tectum lamination with this specific character forms.

Synthesizing of＜polyamidoimide 〉

(synthesis example 4)

In the removable flask of 1L with the water and basis weight susceptor that is connected with reflux exchanger, thermometer, agitator, adding is as (4 of diamine compound, 4 '-diamino) dicyclohexyl methyl hydride (ワ Application ダ ミ Application HM (abbreviation WHM): new Japanese physics and chemistry society system trade(brand)name) 140mmol and ジ エ Off ア-ミ Application D-2000 (サ Application テ Network ノ ケ ミ カ Le society system trade(brand)name) 35mmol, TMA368mmol, 413g stirred 30 minutes down at 80 ℃ as the NMP of non-proton property polar solvent.

After stir finishing, add as can with the toluene 120mL of water azeotropic aromatic hydrocarbons, make temperature rise to 160 ℃ and refluxed 2 hours.If in the water and basis weight susceptor, accumulate the water of theoretical amount, and confirm not see that water distillates, and just remove the water in the water and basis weight susceptor, and meanwhile make temperature rise to 190 ℃, thus remove toluene.

After making the solution of flask turn back to room temperature, the MDI that adds 210mmol is as vulcabond, makes temperature rise to 190 ℃ and make its reaction 2 hours.After the reaction, with the solution cool to room temperature, thus the nmp solution of acquisition polyamidoimide.

The modulation of＜resin primer 〉

(embodiment 11)

The nmp solution 76.0g (resin solid composition 25 weight %) of the polyamidoimide that will obtain by synthesis example 4, be DER331L2.0g (dimethylacetamide solutions of resin solid composition 50 weight %), be that 2-ethyl-4-Methylimidazole of 1 weight % mixes that stir about 1 hour becomes even up to said composition with respect to reactive compounds as the Resins, epoxy of reactive compounds.Then, at room temperature left standstill 2 hours, thereby obtain resin primer for deaeration.

(embodiment 12 and 13)

Except the combined amount with DER331L is defined as 4.2g (embodiment 12) and 9.5g (embodiment 13), obtain resin primer in the same manner with embodiment 11.

(comparative example 10-12)

(Hitachi changes into society's system trade(brand)name except using PAI-100, polyamide-imide resin, resin solid composition 30 weight %) 63.3g is as polyamidoimide, to be as the combined amount separate provision of the DER331L of reactive compounds 2.0g (comparative example 10), 4.2g (comparative example 11) and 9.5g (comparative example 12) in addition, obtain resin primer in the same manner with embodiment 11.

The measurement of＜Copper Foil stripping strength 〉

At first, use the resin primer of embodiment 11-13 and comparative example 10-12, make various two sides copper plate lamination according to the method for (1) shown below-(3).

In the method for (1), at first, in each resin primer, add N,N-DIMETHYLACETAMIDE and solid component concentration is adjusted into 7 weight %, be coated on it on glossy surface (Rz=2 μ m) of electrolytic copper foil through natural curtain coating then, in warm braw circular form drying machine, descended dry 10 minutes again, thereby acquisition has the conductor foil of resin at 160 ℃.

Then, overlapping 4 of low-k semicure impregnation material GXA-67N (Hitachi changes into industrial society system) is formed body material, the overlapping respectively above-mentioned Copper Foil that respectively has resin on two face, this moment, this face contacted with each resin (knitting layer), and under 230 ℃, 3.0MPa, 90 minutes pressurized conditions, carry out crimping, thereby make two sides copper plate lamination.

In the method for (2), at first, each resin primer is coated on the PET film, and it was obtained to have the films of resin in dry 10 minutes in warm braw circular form drying machine under 160 ℃.In addition, the thickness of dried resin layer is 8 μ m.

Then, on both sides with the body material of overlapping 4 formation of low-k semicure impregnation material GXA-67N, overlapping successively resin layer and the electrolytic copper foil that forms behind the PET film of removing by the above-mentioned film that has resin, under 230 ℃, 3.0MPa, 90 minutes pressurized conditions, carry out crimping, thereby make two sides copper plate lamination.Make its glossy surface be contacted with resin layer when in addition, electrolytic copper foil being set.

