CN101432134B - 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

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

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

In the network associated electronic devices such as the mobile communicating equipment that the portable phone of take is representative or its base station apparatus, server, router or mainframe computer etc., require jumbo information low-loss and transmit at high speed, process.In order to tackle this requirement, in the printed wiring board carrying in device as above, the high frequencyization of the handled signal of telecommunication constantly advances.But, because the signal of telecommunication has the character that high frequency is just more easily decayed, therefore for the printed wiring board of processing the signal of telecommunication of high frequency, require to surpass degree reduction loss in the past.

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 relative dielectric constant or the low fluorine resin of dielectric loss angle tangent.But this fluorine resin, because in general melt viscosity is high, mobility is low, therefore need to be set high-temperature and high-pressure conditions etc. when stamping, is shaped not necessarily easy.In addition, as printed wiring board material used in communication equipment as above etc., except processability, also have dimensional stability, with the shortcoming of cementability deficiency of metal coating and so on.

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

In addition, in printed wiring board, preferably the cementability of insulating barrier and conductor layer provided thereon is high.If the cementability of insulating barrier and conductor layer is low, just easily there is producing in use the not good situations such as both peeling off.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 formed, yet in order to obtain the good cementability of insulating barrier and conductor layer, this insulating barrier of plywood and cementability height of conductor foil that posts conductor is also very important.

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

Patent documentation 1: 6-No. 69746 communiques of Japanese Patent Publication

Patent documentation 2: 7-No. 47689 communiques of Japanese Patent Publication

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: 6-No. 92533 communiques of Japanese Patent Publication

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 electronic equipment as above etc., requirement can be tackled the further high frequency of the signal of telecommunication.But, if just for example the resin of the low-k described in above-mentioned patent documentation 1～6, low-dielectric loss angle tangent is used for to dielectric material, realize the low transmission loss of the signal of telecommunication of insulating barrier (dielectric layer), be difficult to tackle fully this kind of high frequency.; the reason of the loss of the signal of telecommunication is the loss (dielectric loss) being caused by insulating barrier, loss (conductor losses) two aspects that caused by conductor layer; and in recent years to the reply of high frequency in; 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 practical most printed wiring board (multilayer circuit board), the thickness attenuation as being disposed at signals layer and the insulating barrier between bottom of conductor layer, reaches below 200 μ m.Thus, in the situation that adopted the low-k that has to a certain degree or the resin of dielectric loss angle tangent in the material of insulating barrier, as the loss of this wiring board integral body, compare with dielectric loss, conductor losses one side is conclusive.

Here, as the method that realizes the minimizing of conductor losses, can enumerate that use conductor layer (roughening treated side, hereinafter referred to as " 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: be Rz) 4 μ m, the conductor foil being particularly preferably below 2 μ m (is called this kind of conductor foil " low roughening paper tinsel " below that possess M face.) the plywood that posts conductor.

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

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

In addition, in the method described in application patent documentation 9,10, use in the situation that the Rz of M face be on the surface of the low roughening Copper Foil below 2 μ m, set in advance thick 0.1～5 μ m polyamide-imide resin with adhesive linkage Copper Foil, make printed wiring board, confirmation can obtain high Copper Foil and draw stripping intensity.But, because the concavo-convex grappling effect causing of the M face by conductor foil is low, therefore the bonding force (engaging force) between polyamide-imide resin and insulating barrier dies down, and distinguishes such as when the heating (while particularly heating after moisture absorption) etc., between these layers, easily produces and peels off.

In addition, method described in application patent documentation 11, use is that on the surface of the low roughening Copper Foil below 4 μ m, to have set in advance thickness 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.In this situation, although can obtain high Copper Foil, draw stripping intensity, yet have the tendency that the concavo-convex grappling effect causing by the M face of conductor foil reduces irrelevantly.Consequently, the bonding force (engaging force) of folder between the insulating barrier that promotes bonding elastomer layer dies down, and distinguishes when heating and easily produces and peel off between these layers.

