CN101432134A - Conductor foil with adhesive layer, conductor-clad laminate, printed wiring board and multilayer wiring board - Google Patents

Abstract

Disclosed is a conductor foil with adhesive layer which enables to produce a printed wiring board having excellent heat resistance wherein transmission loss especially in high frequency band can be reduced and interlayer separation can be sufficiently suppressed. Also disclosed is a conductor-clad laminate. Specifically disclosed is a conductor foil with adhesive layer comprising a conductor foil and an adhesive layer formed on the conductor foil.The adhesive layer is composed of a curable resin composition containing a polyfunctional epoxy resin as a component (A), a polyfunctional phenol resin as a component (B), and a polyamideimide as a component (C). Also specifically disclosed is a conductor-clad laminate comprising an insulating layer, a conductor layer arranged opposite to the insulating layer, and an adhesive layer interposed between the insulating layer and the conductor layer. The adhesive layer is composed of a cured product of the resin composition containing the components (A), (B) and (C).

Description

Conductor foil, the plywood that posts conductor, printed wiring board and the multilayer circuit board of band adhesive linkage

Technical field

The present invention relates to the conductor foil with adhesive linkage, the plywood that posts conductor, printed wiring board and multilayer circuit board.

Background technology

Be in network associated electronic device such as the mobile communicating equipment of representative or its base station apparatus, server, router or the mainframe computer etc. with the portable phone, require the bulky information low-loss and transmit at high speed, handle.In order to tackle this requirement, in the printed wiring board that is carried in the aforesaid device, the high frequencyization of the handled signal of telecommunication constantly advances.But high frequency, requires to surpass degree reduction loss in the past therefore for the printed wiring board of the signal of telecommunication of handling high frequency with regard to the character of easy more decay because the signal of telecommunication has.

In order to obtain the printed wiring board of low transmission loss, in the past as the baseplate material of printed wiring board, use be the thermoplastic resin material that contains the low fluorine resin of relative dielectric constant or dielectric loss angle tangent.But this fluorine resin is because therefore melt viscosity height, mobile low in general need set high-temperature and high-pressure conditions etc. when drawing, and it is not necessarily easy to be shaped.In addition, as used printed wiring board material in the aforesaid communication equipment etc., except processability, also have dimensional stability, with the shortcoming of cementability deficiency of metal coating and so on.

So, attempted the replacement thermoplastic resin material, and used relative dielectric constant and the low hot curing resin composition of dielectric loss angle tangent.As used hot curing resin composition in the raw material of above-mentioned dielectric materials such as electronic equipment, for example known have a material shown in following.That is, in patent documentation 1～3, disclose the resin combination that contains triallylcyanurate or cyanacrylate.In addition, in patent documentation 1,2,4 or 5, disclose the resin combination that contains polybutadiene.In addition, in the patent documentation 6, disclose the Thermocurable polyphenylene oxide that contains the functional group who has been endowed radical crosslinkings such as pi-allyl and the resin combination of triallylcyanurate or cyanacrylate.In addition, in these patent documentations, show substantially,, then, therefore can realize the low transmission loss owing to after curing, do not contain a lot of polar groups if utilize above-mentioned hot curing resin composition.

In addition, in printed wiring board, the best cementability height of insulating barrier and conductor layer provided thereon.If the cementability of insulating barrier and conductor layer is low, not good situations such as both peeling off then just appear producing in use easily.Printed wiring board mostly is by the conductor foil of the plywood that posts conductor of stacked conductor foil on insulating barrier is processed and forms, yet in order to obtain the good cementability of insulating barrier and conductor layer, this cementability height that posts the insulating barrier of plywood of conductor and conductor foil is also very important.

Based on this kind viewpoint, known have with the pre-preg plate with the polybutadiene coating processing of having used by modifications such as epoxy radicals, maleic acid, carboxylic acids the metal-clad (with reference to patent documentation 7,8) of the stacked shaping of Copper Foil.In addition, also known (with reference to the patent documentations 9,10) such as printed wiring boards that has between insulating barrier and conductor layer folder establish to contain the layer of epoxy compounds or polyamidoimide compound.In addition, also proposed between Copper Foil and insulating barrier, to dispose the method (with reference to patent documentation 11) of the bonding elastomer layers of promotion such as ethene-propylene elastomeric.

Patent documentation 1: special fair 6-No. 69746 communiques of Japan

Patent documentation 2: special fair 7-No. 47689 communiques of Japan

Patent documentation 3: 2002-No. 265777 communiques of TOHKEMY

Patent documentation 4: 58-No. 21925 communiques of Japanese Patent Publication

Patent documentation 5: 10-No. 117052 communiques of Japanese kokai publication hei

Patent documentation 6: special fair 6-No. 92533 communiques of Japan

Patent documentation 7: 54-No. 74883 communiques of Japanese kokai publication sho

Patent documentation 8: 55-No. 86744 communiques of Japanese kokai publication sho

Patent documentation 9: 2005-No. 167172 communiques of TOHKEMY

Patent documentation 10: 2005-No. 167173 communiques of TOHKEMY

Patent documentation 11: 2005-No. 502192 communiques of TOHKEMY

But in recent years, for aforesaid electronic equipment etc., requirement can be tackled the further high frequencyization of the signal of telecommunication.But, if just low-k that for example will be described in above-mentioned patent documentation 1～6, the resin of low-dielectric loss angle tangent are used for dielectric material, realize the low transmission lossization of the signal of telecommunication of insulating barrier (dielectric layer), then be difficult to tackle fully this kind high frequency.Promptly, the loss (dielectric loss) that the reason of the loss of the signal of telecommunication is to be caused by insulating barrier, loss (conductor losses) two aspects that cause by conductor layer, and in the reply to high frequencyization in recent years, not only need to utilize the improvement of the dielectric material as in the past to reduce dielectric loss, also need to reduce conductor losses.

Particularly, in recent years in the most printed wiring board (multilayer circuit board) of practicability,, reach below the 200 μ m as the thickness attenuation of the insulating barrier between signals layer that is disposed at conductor layer and the bottom.Thus, adopted in the material of insulating barrier under the situation of resin of the low-k that has to a certain degree or dielectric loss angle tangent, as the loss of this wiring board integral body, compared with dielectric loss, conductor losses one side is conclusive.

Here, as the method for the minimizing that realizes conductor losses, can enumerate that use conductor layer (the roughening treated side below is called " M " face with the face bonding side of insulating barrier.) the method for the little conductor foil of concave-convex surface.Specifically, can consider to use surface roughness (10 mean roughness: Rz) be 4 μ m, be preferably the following conductor foil of 2 μ m (following this kind conductor foil is called " low roughening paper tinsel " especially that possess the M face.) the plywood that posts conductor.

So, based on above-mentioned opinion, the inventor etc. at first made the polymerization that utilizes vinyl or pi-allyl etc. that will be described in patent documentation 1～6 and the resin of the low-k that solidifies and low-dielectric loss angle tangent and above-mentioned low roughening paper tinsel and with and printed wiring board, at length study.Consequently, this kind printed wiring board is because the polarity of insulating barrier is low, and low, so a little less than the bonding force between insulating barrier and the conductor layer (engaging force), can confirm between these layers, to be easy to produce to peel off by the concavo-convex grappling effect that causes of the M face of conductor foil.Particularly, in the printed wiring board heating (in particularly heating after moisture absorption), this has peeled off the significantly tendency that becomes.Like this above-mentioned resin is being used under the situation of dielectric material, is distinguishing when adopting low roughening paper tinsel in order to reduce conductor losses, then be difficult to guarantee fully the cementability of insulating barrier and conductor layer.

In addition, using the method described in the patent documentation 7,8, with the Rz of insulating barrier and M be low roughening Copper Foil below the 2 μ m across modification polybutadiene fit, make under the situation of printed wiring board, distinguish that can't obtain sufficiently high Copper Foil draws stripping intensity, in addition, also can produce the reduction of hear resistance when moisture absorption (particularly hear resistance).

In addition, using the method described in the patent documentation 9,10, use is that the band adhesive linkage Copper Foil that has set in advance the polyamide-imide resin of thick 0.1～5 μ m on the surface of the low roughening Copper Foil below the 2 μ m is made under the situation of printed wiring board at the Rz of M face, and affirmation can obtain high Copper Foil and draw stripping intensity.But, because the concavo-convex grappling effect that causes by the M face of conductor foil is low, therefore the bonding force (engaging force) between polyamide-imide resin and the insulating barrier dies down, and for example distinguishes when heating to be easy to generate (when particularly heating) etc. and to peel off after moisture absorption between these layers.

In addition, use the method described in the patent documentation 11, use is that to have set in advance thickness on the surface of the low roughening Copper Foil below the 4 μ m be the band adhesive linkage Copper Foil that contains the bonding elastomer layers of elastomeric promotion such as styrene-butadiene elastomer of 3～15 μ m at the Rz of M face, has made printed wiring board.Under this situation, draw stripping intensity, yet have the tendency that the concavo-convex grappling effect that causes by the M face of conductor foil reduces irrelevantly though can obtain high Copper Foil.Consequently, the bonding force (engaging force) of folder between the insulating barrier that promotes bonding elastomer layer dies down, and distinguishes to be easy to generate between these layers when heating and peels off.

Summary of the invention

So Given this present invention plants situation and finish, its purpose is, a kind of conductor foil that can make the band adhesive linkage of following printed wiring board is provided, that is, can reduces the particularly loss of high-frequency region well, excellent heat resistance, and be difficult to produce peeling off of interlayer.The present invention also aims to, provide the conductor that uses this kind band adhesive linkage and the plywood that posts conductor, printed wiring board and the multilayer circuit board that obtains.

In order to reach above-mentioned purpose, the conductor foil of band adhesive linkage of the present invention is the conductor foil that possesses conductor foil, is located at the band adhesive linkage of the adhesive linkage on this conductor foil, it is characterized in that adhesive linkage is by containing (A) composition: polyfunctional epoxy resin, (B) composition: multifunctional phenolic resins and (C) composition: the hardening resin composition of polyamidoimide constitutes.

The conductor foil of band adhesive linkage of the present invention is that the hardening resin composition of above-mentioned by containing (A)～(C) composition constitutes.The solidfied material of this hardening resin composition is because because of curing becomes the solidfied material that contains polyfunctional epoxy resin and multifunctional phenolic resins and the material of polyamidoimide, therefore with low roughening paper tinsel or have aspect the cementability of insulating barrier of characteristic such as low-k very good.In addition, therefore the solidfied material of this hardening resin composition also has good hear resistance owing to be the solidfied material of above-mentioned three kinds of compositions.

So, when the conductor foil that uses this kind band adhesive linkage posts the manufacturing of the plywood of conductor or printed wiring board (printed circuit board) as described later, insulating barrier and conductor layer quilt are bonding securely across the solidfied material of the adhesive linkage of the conductor foil of band adhesive linkage of the present invention, thereby can prevent peeling off of they significantly.In addition, utilize the low-k that bonding cured layer has and the characteristic of low-dielectric loss angle tangent, can also realize significantly low transmission lossization.In addition, have benefited from the bonding cured layer of excellent heat resistance, can also obtain good hear resistance as a whole.And, in the following description, layer after will being solidified by the adhesive linkage that hardening resin composition constitutes is called " bonding cured layer ", to be called " insulating barrier " or " insulating resin layer " as the insulating barrier of the baseplate material of plywood that posts conductor or printed wiring board etc., and their differences will be come.

In the conductor foil of the band adhesive linkage of the invention described above, (C) to be preferably weight average molecular weight be the polyamidoimide below 300,000 more than 50,000 to composition.

If it is said, (C) composition (polyamidoimide) has the weight average molecular weight below 300,000 more than 50,000, then except stable on heating further raising, can also obtain to utilize that bonding cured layer obtains has more good adhesive strength with conductor foil or insulating barrier.Though it be unclear that for this essential factor, can consider reason as follows.That is,, then after curing, can form (A), (B) and (C) island structure of composition if utilize the adhesive linkage of the conductor foil of band adhesive linkage of the present invention.Can think specifically, form sea layer that the zone by (C) composition constitutes, by (A) and (B) the island layer that constitutes of the zone of composition.In bonding cured layer, utilize this kind island structure, good cementability, (A) that can bring into play (C) composition well reach (B) high-fire resistance two aspects of composition.In addition, be more than 50,000 particularly by the weight average molecular weight that makes (C) composition, just can clearly form above-mentioned island structure, and by being below 300,000, just can in adhesive linkage, keep the good flowability of (C) composition, so just can carry out bonding with conductor foil or insulating barrier well.Its structure is, the conductor foil of the band adhesive linkage of the application of the invention, can obtain very well bonding cured layer hear resistance and with the cementability of conductor foil etc.

In the conductor foil of the band adhesive linkage of the invention described above, preferably constitute adhesive linkage hardening resin composition (A) composition and (B) mixture of ingredients reach more than 150 ℃ in the vitrification point after the curing.By satisfying this kind condition, it is more good that the hear resistance of bonding cured layer will become, and the printed wiring board that uses the conductor foil of band adhesive linkage of the present invention to obtain also can have good hear resistance in the temperature range of practicality.And this vitrification point (Tg) can utilize differential scanning calorimetry (DSC) to measure according to JIS-K7121-1987.

In hardening resin composition, (A) composition is preferably from phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, the bromination phenol novolak type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, biphenyl type epoxy resin, the epoxy resin that contains the naphthalene skeleton, the epoxy resin that contains inferior aralkyl skeleton, the epoxy resin that contains biphenyl-inferior aralkyl skeleton, phenol salicylide phenolic resin varnish type epoxy resin, low alkyl group substituted phenol salicylide phenolic resin varnish type epoxy resin, the epoxy resin that contains the bicyclopentadiene skeleton, at least a polyfunctional epoxy resin of selecting in the group that multifunctional glycidyl group amine type epoxy resin and multifunctional alicyclic epoxy resin constitute.

In addition, preferably contain at least a multifunctional phenolic resins of from constitute, selecting as the multifunctional phenolic resins of (B) composition by the copoly type resin of aralkyl-type phenol resin, dicyclopentadiene-type phenolic resins, salicylide type phenolic resins, benzaldehyde type phenolic resins and aralkyl-type phenol resin and phenolic varnish type phenolic resins.

By with the combination of the composition outside among these polyfunctional epoxy resins or multifunctional phenolic resins and the present invention they, just can give good cementability or hear resistance to bonding cured layer.

In addition, the polyamidoimide for as (C) composition preferably contains the construction unit that is made of saturated hydrocarbons.When use contains the construction unit that is made of saturated hydrocarbons as polyamidoimide, then the cementability of conductor foil or insulating barrier etc. being improved, particularly when moisture absorption, also can keep good cementability except utilizing bonding cured layer.Consequently, even the printed wiring board that uses the conductor foil of band adhesive linkage of the present invention to obtain will have after moisture absorption the characteristic of peeling off that interlayer is given birth in also utmost point difficult labour.

In the hardening resin composition that constitutes adhesive linkage, reach (B) total 100 mass parts of composition with respect to (A) composition, (C) the cooperation ratio of composition is preferably 0.5～500 mass parts, more preferably 10～400 mass parts.If (C) the cooperation ratio of composition is in this scope, then except can obtaining good cementability, also have the toughness that improves bonding cured layer especially or the tendency of hear resistance, resistance to chemical reagents etc.

In addition, hardening resin composition preferably also contains cross-linked rubber particle and/or polyvinyl acetal resin as (D) composition.Utilize bonding cured layer and to the cementability of conductor foil etc. by also containing these compositions, can further improve.

Wherein, consider from the viewpoint that obtains above-mentioned characteristic especially well, as (D) composition, the preferred at least a cross-linked rubber particle of from the group that constitutes by the core shell particles of acrylonitrile butadiene rubber particle, carboxyl acid modified acrylonitrile butadiene rubber particle and butadiene rubber-acrylic resin, selecting.

In the conductor foil of band adhesive linkage of the present invention, adhesive linkage is by after forming the resin varnish layer on the surface of coating described conductor foil at the resin varnish that will contain hardening resin composition and solvent, removes described solvent and get from described resin varnish layer.So the adhesive linkage that forms becomes thickness or the uniform layer of characteristic, solidifies the back good cementability of performance and conductor foil etc. easily at it.

In addition, the adhesive linkage of the conductor foil of band adhesive linkage preferably has the thickness of 0.1～10 μ m, more preferably has the thickness of 0.1～5 μ m.If utilize adhesive linkage, then except can obtaining enough and cementability conductor foil, can also realize the minimizing of dielectric loss well with this kind thickness.

In addition, 10 mean roughness (Rz) of the face of the adhesive linkage side of conductor foil are preferably below the 4 μ m, more preferably below the 2 μ m.If the surface roughness of M face is very little as mentioned above, then the conductor losses of the conductor layer that is formed by this conductor foil will diminish, the printed wiring board that uses the conductor foil of band adhesive linkage of the present invention to obtain not only can reduce dielectric loss well, and can reduce conductor losses well.Here, so-called 10 mean roughness (Rz) are meant 10 mean roughness by JIS B0601-1994 definition.

In addition, the plywood that posts conductor of the present invention is characterised in that, get by following operation, described being operating as: on the one side at least of the insulative resin film that contains resin with insulating properties, so that the mode that the adhesive linkage of the conductor foil of band adhesive linkage contacts with it, the conductor foil of the band adhesive linkage of stacked the invention described above, obtain laminated body after, to heating of this laminated body and pressurization.

The plywood that posts conductor that so obtains has following formation, promptly, possess insulating barrier, be laminated in conductor layer on this insulating barrier across bonding cured layer, bonding cured layer and conductor layer are formed by the conductor foil of the band adhesive linkage of the invention described above, bonding cured layer is made of the solidfied material of the adhesive linkage of the conductor foil of band adhesive linkage, and conductor layer is made of the conductor foil of the conductor foil of band adhesive linkage.

Promptly, the plywood that posts conductor of the present invention also can be with following content as feature, promptly, possess insulating barrier, with the conductor layer of this insulating barrier subtend configuration, be insulated the bonding cured layer of layer and conductor layer clamping, bonding cured layer is by containing (A) composition: polyfunctional epoxy resin, (B) composition: multifunctional phenolic resins, (C) composition: the solidfied material of the resin combination of polyamide constitutes.