In the method for (3), at first, above-mentioned resin primer is coated on the low-k semicure impregnation material GXA-67N through natural curtain coating, and it was obtained to have the semicure impregnation materials of resin in dry 10 minutes in warm braw circular form drying machine under 160 ℃.In addition, the thickness of dried resin layer is 1-2 μ m.

Then, on both sides with the body material of overlapping 4 formation of low-k semicure impregnation material GXA-67N, the overlapping above-mentioned semicure impregnation material that has resin, make semicure impregnation material layer contact with body material this moment, while overlapping electrolytic copper foil on the resin layer in the outside, and these are carried out crimping under 230 ℃, 3.0MPa, 90 minutes pressurized conditions, thereby make two sides copper plate lamination.Make its glossy surface be contacted with resin layer when in addition, electrolytic copper foil being set.

In addition, as a comparative example 13, crimping does not have the electrolytic copper foil of resin (knitting layer) on the duplexer that the overlapping regulation number of above-mentioned semicure impregnation material is formed, and has made two sides copper plate lamination.

Copper Foil in the two sides copper plate lamination that will obtain is wide at 5mm by measuring, under the condition of 5cm/ minute respectively the stripping strength when 90 degree directions are peeled off (90 ° of stripping strengths are according to JIS

C6481), carry out the measurement of Copper Foil stripping strength (kN/m).In addition, also measured the two sides copper plate lamination that similarly obtains and in 121 ℃, the constant temperature and humidity cabinet of 100%RH, left standstill 2 hours Copper Foil tensile strengths after (PCT processing) with identical method.What obtain the results are shown in the table 5.

The stable on heating evaluation of＜scolding tin 〉

Above-mentioned each two sides copper plate lamination is cut into 5mm * 5mm size, again the Copper Foil on two sides is etched into only remaining its half area, with thus obtained material soaking in 260 ℃ solder bath 20 seconds.At this moment, with the naked eye confirm on the joint interface of Copper Foil and body material, whether to produce bubble.In addition, each two sides copper plate lamination after the PCT processing is also carried out same test.Observe not that bubble (bubbling) produces to be defined as the scolding tin thermotolerance outstanding and represent with zero, be defined as the also usefulness * expression of scolding tin poor heat resistance to what observe the bubble generation.What obtain the results are shown in the table 5.

(table 5)

Can judge by table 5, in the two sides copper plate lamination that the resin primer that uses embodiment 11-13 obtains,, also very good with the connectivity of body material even have the Copper Foil of smooth-flat-surface.In addition, the scolding tin thermotolerance of these two sides copper plate laminations is also outstanding.In addition, even the scolding tin thermotolerance also can keep good under hot and humid situation of preserving down as can be known.

The stable on heating evaluation of the scolding tin of＜internal layer knitting layer 〉

At first, obtain various two sides copper plate lamination in the same manner, remove the Copper Foil in this plywood and obtain inner plating with etching method then with above-mentioned (1) method.Then, on the single face of each inner plating, the material of the resin layer identical component that is exposed to the inner plating surface in the resin primer of natural curtain coating separate application and embodiment 11-13 and comparative example 10-12 (that is, the resin primer of identical type), drying is 10 minutes under 160 ℃.In addition, the thickness of the resin layer of being made up of dried resin primer (internal layer knitting layer) is 2-3 μ m.

Then, on the resin layer that is formed at the inner plating surface (internal layer knitting layer), an overlapping GEA-679 (Hitachi changes into industrial society system) as semicure impregnation material, then the duplexer that obtains is carried out crimping under 180 ℃, 70 minutes, the pressurized conditions of 2.5MPa, thereby obtain to be used to estimate the stable on heating duplexer of internal layer knitting layer.

In addition, as a comparative example 14, the electrolytic copper foil that crimping does not have a resin (knitting layer) on overlapping 4 body materials that form with GEA-679 forms two sides copper plate lamination, Copper Foil to this two sides copper plate lamination carries out etching then, stacked GEA-679 on a face is produced on the duplexer that carries out crimping under the above-mentioned pressurized conditions again.