Summary of the invention

So Given this present invention plants situation and complete, its object is, a kind of conductor foil with adhesive linkage that can manufacture following printed wiring board is provided, that is, can reduces well the particularly loss of high-frequency region, excellent heat resistance, and be difficult to produce peeling off of interlayer.The present invention also aims to, the plywood that posts conductor, printed wiring board and the multilayer circuit board that use this kind to obtain with the conductor of adhesive linkage are provided.

In order to reach above-mentioned purpose, conductor foil with adhesive linkage of the present invention is the conductor foil with adhesive linkage that possesses conductor foil, is located at 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 forms.

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

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

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

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

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

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

In addition, as the multifunctional phenolic resins of (B) composition, preferably contain at least one multifunctional phenolic resins of selecting from the copoly type resin by 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 form.

By the composition outside they in these polyfunctional epoxy resins or multifunctional phenolic resins and the present invention is combined, just can give good cementability or heat resistance to bonding cured layer.

In addition, the polyamidoimide for as (C) composition, preferably contains the construction unit consisting of saturated hydrocarbons.When use contains the construction unit that consists of saturated hydrocarbons as polyamidoimide, except utilizing bonding cured layer, the cementability of conductor foil or insulating barrier etc. is improved, particularly when moisture absorption, also can maintain good cementability.Consequently, even if use the printed wiring board obtaining with the conductor foil of adhesive linkage of the present invention will there is after moisture absorption the also characteristic of peeling off of the raw interlayer of utmost point difficult labour.

In forming the hardening resin composition of adhesive linkage, with respect to (A) composition and (B) total 100 mass parts of composition, (C) mixing ratio of composition is preferably 0.5～500 mass parts, more preferably 10～400 mass parts.If (C) mixing ratio of composition is within the scope of this,, except can obtaining good cementability, also has and improve especially the toughness of bonding cured layer or the tendency of heat 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.By also containing these compositions, can further improve, utilize bonding cured layer and cementability to conductor foil etc.

Wherein, from obtaining well especially the viewpoint of above-mentioned characteristic, consider, as (D) composition, at least one cross-linked rubber particle of selecting in the group preferably forming from the core shell particles by acrylonitrile butadiene rubber particle, carboxyl acid modified acrylonitrile butadiene rubber particle and butadiene rubber-acrylic resin.

In conductor foil with adhesive linkage of the present invention, adhesive linkage is by forming after resin varnish layer on the surface the resin varnish that contains hardening resin composition and solvent being coated to described conductor foil, removes described solvent and obtain from described resin varnish layer.The adhesive linkage so forming becomes thickness or the uniform layer of characteristic, the easy good cementability of performance and conductor foil etc. after it solidifies.

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

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

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

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

; the plywood that posts conductor of the present invention also can be using following content as feature;; 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 forms.

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

In the plywood that posts conductor of the present invention, preferably insulating barrier consists 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 one material of selecting in the group from consisting of glass, paper wood and organic high molecular compound makes.Like this, just can realize more reliably the inhibition of peeling off of the minimizing of loss, stable on heating raising and interlayer.

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

Or insulative resin preferably contains at least one resin of selecting in the group from consisting of polyphenylene oxide and thermoplastic elastomer (TPE).These resins, because dielectric constant is low and dielectric loss angle tangent is low, therefore can significantly reduce dielectric loss.

Insulating barrier preferably has the ratio dielectric constant below 4.0 under 1GHz.If utilize the insulating barrier that meets this condition, can significantly reduce dielectric loss.Consequently, the printed wiring board that the plywood that posts conductor by this obtains 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 that the circuit pattern by the conductor foil that posts the plywood of conductor of the present invention is processed into regulation obtains.Even if this printed wiring board is in the situation that being used low roughening paper tinsel, also the raw circuit pattern consisting of conductor foil of utmost point difficult labour and insulating resin layer peels off, in addition,, because bonding cured layer has good heat resistance, therefore also there is as a whole good heat resistance.