The layer (bonding cured layer) that constitutes of the solidfied material of the resin combination of composition is bonding because insulating barrier (insulating resin film) and conductor layer (conductor foil) are across above-mentioned by containing (A), (B) and (C) for the plywood that posts conductor of the invention described above, so the cementability of conductor layer and insulating barrier is good.So,, also be difficult to produce peeling off of interlayer even in conductor layer, used under the situation of low roughening paper tinsel.In addition, bonding cured layer has the characteristic of low-k and low-dielectric loss angle tangent.Consequently, post the printed wiring plate difficult labour that the plywood of conductor obtains by this class and give birth to peeling off of interlayer.

In the plywood that posts conductor of the present invention, preferably insulating barrier is made of insulative resin, the base material that is disposed in this insulative resin, as this base material, possess weaving cotton cloth or nonwoven of fiber that at least a material selected makes from the group that is made of glass, paper wood and organic high molecular compound.Like this, just can realize the inhibition of peeling off of the minimizing of loss, stable on heating raising and interlayer more reliably.

In addition, insulating barrier preferably contains the resin with ethene unsaturated bond as insulative resin.More particularly, insulative resin preferably contains at least a resin of selecting from the group that is made of polybutadiene, poly-triallylcyanurate, poly-cyanacrylate, the polyphenylene oxide that contains unsaturated group and maleimide compound.Therefore these resins can reduce dielectric loss significantly because dielectric constant is low and dielectric loss angle tangent is low.

Perhaps, insulative resin preferably contains at least a resin of selecting from the group that is made of polyphenylene oxide and thermoplastic elastomer (TPE).Therefore these resins can reduce dielectric loss significantly because dielectric constant is low and dielectric loss angle tangent is low.

Insulating barrier preferably has the ratio dielectric constant below 4.0 under 1GHz.If utilize the insulating barrier that satisfies this condition, then can reduce dielectric loss significantly.Consequently, the printed wiring board that is obtained by this plywood that posts conductor becomes the few printed wiring board of loss.

In addition, printed wiring board of the present invention is the material that can be suitable for use as printed wiring board, is to get by the conductor foil that posts the plywood of conductor of the present invention is processed into the circuit pattern with regulation.Even this printed wiring board is under the situation of using low roughening paper tinsel, also peeling off of the circuit pattern that is made of conductor foil and insulating resin layer given birth in utmost point difficult labour, in addition, because bonding cured layer has good hear resistance, therefore also has good hear resistance as a whole.

In addition, the present invention is by possessing the printed wiring board of the invention described above, can provide the multilayer circuit board of peeling off and having high-fire resistance that is difficult to produce interlayer.Promptly, multilayer circuit board of the present invention is to possess: have the core substrate of one deck printed wiring board at least, the one side at least that is disposed at this core substrate goes up and have the multilayer circuit board of the outer-layer circuit plate of one deck printed wiring board at least, it is characterized in that the one deck at least in the printed wiring board of core substrate is a printed wiring board of the present invention.

And, in the aforesaid printed wiring board that is applicable to the reply high frequency in the electronic equipment, not only require to realize the low transmission lossization, but also require good impedance Control.In order to realize this point, when the manufacturing of printed wiring board, the precision that improves the good pattern width that is used to form conductor layer is just very important.Here, under the situation of the little conductor foil of the surface roughness of using slim (low profile) paper tinsel and so on, have that the precision of pair conductive pattern in forming improves, the further favourable tendency of precise patternization.

Under this kind situation, if utilize the conductor foil of the band adhesive linkage of the invention described above, even then using low roughening paper tinsel, and in insulating barrier, use under the situation of insulative resin material, also can obtain the enough cementabilities between insulating barrier and the conductor foil with low-k and low-dielectric loss angle tangent.So,, then not only can realize the low transmission lossization, but also can realize good impedance Control if utilize the printed wiring board etc. of the conductor foil used band adhesive linkage of the present invention.

For the conductor foil that utilizes band adhesive linkage of the present invention, can obtain the essential factor of aforesaid good cementability, though still be not clear fully now, the inventor etc. have carried out supposition as follows.For example, under the situation of using low roughening paper tinsel as conductor foil, this low roughening paper tinsel reduces the cementability of insulating barrier etc., in addition, when the plywood that posts conductor that has this low roughening paper tinsel in use carries out multiple stratification, also have the situation about peeling off that is easy to generate interlayer.Promptly, be after the conductor foil of the plywood that posts conductor of the low roughening paper tinsel below the 4 μ m is removed by will be on the two sides of the insulating resin layer stacked Rz of M face, on its face, stack gradually prepreg and conductor foil is made multilayer laminate, and then make under the situation of printed wiring board, also very little by low roughening paper tinsel to the roughness of the insulating resin layer transfer printing of internal layer.

In the multilayer laminate that so obtains, with regard to the plywood that posts conductor, owing to compare with the situation of having used general Copper Foil (Rz is more than the 6 μ m), grappling effect between insulating resin layer and the prepreg diminishes, so the bonding force between insulating resin layer and the prepreg (engaging force) will diminish therefrom.Therefore, as its result, the conductor foil that is disposed at the surface of prepreg just is easy to peel off with insulating resin layer.Particularly carrying out heating under the situation of (especially heating after the moisture absorption), this kind tendency is fairly obvious.

In such cases, as the plywood that posts conductor, the plywood by the conductor foil that uses at the surperficial stacked band adhesive linkage of insulating resin layer gets just can reduce the reduction of aforesaid bonding force.That is, using this plywood that posts conductor to form under the situation of multilayer laminate, owing to be folded with the adhesive linkage of the conductor foil that derives from the band adhesive linkage between insulating resin layer and prepreg, therefore two-layer cementability is enhanced thus to a certain extent.

But under this situation, having adopted in adhesive linkage only is that for being used as printed wiring board, it is insufficient that hear resistance becomes under polyamidoimide or the situations such as resin material with polyamidoimide and epoxy resin combination.This can think because though these resin materials can show good cementability, owing to easy and water generates hydrogen bond etc., so the hear resistance after the moisture absorption is not very good.

Different with it, in the conductor foil of band adhesive linkage of the present invention, contained (A) and (B) composition is good aspect the hear resistance after the curing (the particularly hear resistance after the moisture absorption) in the adhesive linkage.So, use the conductor foil of this band adhesive linkage and the multilayer circuit board or the printed wiring board that obtain just have good hear resistance as a whole.In addition, because (A) and (B) composition is also good aspect the cementability of insulating resin layer or conductor foil, even therefore reduce the addition of the polyamidoimide of conduct (C) composition, bonding cured layer also can be kept enough cementabilities.In addition, as a rule, because polyamidoimide has the tendency of hear resistance (the particularly hear resistance after the moisture absorption) reduction that makes bonding cured layer, if therefore utilize the conductor foil of band adhesive linkage of the present invention, then be made as essential Min., also can realize stable on heating further raising by addition with polyamidoimide.

Utilize these essential factors, use the conductor foil of band adhesive linkage of the present invention or post the plywood of conductor and the printed wiring board that obtains or multilayer circuit board etc. because of between conductor layer (circuit pattern) and insulating barrier, having specific bonding cured layer, even thereby under the situation that possesses the few insulating barrier of level and smooth conductor layer of bonding plane and dielectric loss, the cementability of conductor layer and insulating barrier is also very good, and hear resistance is also very good.

According to the present invention, the conductor foil of the band adhesive linkage that can make following printed wiring board can be provided and post the plywood of conductor, that is, can reduce the loss in the high-frequency region particularly well, and be difficult to produce peeling off of interlayer.In addition, can also provide the conductor foil that uses this kind band adhesive linkage or post printed wiring board and the multilayer circuit board that the plywood of conductor obtains.

Description of drawings

Fig. 1 is the partial perspective view of the conductor foil of band adhesive linkage preferred embodiment.

Fig. 2 is the figure that the section of part of the plywood that posts conductor of expression first example constitutes.

Fig. 3 is the figure that the section of part of the plywood that posts conductor of expression second example constitutes.

Fig. 4 is the figure that the section of part of the printed wiring board of expression first example constitutes.

Fig. 5 is the figure that the section of part of the printed wiring board of expression second example constitutes.

Fig. 6 schematically shows the figure that the section of part of the multilayer circuit board of first example constitutes.

Fig. 7 schematically shows the figure that the section of part of the multilayer circuit board of second example constitutes.

Wherein, 10 ... conductor foil, 11 ... circuit pattern, 12 ... the M face, 20 ... adhesive linkage, 22 ... insulating barrier, 24 ... bonding cured layer, 26 ... conductor layer, 30 ... bonding cured layer, 32 ... insulating barrier, 34 ... bonding cured layer, 36 ... circuit pattern, 40 ... insulating resin layer, 50 ... insulating barrier, 60 ... the plating overlay film, 62 ... insulating barrier, 64 ... bonding cured layer, 66 ... the internal layer circuit pattern, 68 ... interlayer insulating film, 70 ... through hole (through hole), 72 ... the outer circuit pattern, 74 ... mesoporous (via hole), 76 ... through hole, 80 ... core substrate, 90 ... bonding cured layer, 92 ... insulating resin layer, 94 ... the plating overlay film, 96 ... through hole, 100 ... the conductor foil of band adhesive linkage, 110 ... the outer circuit pattern, 200 ... post the plywood of conductor, 300 ... post the plywood of conductor, 400 ... printed wiring board, 500 ... printed wiring board, 510 ... core substrate, 600 ... multilayer circuit board, 700 ... multilayer circuit board.

The specific embodiment

In the time of below as required with reference to accompanying drawing, preferred embodiment be elaborated to of the present invention.Need to prove that among the figure, use same-sign for identical element, the repetitive description thereof will be omitted.In addition, wait short of the particularly pointing out of position relation up and down, just be based on the position relation shown in the figure.In addition, the dimensional ratios of accompanying drawing is not limited to illustrated ratio.

[conductor foil of band adhesive linkage]

At first, the conductor foil to preferred embodiment band adhesive linkage describes.Fig. 1 is the partial perspective view of the conductor foil of band adhesive linkage preferred embodiment.The adhesive linkage 20 that constituting of band adhesive linkage conductor foil 100 shown in Figure 1 possess conductor foil 10, form with the roughening treated side (M face) 12 of this conductor foil 10 with joining.

(conductor foil)

As conductor foil 10,, just be not particularly limited so long as be applicable to material in the conductor layer of in the past printed wiring board etc.As conductor foil, for example can use metal formings such as Copper Foil, nickel foil, aluminium foil.Wherein, preferred electrolytic copper foil or rolled copper foil.In addition, consider that the preferred screen layer of implementing to utilize nickel, tin, zinc, chromium, molybdenum, cobalt etc. forms to be handled from the viewpoint of the rust-preventing characteristic that improves conductor foil 10, resistance to chemical reagents, hear resistance etc.In addition, consider, preferably implement the surface treatments such as processing that silane coupler was handled or utilized to surface roughening from the raising and the viewpoint of the cementability of insulating barrier.

In the middle of these surface treatments, with regard to surface roughening is handled, preferably implement roughening as follows and handle, that is, the surface roughness of M face 12 (Rz) is preferably below the 4 μ m, more preferably below the 2 μ m.The tendency that can further improve the high-frequency transmission characteristic like this, is just arranged.In addition, as used silane coupler in the silane coupler processing, be not particularly limited, yet can enumerate epoxy radicals silicone hydride, amino silane, cationic silane, vinyl silanes, acryloyl-oxy base silane, methacryloxy silane, urea groups silane, hydrosulphonyl silane, sulfide silane, isocynate silane etc.

Conductor foil 10 both can be the single layer structure that is made of a kind of metal material, also can be the single layer structure that is made of multiple metal material, can also be with the metal level of unlike material stacked the stepped construction of multilayer.In addition, the thickness of conductor foil 10 is not particularly limited.In the above-mentioned conductor foil 10, for example on market, can buy F1-WS (Furukawa CIRCUIT FOIL corporate system as Copper Foil, trade name, Rz=1.9 μ m), F2-WS (Furukawa CIRCUIT FOIL corporate system, trade name, Rz=2.0 μ m), F0-WS (Furukawa CIRCUIT FOIL corporate system, trade name, Rz=1.0 μ m), HLP (day ore deposit metal company system, trade name, Rz=0.7 μ m), T9-SV (paper tinsel powder industrial group of FUKUDA METAL system, Rz=1.8 μ m) etc., they all are suitable.

(adhesive linkage)

The adhesive linkage 20 of conductor foil 100 of band adhesive linkage is by containing (A) composition: polyfunctional epoxy resin, (B) composition: multifunctional phenolic resins and (C) composition: the layer that the hardening resin composition of polyamidoimide constitutes.The thickness of this adhesive linkage 20 is preferably 0.1～10 μ m, more preferably 0.1～5 μ m.If this thickness is less than 0.1 μ m, then in the plywood that posts conductor described later, have the tendency of drawing stripping intensity that is difficult to obtain enough conductor foils (conductor layer) etc.On the other hand, if surpass 10 μ m, then have the tendency of the high-frequency transmission characteristic reduction of the plywood that posts conductor.Below each composition of the hardening resin composition that constitutes adhesive linkage 20 is described.

At first, (A) composition is described.

Polyfunctional epoxy resin as (A) composition is the compound that has a plurality of epoxy radicals in a molecule, is the compound that is in the state of a plurality of molecules of reaction bonded that can utilize between the epoxy radicals.As this kind (A) composition, for example can enumerate phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, the bromination phenol novolak type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, biphenyl type epoxy resin, the epoxy resin that contains the naphthalene skeleton, the epoxy resin that contains inferior aralkyl skeleton, the epoxy resin that contains biphenyl-inferior aralkyl skeleton, phenol salicylide phenolic resin varnish type epoxy resin, low alkyl group substituted phenol salicylide phenolic resin varnish type epoxy resin, the epoxy resin that contains the bicyclopentadiene skeleton, multifunctional glycidyl group amine type epoxy resin and multifunctional alicyclic epoxy resin etc.As (A) composition, both can contain a kind of in them separately, also can make up contain two or more.

Wherein, as (A) composition, preferred cresols phenolic resin varnish type epoxy resin, biphenyl type epoxy resin or phenol novolak type epoxy resin.By containing these polyfunctional epoxy resins, just can obtain the good cementability and the electrical characteristic of the solidfied material (bonding cured layer) of adhesive linkage 20 at an easy rate as (A) composition.

Below, (B) composition is described.

Multifunctional phenolic compound as (B) composition is the compound that has a plurality of phenol hydroxyls in a molecule, plays a role as the curing agent of the polyfunctional epoxy resin that belongs to (A) composition.As this kind (B) composition, can enumerate copoly type resin, phenolic varnish type phenolic resins of aralkyl-type phenol resin, dicyclopentadiene-type phenolic resins, salicylide type phenolic resins, benzaldehyde type phenolic resins and aralkyl-type phenol resin etc.As (B) composition, just these compounds can be contained individually, also can make up contain two or more.

Above-mentioned (A) composition and (B) composition preferred so that their are mixed the curing of mixture after the mode that reaches more than 150 ℃ of vitrification point select.By making (A) composition and (B) solidfied material of mixture of ingredients satisfy this kind condition, the hear resistance after the moisture absorption of the bonding cured layer that obtains after the curing just has the tendency of raising.Consequently, use the conductor foil 100 of band adhesive linkage and printing (printed) wiring board that obtains also can have good hear resistance in the temperature range of practicality.

Below, (C) composition is described.

Polyamidoimide as (C) composition is the polymer with the repetitive that comprises amide structure and imide structure.(C) composition of present embodiment preferably has the weight average molecular weight below 300,000 more than 20,000 (following table is shown " Mw "), more preferably has the Mw below 300,000 more than 50,000, further preferably has the Mw below 250,000 more than 50,000.Here, in Mw, can use following value, that is, utilize gel permeation chromatography to measure, the value that the lubber-line made from the use polystyrene standard converts.

If (C) molecular weight of composition is less than 20,000, then contain the hardening resin composition of this (C) composition and in the conductor foil of the band adhesive linkage that obtains in use, and then in the printed wiring board that obtains at the conductor foil that uses this band adhesive linkage, the cementability of bonding cured layer and conductor foil (conductor layer) just has the tendency that reduces irrelevantly.Especially under the situation of the thickness that has reduced conductor foil, it is more obvious that this tendency becomes.On the other hand, because molecular weight surpasses 300,000, the flowability of polyamidoimide will variation, and therefore the cementability of bonding cured layer and conductor foil (conductor layer) just has the tendency of reduction.Similarly, when the thickness attenuation of conductor foil, it is obvious that this tendency also can become.

(C) composition preferably contains the construction unit that is made of saturated hydrocarbons in its molecule.By making (C) composition contain saturated hydrocarbons, the cementability to conductor foil etc. that utilizes bonding cured layer to obtain will become good.In addition, because (C) moisture-proof of composition improves, can also keep the cementability of the bonding cured layer after the moisture absorption well.Consequently, use present embodiment the band adhesive linkage conductor foil 100 and the moisture-proof hear resistance of the printed wiring board that obtains etc. improves.(C) composition is particularly preferably in having the construction unit that is made of saturated hydrocarbons in the main chain.

The construction unit that should be made of saturated hydrocarbons is preferably saturated fat ring type alkyl especially.Under situation with saturated fat ring type alkyl, the cementability during except the moisture absorption of bonding cured layer become good especially, this bonding cured layer also can have very high Tg, the hear resistance that possesses its printed wiring board etc. further improves.In addition, the Mw of (C) composition be more than 20,000, in particular for the situation more than 50,000 under, have the tendency that can stably obtain aforesaid effect.

In addition, (C) composition more preferably contains siloxane structure in its main chain.The so-called siloxane structure construction unit that to be the substituent silicon atom that will have a regulation alternatively combine repeatedly with oxygen atom.By making (C) composition in main chain, contain siloxane structure, characteristics such as the elastic modelling quantity of the bonding cured layer after adhesive linkage 20 solidifies or flexibility will improve, can improve the durability of the printed wiring board etc. of gained, in addition, the drying efficiency of hardening resin composition becomes well, thereby the tendency of easy formation adhesive linkage 20 is arranged.

As the polyamidoimide that belongs to (C) composition, for example can enumerate the synthetic polyamidoimide of so-called isocyanates method with the reaction that utilizes trimellitic anhydride and aromatic diisocyanate.Concrete example as this isocyanates method, can enumerate following method (for example method described in 04-No. 182466 communiques of Japanese kokai publication hei) etc., promptly, after reaction under the state that diamine compound exists superfluously, vulcabond is reacted at the diamine compound that makes the aromatic tricarboxylic acids acid anhydride and have ehter bond with it.