These plywoods are cut into 5mm * 5mm size make scolding tin thermotolerance evaluation sample, when each sample that will obtain impregnated in 260 ℃ the solder bath 20 seconds, with the naked eye confirm on the interface between outer field semicure impregnation material (GEA-679) and the body material, whether to produce bubble.In addition, handle after 1 hour to PCT and each two sides copper plate lamination after 2 hours also carries out same test.Observe not that bubble produces to be defined as the scolding tin thermotolerance outstanding and represent with zero, be defined as the also usefulness * expression of scolding tin poor heat resistance to what observe the bubble generation.What obtain the results are shown in the table 6

(table 6)

Can confirm that by table 6 resin primer of embodiment 11-13 is even the scolding tin thermotolerance that also can play very well when being used as the knitting layer of internal layer in plywood.

The measurement of＜printing distributing board transmission loss 〉

By the resin primer that uses embodiment 11 is carried out etching with the Copper Foil in the two sides copper plate lamination of above-mentioned (3) method acquisition, obtained to possess the wiring board of linearity pattern conductor.On the conductor of this wiring board, the signal that transmission has 0.1-10GHz frequency is measured transmission loss at this moment.

In addition, except use Rz be 5.0 μ m as the Copper Foil, the wiring board that other obtains same as described abovely is measured transmission loss afterwards similarly to this.

Fig. 7 be expression when using these wiring boards, the transmission loss value is with respect to the curve of signal frequency.Among Fig. 7, the situation when solid line is represented to use Rz=2.0 μ m Copper Foil, the situation when dotted line is represented to use Rz=5.0 μ m Copper Foil.Can be confirmed that by Fig. 7 to use Rz be the wiring board that obtains of the Copper Foil of 2.0 μ m compares when using Rz to be the Copper Foil of 5.0 μ m, transmission loss is less.

The evaluation of＜fine pattern formation property 〉

With the various two sides copper plate lamination of the method acquisition of above-mentioned (1)-(3) and the two sides copper plate lamination of comparative example 13, carry out the evaluation that fine pattern forms property for the resin primer that uses embodiment 11-13 and comparative example 10-12.That is, at first, in each two sides copper plate lamination, to form on the Copper Foil of circuit, being undertaken overlapping by lamination as the NIT-215 of resist (Japanese synthetic chemistry society system, thick 15 μ m).Then, by exposure, develop to form have that L/S is respectively 20/20,30/30,50/50,75/75,100/100 comb type pattern remove erosion resisting coating (etching resist).Then, with ferric chloride in aqueous solution to Copper Foil do not need part to carry out etching after, peel off except that erosion resisting coating, thereby form comb type circuit pattern.With the top of observation by light microscope circuit in the circuit pattern that obtains at interval, bottom interval and have or not etch residue.

Its result, the two sides copper plate lamination that the resin primer of use embodiment 11-13 obtains can form the pattern of L/S=20/20 (μ m).In contrast, peeling off of conductive pattern when wanting to form this pattern, taken place in the two sides copper plate lamination that the resin primer of use comparative example 10-12 obtains and the two sides copper plate lamination of comparative example 13.Hence one can see that, according to the resin primer of embodiment 11-13, even have the conductor foil of fine pattern, also can fully engage with respect to substrate.

Industrial utilizability

According to the present invention, can provide and to engage the resin priming paint of the not too coarse conductor paper tinsel in insulator layer and surface with enough intensity, with conductor paper tinsel and the plywood of resin.

Claims (16)

1. resin primer that contains resin, wherein, in described resin, the quality that contains with this resin is that standard is counted the imide bond more than the 6 quality %,

Described resin contains polyamidoimide, and,

Described polyamidoimide has the structural unit with following chemical formula (5) expression,

2. resin primer as claimed in claim 1, wherein said resin contains the polyamidoimide that has siloxane structure on main chain, the content of all amide group that contain in described resin is defined as A weight %, when the content of all Siliciumatoms that contain in the described resin is defined as C weight %, satisfy with following formula (a) and (b):

3≤A≤11…(a)

1≤C≤16…(b)。

3. resin primer as claimed in claim 1 or 2, wherein contain resin, and described resin contains the polyamidoimide that has siloxane structure on main chain, with have functional group that can react and the reactive compounds that can have amide group and/or Siliciumatom with the amide group in this polyamidoimide, when the content of the amide group in the described polyamidoimide being defined as Pa weight %, the content of the amide group in the described reactive compounds is defined as Ea weight %, the content of the Siliciumatom in the described polymeric amide is defined as Pc weight %, when the content of the Siliciumatom in the described reactive compounds is defined as Ec weight %, described reactive compounds in the described resin is with respect to the weight part B of described polyamidoimide 100 weight parts, satisfies following formula (I) and (II):