In addition, (C) composition that contains siloxane structure in main chain also can synthesize according to the isocyanates method.As concrete synthetic method, for example can enumerate: the method (for example method described in 05-No. 009254 communique of Japanese kokai publication hei) that makes aromatic tricarboxylic acids acid anhydride, aromatic diisocyanate and the polycondensation of siloxane diamine compound; Make the method (for example method described in 06-No. 116517 communiques of Japanese kokai publication hei) of aromatic dicarboxylic acid or aromatic tricarboxylic acids and the polycondensation of siloxane diamine compound; Make and contain the diamine compound with 3 above aromatic rings and the mixture and the trimellitic acid anhydride reactant of siloxane diamine, make the mixture of the imidodicarbonic diamide dicarboxylic acids that contains gained and the method (for example method described in 06-No. 116517 communiques of Japanese kokai publication hei) of aromatic diisocyanate reaction etc.If utilize the hardening resin composition of the present embodiment that constitutes adhesive linkage 20, then use with synthetic (C) composition of these known method, also can obtain sufficiently high conductor foil and draw stripping intensity.

Below, be elaborated as the manufacture method of the polyamidoimide that in main chain, has the construction unit (especially saturated fat ring type alkyl) that constitutes by saturated hydrocarbons of (C) composition to being suitable for.

This kind polyamidoimide for example can obtain by following operation, promptly, make diamine compound and trimellitic acid anhydride reactant with saturated hydrocarbyl, the dicarboxylic acids that contains imide that makes gained derive become sour halide after, perhaps use condensing agent and diamine compound the reaction.Perhaps, also can obtain, that is, make diamine compound and trimellitic acid anhydride reactant, make the dicarboxylic acids reaction that contains imide of vulcabond and gained with saturated hydrocarbyl by following operation.And the polyamidoimide with saturated fat ring type alkyl can obtain by following operation, that is, in these methods, the diamine compound that will have saturated fat ring type alkyl as saturated hydrocarbyl uses as raw material.

As diamine compound with saturated hydrocarbyl, specifically, can enumerate with following general formula (1a) or (1b) expression compound.

[changing 1]

Here, during formula (1a) reaches (1b), L ¹The expression carbon number that also can be replaced by halogen is the aliphatic alkyl, sulfonyl, oxygen base, carbonyl, singly-bound of 1～3 divalent or with the following formula (2a) or (2b) group of the divalent of expression, L ²The expression carbon number that also can be replaced by halogen is aliphatic alkyl, sulfonyl, oxygen base or the carbonyl of 1～3 divalent, R ⁵, R ⁶And R ⁷Represent hydrogen atom, hydroxyl, methoxyl group, the methyl that also can be replaced by halogen independently of one another.

[changing 2]

Wherein, in the formula (2a), L ³The expression carbon number that also can be replaced by halogen is aliphatic alkyl, sulfonyl, oxygen base, carbonyl or the singly-bound of 1～3 divalent.

As with the above-mentioned formula (1a) or (1b) diamine compound with saturated hydrocarbyl of expression, specifically, can compound as follows be shown example.Promptly; for example can example illustrate 2; 2-two [4-(4-aminocyclohexyl oxygen base) cyclohexyl] propane; two [4-(3-aminocyclohexyl oxygen base) cyclohexyl] sulfone; two [4-(4-aminocyclohexyl oxygen base) cyclohexyl] sulfone; 2; 2-two [4-(4-aminocyclohexyl oxygen base) cyclohexyl] HFC-236fas; two [4-(4-aminocyclohexyl oxygen base) cyclohexyl] methane; 4; 4 '-two (4-aminocyclohexyl oxygen base) bicyclohexane; two [4-(4-aminocyclohexyl oxygen base) cyclohexyl] ether; two [4-(4-aminocyclohexyl oxygen base) cyclohexyl] ketone; 1; 3-two (4-aminocyclohexyl oxygen base) benzene; 1; 4-two (4-aminocyclohexyl oxygen base) benzene; 2; 2 '-dimethyl dicyclohexyl-4; 4 '-diamines; 2; 2 '-two (trifluoromethyl) dicyclohexyl-4; 4 '-diamines; 2; 6; 2 '; 6 '-tetramethyl-4; 4 '-diamines; 5; 5 '-dimethyl-2; 2 '-sulfonyl dicyclohexyl-4; 4 '-diamines; 3; 3 '-dihydroxy dicyclohexyl-4; 4 '-diamines; (4; 4 '-diaminourea) dicyclohexyl ether; (4; 4 '-diaminourea) dicyclohexyl sulfone; (4; 4 '-diaminourea cyclohexyl ketone) ketone; (3; 3 '-diaminourea) benzophenone; (4; 4 '-diaminourea) dicyclohexyl methyl hydride; (4; 4 '-diaminourea) dicyclohexyl ether; (3; 3 '-diaminourea) dicyclohexyl ether; (4; 4 '-diaminourea) dicyclohexyl methyl hydride; (3; 3 '-diaminourea) dicyclohexyl ether; 2,2-two (4-aminocyclohexyl) propane etc.Diamine compound both can use a kind of in these compounds individually, also can be used in combination two or more.And, in the manufacturing of the polyamidoimide of present embodiment, as described later, can promptly not have the diamine compound of saturated hydrocarbyl also with other diamine compound yet.

Diamine compound with saturated hydrocarbyl for example can easily obtain its aromatic rings hydrogenating reduction by the aromatic diamine compound to aromatic rings with structure corresponding with saturated hydrocarbyl.As this kind aromatic diamine compound, for example can example illustrate 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane (below be expressed as " 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-236fas; 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 (4-amino-benzene oxygen) benzene; 2; 2 '-dimethyl diphenyl base-4; 4 '-diamines; 2; 2 '-two (trifluoromethyl) xenyl-4; 4 '-diamines; 2; 6; 2 '; 6 '-tetramethyl-4; 4 '-diamines; 5; 5 '-dimethyl-2; 2 '-sulfonyl xenyl-4; 4 '-diamines; 3; 3 '-dihydroxybiphenyl base-4; 4 '-diamines; (4; 4 '-diaminourea) diphenyl ether; (4; 4 '-diaminourea) diphenyl sulfone; (4; 4 '-diaminourea) benzophenone; (3; 3 '-diaminourea) benzophenone; (4; 4 '-diaminourea) diphenyl methane; (4; 4 '-diaminourea) diphenyl ether; (3,3 '-diaminourea) diphenyl ether etc.

The hydrogenating reduction of aromatic diamine compound can utilize the general method of reducing of aromatic rings to carry out.As this method of reducing, for example can enumerate and draw Buddhist nun's Raney nickel or platinum-oxide catalyst (D.Varech etc., Tetrahedron Letter, 26,61 (1985); R.H.Baker etc., J.Am.Chem.Soc., 69,1250 (1947)), rhodium-aluminium oxide catalyst (J.C.Sircar etc., J.Org.Chem., 30,3206 (1965); A.I.Meyers etc., Organic Synthesis CollectiveVolume VI, 371 (1988); A.W.Burgstahler, Organic Synthesis CollectiveVolume V, 591 (1973); A.J.Briggs, Synthesis, 1988,66), rhodium oxide-platinum-oxide catalyst (S.Nishimura, Bull.Chem.Soc.Jpn., 34,32 (1961); E.J.Corey etc., J.Am.Chem.Soc.101,1608 (1979)), support the rhodium catalyst (K.Chebaane etc. of charcoal, Bull.Soc.Chim.Fr., 1975,244), sodium borohydride-radium chloride series catalysts (P.G.Gassman etc., Organic Synthesis Collective Volume VI, 581 (1988); P.G.Gassman etc., Organic Synthesis Collective Volume VI, 601 (1988)) etc. the hydrogenating reduction under the existence of catalyst etc.

Be to use under the situation of the aforesaid material that has the diamine compound of saturated hydrocarbyl and obtain at polyamidoimide, in the main chain of polyamidoimide, will comprise the construction unit that constitutes by saturated hydrocarbyl as (C) composition.This kind polyamidoimide derives from the construction unit that is made of this saturated hydrocarbyl, and water absorption resistance or hydrophobicity are compared high with polyamidoimide in the past.In addition, if utilize the conductor foil 100 of the band adhesive linkage that in adhesive linkage 20, has used the hardening resin composition that comprises polyamidoimide with the construction unit that constitutes by saturated hydrocarbyl, then compare with the situation of for example having used the resin combination that comprises polyamidoimide with aromatic rings, when the plywood of conductor is posted in manufacturing, in the time of can suppressing its moisture absorption significantly and conductor foil (conductor layer) and insulating barrier etc. between the reduction of cementability.And, as diamine compound, to have used under the situation of diamine compound with ester ring type saturated hydrocarbyl with saturated hydrocarbyl, it is obvious especially that this kind effect will become.

As the polyamidoimide of (C) composition also can be the diamine compound beyond also having added the diamine compound with ester ring type saturated hydrocarbyl in its fabrication stage and the material that obtains.If so operation then can import the structure construction unit in addition that is made of saturated hydrocarbyl, the characteristic that easier acquisition is required in polyamidoimide.

As the diamine compound beyond the diamine compound with saturated hydrocarbyl, at first can enumerate compound with following general formula (3) expression.

[changing 3]

Here, in the formula (3), L ⁴Expression methylene, sulfonyl, oxo base, carbonyl or singly-bound, R ⁸And R ⁹Represent hydrogen atom, alkyl independently of one another or also can have substituent phenyl, k represents 1～50 integer.

In the diamine compound with above-mentioned formula (3) expression, best R ⁸And R ⁹Be 1～3 alkyl or also can have substituent phenyl for hydrogen atom, carbon number independently of one another.As the substituting group that also can combine with this phenyl, can example carbon number be shown is 1～3 alkyl, halogen atom etc.In diamine compound, consider L from the viewpoint that realizes low elastic modulus and high Tg simultaneously with general formula (3) expression ⁴Be preferably the oxygen base especially.As this kind diamine compound, specifically, can Jeffermine D-400, Jeffermine D-2000 (above is Suntechno Chemical corporate system, trade name) etc. be shown example.

In addition, as with the diamine compound of diamines combination with saturated hydrocarbyl, also preferably have the aromatic diamine of aromatic rings.As aromatic diamine, can enumerate direct compound on aromatic rings in conjunction with 2 amino; Aromatic rings more than 2 is directly or by specific group combination, is combined with amino compound respectively at least 2 in these aromatic rings, as long as have this kind structure, just is not particularly limited.

As aromatic diamine compound, for example preferably with following general formula (4a) or (4b) expression compound.

[changing 4]

During formula (4a) reaches (4b), L ⁵The expression carbon number that also can be replaced by halogen is the aliphatic alkyl, sulfonyl, oxygen base, carbonyl, singly-bound of 1～3 divalent or with the following formula (5a) or (5b) group of the divalent of expression, L ⁶The expression carbon number that also can be replaced by halogen is aliphatic alkyl, sulfonyl, oxygen base or the carbonyl of 1～3 divalent, R ¹⁰, R ¹¹And R ¹²Represent hydrogen atom, hydroxyl, methoxyl group, the methyl that also can be replaced by halogen independently of one another.In addition, in the following formula (5a), L ⁷The expression carbon number that also can be replaced by halogen is aliphatic alkyl, sulfonyl, oxygen base, carbonyl or the singly-bound of 1～3 divalent.

[changing 5]

As aromatic diamine; specifically; 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-236fas; 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 (4-amino-benzene oxygen) benzene; 2; 2 '-dimethyl diphenyl base-4; 4 '-diamines; 2; 2 '-two (trifluoromethyl) xenyl-4; 4 '-diamines; 2; 6; 2 '; 6 '-tetramethyl-4; 4 '-diamines; 5; 5 '-dimethyl-2; 2 '-sulfonyl xenyl-4; 4 '-diamines; 3; 3 '-dihydroxybiphenyl base-4; 4 '-diamines; (4; 4 '-diaminourea) diphenyl ether; (4; 4 '-diaminourea) diphenyl sulfone; (4; 4 '-diaminourea) benzophenone; (3; 3 '-diaminourea) benzophenone; (4; 4 '-diaminourea) diphenyl methane; (4; 4 '-diaminourea) diphenyl ether; (3,3 '-diaminourea) diphenyl ether etc.Aromatic diamine compound both can use a kind of in the above-mentioned compound separately, also can be used in combination two or more.

By also using these aromatic diamines, in polyamidoimide, except the construction unit that constitutes by saturated hydrocarbons, can also import aromatic ring structure.The hardening resin composition that contains this kind polyamidoimide can further improve the Tg of its solidfied material (and then being the cured layer of adhesive linkage), can be so that their hear resistance is more good.

In addition, as with the diamine compound of diamine compound with saturated hydrocarbyl and usefulness, preferably with the siloxane diamine of following general formula (6) expression.

[changing 6]

In the formula (6), R ¹³, R ¹⁴, R ¹⁵, R ¹⁶, R ¹⁷And R ¹⁸(below be expressed as " R ¹³～R ¹⁸" preferably carbon number is 1～3 alkyl or also can has substituent phenyl independently of one another.As the substituting group that also can combine with phenyl, preferred carbon number is 1～3 alkyl or halogen atom.In addition, R ¹⁹And R ²⁰Preferred independently of one another carbon number is 1～6 alkylidene or also can has substituent arlydene.As this arlydene, preferably also can have substituent phenylene or also can have substituent naphthylene.In addition, as the substituting group that also can combine with this arlydene, preferred carbon number is 1～3 alkyl or halogen atom.In addition, in the formula (6), a and b are respectively 1～15 integer.

As this kind siloxane diamine, preferred especially R ¹³～R ¹⁸Be the compound of methyl, that is, especially preferably have the compound that combines amino structure at two ends of dimethyl siloxane.And, as siloxane diamine, both can be used alone compound, also two or more compounds can be used in combination.

As siloxane diamine with above-mentioned general formula (6) expression, specifically, can be used as silicone oil X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1500), X-22-9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200) (above be chemical industry society of SHIN-ETSU HANTOTAI system, trade name), BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200) (above, Dow Corning Corporation's system: Toray Dowconing Silicone corporate system, trade name) etc. can buy on market.

By as diamine compound and with above-mentioned siloxane diamine, will become the compound that on main chain, has siloxane structure as the polyamidoimide of (C) composition.In addition, contain hardening resin composition that this kind have the polyamidoimide of siloxane structure and can form the solidfied material that expansion under the hot conditions etc. is given birth in the good and utmost point difficult labour of flexibility, can further improve the conductor foil 100 of the band adhesive linkage that uses present embodiment and the durability and the hear resistance of the printed wiring board that obtains etc.

In the manufacturing of polyamidoimide, at first,, prepare to contain the diamine compound of the diamine compound that has saturated hydrocarbyl at least as diamine compound with the construction unit that constitutes by saturated hydrocarbons.Then, make these diamine compounds and trimellitic acid anhydride reactant.At this moment, between carboxyl that amino, trimellitic anhydride had that diamine compound had or acid anhydride, produce reaction, generate amide groups.In this reaction, the reaction that especially preferably produces the acid anhydride of the amino of diamine compound and trimellitic anhydride.

This reaction preferably is dissolved or dispersed in diamine compound, trimellitic anhydride in the non-proton property polar solvent, carries out under 70～100 ℃.As non-proton property polar solvent, can N-methyl-2-pyrrolidones (NMP), γ-butyrolactone, N, N-dimethyl formamide, N, N-dimethyl acetamide, methyl-sulfoxide, sulfolane, cyclohexanone etc. be shown example.Wherein, preferred especially NMP.These non-proton property polar solvents both can be used alone, and also can be used in combination two or more.

Non-proton property polar solvent is with respect to the total quality of this non-proton property polar solvent, diamine compound and trimellitic anhydride, and solid constituent preferably reaches the amount of 10～70 quality %, more preferably reaches the amount of 20～60 quality %.Solid constituent in this solution is during less than 10 quality %, and the use amount of solvent will be too much, has in the industrial disadvantageous tendency that becomes.On the other hand, when surpassing 70 quality %, then the dissolubility of trimellitic anhydride reduces, and the tendency that is difficult to react is fully arranged.

Then, in above-mentioned reacted solution, interpolation can with the aromatic hydrocarbon of water azeotropic, 150～200 ℃ of down further reactions.Like this, between adjacent carboxyl and amide groups, will produce the dehydration closed-loop reaction, consequently, can obtain containing the diacid of imide.Here, as can with the aromatic hydrocarbon of water azeotropic, can toluene, benzene, dimethylbenzene, ethylbenzene etc. be shown example.Wherein, preferred toluene.Aromatic hydrocarbon is with respect to non-proton property polar solvent 100 mass parts, and preferred interpolation is equivalent to the amount of 10～50 mass parts.With respect to non-proton property polar solvent 100 mass parts under the situation less than 10 mass parts, what not only have water removes the effect inadequate tendency that becomes, but also the growing amount of the diacid that contains imide is reduced at the addition of this aromatic hydrocarbon.On the other hand, surpass 50 mass parts if be made as, then the reaction temperature of solution will reduce, thereby the tendency of the growing amount minimizing of the diacid that contains imide is arranged.

In the reaction of this dehydration closed-loop, because of the aromatic hydrocarbon in the solution also can distillate with water, thereby the aromatic hydrocarbon amount in the reaction solution of having is less than the situation of above-mentioned preferred range.So, for example also can promptly, water and aromatic hydrocarbon be distillated in the water and basis weight recipient of band cock by carrying out as inferior operation, after aromatic hydrocarbon is separated, in reaction solution, return, and the aromatic hydrocarbon amount in the reaction solution is remained certain proportion.And, after being preferably in dehydration closed-loop reaction and finishing, the temperature of solution remained about 150～200 ℃ and remove can with the aromatic hydrocarbon of water azeotropic.

The diacid that contains imide that utilizes reaction up to now to obtain for example becomes the compound that has with the structure of following general formula (7) expression.

[changing 7]

In the formula (7), L ⁸Expression is with the amino residue of having removed of the diamine compound of above-mentioned general formula (1a), (1b), (3), (4a), (4b) or (6) expression.Like this, as the diacid that contains imide, can obtain having the L of the structure corresponding with the diamine compound that uses as raw material ⁸All cpds.

As using the diacid that contains imide that so obtains to come the imido method of synthesizing polyamides, can enumerate method as follows.That is, at first,, can enumerate after deriving the aforesaid diacid that contains imide for sour halide, the method for itself and aforesaid diamine compound copolymerization as first method.

Contain the diacid of imide can utilization and the reaction of thionyl chloride or phosphorus trichloride, phosphorus pentachloride, dichloromethyl ether derive at an easy rate and be sour halide.The halide of the diacid that contains imide that so obtains in addition, can be under room temperature or heating condition at an easy rate with the diamine compound copolymerization.

As second method, can enumerate the method that the diacid that contains imide is made with aforesaid diamine compound copolymerization in the presence of condensing agent.In this reaction,, can use the general condensing agent that forms amido link as condensing agent.Wherein, preferably dicyclohexylcarbodiimide, DIC or N-ethyl-N '-3-dimethylaminopropyl carbodiimide is used individually, perhaps with they and N-HOSu NHS or 1-hydroxybenzotriazole and use.

As third party's method, can enumerate the diacid that contains imide and the method for di-isocyanate reaction of making.Under situation, set with the ratio of vulcabond is best as the diamine compound and the trimellitic anhydride of the raw material of the diacid that contains imide via this reaction as followsly.That is, (diamine compound: trimellitic anhydride: vulcabond) preferably reach 1.0:(2.0～2.2 with mol ratio calculating): the scope of (1.0～1.5) more preferably reaches 1.0:(2.0～2.2): the scope of (1.0～1.3).Be this kind mol ratio by adjusting, just can obtain HMW more and help the polyamidoimide of film formation.

As vulcabond used in third party's method, can the compound of representing with following general formula (8) be shown example.

[changing 8]

OCN—L ⁹—NCO (8)

In the formula (8), L ⁹Be to have the organic group of divalent of more than one aromatic rings or the aliphatic hydrocarbon groups of divalent.Especially preferably from by with the group of following formula (9a) expression, with group, methylene phenyl, naphthylene, the hexylidene and 2,2 of following formula (9b) expression, at least a group of selecting in the group that 4-trimethyl hexylidene constitutes.

[changing 9]

As vulcabond with above-mentioned general formula (8) expression, can enumerate aliphatic diisocyanate or aromatic diisocyanate, the preferred fragrance (cyclo) aliphatic diisocyanates is especially preferably with both and usefulness.As aromatic diisocyanate, can example illustrate 4,4 '-methyl diphenylene diisocyanate (MDI), 2,4-inferior cresyl vulcabond, 2,6-inferior cresyl vulcabond, naphthylene-1,5-vulcabond, 2,4-methylene phenyl dimer etc.Wherein, preferred especially MDI.By using MDI, can improve the flexibility of the polyamidoimide of gained, and reduce crystallinity as aromatic diisocyanate.Consequently, can improve film formation property of polyamidoimide.On the other hand, as aliphatic diisocyanate, can hexylidene diisocyanate, 2,2 be shown example, 4-trimethyl hexylidene diisocyanate, IPDI etc.

Under situation, preferably with respect to the aliphatic diisocyanate about aromatic diisocyanate 100 molar part interpolation 5～10 molar part with aromatic diisocyanate and aliphatic diisocyanate and usefulness.So just can further improve the hear resistance of the polyamidoimide of gained.

The diacid that contains imide in third party's method and the reaction of vulcabond can make it to react under 130～200 ℃ reaction temperature and carry out by add vulcabond in the solution of the diacid that contains imide.In addition, this reaction also can use base catalyst to carry out.Under this situation, preferably reaction temperature is made as 70～180 ℃, more preferably is made as 120～150 ℃.Because when in the presence of base catalyst, carrying out this reaction, with compare in the situation that does not have to react under the condition of base catalyst, can reaction be carried out, therefore can suppress the carrying out of the side reaction of the reaction and so between the vulcabond under the hot conditions.Consequently, can obtain the more polyamidoimide compound of HMW.

As base catalyst, can trialkylamines such as Trimethylamine, triethylamine, tripropylamine, three (2-ethylhexyl) amine, trioctylphosphine amine be shown example.Wherein, because triethylamine is the preferred base catalyst that can promote above-mentioned reaction, and is easy to remove in reacted system, therefore preferred especially.

The polyamidoimide that obtains as utilizing above-mentioned the whole bag of tricks for example can be enumerated the material that has with the construction unit of following general formula (10) expression.And, in the following formula (10), L ⁸And L ⁹With above-mentioned L ⁸And L ⁹Synonym.

[changing 10]

Hardening resin composition preferred embodiment is the composition that contains aforesaid (A)～(C) composition.In addition, in this kind hardening resin composition, preferably comprise (A)～(C) composition with the cooperation ratio that satisfies condition as follows.

At first, for the cooperation ratio of (B) composition in the hardening resin composition,, be preferably 0.5～200 mass parts, more preferably 10～150 mass parts with respect to (A) composition 100 mass parts.If (B) the cooperation ratio of composition is less than 0.5 mass parts,, have the toughness of bonding cured layer or the tendency that reduces with the cementability of conductor foil (conductor layer) then at the conductor foil 100 of band adhesive linkage or use in the printed wiring board that it obtains.On the other hand, if surpass 200 mass parts, then not only the Thermocurable of adhesive linkage 20 reduces, and because the reactivity reduction of bonding cured layer and insulating resin layer etc., therefore under the plywood that posts conductor or the situation of printed wiring board that have formed as described later, hear resistance, resistance to chemical reagents and the breakdown strength of the near interface of bonding cured layer itself or bonding cured layer and insulating resin layer etc. just might reduce.

In addition,, reach (B) total 100 mass parts of composition, preferably be made as 10～400 mass parts with respect to (A) composition for the cooperation ratio of (C) composition.If cooperation ratio that should (C) composition is less than 10 mass parts,, have the toughness of bonding cured layer or the tendency that reduces with the cementability of its conductor foil (conductor layer) then at the conductor foil 100 of band adhesive linkage or use it and in the printed wiring board that obtains.On the other hand, if surpass 400 mass parts, hear resistance, resistance to chemical reagents and the breakdown strength of the near interface of then bonding cured layer itself or bonding cured layer and insulating resin layer etc. just might reduce.

The hardening resin composition that constitutes adhesive linkage 20 also can also contain required composition as required except above-mentioned (A)～(C) composition.As the composition beyond (A)～(C) composition, at first, can enumerate to have and promote as the polyfunctional epoxy resin of (A) composition and curing accelerator as the catalyst for reaction function of the multifunctional phenolic resins of (B) composition.As curing accelerator, be not particularly limited, yet for example can enumerate amines, imidazolium compounds, organic phosphorus compound, alkali metal compound, alkali earth metallic compound, quaternary ammonium salt etc.As curing accelerator, both can be used alone, also can be used in combination two or more.

The cooperation ratio of the curing accelerator in the hardening resin composition preferably decides according to the cooperation ratio of (A) composition.Specifically, with respect to (A) composition 100 mass parts, preferably be made as 0.05～10 mass parts.If in this scope, cooperate curing accelerator, then can obtain (A) composition and (B) the good reaction speed of composition, and the hardening resin composition of adhesive linkage 20 can become more good aspect reactive and curing property.Consequently, the cured layer that is obtained by adhesive linkage 20 (bonding cured layer) will have more good resistance to chemical reagents, hear resistance or moisture-proof hear resistance.

In addition, as the composition beyond (A)～(C) composition, also can contain as (D1) cross-linked rubber particle of (D) composition and/or (D2) polyvinyl acetal resin.

At first, as (D) composition, especially preferably contain (D1) cross-linked rubber particle.As the cross-linked rubber particle, be preferably selected from least a in the core shell particles of acrylonitrile butadiene rubber particle, carboxyl acid modified acrylonitrile butadiene rubber particle, butadiene rubber-acrylic resin.

Here, so-called acrylonitrile butadiene rubber particle is with acrylonitrile and butadiene copolymer, and in the stage of copolymerization that it is crosslinked partly, makes emboliform material.In addition, carboxyl acid modified acrylonitrile butadiene rubber particle is by in above-mentioned copolymerization, carboxylic acid such as co-polypropylene acid simultaneously, methacrylic acid and material.In addition, the core shell particles of butadiene rubber-acrylic resin is the material that utilizes the polymerization of following two-stage to obtain, that is, utilize emulsion polymerization to make the polymerization of butadiene particle, adds monomers such as acrylate or acrylic acid then and continues polymerization.The size of these cross-linked rubber particles is calculated with an average grain diameter, preferably is made as 50nm～1 μ m.As the cross-linked rubber particle, both above-mentioned materials of interpolation that can be independent, also can make up add two or more.

More particularly, in the middle of this kind cross-linked rubber particle,, can enumerate the XER-91 of Japan Synthetic Rubber Co. Ltd's system as carboxyl acid modified acrylonitrile butadiene rubber particle.In addition, as the core shell particles of butadiene rubber-acrylic resin, can enumerate the EXL-2655 of Kureha Kagaku Kogyo K.K.'s system, the AC-3832 of Takede Chemical Industries Ltd.

In addition, as (D) composition, more preferably contain (D2) polyvinyl acetal resin.Particularly, when as (D) composition with (D1) cross-linked rubber particle, (D2) polyvinyl acetal resin and time spent, since utilize that bonding cured layer obtains to the drawing stripping intensity, the stripping intensity of drawing of the electroless plating behind the chemical roughening improved of conductor foil, therefore preferred especially.

As the polyvinyl acetal resin of (D2) composition, can enumerate Pioloform, polyvinyl acetal or as the carboxyl acid modified polyacetal resin of its carboxyl acid modified thing.As polyvinyl acetal resin, can use various resins, yet special preferred degree of polymerization is 1000～2500 resin with various amount of hydroxyl groups or acetyl base unit weight with being not particularly limited.If the degree of polymerization of polyvinyl acetal resin is this scope, then can guarantee the scolding tin hear resistance of bonding cured layer fully.In addition, contain the viscosity of the varnish of hardening resin composition, the property disposed can become good, make the manufacturing of conductor foil 20 of band adhesive linkage become to be easy to tendency thereby have.

Here the number-average degree of polymerization of said polyvinyl acetal resin for example can adopt by the value as number-average molecular weight (using the lubber-line of the polystyrene standard of (gel permeation chromatography) to measure) decision of the polyvinyl acetate of its raw material.And so-called carboxyl acid modified polyvinyl acetal resin is the carboxyl acid modified thing of above-mentioned polyvinyl acetal resin, preferably satisfies the condition identical with polyvinyl acetal resin.

As polyvinyl acetal resin, for example can enumerate commodity S by name-Lec BX-1, BX-2, BX-5, BX-55, BX-7, BH-3, BH-S, KS-3Z, KS-5, KS-5Z, KS-8, KS-23Z, commodity electrochemical Butyral 4000-2, the 5000A by name of electrochemical industry (strain) system, 6000C, the 6000EP etc. of ponding chemical industry (strain) system.As polyvinyl acetal resin, above-mentioned material can be used separately, it is two or more perhaps to mix use.

In hardening resin composition, reach (B) total 100 mass parts of composition with respect to (A) composition, preferably the cooperation ratio of (D) composition is made as the scope of 0.5～100 mass parts, more preferably be made as 1～50 mass parts.If (D) the cooperation ratio of composition is less than 0.5 mass parts,, have the tendency of the cementability reduction of the toughness of bonding cured layer or this bonding cured layer and conductor foil (conductor layer) then at the conductor foil 100 of band adhesive linkage or use in the printed wiring board that it obtains.On the other hand, if surpass 100 mass parts, hear resistance, resistance to chemical reagents and the breakdown strength of the near interface of then bonding cured layer itself or bonding cured layer and insulating resin layer etc. just might reduce.And, containing under the situation of multiple composition as (D) composition, preferably the total of each composition satisfies above-mentioned cooperation ratio.

In addition, hardening resin composition also can be according to required characteristic, contains various additives such as fire retardant, filler, coupling agent with the degree that can not make characteristic degradations such as the hear resistance that forms cured layer that the utilization in the printed wiring board etc. is made of adhesive linkage 20 and obtain, cementability, anti-hygroscopicity.

As fire retardant, be not particularly limited, however fire retardants such as preferred bromine system, phosphorus system, metal hydroxides.More particularly, as bromide fire retardant, can enumerate brominated epoxy resins such as brominated bisphenol a type epoxy resin, bromination phenol novolak type epoxy resin; HBB, pentabromotoluene, ethylenebis (penta-bromophenyl), ethylenebis tetrabromo phthalimide, 1,2-dibromo-4-(1,2-two bromoethyls) cyclohexane, tetrabromo cyclooctane, HBCD, two (tribromophenoxy) ethane, brominated polyphenylether, brominated Polystyrene, 2,4,6-three (tribromophenoxy)-1, bromination additive flame retardants such as 3,5-triazine; Tribromo phenyl maleimide, tribromo phenyl acrylate, tribromo-benzene ylmethyl acrylate, tetrabromobisphenol A type dimethylacrylate, pentabromobenzyl acrylate, brominated styrene etc. contain the bromination reaction type fire retardant of unsaturated double-bond etc.

In addition, as phosphorus flame retardant, can triphenyl, trimethylphenyl phosphate, three xylyl phosphates, tolyl diphenyl phosphoester, tolyl two-2,6-xylyl phosphate, the two fragrant family phosphates such as (diphenyl phosphoesters) of resorcinol be shown example; Phenyl-phosphonic acid divinyl ester, phenyl-phosphonic acid diallyl, the two phosphonate esters such as (1-butene esters) of phenyl-phosphonic acid; Diphenyl phosphonic acid phenylester, diphenyl phosphonic acid methyl esters, 9,10-dihydro-9-oxa--10-phospho hetero phenanthrene-phosphinates such as 10-oxide derivative; Phosphocreatine compounds such as two (2-pi-allyl phenoxy group) phosphocreatine, xylyl phosphocreatine; Phosphorus flame retardants such as melamine phosphate, melamine pyrophosphate, polyphosphoric acid melamine, polyphosphoric acid melam, ammonium polyphosphate, red phosphorus.In addition, can magnesium hydroxide or aluminium hydroxide etc. be shown example as metal hydroxide combustion inhibitor.These fire retardants can be used alone, and also can be used in combination multiple.

Under the situation of adding fire retardant, its cooperation ratio is not particularly limited, however with respect to (A) composition and (B) total of composition measure 100 mass parts, preferably be made as 5～150 mass parts, more preferably be made as 5～80 mass parts, further preferably be made as 5～60 mass parts.If the cooperation ratio of fire retardant, then has the anti-flammability of adhesive linkage 20 or the bonding cured layer inadequate tendency that becomes less than 5 mass parts.On the other hand, if surpass 100 mass parts, then have the tendency of the hear resistance reduction of bonding cured layer.

In addition, the filler as belonging to additive is not particularly limited, however preferred inorganic filler.As inorganic filler, for example can enumerate aluminium oxide, titanium oxide, mica, silica, beryllium oxide, barium titanate, potassium titanate, strontium titanates, calcium titanate, aluminium carbonate, magnesium hydroxide, aluminium hydroxide, alumina silicate, calcium carbonate, calcium silicates, magnesium silicate, silicon nitride, boron nitride, burn till clay, talcum, aluminium borate, aluminium borate, carborundum etc. such as clay.

These fillers both can be used alone, and also can be used in combination two or more.In addition, be not particularly limited for shape, the particle diameter of filler, particle diameter is preferably 0.01～50 μ m, more preferably 0.1～15 μ m.For the cooperation ratio of the filler in the hardening resin composition, for example with respect to (A) composition and (B) total of composition measure 100 mass parts, be preferably 1～1000 mass parts, more preferably 1～800 mass parts.

In addition,, be not particularly limited, yet for example can enumerate silane series coupling agent, titanate esters is coupling agent etc. as coupling agent.As silane series coupling agent, can the carbon functional silanes be shown example.Specifically, can enumerate 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group (methyl) dimethoxy silane, 2-(2,3-ethyoxyl cyclohexyl) ethyl trimethoxy silanes etc. and contain the silane of epoxy radicals; 3-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl (methyl) dimethoxy silane etc. contain amino silane; Cationic silane such as 3-(trimethoxysilyl) propyl group tetramethyl ammonium chlorides; VTESs etc. contain the silane of vinyl; 3-methacryloxypropyl trimethoxy silane etc. contain the silane of acryloyl group; 3-sulfydryl propyl trimethoxy etc. contains the silane of sulfydryl etc.On the other hand, be coupling agent as titanate esters, for example can enumerate phthalandione Arrcostabs such as titanium propanolate, butanols titanium.As these coupling agents, both can be used alone, also can be used in combination two or more.

The cooperation ratio of the coupling agent in the hardening resin composition is not particularly limited, however with respect to (A) composition and (B) total of composition measure 100 mass parts, be preferably 0.05～20 mass parts, more preferably 0.1～10 mass parts.

In addition, the hardening resin composition that contains each above-mentioned composition can be prepared by (A) composition, (B) composition, (C) composition and other adding ingredient being utilized known method cooperation, mixing.

[manufacture method of the conductor foil of band adhesive linkage]

Below, the preferred manufacture method of the conductor foil 100 of band adhesive linkage with above-mentioned formation is described.The conductor foil 100 of band adhesive linkage for example can obtain by following operation, promptly, at first, prepare above-mentioned hardening resin composition, with it directly or after will in solvent, dissolving or disperse the varnish of this resin combination to coat on the M face 12 of aforesaid conductor foil 10, carry out drying etc. and form adhesive linkage 20.At this moment, also can make hardening resin composition semi-solid preparation (B stageization).

The coating of hardening resin composition or its varnish can utilize known method to carry out, and for example can use to lick the machine of being coated with (kiss coater), roll coater (roll coater), knife type coater (commacoater), intaglio plate (gravure) coating machine and wait and carry out.In addition, drying can utilize following method to implement, that is, in heat drying stove etc., for example at 70～250 ℃, preferably under 100～200 ℃ temperature, carried out 1～30 minute, handles in preferred 3～15 minutes.For with hardening resin composition dissolving etc. and used under the situation of solvent, baking temperature preferably is made as more than the temperature that solvent can volatilize.

Used solvent when being used for hardening resin composition varnish is not particularly limited, yet for example can enumerate methyl alcohol, alcohols such as ethanol, butanols; Ethers such as ethyl cellosolve, butyl cellosolve, glycol monoethyl ether, carbitol, BC; Ketones such as acetone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone; Toluene, dimethylbenzene, mesitylene etc. are aromatic hydrocarbon based; Ester classes such as methoxy ethyl acetic acid esters, ethoxyethyl group acetic acid esters, butoxyethyl group acetic acid esters, ethyl acetate; N, N-dimethyl formamide, N, N-dimethyl acetamide, N-methyl-nitrogenous class equal solvents such as 2-pyrrolidones.In varnishization, solvent both can be used alone, and also can be used in combination two or more.