3≤(Pa×100+Ea×B)/(100+B)≤11…(I)

1≤(Pc×100+Ec×B)/(100+B)≤16…(II)。

4. as claim 1 or 2 described resin primers, wherein said polyamidoimide is to make imide dicarboxylic acid and di-isocyanate reaction and the material that obtains, described imide dicarboxylic acid obtains by making diamine compound and trimellitic acid anhydride reactant, as described diamine compound, the compound that contains useful following general formula (6a), (6b) or (6c) represent

In the formula, R ⁶¹Expression hydrogen atom, hydroxyl, methoxyl group, methyl or halogenation methyl, R ⁶²Expression is with following general formula (7a), (7b), (7c) with the base of any one expression (7d), the alkylidene group of carbonatoms 1-3, halogenation alkylidene group, alkylsulfonyl, ether, carbonyl or the singly-bound of carbonatoms 1-3, R ⁶³The alkylidene group of expression carbonatoms 1-3, halogenation alkylidene group, alkylsulfonyl, ether or the carbonyl of carbonatoms 1-3,

Wherein, in the formula (7a), R ⁷The alkylidene group of expression carbonatoms 1-3, halogenation alkylidene group, alkylsulfonyl, ether, carbonyl or the singly-bound of carbonatoms 1-3 also have the R of a plurality of existence ⁶¹Can be the same or different each other.

5. resin primer as claimed in claim 4 wherein as described diamine compound, also comprises the compound with following general formula (8) expression,

In the formula, R ⁸¹Expression methylene radical, alkylsulfonyl, ether, carbonyl or singly-bound, R ⁸²And R ⁸³Represent hydrogen atom, alkyl, phenyl or substituted-phenyl independently of one another, m represents the integer of 1-50.

6. resin primer as claimed in claim 4 wherein as described vulcabond, contains aromatic diisocyanate.

7. resin primer as claimed in claim 1 wherein also contains the reactive compounds with the functional group that can react with the amide group of described polyamidoimide.

8. resin primer as claimed in claim 1 wherein also contains rubber constituent, and the content of this rubber constituent is that benchmark is counted more than the 40 quality % with the quality of described resin.

9. conductor foil that has resin, it has conductor foil and the resin layer that is arranged on this conductor foil, 10 mean roughness on described conductor foil surface are below the 3 μ m, and described resin layer forms by coating claim 1 or 2 described resin primers.

10. conductor foil that has resin, it has conductor foil and is arranged on resin layer on this conductor foil, and described conductor foil is a tinsel, and described resin layer is made of claim 1 or 2 described resin primers.

11. plywood, it is by heating duplexer and the acquisition of pressurizeing, and described duplexer has that claim 9 is described to be had the conductor foil of resin and be laminated in semicure impregnation material on the described resin layer in this conductor foil that has resin.

12. plywood, it is by heating duplexer and the acquisition of pressurizeing, and described duplexer has that claim 10 is described to be had the conductor foil of resin and be laminated in semicure impregnation material on the described resin layer in this conductor foil that has resin.

13. a plywood, its have conductor foil, with the insulation layer that contains resin of described conductor foil subtend setting and be arranged on described conductor foil and described insulation layer between and the resin layer that constitutes by the described resin primer of claim 1 that contacts with these.

14. plywood as claimed in claim 13,10 mean roughness on the surface that contacts with described resin layer at least in the wherein said conductor foil are below the 3 μ m.

15. the manufacture method of a plywood, wherein following duplexer is heated and pressurize, described duplexer has that claim 9 is described to be had the conductor foil of resin and be layered in semicure impregnation material on the described resin layer in this conductor foil that has resin.

16. the manufacture method of a plywood, wherein following duplexer is heated and pressurize, described duplexer has that claim 10 is described to be had the conductor foil of resin and be layered in semicure impregnation material on the described resin layer in this conductor foil that has resin.

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