Under situation with the nitrogenous class in these solvents and ketone and usefulness, for their cooperation ratio,, preferably ketone is made as 1～500 mass parts with respect to nitrogenous class 100 mass parts, more preferably ketone is made as 3～300 mass parts, further preferably ketone is made as 5～250 mass parts.

In addition, in hardening resin composition varnishization, preferably quantity of solvent is adjusted to solid constituent (nonvolatile component) concentration that makes in the varnish and reaches 3～80 quality %.Under the situation of the conductor foil 100 of making the band adhesive linkage, by moderately regulating quantity of solvent, just be easy to adjust solid component concentration or varnish viscosity, thereby can obtain aforesaid adhesive linkage 20 with preferred thickness.

The conductor foil 100 of band adhesive linkage that can be by will having above-mentioned formation and forms the plywood that posts conductor etc. at an easy rate on this adhesive linkage 20 is laminated in insulating resin layer etc.In addition, the plywoods that post conductor that so obtain etc. are because bonding across the solidfied material (bonding cured layer) of adhesive linkage 20 with conductor foil 1 and insulating resin layer, even therefore for example in the material of insulating resin layer, adopted under the situation of low-k resins such as polybutadiene, triallylcyanurate, cyanacrylate, functionalized polyphenylene ether, also can embody and good conductor (conductor foil) be drawn stripping intensity.And, draw stripping intensity even when moisture absorption, also can keep this fully.Consequently, post the stacked plate difficult labour of conductor and give birth to peeling off of interlayer, even when moisture absorption, also can keep its characteristic fully.

In addition, even have under the situation of the less conductor foil 10 of the roughness ratio of M face, also can obtain these characteristics fully at the conductor foil 100 of band adhesive linkage.So, use printed wiring board that the plywood post conductor obtains etc. will have the cementability and the stable on heating complete characteristic of high frequency characteristics, conductor layer well concurrently.So the conductor foil 100 of the band adhesive linkage of present embodiment just is suitable for use as the member or the raw material of the plywood that posts conductor that is used to form the printed wiring board that is possessed of handling high-frequency signal etc. in motor electronics.

[posting the plywood and the manufacture method thereof of conductor]

Below, preferred embodiment plywood that posts conductor and manufacture method thereof described.

(first example)

Fig. 2 is the figure that the section of part of the plywood that posts conductor of expression first example constitutes.The plywood that posts conductor 200 shown in Fig. 2 has the structure that has stacked gradually insulating barrier 22, bonding cured layer 24 and conductor layer 26.

Post in the plywood 200 of conductor,, for example can adopt known prepreg has been fitted behind the sheet number of regulation as insulating barrier 22, heat and/or pressurize and must material.As this prepreg, the fiber that can use the resin varnish that will be prepared impregnated in to make by at least a material that is selected from glass, paper wood and the organic high molecular compound weave cotton cloth or nonwoven in and the material that utilizes known method to make.As the fiber of making by glass (glass fibre), can E glass, S glass, NE glass, D glass, Q glass be shown example.In addition, as the fiber of making by organic high molecular compound (organic fiber), can aramid fiber, fluorine resin, polyester, liquid crystal liquid crystal property macromolecule etc. be shown example.They both can be used alone, and also can be used in combination two or more.

As resin contained in the resin varnish, preferably have the resin (insulative resin) of insulating properties, more preferably have the resin of ethene unsaturated bond.As this kind insulative resin, can enumerate polybutadiene, poly-triallylcyanurate, poly-cyanacrylate, the polyphenylene oxide that contains unsaturated group, maleimide compound etc. with the construction unit that comprises the ethene unsaturated bond.Therefore these insulative resins can reduce the loss of the wiring board that is obtained by the plywood 200 that posts conductor because relative dielectric constant and dielectric loss angle tangent are low.They both can be used alone, and also can be used in combination two or more.

In addition, insulative resin preferably contains and is selected from least a in polyphenylene oxide and the thermoplastic elastomer (TPE), particularly as thermoplastic elastomer (TPE), and the thermoplastic elastomer (TPE) of preferred saturation type.Therefore these resins can reduce dielectric loss significantly because dielectric constant is low and dielectric loss angle tangent is low.

Maleimide compound (poly maleimide) as insulative resin both can be the resin that has the maleimide skeleton in main chain, also can be at side chain and/or terminal resin with dimaleoyl imino.But, preferably in the crosslinking coagent of above-mentioned insulative resin, used the material of maleimide.Like this, owing to not only can reduce the loss of the wiring board that obtains by the plywood 200 that posts conductor, and can improve curing, so the coefficient of thermal expansion of resin or hear resistance will become more good.

The relative dielectric constant of insulating barrier 22 preferably is below 4.0 under 1GHz.If utilize the insulating barrier 22 that satisfies this kind condition, then can reduce dielectric loss significantly.Consequently, the loss of the printed wiring board that is obtained by this plywood 200 that posts conductor is few.

In addition, as conductor layer 26, can use the material in the conductor layer that is generally used for printed wiring board etc. with being not particularly limited.As this kind conductor layer 26, can conductor foil be shown example, can the material of being made by metal forming be shown example specifically.As metal forming, can use in the conductor foil 100 of above-mentioned band adhesive linkage as conductor foil 10 illustrative materials.

In addition, bonding cured layer 24 is by containing (A) composition: polyfunctional epoxy resin, (B) composition: multifunctional phenolic resins and (C) composition: the layer that the solidfied material of the hardening resin composition of polyamidoimide constitutes.As the hardening resin composition that constitutes this bonding cured layer 24 (material before solidifying), can use the identical composition of hardening resin composition of the formation adhesive linkage 20 in the conductor foil 100 with above-mentioned band adhesive linkage.

Used at the plywood that posts conductor 200 under the situation of above-mentioned band adhesive linkage conductor foil 100, for example can utilize manufacture method as follows to make with above-mentioned formation.

That is, at first, prepare conductor foil 100 with adhesive linkage same as described abovely.In the conductor foil 100 of this kind band adhesive linkage, the bonding cured layer 24 before adhesive linkage 20 is equivalent to solidify.In addition, therewith, prepare to be used to form the prepreg of insulating barrier 22.As prepreg, can enumerate and above-mentioned insulative resin be impregnated in the reinforcing fibers such as glass fibre, organic fiber the material that for example utilizes known method such as making the resin semi-solid preparation to make.

Then, with the sheet number of the overlapping regulation of this prepreg and form the insulative resin film.In addition, on the one side of this insulative resin film, so that the mode that the adhesive linkage 20 of the conductor foil 100 of above-mentioned band adhesive linkage and insulating resin film join, the conductor foil 100 of stacked above-mentioned band adhesive linkage.By with their heating and/or pressurization, obtain post the plywood 200 of conductor thereafter.Utilize this heating pressurization, the resin solidification with insulating properties of insulative resin film, and the hardening resin composition of formation adhesive linkage 20 solidifies.Consequently, form insulating barrier 22, form bonding cured layer 24 by adhesive linkage 20 by the insulative resin film.

Heating is preferably carried out under 150～250 ℃ temperature, and pressurization is preferably carried out with the pressure of 0.5～10.0MPa.In addition, the heating and preferably be made as pressing time 0.5～10 hour.This heating and pressurization for example can side by side be carried out by using vacuum press.Will advance the curing of adhesive linkage 20 and insulative resin film so fully, obtain by the conductor layer 26 and the cementability between the insulating barrier 22 of bonding cured layer 24 realizations good; And the plywood that posts conductor 200 of resistance to chemical reagents, hear resistance and moisture-proof excellent heat resistance.

(second example)

Fig. 3 is the figure that the section of part of the plywood that posts conductor of expression second example constitutes.The plywood that posts conductor 300 of second example is different with the above-mentioned plywood that posts conductor 200, has the formation that has formed conductor layer in the both sides of insulating barrier.

The plywood that posts conductor 300 shown in Figure 2 has following formation, that is, possess: insulating resin layer 40, be laminated in the two sides of this insulating resin layer 40 bonding cured layer 30, be laminated in the conductor foil on the face of insulating resin layer 40 opposite sides 10 of these bonding cured layers 30.

Insulating resin layer 40 has a plurality of layer by layer folded and incorporate formations.As this insulating resin layer 40, can enumerate the layer identical with the insulating barrier 22 of the plywood that posts conductor 200 of the first above-mentioned example.In the plywood 300 that posts conductor, this insulating resin layer 40 and bonding cured layer 30 are formed insulating barrier 50 thus by integrated.

The conductor foil 100 that has the conductor foil 10 of the plywood that posts conductor 300 of this kind formation and bonding cured layer 30 and be by the band adhesive linkage of above-mentioned embodiment forms.That is, bonding cured layer 30 is the cured layers after the adhesive linkage 20 of the conductor foil 100 of band adhesive linkage solidifies, and conductor foil 10 is to utilize the conductor foil 10 of the conductor foil 100 of band adhesive linkage to constitute.

The plywood that posts conductor 300 of second example for example can obtain as followsly.At first, prepare the insulative resin film in the same manner with the situation of first example.Then, on the two sides of this insulative resin film, so that the mode that the adhesive linkage 20 of the conductor foil 100 of band adhesive linkage and insulating resin film join, the conductor foil 100. of overlapping a pair of band adhesive linkage thereafter respectively, by with their heating and/or pressurization, obtain posting the plywood 300 of conductor.Utilize this heating pressurization, the resin solidification with insulating properties of insulative resin film, and the hardening resin composition of formation adhesive linkage 20 solidifies.Consequently, form insulating resin layer 40, form bonding cured layer 30 by adhesive linkage 20 by the insulative resin film.

The heating pressurized conditions of this moment can be made as the identical condition of situation with the first above-mentioned example.Like this, just can advance the curing of adhesive linkage 20 and insulative resin film fully, obtain the plywood that posts conductor 300 of conductor foil 10 and resistance to chemical reagents, hear resistance and moisture-proof excellent heat resistance good with the cementability of insulating barrier 50.

The plywood that posts conductor 300 that so obtains has above-mentioned formation, in other words, has had between pair of conductors paper tinsel 10 clamping with the formation of insulating resin layer 40 with the bonding cured layer 30 integrated insulating barriers that form 50.The plywood 300 that this kind posts conductor is to use the conductor foil 100 of band adhesive linkage to form.Thus, be favourable for making the printed wiring board that can suppress the loss in the high-frequency region fully, and the adhesive linkage between insulating barrier 50 and the conductor foil 10 is enough good.

[printed wiring board and manufacture method thereof]

Below, preferred embodiment printed wiring board and manufacture method thereof described.These printed wiring boards are can be as the wiring board of printed wiring board.

(first example)

Fig. 4 is the figure that the section of part of the printed wiring board of expression first example constitutes.Printed wiring board 400 shown in Figure 4 has and possesses insulating barrier 32 successively, the formation of bonding cured layer 34, circuit pattern 36.The wiring board that this printed wiring board 400 is to use the plywood that posts conductor 200 in the first above-mentioned example to obtain rightly.That is, insulating barrier 32, bonding cured layer 34 and circuit pattern 36 are made of insulating barrier 22, bonding cured layer 24 and conductor layer 26 identical materials with the plywood 200 that posts conductor respectively.

Printed wiring board 400 with this kind formation for example can be made by following operation,, by using known engraving method, the conductor layer 26 of the above-mentioned plywood that posts conductor 200 is processed into required circuit pattern that is.

(second example)

Fig. 5 is the figure that the section of part of the printed wiring board of expression second example constitutes.The wiring board that printed wiring board 500 shown in Figure 5 is to use the plywood that posts conductor 300 of the second above-mentioned example to obtain rightly has the formation that possesses circuit pattern on the two sides.

Printed wiring board 500 has following formation, that is, possess: insulating resin layer 40, be laminated in the two sides of this insulating resin layer 40 bonding cured layer 30, be formed at the circuit pattern on the face of insulating resin layer 40 opposite sides 11 (conductor layer) of these bonding cured layers 30.In addition, the position in the regulation of this printed wiring board 500 is formed with the through hole 70 that runs through along stacked direction, on the surface of its wall and circuit pattern 11, is formed with plating overlay film 60.Utilize this plating overlay film 60 will show conducting between the circuit pattern 11 at the back side.

In this printed wiring board 500, bonding cured layer 30 and insulating resin layer 40 have the formation identical with the bonding cured layer 30 of the above-mentioned plywood that posts conductor 300 and insulating resin layer 40.In addition, bonding cured layer 30 and insulating resin layer 40 are constituted the insulating barrier 50 that plays a role as substrate by integrated.

Shown in for example being preferably as follows, makes printed wiring board 500 with this kind formation.That is, at first, prepare the plywood that posts conductor 300 of above-mentioned embodiment.Then, after the plywood 300 that this is posted conductor utilizes known method to implement perforate processing, implement plating.So just form through hole 70 and plating overlay film 60.In addition, utilize known method such as etching to be processed into the circuitry shapes of regulation the conductor foil 10 on surface that posts the plywood 300 of conductor.So just form circuit pattern 11 by conductor foil 10.Like this just can obtain printed wiring board 500.

This kind printed wiring board 500 is to be formed by the plywood that posts conductor 100 that the conductor foil 100 that uses the band adhesive linkage obtains.Thus, in printed wiring board 500, bonding securely across bonding cured layer 30 with insulating resin layer 40 by the circuit pattern 11 that conductor foil 10 obtains.That is to say that circuit pattern 11 becomes very good with the cementability of insulating barrier 50.So,, also be difficult to produce circuit pattern 11 peeling off from the insulating barrier 50 even will hang down under the situation that the roughening paper tinsel uses as the conductor foil 10 that is used to form circuit pattern 11.Like this, this kind printed wiring board 500 just can become the little wiring board of loss in the high-frequency region.

In addition, even, used resin, also can reduce peeling off of circuit pattern 11 fully with high-insulativity and high-fire resistance as the resin material of insulating resin layer 40.In addition, even under high humidity, bonding cured layer 30 also can be kept good cementability.So printed wiring board 500 not only can be realized further high frequency reply because its insulating barrier 50 has good insulating properties, but also has good hear resistance, particularly has the good hear resistance under the super-humid conditions.

[multilayer circuit board and manufacture method thereof]

Below, preferred embodiment multilayer circuit board and manufacture method thereof described.

(first example)

Fig. 6 schematically shows the figure that the section of part of the multilayer circuit board of first example constitutes.Multilayer circuit board 600 shown in Figure 6 has following structure, promptly, with having one group of wiring board of insulating barrier 62, bonding cured layer 64, internal layer circuit pattern 66, interlayer insulating film 68 and outer circuit pattern 72 successively, so that opposed facing mode is gluing between their insulating barrier 62.In this multilayer circuit board 600, internal layer circuit pattern 66 is connected by being located at mesoporous 74 on the interlayer insulating film 68 with outer circuit pattern 72.In addition, connect by through hole 76 between the internal layer circuit pattern 66 of one group of wiring board.

In the multilayer circuit board 600, insulating barrier 62, bonding cured layer 64 and internal layer circuit pattern 66 are made of insulating barrier 32, bonding cured layer 34 and circuit pattern 36 identical materials with printed wiring board 400 respectively.That is, multilayer circuit board 600 possesses above-mentioned printed wiring board 400 as core substrate 80.In addition, as interlayer insulating film 68, can enumerate the layer that constitutes by known resin material (for example contained resin material in the insulating barrier 32 of printed wiring board 400) with insulating properties; Or the layer that constitutes by the prepreg of the reinforcement base material that in the resin material of this insulating properties, has cooperated regulation etc.

In addition, outer circuit pattern 72 is made of the conductive material identical with internal layer circuit pattern 66.Like this, utilize mesoporous 74 or through hole 76, with between internal layer circuit pattern 66 and outer circuit pattern 72 or the internal layer circuit pattern 66 in the position conducting of regulation.

Multilayer circuit board 600 with this kind formation can utilize method manufacturing as follows.That is, at first, preparation should become one group of printed wiring board 400 of core substrate 80, so that opposed facing mode is overlapping between their insulating barrier 32.It is carried out perforate as required, implement metal-plated etc., form through hole 76.Then, on the circuit pattern 36 (internal layer circuit pattern 66) of printed wiring board 400, the prepreg that should constitute interlayer insulating film 68 of the sheet number of overlapping regulation etc.

After this, to prepreg after the perforate of desired position, carry out operations such as filled conductive material, form mesoporous 74.Thereafter, the identical conductor foil of stacked and internal layer circuit pattern 66 on prepreg is by with their heating pressurizations and with its crimping.In addition, utilize known engraving method etc. to be processed into required circuit pattern outermost conductor foil, form outer circuit pattern 72 thus, obtain multilayer circuit board 600.

And the multilayer circuit board 600 of first example also can have above-mentioned formation in addition.For example, also can be between interlayer insulating film 68 and outer circuit pattern 72, form the bonding cured layer identical again with bonding cured layer 64.Like this because interlayer insulating film 68 and outer circuit pattern 72 be by bonding securely across this bonding cured layer, so multilayer circuit board 600 not only utmost point difficult labour give birth to peeling off of internal layer circuit pattern 66, and peeling off of outer circuit pattern 72 given birth in difficult labour.

Like this at the multilayer circuit board of the formation that has bonding cured layer between interlayer insulating film 68 and the outer circuit pattern 72 except can utilizing the aforesaid method that stacks gradually interlayer insulating film 68 and outer circuit pattern 72 obtains, can also by stacked in the manufacturing of wiring board 400 conductor foil 100 of the band adhesive linkage used obtain.In addition, this kind multilayer circuit board 600 also can be made by the stacked printed wiring board 400 that possesses identical or different with it circuit pattern 36 on core substrate 80.

In addition, multilayer circuit board 600 is not limited to illustrated stacked number, can be made as to have required stacked number.This kind multilayer circuit board 600 can be made by following operation, that is, in the both sides of core substrate 80, according to required stacked number, alternatively stacked interlayer insulating film 68 and outer circuit pattern 72, or printed wiring board 400 is stacked for reaching the required number of plies.

(second example)

Fig. 7 schematically shows the figure that the section of part of the multilayer circuit board of second example constitutes.Multilayer circuit board 700 shown in Figure 2 possesses: insulating resin layer 92, the bonding cured layer 90 on the face of core substrate 510 opposite sides that is formed at these insulating resin layers 92 that is made of the solidfied material (base material) of the prepreg on the two sides that is laminated in core substrate 510, the lip-deep more in the outer part outer circuit pattern 110 of being located at these bonding cured layers 90.Here, core substrate 510 has the formation identical with above-mentioned printed wiring board 500, and the circuit pattern 11 of this core substrate 510 is equivalent to internal layer circuit pattern 11.In other words, multilayer circuit board 700 possesses above-mentioned printed wiring board 500 as core substrate 510.

Multilayer circuit board 700 with this kind formation can use printed wiring board 500 to make rightly.That is, at first, prepare printed wiring board 500, with it as internal layer core substrate 510.At overlapping one or more layers prepreg used during as manufacturing on the two sides of this internal layer core substrate 510 at the plywood 300 that posts conductor.Then, on two surfaces in the outside of this prepreg, so that the mode that the adhesive linkage 20 of the conductor foil 100 of above-mentioned band adhesive linkage contacts with it, overlapping again conductor foil 100 that should the band adhesive linkage.

Then, with the duplexer heating press molding of gained, with bonding between each layer.So just form insulating resin layer 92, form bonding cured layer 90 by the adhesive linkage 20 of conductor foil 100 of band adhesive linkage by the prepreg that is laminated on the internal layer core substrate 510.Afterwards, identical during with the manufacturing of printed wiring board 500, suitably implement perforate processing and plating overlay film, form through hole 96 and plating overlay film 94.At this moment, perforate processing both can only be carried out the part that is laminated on the internal layer core substrate 510 as shown in the figure, also can run through internal layer core substrate 510 ground and carry out.In addition, utilize known method to be processed as the circuitry shapes of regulation outermost conductor foil (conductor foil 10) and plating overlay film 94 formed thereon, form outer circuit pattern 110, obtain multilayer circuit board 700 thus.

And the multilayer circuit board of second example also can be the wiring board with above-mentioned formation in addition.For example, the multilayer circuit board of second example also can be by on the surface as the printed wiring board 500 of core substrate, and alternatively stacked above-mentioned prepreg and printed wiring board 500 are with the duplexer heating press molding of gained and obtain.And, in this kind multilayer circuit board, outermost outer circuit pattern both can be to process across the bonding conductor foil of prepreg, also can be that the conductor foil 10 that will be laminated in the conductor foil 100 of the most surperficial band adhesive linkage processes, can also be the circuit pattern 11 that is laminated in outermost printed wiring board 500.

More than, though the conductor foil of band adhesive linkage preferred embodiment of the present invention, the plywood that posts conductor, printed wiring board and multilayer circuit board are illustrated, yet the present invention is not limited to above-mentioned embodiment, the embodiment that also can suitably be out of shape in the scope that does not break away from its purport.

Embodiment

Below, will utilize embodiment that the present invention is described in more detail, yet the present invention is not limited to these embodiment.

[synthesizing of polyamidoimide]

(synthesis example 1A)

At first, to possessing Dean-Stark reflux cooler, thermometer, in the separable flask of the 1L of agitator, add as (4 of the diamine compound with saturated fat ring type alkyl, 4 '-diaminourea) dicyclohexyl methyl hydride (Wandamin HM (WHM), new Japanese physics and chemistry corporate system, trade name) 45mmol, reactive silicone oil (X-22-161-B as the siloxane diamine compound, chemical industrial company of SHIN-ETSU HANTOTAI system, amine equivalent: 1500, trade name) 5mmol, trimellitic anhydride (TMA) 105mmol, as N-methyl-2-pyrrolidones (NMP) 145g of non-proton property polar solvent, the temperature in the flask is set at 80 ℃ and stirred 30 minutes.

After stirring end,, the temperature in the flask is elevated to 160 ℃, refluxed 2 hours as adding toluene 100mL again with the aromatic hydrocarbon of water azeotropic.Stored the water of theoretical amount in the water and basis weight recipient, affirmation when the water in the water and basis weight recipient is removed, is elevated to 190 ℃ with the temperature in the flask after can't see distillating of water, removes the toluene in the reaction solution.

After the solution in the flask is returned to room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 60mmol, temperature in the flask is elevated to 190 ℃, react after 2 hours, with the NMP dilution, obtained the nmp solution (solid component concentration is 30 quality %) of the polyamidoimide of synthesis example 1A.Utilized gel permeation chromatography the weight average molecular weight of this nmp solution (Mw), its result is 50000.

(synthesis example 2A)

At first, to possessing Dean-Stark reflux cooler, thermometer, in the separable flask of the 1L of agitator, add as having Jeffermine D-2000 (the Suntechno Chemical corporate system of the diamine compound of representative examples of saturated aliphatic alkyl, trade name) 30mmol, as (4 of aromatic diamine compound, 4 '-diaminourea) diphenyl methane (DDM) 120mmol, trimellitic anhydride (TMA) 315mmol, as N-methyl-2-pyrrolidones (NMP) 442g of non-proton property polar solvent, the temperature in the flask is set at 80 ℃ and stirred 30 minutes.

After stirring end,, the temperature in the flask is elevated to 160 ℃, refluxed about 2 hours as adding toluene 100mL again with the aromatic hydrocarbon of water azeotropic.Stored the water of theoretical amount in the water and basis weight recipient, affirmation when the water in the water and basis weight recipient is removed, is elevated to 190 ℃ with the temperature in the flask after can't see distillating of water, removes the toluene in the reaction solution.

After the solution in the flask is returned to room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 180mmol, temperature in the flask is elevated to 190 ℃, react after 2 hours, with the NMP dilution, obtained the nmp solution (solid component concentration is 30 quality %) of the polyamidoimide of synthesis example 2A.The Mw of this nmp solution that utilized gel permeation chromatography, its result is 74000.

[the adhesive linkage preparation of resin varnish (hardening resin composition)]

(formulation example 1A)

Will be as the cresols phenolic resin varnish type epoxy resin (YDCN-500 of (A) composition, Dongdu changes into corporate system, trade name) 5.0g, novolaks phenolic resins (MEH7500 as (B) composition, bright and change into corporate system, trade name) the polyamidoimide nmp solution 18g that obtains among 3.1g and the conduct synthesis example 1A of (C) composition cooperates, then added 2-ethyl-4-methylimidazole (2E4MZ as curing accelerator, four countries change into industrial group's system, trade name) behind the 0.025g, cooperate N-methyl-2-pyrrolidones 28g and MEK 13g, the adhesive linkage that is mixed with formulation example 1A is with resin varnish (solid component concentration is about 20 quality %).

And, will in YDCN-500 and MEH7500, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 190 ℃.Here, vitrification point Tg is according to JIS-K7121-1987, the value of utilizing differential scanning calorimetry (DSC) to measure.

(formulation example 2A)

Will be as the phenol novolak type epoxy resin (N-770 of (A) composition, big Japanese ink chemical industrial company system, trade name) 5.0g, cresols novolaks phenolic resins (KA-1163 as (B) composition, big Japanese ink chemical industrial company system, trade name) 3.9g, the carboxyl acid modified acrylonitrile butadiene rubber particle (XER-91SE-15 of the polyamidoimide nmp solution 55g that obtains among the synthesis example 2A as (C) composition and conduct (D) composition, JSR (strain) system, trade name, solid component concentration is 15 quality %) the 8.5g cooperation, then added 2-ethyl-4-methylimidazole (2E4MZ as curing accelerator, four countries change into industrial group's system, trade name) behind the 0.025g, cooperate N-methyl-2-pyrrolidones 39g and MEK 20g, the adhesive linkage that is mixed with formulation example 2A is with resin varnish (solid component concentration is about 20 quality %).

And, will in N-770 and KA-1163, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 190 ℃.

(formulation example 3A)

Will be as the phenolic resin varnish type epoxy resin (NC-3000H with biphenyl structural of (A) composition, Japan's chemical drug corporate system, trade name) 5.0g, bisphenol-A phenolic varnish gum (YLH129 as (B) composition, the japan epoxy resin corporate system, trade name) 2.0g, carboxyl acid modified polyvinyl acetal resin (KS-the 23Z of the polyamidoimide nmp solution 38g that obtains among the synthesis example 1A as (C) composition and conduct (D) composition, Sekisui Chemical Co., Ltd's system, trade name) 0.8g cooperates, then added 2-ethyl-4-methylimidazole (2E4MZ as curing accelerator, four countries change into industrial group's system, trade name) behind the 0.025g, cooperate N-methyl-2-pyrrolidones 35g and MEK 13g, the adhesive linkage that is mixed with formulation example 3A is with resin varnish (solid component concentration is about 20 quality %).

And, will in NC-3000H and YLH129, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 170 ℃.

(formulation example 4A)

With bisphenol A type epoxy resin (DER-331L, Dowchemical Japanese firm system, trade name) 5.0g, cresols novolaks phenolic resins (KA-1163, big Japanese ink chemical industrial company system, trade name) the polyamidoimide nmp solution 50g that obtains among 3.2g and the synthesis example 1A cooperates, then added 2-ethyl-4-methylimidazole (2E4MZ as curing accelerator, four countries change into industrial group's system, trade name) behind the 0.025g, cooperate N-methyl-2-pyrrolidones 46g and MEK 15g, the adhesive linkage that is mixed with formulation example 4A is with resin varnish (solid component concentration is about 20 quality %).

And, will in DER-331L and KA1163, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 135 ℃.

(relatively formulation example 1A)

Among the polyamidoimide nmp solution 50g that obtains in synthesis example 1A, cooperate N-methyl-2-pyrrolidones 50g, the adhesive linkage that is mixed with comparison formulation example 1A is with resin varnish (solid component concentration is 15 quality %).

(relatively formulation example 2A)

Among the polyamidoimide nmp solution 50g that in synthesis example 2A, obtains, cooperate cresols phenolic resin varnish type epoxy resin (YDCN-500, Dongdu change into corporate system, trade name) 8.8g, then after having added 2-ethyl-4-methylimidazole (2E4MZ, four countries change into industrial group's system, trade name) 0.088g as curing accelerator, cooperate N-methyl-2-pyrrolidones 101g and MEK 34g, the adhesive linkage that is mixed with comparison formulation example 2A is with resin varnish (solid component concentration is about 15 quality %).

[the insulating resin layer making of prepreg]

(making example 1)

At first, in the separable flask of the 2L that possesses cooling tube, thermometer, agitator, add toluene 400g and polyphenylene oxide resin (MODIFIED PP O NORYL PKN4752, Japanese GE Plastics corporate system, trade name) 120g, stirring and dissolving when the temperature in the flask is heated to be 90 ℃.

Then, when stirring, in flask, add cyanacrylate (TAIC, Japan change into corporate system, trade name) 80g, after confirming dissolving or disperseing equably, cool to room temperature.Then, added α as radical polymerization initiator, behind α '-two (tert-butyl peroxy base) diisopropyl benzene (Perbutyl P, Nof Corp.'s system, the trade name) 2.0g, cooperate toluene 70g again, obtained the insulating resin layer varnish that solid component concentration is about 30 quality %.

Behind the insulating resin layer of the gained glass fibre (E glass, day eastern textile company system) with the thick 0.1mm of varnish impregnation, 120 ℃ of heat dryings 5 minutes, having obtained resin, to contain proportional be the insulating resin layer prepreg of the making example 1 of 50 quality %.

(making example 2)

At first, in the separable flask of the 2L that possesses cooling tube, thermometer, agitator, add toluene 400g and polyphenylene oxide resin (MODIFIED PP O NORYL PKN4752, Japanese GE Plastics corporate system, trade name) 120g, stirring and dissolving when the temperature in the flask is heated to be 90 ℃.

Then, when stirring, in flask, add 1,2-polybutadiene (B-1000, Japanese Cao Da corporate system, trade name) 80g, as divinylbenzene (DVB) 10g of crosslinking coagent, after confirming dissolving or disperseing equably, cool to room temperature.

Then, added α as radical polymerization initiator, behind α '-bis(t-butylperoxy) diisopropyl benzene (Perbutyl P, Nof Corp.'s system, the trade name) 2.0g, cooperate toluene 70g again, obtained the insulating resin layer varnish that solid component concentration is about 30 quality %.

Behind the insulating resin layer of the gained glass fibre (E glass, day eastern textile company system) with the thick 0.1mm of varnish impregnation, 120 ℃ of heat dryings 5 minutes, having obtained resin, to contain proportional be the insulating resin layer prepreg of the making example 2 of 50 quality %.

(making example 3)

At first, in the separable flask of the 10L that possesses cooling tube, thermometer, agitator, add oxolane (THF) 5000mL, polyphenylene oxide resin (NORYL PPO646-111, Japanese GEPlastics corporate system, trade name) 100g, stirring and dissolving when the temperature in the flask is heated to be 60 ℃.After it is returned to room temperature, under stream of nitrogen gas, add n-BuLi (1.55mol/L, hexane solution) 540mL, stirred 1 hour.Then, add bromination allyl ester 100g and after stirring 30 minutes, cooperate amount of methanol, with the polymer segregation that precipitated and obtain allylation polyphenylene oxide.

Then, in the separable flask of the 2L that possesses cooling tube, thermometer, agitator, add toluene 400g and above-mentioned allylation polyphenylene oxide 100g, stirring and dissolving when the temperature in the flask is heated to be 90 ℃.

, when stirring to flask in add cyanacrylate (TAIC, Japan change into corporate system, trade name) 100g thereafter, after confirming dissolving or disperseing equably, cool to room temperature.

Then, added α as radical polymerization initiator, behind α '-two (tert-butyl peroxy base) diisopropyl benzene (Perbutyl P, Nof Corp.'s system, the trade name) 2.5g, cooperate toluene 70g again, obtained the insulating resin layer varnish that solid component concentration is about 30 quality %.

Behind the insulating resin layer of the gained glass fibre (E glass, day eastern textile company system) with the thick 0.1mm of varnish impregnation, 120 ℃ of heat dryings 5 minutes, having obtained resin, to contain proportional be the insulating resin layer prepreg of the making example 3 of 50 quality %.

[embodiment 1A～4A and comparative example 1A～2A]

(making of the conductor foil of band adhesive linkage)

After the M face [surface roughness (Rz): 0.8 μ m] that the adhesive linkage that obtains among formulation example 1A～4A and the comparison formulation example 1A～2A is coated on the electrolytic copper foil (F0-WS-18, slim Copper Foil, Furukawa Electric Industrial Co., Ltd system) of thick 18 μ m with the natural respectively curtain coating of resin varnish is gone up, 170 ℃ of dryings 5 minutes, embodiment 1A, 2A, 3A and 4A have been made; And the conductor foil of the band adhesive linkage of comparative example 1A and 2A.The thickness of dried adhesive linkage is 2 μ m.And the adhesive linkage that has used formulation example 1A, 2A, 3A and 4A is equivalent to embodiment 1A, 2A, 3A and 4A with the situation of resin varnish, has used the adhesive linkage that obtains among relatively the formulation example 1A and 2A to be equivalent to comparative example 1A and 2A with the situation of resin varnish.

(the two-sided making that is covered with the plywood and the multilager base plate of copper)

Respectively with the conductor foil of the band adhesive linkage that is used in combination embodiment 1A～4A and comparative example 1A～2A of regulation, make the insulating resin layer prepreg of example 1～3, according to method shown below, made corresponding two-sided plywood and the multilager base plate that is covered with copper of situation with the prepreg of the band adhesive linkage that uses each embodiment and comparative example.And the prepreg of the band adhesive linkage of each embodiment or comparative example and insulating resin layer are with shown in the combination table 1 described as follows of prepreg.

(the two-sided making that is covered with the plywood of copper)

On the two sides of overlapping 4 insulating resin layers with the base material of prepregs, so that after the mode that the adhesive linkage separately of conductor foil of band adhesive linkage contacts with it adhered to the conductor foil of band adhesive linkage, heat press molding under the punching press condition of 200 ℃ of temperature, pressure 3.0MPa and 70 minutes, the two-sided plywood that is covered with copper of having made the conductor foil that uses various band adhesive linkages respectively is (thick: 0.55mm).

(making of multilager base plate)

At first, made the various two-sided plywood that is covered with copper same as described above.Then, after the two-sided Copper Foil that is covered with the plywood of copper partly utilizes etching to remove fully with each, insulating resin layer used in the time of will making with the plywood that respectively is covered with copper disposes 1 in the two-sided two sides that is covered with the plywood of copper after removing Copper Foil respectively with the identical prepreg of prepreg, so that the mode that the M face of electrolytic copper foil contacts has with it adhered to the electrolytic copper foil [GTS-18, common Copper Foil, Furukawa Electric Industrial Co., Ltd system, M face surface roughness (Rz): 8 μ m, trade name] that the thick 18 μ m of adhesive linkage are not set in its outside., under the punching press condition of temperature 200 ℃, pressure 3.0MPa and 70 minute heat press molding, made multilager base plate thereafter.

[comparative example 3A and 4A]

In order to compare, on overlapping 4 two sides that make the insulating resin layer of example 1 or 2 with the base material of prepreg, so that the mode that the M face of electrolytic copper foil contacts with it adheres to the electrolytic copper foil (F0-WS-18, Furukawa Electric Industrial Co., Ltd system, trade name) of the thick 18 μ m that adhesive linkage is not set or the electrolytic copper foil (GTS-18, common Copper Foil, Furukawa Electric Industrial Co., Ltd system, M face surface roughness (Rz): 8 μ m, trade name) of the thick 18 μ m of adhesive linkage is not set.It under temperature 200 ℃, 3.0MPa, 70 minute punching press condition heated press molding thereafter.It is (thick: 0.55mm) to have made the two-sided plywood that is covered with copper of two kinds of possessing different electrolytic copper foils on the surface like this, respectively.The two-sided plywood that is covered with copper that will possess the former electrolytic copper foil is made as comparative example 3A, and the two-sided plywood that is covered with copper that will possess the latter's electrolytic copper foil is made as comparative example 4A.In addition, use these two-sided plywoods that is covered with copper, made multilager base plate same as described abovely.

[evaluating characteristics]

(Copper Foil that is covered with the plywood of copper draws the mensuration of shelling intensity)

At first, use the two-sided plywood that is covered with copper of embodiment 1A～4A and comparative example 1A～4A, utilize method shown below, measured each two-sided Copper Foil that is covered with the plywood of copper and drawn stripping intensity.That is, at first, to the two-sided Copper Foil that is covered with the plywood of copper, the plywood sample of the flat shape with 2.5cm * 10cm has been made in the processing that implement to utilize the mode that is etched with the circuitry shapes with live width 5mm that unwanted Copper Foil is partly removed.Manufactured samples like this was kept respectively 5 hours in device (condition: 121 ℃, 2.2 atmospheric pressure, 100%RH) at normality and pressure cooker testing (PCT).In addition, the two-sided Copper Foil that is covered with the plywood of copper after having measured through 5 hours under the following condition draws stripping intensity (unit: kN/m).The result of gained is shown in the table 1.

Test method: 90 ° of direction tension tests

Draw speed: 50mm/ minute

Determinator: the system Autograph AG-100C of Shimadzu Seisakusho Ltd.

And, draw stripping intensity for Copper Foil, be meant that with "-" expression because after keeping, Copper Foil is peeled off, therefore can't measure Copper Foil draws stripping intensity in PCT in the table.

(the two-sided stable on heating evaluation of scolding tin that is covered with the plywood and the multilager base plate of copper)

Measured the two-sided scolding tin hear resistance that is covered with the plywood and the multilager base plate of copper of embodiment 1A～4A and comparative example 1A～4A respectively according to method shown below.That is, at first, it is square that the two-sided plywood that is covered with copper and multilager base plate are cut into 50mm respectively.Then, the Copper Foil of a side of the two-sided plywood that is covered with copper is etched to the regulation shape, in addition, utilizes etching to remove fully the outer field Copper Foil of multilager base plate, obtained estimating and used sample.And the evaluation corresponding with each embodiment or comparative example prepared a plurality of with sample for corresponding test described later.

, to each embodiment or comparative example corresponding evaluation sample, respectively in normality or pressure cooker testing (PCT) use in device (condition: 121 ℃, 2.2 atmospheric pressure), carried out the processing of maintenance stipulated time (1,2,3,4 or 5 hour) thereafter.This processing after each estimated with sample respectively impregnated in 260 ℃ fusion scolding tin thereafter.After this, utilize the visual evaluation of having investigated corresponding with each embodiment or comparative example two-sided plywood that is covered with copper and multilager base plate with each outward appearance of 3 of sample.The result of gained is shown in the table 1.

And the numeral in the table, is not seen expansion or is peeled off the sheet number of sample of the generation of (ミ-ズ リ Application グ) with in the middle of the samples in 3 evaluations having carried out identical test between insulating barrier and Copper Foil (conductive layer).That is to say that this number is big more, represent that then pairing evaluation is good more with the hear resistance of sample.

(evaluation of the loss of the two-sided plywood that is covered with copper)

Three circuit resonator methods of vector type Network Analyzer have been used in utilization, have measured the two-sided loss (unit: dB/m) that is covered with the plywood of copper of embodiment 1A～4A and comparative example 1A～4A.And condition determination is made as, live width: 0.6mm, and insulating barrier distance: 1.04mm between earth conductor up and down, line length: 200mm, characteristic impedance 50 Ω, frequency: 3GHz measures temperature: 25 ℃.The result of gained is shown in the table 1.

[table 1]

Distinguish according to table 1, under the situation of the conductor foil of the band adhesive linkage that has used embodiment 1A～4A, good Copper Foil be can obtain to have and stripping intensity and scolding tin hear resistance drawn, but also two-sided plywood and the multilager base plate that is covered with copper that loss can be kept enough low.On the other hand, confirm under the situation of comparative example 1A～4A that the Copper Foil behind the PCT draws the reduction of stripping intensity obvious, the scolding tin hear resistance is abundant inadequately, and it is big that loss becomes irrelevantly.

[synthesizing of polyamidoimide]

(synthesis example 1B)

At first, to possessing Dean-Stark reflux cooler, thermometer, in the separable flask of the 1L of agitator, add as (4 of the diamine compound with saturated fat ring type alkyl, 4 '-diaminourea) dicyclohexyl methyl hydride (Wandamin HM (WHM), new Japanese physics and chemistry corporate system, trade name) 45mmol, reactive silicone oil (X-22-161-B as the siloxane diamine compound, chemical industrial company of SHIN-ETSU HANTOTAI system, amine equivalent: 1500, trade name) 5mmol, trimellitic anhydride (TMA) 105mmol, as N-methyl-2-pyrrolidones (NMP) 145g of non-proton property polar solvent, the temperature in the flask is set at 80 ℃ and stirred 30 minutes.

After stirring end,, the temperature in the flask is elevated to 160 ℃, refluxed about 2 hours as adding toluene 100mL again with the aromatic hydrocarbon of water azeotropic.Stored the water of theoretical amount in the water and basis weight recipient, affirmation when the water in the water and basis weight recipient is removed, is elevated to 190 ℃ with the temperature in the flask after can't see distillating of water, removes the toluene in the reaction solution.

After the solution in the flask is returned to room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 60mmol, temperature in the flask is elevated to 190 ℃, react after 2 hours, with the NMP dilution, obtained the nmp solution (solid component concentration is 30 quality %) of the polyamidoimide of synthesis example 1B.Utilized gel permeation chromatography the weight average molecular weight of this nmp solution (Mw), its result is 53000.

(synthesis example 2B)

At first, to possessing Dean-Stark reflux cooler, thermometer, in the separable flask of the 1L of agitator, add as having Jeffermine D-2000 (the Suntechno Chemical corporate system of the diamine compound of representative examples of saturated aliphatic alkyl, trade name) 30mmol, as (4 of aromatic diamine compound, 4 '-diaminourea) diphenyl methane (DDM) 120mmol, trimellitic anhydride (TMA) 315mmol, as N-methyl-2-pyrrolidones (NMP) 442g of non-proton property polar solvent, the temperature in the flask is set at 80 ℃ and stirred 30 minutes.

After stirring end,, the temperature in the flask is elevated to 160 ℃, refluxed about 2 hours as adding toluene 100mL again with the aromatic hydrocarbon of water azeotropic.Stored the water of theoretical amount in the water and basis weight recipient, affirmation when the water in the water and basis weight recipient is removed, is elevated to 190 ℃ with the temperature in the flask after can't see distillating of water, removes the toluene in the reaction solution.

After the solution in the flask is returned to room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 180mmol, temperature in the flask is elevated to 190 ℃, react after 2 hours, with the NMP dilution, obtained the nmp solution (solid component concentration is 30 quality %) of the polyamidoimide of synthesis example 2B.The Mw of this nmp solution that utilized gel permeation chromatography, its result is 74000.

(synthesis example 3B)

Except with the MDI quantitative change more the 50mmol, obtained the nmp solution of polyamidoimide in the same manner with synthesis example 1B.And, the Mw of this nmp solution that utilized gel permeation chromatography, consequently 23000.

(synthesis example 4B)

Except with MDI quantitative change 190mmol more, beyond will changing in the reaction time 3 hours, obtained the nmp solution of polyamidoimide in the same manner with synthesis example 2B.And, the Mw of this nmp solution that utilized gel permeation chromatography, consequently 27000.

[the tack coat preparation of resin varnish (hardening resin composition)]

(formulation example 1B)

At cresols phenolic resin varnish type epoxy resin (YDCN-500 as (A) composition, Dongdu changes into corporate system, trade name) among the 5.0g, cooperate novolaks phenolic resins (MEH7500 as (B) composition, bright and change into corporate system, trade name) the polyamidoimide nmp solution 18g that obtains among 3.1g and the conduct synthesis example 1B of (C) composition, then added 2-ethyl-4-methylimidazole (2E4MZ as curing accelerator, four countries change into industrial group's system, trade name) behind the 0.025g, cooperate N-methyl-2-pyrrolidones 28g and MEK 13g, the adhesive linkage that is mixed with formulation example 1B is with resin varnish (solid component concentration is about 20 quality %).

And, will in YDCN-500 and MEH7500, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 190 ℃.

(formulation example 2B)

At phenolic resin varnish type epoxy resin (NC-3000H with biphenyl structural as (A) composition, Japan's chemical drug corporate system, trade name) among the 5.0g, cooperate bisphenol-A phenolic varnish gum (YLH129 as (B) composition, the japan epoxy resin corporate system, trade name) 2.0g, carboxyl acid modified polyvinyl acetal resin (KS-the 23Z of the polyamidoimide nmp solution 38g that obtains among the synthesis example 2B as (C) composition and conduct (D) composition, Sekisui Chemical Co., Ltd's system, trade name) 0.8g, then added 2-ethyl-4-methylimidazole (2E4MZ as curing accelerator, four countries change into industrial group's system, trade name) behind the 0.025g, cooperate N-methyl-2-pyrrolidones 28g and MEK 13g, the adhesive linkage that is mixed with formulation example 2B is with resin varnish (solid component concentration is about 20 quality %).

And, will in NC-3000H and YLH129, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 170 ℃.

(formulation example 3B)

At phenol novolak type epoxy resin (N-770 as (A) composition, big Japanese ink chemical industrial company system, trade name) among the 5.0g, cooperate cresols novolaks phenolic resins (KA-1163 as (B) composition, big Japanese ink chemical industrial company system, trade name) 3.9g, the carboxyl acid modified acrylonitrile butadiene rubber particle (XER-91SE-15 of the polyamidoimide nmp solution 55g that obtains among the synthesis example 2B as (C) composition and conduct (D) composition, JSR (strain) system, trade name, solid component concentration is 15 quality %) 8.5g, then added 2-ethyl-4-methylimidazole (2E4MZ as curing accelerator, four countries change into industrial group's system, trade name) behind the 0.025g, cooperate N-methyl-2-pyrrolidones 39g and MEK 20g, the adhesive linkage that is mixed with formulation example 3B is with resin varnish (solid component concentration is about 20 quality %).

And, will in N-770 and KA-1163, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 190 ℃.

(formulation example 4B)

At bisphenol A type epoxy resin (DER-331L, Dowchemical Japanese firm system, trade name) among the 5.0g, cooperate cresols novolaks phenolic resins (KA-1163, big Japanese ink chemical industrial company system, trade name) the polyamidoimide nmp solution 50g that obtains among 3.2g and the synthesis example 2B, then added 2-ethyl-4-methylimidazole (2E4MZ as curing accelerator, four countries change into industrial group's system, trade name) behind the 0.025g, cooperate N-methyl-2-pyrrolidones 46g and MEK 15g, the adhesive linkage that is mixed with formulation example 4B is with resin varnish (solid component concentration is about 20 quality %).

And, will in DER-331L and KA1163, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 135 ℃.

(formulation example 5B)

Except nmp solution as polyamidoimide, replace the solution that obtains among the synthesis example 2B, used beyond the solution that obtains among the synthesis example 3B, disposed the adhesive linkage resin varnish in the same manner with formulation example 2B.

(formulation example 6B)

Except nmp solution as polyamidoimide, replace the solution that obtains among the synthesis example 2B, used beyond the solution that obtains among the synthesis example 4B, disposed the adhesive linkage resin varnish in the same manner with formulation example 2B.

[the insulating resin layer making of prepreg]

The insulating resin layer prepreg of making example 1～3 has been made on ground same as the above-mentioned method respectively.

[embodiment 1B～6B]

(making of the conductor foil of band adhesive linkage)

The adhesive linkage that obtains among formulation example 1B～6B is coated on the M face (surface roughness (Rz): after 0.8 μ m) of the electrolytic copper foil (F0-WS-12, slim Copper Foil, Furukawa Electric Industrial Co., Ltd system) of thick 12 μ m with the natural respectively curtain coating of resin varnish, 150 ℃ of dryings 5 minutes, made the conductor foil of the band adhesive linkage of embodiment 1B～6B.The thickness of dried adhesive linkage is 3 μ m.And, used the situation of the varnish of formulation example 1B, 2B, 3B, 4B, 5B and 6B to be equivalent to embodiment 1B, 2B, 3B, 4B, 5B and 6B.

(the two-sided making that is covered with the plywood of copper)

The insulating resin layer of any one in overlapping 4 above-mentioned making examples 1～3 is with the two sides of the base material of prepreg, so that after mode that the adhesive linkage separately of the conductor foil of the band adhesive linkage of embodiment 1B～6B contacts with it adhered to the conductor foil of band adhesive linkage, heat press molding under 200 ℃, 3.0MPa, 70 minutes punching press condition, the plywood that conductor foil two-sided of having made the band adhesive linkage that uses embodiment 1B～6B respectively is covered with copper is (thick: 0.55mm).The conductor foil of the band adhesive linkage of each embodiment or comparative example and insulating barrier are as shown in table 2 with the combination of prepreg.

(making of multilager base plate)

At first, same as described above, form the two-sided plywood that is covered with copper of the conductor foil of the band adhesive linkage used embodiment 1B～6B respectively, partly utilize etching to remove fully their Copper Foil.Thereafter, the two-sided two sides that is covered with the plywood of copper after will the prepreg identical with prepreg with insulating resin layer used when the plywood that is covered with copper is made removing Copper Foil respectively disposes 1, so that the mode that the M face of electrolytic copper foil contacts has with it adhered to after its outside is not provided with the electrolytic copper foil (GTS-18, common Copper Foil, Furukawa Electric Industrial Co., Ltd system, M face surface roughness (Rz): 8 μ m, trade name) of the thick 18 μ m of adhesive linkage, under 200 ℃, 3.0MPa, 70 minutes punching press condition, heat press molding, made multilager base plate.And, for the conductor foil and of the combination of the insulating resin layer of making example 1～3 of the band adhesive linkage of embodiment 1B～6B, as shown in table 2 with prepreg.

[comparative example 1B～2B]

In order to compare, on overlapping 4 two sides that make the insulating resin layer of examples 1 with the base material of prepreg, so that the mode that the M face of electrolytic copper foil contacts with it adheres to electrolytic copper foil (F0-WS-12 of the thick 12 μ m that adhesive linkage is not set, Furukawa Electric Industrial Co., Ltd system, trade name) or the electrolytic copper foil (GTS-12 of the thick 12 μ m of adhesive linkage is not set, common Copper Foil, Furukawa Electric Industrial Co., Ltd system, M face surface roughness (Rz): 8 μ m, trade name) after, at 200 ℃, 3.0MPa, heat press molding under 70 minutes the punching press condition, it is (thick: 0.55mm) to have made the two-sided plywood that is covered with copper respectively.In addition, by this two-sided plywood that is covered with copper, ground same as described above has made multilager base plate respectively.In the middle of them, use the situation of the former electrolytic copper foil to be equivalent to comparative example 1B, used the situation of the latter's electrolytic copper foil to be equivalent to comparative example 2B.

[evaluating characteristics]

(Copper Foil that is covered with the plywood of copper draws the mensuration of shelling intensity)

Use the two-sided plywood that is covered with copper that obtains among embodiment 1B～6B, the comparative example 1B～2B, measured these two-sided Copper Foils that are covered with the plywood of copper same as the above-mentioned methodly and drawn stripping intensity (unit: kN/m).The result of gained is shown in the table 2.

And, draw stripping intensity for this Copper Foil, be meant that with "-" expression because after keeping, Copper Foil is peeled off, therefore can't measure Copper Foil draws stripping intensity in PCT in the table.

(the two-sided stable on heating evaluation of scolding tin that is covered with the plywood and the multilager base plate of copper)

Use two-sided plywood and the multilager base plate that is covered with copper that obtains among embodiment 1B～6B and the comparative example 1B～2B, carried out their the stable on heating evaluation of scolding tin same as the above-mentioned methodly.The result of gained is shown in the table 2.

(evaluation of the loss of the two-sided plywood that is covered with copper)

Two-sided loss (the unit: dB/m) that is covered with the plywood of copper of embodiment 1B～6B and comparative example 1B～2B has been measured on ground same as the above-mentioned method respectively.The result of gained is shown in the table 2.

[table 2]

Distinguish that according to table 2 among embodiment 1B～6B, 1B～2B compares with comparative example, can obtain more good Copper Foil and draw stripping intensity and scolding tin hear resistance, in addition, can realize enough low transmission lossizationes.Confirm in addition, among embodiment 1B～4B, compare, can obtain higher Copper Foil and draw stripping intensity and scolding tin hear resistance with embodiment 5B and 6B.

[synthesizing of polyamidoimide]

(synthesis example 1C)

At first, to possessing Dean-Stark reflux cooler, thermometer, in the separable flask of the 1L of agitator, add as (4 of the diamine compound with saturated fat ring type alkyl, 4 '-diaminourea) dicyclohexyl methyl hydride (Wandamin HM (WHM), new Japanese physics and chemistry corporate system, trade name) 45mmol, reactive silicone oil (X-22-161-B as the siloxane diamine compound, chemical industrial company of SHIN-ETSU HANTOTAI system, amine equivalent: 1500, trade name) 5mmol, trimellitic anhydride (TMA) 105mmol, as N-methyl-2-pyrrolidones (NMP) 85g of non-proton property polar solvent, the temperature in the flask is set at 80 ℃ and stirred 30 minutes.

After stirring end,, the temperature in the flask is elevated to 160 ℃, refluxed about 2 hours as adding toluene 100mL again with the aromatic hydrocarbon of water azeotropic.Stored the water of theoretical amount in the water and basis weight recipient, affirmation when the water in the water and basis weight recipient is removed, is elevated to 190 ℃ with the temperature in the flask after can't see distillating of water, removes the toluene in the reaction solution.

After the solution in the flask is returned to room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 60mmol, temperature in the flask is elevated to 190 ℃, react after 2 hours, with the NMP dilution, obtained the nmp solution (solid component concentration is 30 quality %) of the polyamidoimide of synthesis example 1C.Utilized gel permeation chromatography the weight average molecular weight of this nmp solution (Mw), its result is 34000.

(synthesis example 2C)

At first, to possessing Dean-Stark reflux cooler, thermometer, in the separable flask of the 1L of agitator, add as having Jeffermine D-2000 (the Suntechno Chemical corporate system of the diamine compound of representative examples of saturated aliphatic alkyl, trade name) 10mmol, as (4 of the diamine compound with saturated fat ring type alkyl, 4 '-diaminourea) dicyclohexyl methyl hydride (Wandamin HM (WHM), new Japanese physics and chemistry corporate system, trade name) 40mmol, trimellitic anhydride (TMA) 105mmol, as N-methyl-2-pyrrolidones (NMP) 150g of non-proton property polar solvent, the temperature in the flask is set at 80 ℃ and stirred 30 minutes.

After stirring end,, the temperature in the flask is elevated to 160 ℃, refluxed about 2 hours as adding toluene 100mL again with the aromatic hydrocarbon of water azeotropic.Stored the water of theoretical amount in the water and basis weight recipient, affirmation when the water in the water and basis weight recipient is removed, is elevated to 190 ℃ with the temperature in the flask after can't see distillating of water, removes the toluene in the reaction solution.

After the solution in the flask is returned to room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 180mmol, temperature in the flask is elevated to 190 ℃, react after 2 hours, with the NMP dilution, obtained the nmp solution (solid component concentration is 30 quality %) of the polyamidoimide of synthesis example 2C.The Mw of this nmp solution that utilized gel permeation chromatography, its result is 84000.

(synthesis example 3C)

At first, to possessing Dean-Stark reflux cooler, thermometer, in the separable flask of the 1L of agitator, add as having Jeffermine D-2000 (the Suntechno Chemical corporate system of the diamine compound of representative examples of saturated aliphatic alkyl, trade name) 30mmol, as (4 of aromatic diamine compound, 4 '-diaminourea) diphenyl methane (DDM) 120mmol, trimellitic anhydride (TMA) 315mmol, as N-methyl-2-pyrrolidones (NMP) 100g of non-proton property polar solvent, the temperature in the flask is set at 80 ℃ and stirred 30 minutes.

After stirring end,, the temperature in the flask is elevated to 160 ℃, refluxed about 2 hours as adding toluene 100mL again with the aromatic hydrocarbon of water azeotropic.Stored the water of theoretical amount in the water and basis weight recipient, affirmation when the water in the water and basis weight recipient is removed, is elevated to 190 ℃ with the temperature in the flask after can't see distillating of water, removes the toluene in the reaction solution.

After the solution in the flask is returned to room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 180mmol, temperature in the flask is elevated to 190 ℃, react after 2 hours, with the NMP dilution, obtained the nmp solution (solid component concentration is 30 quality %) of the polyamidoimide of synthesis example 3C.The Mw of this nmp solution that utilized gel permeation chromatography, its result is 74000.

[the adhesive linkage preparation of resin varnish (hardening resin composition)]

(formulation example 1C)

To as among cresols phenolic resin varnish type epoxy resin (YDCN-500, Dongdu change into corporate system, the trade name) 5.0g of (A) composition, cooperate novolaks phenolic resins as (B) composition (MEH7500, bright and change into corporate system, trade name) 3.1g and as the nmp solution 18g of the polyamidoimide that obtains among the synthesis example 1C of (C) composition.Then behind 2-ethyl-4-methylimidazole (2E4MZ, four countries change into industrial group's system, the trade name) 0.025g that has wherein added as curing accelerator, cooperate N-methyl-2-pyrrolidones 28g and MEK 13g, the adhesive linkage that is mixed with formulation example 1C is with resin varnish (solid component concentration is about 20 quality %).

And, will in YDCN-500 and MEH7500, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 190 ℃.

(formulation example 2C)

In phenol novolak type epoxy resin (N-770, big Japanese ink chemical industrial company system, trade name) 5.0g as (A) composition, the nmp solution 55g of the polyamidoimide that obtains among the synthesis example 2C of the cresols novolaks phenolic resins of cooperation conduct (B) composition (KA-1165, big Japanese ink chemical industrial company system, trade name) 3.9g, conduct (C) composition.Then behind 2-ethyl-4-methylimidazole (2E4MZ, four countries change into industrial group's system, the trade name) 0.025g that has wherein added as curing accelerator, cooperate N-methyl-2-pyrrolidones 39g and MEK 20g, the adhesive linkage that is mixed with formulation example 2C is with resin varnish (solid component concentration is about 20 quality %).

And, will in N-770 and KA-1165, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 190 ℃.

(formulation example 3C)

To as among the phenolic resin varnish type epoxy resin with biphenyl structural (NC-3000H, Japanese chemical drug corporate system, the trade name) 5.0g of (A) composition, cooperate as bisphenol-A phenolic varnish gum (YLH129, japan epoxy resin corporate system, the trade name) 2.0g of (B) composition and as the polyamidoimide nmp solution 38g that obtains among the synthesis example 3C of (C) composition.Then behind 2-ethyl-4-methylimidazole (2E4MZ, four countries change into industrial group's system, the trade name) 0.025g that has wherein added as curing accelerator, cooperate N-methyl-2-pyrrolidones 35g and MEK 13g, the adhesive linkage that is mixed with formulation example 3C is with resin varnish (solid component concentration is about 20 quality %).

And, will in NC-3000H and YLH129, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 170 ℃.

(formulation example 4C)

In conduct bisphenol A type epoxy resin (DER-331L, Dowchemical Japanese firm system, the trade name) 5.0g of (A) composition, the nmp solution 50g of the polyamidoimide that obtains among the synthesis example 1C of the cresols novolaks phenolic resins of cooperation conduct (B) composition (KA-1163, big Japanese ink chemical industrial company system, trade name) 3.2g, conduct (C) composition.Then behind 2-ethyl-4-methylimidazole (2E4MZ, four countries change into industrial group's system, the trade name) 0.025g that has wherein added as curing accelerator, cooperate N-methyl-2-pyrrolidones 46g and MEK 15g, the adhesive linkage that is mixed with formulation example 4C is with resin varnish (solid component concentration is about 20 quality %).

And, will in DER-331L and KA1163, add 2E4MZ resin solidification and the vitrification point (Tg) of resin combination be 135 ℃.

(relatively formulation example 1C)

Among the nmp solution 50g of the polyamidoimide that obtains in synthesis example 1C, cooperate N-methyl-2-pyrrolidones 50g, the adhesive linkage that is mixed with comparison formulation example 1C is with resin varnish (solid component concentration is 15 quality %).

(relatively formulation example 2C)

Among the nmp solution 50g of the polyamidoimide that in synthesis example 2C, obtains, cooperate cresols phenolic resin varnish type epoxy resin (YDCN-500, Dongdu change into corporate system, trade name) 8.8g.Then behind 2-ethyl-4-methylimidazole (2E4MZ, four countries change into industrial group's system, the trade name) 0.088g that has wherein added as curing accelerator, cooperate N-methyl-2-pyrrolidones 101g and MEK 34g, the adhesive linkage that is mixed with comparison formulation example 2 is with resin varnish (solid component concentration is about 15 quality %).

[insulating resin layer (insulating barrier) making of prepreg]

Same as the above-mentioned method, made the insulating resin layer prepreg of example 1 and 3 respectively.In addition, according to method shown below, made the insulating resin layer prepreg of example 4.

(making example 4)

At first, in the separable flask of the 2L that possesses cooling tube, thermometer, agitator, add toluene 333g and polyphenylene oxide resin (Zylon S202A, the Chemicals of Asahi Chemical Industry corporate system, trade name) 26.5g, stirring and dissolving when the temperature in the flask is heated to be 90 ℃.Then, when stirring, in flask, add 1,2-polybutadiene (B-3000, Japanese Cao Da corporate system, trade name) 100g, as the N-phenyl maleimide 15.9g of crosslinking coagent, after confirming dissolving or disperseing equably, cool to room temperature.Then, added α as radical polymerization initiator, behind α '-two (tert-butyl peroxy base) diisopropyl benzene (Perbutyl P, Nof Corp.'s system, the trade name) 3.0g, cooperate toluene 70g again, obtained the insulating resin layer varnish that solid component concentration is about 30 quality %.

Behind the insulating resin layer of the gained glass fibre (E glass, day eastern textile company system) with the thick 0.1mm of varnish impregnation, 120 ℃ of heat dryings 5 minutes, having obtained resin, to contain proportional be the insulating resin layer prepreg of the making example 4 of 50 quality %.

[embodiment 1C～4C and comparative example 1C～4C]

(making of the conductor foil of band adhesive linkage)

The adhesive linkage that obtains among formulation example 1C～4C and the comparison formulation example 1C～2C is coated on the M face (surface roughness (Rz): after 0.8 μ m) of the electrolytic copper foil (F0-WS-12, slim Copper Foil, Furukawa Electric Industrial Co., Ltd system) of thick 12 μ m with the natural respectively curtain coating of resin varnish, 150 ℃ of dryings 5 minutes, made the conductor foil of the band adhesive linkage of embodiment 1C～4C and comparative example 1C～2C.And the thickness of dried curing front attachment layer all is 3 μ m.The adhesive linkage that has used formulation example 1C, 2C, 3C and 4C is equivalent to embodiment 1C, 2C, 3C and 4C with the situation of resin varnish, and the adhesive linkage that has used relatively formulation example 1C and 2C is equivalent to comparative example 1C and 2C with the situation of resin varnish.

(the two-sided making that is covered with the plywood of copper)

On overlapping 4 certain two interareas of insulating resin layer of making example 1,3 and 4 with the base material of prepreg, so that after the mode that the adhesive linkage separately of the conductor foil of above-mentioned band adhesive linkage contacts with it adhered to any one of conductor foil of above-mentioned band adhesive linkage, by with duplexer at 200 ℃, 3.0MPa, 70 minutes punching press condition lower edge stacked direction heating press molding, the two-sided plywood that is covered with copper of having made embodiment 1C, 2C, 3C and 4C and comparative example 1C and 2C respectively is (thick: 0.55mm).The adhesive linkage of each embodiment or comparative example is as shown in table 3 with the combination of prepreg with resin varnish and insulating resin layer.

In addition, on two interareas of insulating resin layer overlapping base material that forms of 4 being made example 1 with prepreg, so that the mode that the M face of electrolytic copper foil contacts with it adhered to the electrolytic copper foil A (F0-WS-12, Furukawa Electric Industrial Co., Ltd system, trade name, Rz=0.8 μ m) of the thick 18 μ m that adhesive linkage is not set or the electrolytic copper foil B (GTS-18, common Copper Foil, Furukawa Electric Industrial Co., Ltd system, the Rz=8 μ m of M face, trade name) of the thick 18 μ m of adhesive linkage is not set, and obtained duplexer.Thereafter, duplexer is utilized the heating press molding of stacked direction under 200 ℃, 3.0MPa, 70 minutes punching press condition, the two-sided plywood that is covered with copper of having made comparative example 3C and 4C is (thick: 0.55mm).In these, will use the 3C as a comparative example of electrolytic copper foil A, the plywood that 4C as a comparative example two-sided of having used electrolytic copper foil B is covered with copper is (thick: 0.55mm).

(making of multilager base plate)

At first, same as described above, the two-sided plywood that is covered with copper of formation embodiment 1C～4C and comparative example 1C～4C utilizes etching that these Copper Foils parts are removed fully.Then, the insulating resin layer that will use in the time of will being covered with the plywood of copper with making is disposed at the two-sided two sides that is covered with plywood of removing behind the Copper Foil with the identical prepreg of prepreg in the mode of each face a slice, so that the mode that its M face contacts has with it adhered to the electrolytic copper foil (GTS-12 that the thick 12 μ m of adhesive linkage are not set in its outside, common Copper Foil, Furukawa Electric Industrial Co., Ltd system, the Rz=0.8 μ m of M face, trade name) after, with duplexer at 200 ℃, 3.0MPa, utilize the heating press molding of stacked direction under 70 minutes the punching press condition, made and embodiment 1C～4C and the corresponding multilager base plate of comparative example 1C～4C.

[evaluating characteristics]

(the two-sided Copper Foil that is covered with the plywood of copper draws the mensuration of stripping intensity)

At first, use the two-sided plywood that is covered with copper that obtains among embodiment 1C～4C, the comparative example 1C～4C, measured each two-sided Copper Foil that is covered with the plywood of copper same as the above-mentioned methodly and drawn stripping intensity (unit: kN/m).The result of gained is shown in the table 3.

And, draw stripping intensity for this Copper Foil, be meant that with "-" expression because after keeping, Copper Foil is peeled off, therefore can't measure Copper Foil draws stripping intensity in PCT in the table.

(the two-sided stable on heating evaluation of scolding tin that is covered with the plywood and the multilager base plate of copper)

Use two-sided plywood and the multilager base plate that is covered with copper that obtains among embodiment 1C～4C and the comparative example 1C～4C, utilize method same as described above to estimate their scolding tin hear resistance.The result of gained is shown in the table 3.

(evaluation of the loss of the two-sided plywood that is covered with copper)

Two-sided loss (the unit: dB/m) that is covered with the plywood of copper of embodiment 1C～4C and comparative example 1C～4C has been measured on ground same as the above-mentioned method respectively.

[table 3]

Result according to the above embodiments and comparative example can confirm, if utilize the present invention, the conductor foil of following band adhesive linkage then can be provided and post the plywood of conductor, promptly, the particularly loss in high-frequency region can be reduced fully, and the printed wiring board that has strengthened the bonding force between insulating barrier and the conductor layer fully can be formed.So distinguish, use them and the loss of the printed wiring board that obtains or multilayer circuit board is low, can have good heat-resisting property (especially after moisture absorption also very good heat-resisting property).

Claims (22)

1. conductor foil with adhesive linkage, it is the conductor foil that possesses conductor foil, is located at the band adhesive linkage of the adhesive linkage on the described conductor foil, it is characterized in that,

Described adhesive linkage is by containing

(A) composition: polyfunctional epoxy resin,

(B) composition: multifunctional phenolic resins and

(C) composition: the hardening resin composition of polyamidoimide constitutes.

2. the conductor foil of band adhesive linkage according to claim 1 is characterized in that, described (C) composition is that weight average molecular weight is the polyamidoimide below 300,000 more than 50,000.

3. the conductor foil of band adhesive linkage according to claim 1 and 2 is characterized in that, described (A) composition and described (B) mixture of ingredients reach more than 150 ℃ in the vitrification point after the curing.

4. according to the conductor foil of each described band adhesive linkage in the claim 1～3, it is characterized in that described (A) composition contains from by phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, the bromination phenol novolak type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, biphenyl type epoxy resin, the epoxy resin that contains the naphthalene skeleton, the epoxy resin that contains inferior aralkyl skeleton, the epoxy resin that contains biphenyl-inferior aralkyl skeleton, phenol salicylide phenolic resin varnish type epoxy resin, low alkyl group substituted phenol salicylide phenolic resin varnish type epoxy resin, the epoxy resin that contains the bicyclopentadiene skeleton, at least a epoxy resin of selecting in the group that multifunctional glycidyl group amine type epoxy resin and multifunctional alicyclic epoxy resin constitute.

5. according to the conductor foil of each described band adhesive linkage in the claim 1～4, it is characterized in that described (B) composition contains from by at least a multifunctional phenolic resins of selecting the copoly type resin of aralkyl-type phenol resin, dicyclopentadiene-type phenolic resins, salicylide type phenolic resins, benzaldehyde type phenolic resins and aralkyl-type phenol resin and the group that phenolic varnish type phenolic resins constitutes.

6. according to the conductor foil of each described band adhesive linkage in the claim 1～5, it is characterized in that described (C) composition contains the construction unit that is made of saturated hydrocarbons.

7. according to the conductor foil of each described band adhesive linkage in the claim 1～6, it is characterized in that with respect to total 100 mass parts of described (A) composition and described (B) composition, the cooperation ratio of described (C) composition is 0.5～500 mass parts.

8. according to the conductor foil of each described band adhesive linkage in the claim 1～7, it is characterized in that described hardening resin composition also contains cross-linked rubber particle and/or polyvinyl acetal resin conduct (D) composition.

9. the conductor foil of band adhesive linkage according to claim 8, it is characterized in that described (D) composition is at least a cross-linked rubber particle of selecting from the group that the core shell particles by acrylonitrile butadiene rubber particle, carboxyl acid modified acrylonitrile butadiene rubber particle and butadiene rubber-acrylic resin constitutes.

10. according to the conductor foil of each described band adhesive linkage in the claim 1～9, it is characterized in that, described adhesive linkage be by the resin varnish that will contain described hardening resin composition and described solvent coat form the resin varnish layer on the surface of described conductor foil after, remove described solvent and get from described resin varnish layer.

11. the conductor foil according to each described band adhesive linkage in the claim 1～10 is characterized in that described adhesive linkage has the thickness of 0.1～10 μ m.

12. the conductor foil according to each described band adhesive linkage in the claim 1～11 is characterized in that, 10 mean roughness (Rz) of the face of a side that is formed with described adhesive linkage of described conductor foil are below the 4 μ m.

13. plywood that posts conductor, it is characterized in that, get by following operation, described being operating as: on the one side at least of the insulative resin film that contains resin with insulating properties, so that the mode that the adhesive linkage of the conductor foil of band adhesive linkage contacts with it, the conductor foil of each described band adhesive linkage in the stacked claim 1～12 and after obtaining laminated body is to described laminated body heating and pressurization.

14. a plywood that posts conductor,

Possess insulating barrier, be laminated in conductor layer on the described insulating barrier across bonding cured layer,

Described bonding cured layer and described conductor layer are formed by the conductor foil of each described band adhesive linkage in the claim 1～12,

Described bonding cured layer is made of the solidfied material of the described adhesive linkage of the conductor foil of described band adhesive linkage, and described conductor layer is made of the described conductor foil of the conductor foil of described band adhesive linkage.

15. a plywood that posts conductor,

Possess insulating barrier, with the conductor layer of described insulating barrier subtend configuration, by the bonding cured layer of described insulating barrier and described conductor layer clamping,

Described bonding cured layer is by containing

(A) composition: polyfunctional epoxy resin,

(B) composition: multifunctional phenolic resins and

(C) composition: the solidfied material of the resin combination of polyamide constitutes.

16. according to claim 14 or the 15 described plywoods that post conductor, it is characterized in that,

Described insulating barrier is made of insulative resin, the base material that is disposed in the described insulative resin,

As described base material, possess weaving cotton cloth or nonwoven of the fiber made by at least a material of from the group that constitutes by glass, paper wood and organic high molecular compound, selecting.

17. the plywood that posts conductor according to claim 16 is characterized in that, described insulating barrier contain have the ethene unsaturated bond resin as described insulative resin.

18. according to claim 16 or the 17 described plywoods that post conductor, it is characterized in that described insulative resin contains at least a resin of selecting from the group that is made of polybutadiene, poly-triallylcyanurate, poly-cyanacrylate, the polyphenylene oxide that contains unsaturated group and maleimide compound.

19., it is characterized in that described insulative resin contains at least a resin of selecting from the group that is made of polyphenylene oxide and thermoplastic elastomer (TPE) according to each described plywood that posts conductor in the claim 16～18.

20., it is characterized in that described insulating barrier has the relative dielectric constant below 4.0 under 1GHz according to each described plywood that posts conductor in the claim 14～19.

21. a printed wiring board is characterized in that, gets by the described conductor layer in each described plywood that posts conductor in the claim 14～20 is processed into the circuit pattern with regulation.

22. a multilayer circuit board, it is to possess: have the core substrate of one deck printed wiring board at least, the one side at least that is disposed at described core substrate goes up and has the multilayer circuit board of the outer-layer circuit plate of one deck printed wiring board at least, it is characterized in that,

One deck at least in the printed wiring board of described core substrate is the described printed wiring board of claim 21.

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