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 have high-fire resistance that is difficult to produce interlayer.; multilayer circuit board of the present invention is to possess: have the core substrate of one deck printed wiring board at least, at least one side that is disposed at this core substrate goes up and have at least multilayer circuit board of the outer-layer circuit plate of one deck printed wiring board; it is characterized in that, at least one deck in the printed wiring board of core substrate is printed wiring board of the present invention.

And, in the printed wiring board that is applicable to the reply high frequency in electronic equipment as above, not only require to realize low transmission loss, but also require good impedance Control.In order to realize this point, when the manufacture of printed wiring board, the precision that improves the good pattern width that is used to form conductor layer is just very important.Here, in the situation that use the little conductor foil of surface roughness of 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 of situation, if utilize the conductor foil with adhesive linkage of the invention described above, even if using low roughening paper tinsel, and in the situation that use the insulative resin material with low-k and low-dielectric loss angle tangent in insulating barrier, also can obtain the enough cementabilities between insulating barrier and conductor foil.So, if the printed wiring board of the conductor foil with adhesive linkage of the present invention etc. has been used in utilization, not only can realize low transmission loss, but also can realize good impedance Control.

For utilizing the conductor foil with adhesive linkage of the present invention, can obtain the essential factor of good cementability as above, although be not still clear fully now, the inventor etc. have carried out supposition as follows.For example, in the situation that 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 of easy generation interlayer.; after the conductor foil that is the plywood that posts conductor of the low roughening paper tinsel below 4 μ m at the Rz by the stacked M face by the two sides at insulating resin layer is removed; on its face, stack gradually prepreg and conductor foil is made multilayer laminate; and then make in the situation of printed wiring board, also very little to the roughness of the insulating resin layer transfer printing of internal layer by low roughening paper tinsel.

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

In such cases, as the plywood that posts conductor, by using at the stacked plywood obtaining with the conductor foil of adhesive linkage in the surface of insulating resin layer, just can reduce the reduction of bonding force as above.That is,, in the situation that use this plywood that posts conductor to form multilayer laminate, owing to being folded with the adhesive linkage deriving from the conductor foil of adhesive linkage between insulating resin layer and prepreg, therefore two-layer cementability is enhanced thus to a certain extent.

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

Different with it, in the conductor foil with adhesive linkage of the present invention, contained (A) and (B) good aspect the heat resistance (the particularly heat resistance after moisture absorption) of composition after solidifying in adhesive linkage.So, use this multilayer circuit board obtaining with the conductor foil of adhesive linkage or printed wiring board just to there is good heat resistance as a whole.In addition, due to (A) and (B), composition is also good aspect the cementability of insulating resin layer or conductor foil, even if therefore reduce the addition as the polyamidoimide of (C) composition, bonding cured layer also can maintain enough cementabilities.In addition, as a rule, because polyamidoimide has the tendency that the heat resistance (the particularly heat resistance after moisture absorption) of bonding cured layer is reduced, if therefore utilize the conductor foil with adhesive linkage of the present invention,, by the addition of polyamidoimide being made as to essential Min., also can realize stable on heating further raising.

Utilize these essential factors, use the conductor foil with 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 there is specific bonding cured layer between conductor layer (circuit pattern) and insulating barrier, even thereby in the situation that possess conductor layer and the few insulating barrier of dielectric loss that bonding plane is level and smooth, the cementability of conductor layer and insulating barrier is also very good, and heat resistance is also very good.

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

Accompanying drawing explanation

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

Fig. 2 means the figure that the local section of the plywood that posts conductor of first case forms.

Fig. 3 means the figure that the local section of the plywood that posts conductor of second case forms.

Fig. 4 means the figure that the local section of the printed wiring board of first case forms.

Fig. 5 means the figure that the local section of the printed wiring board of second case forms.

Fig. 6 schematically shows the figure that the local section of the multilayer circuit board of first case forms.

Fig. 7 schematically shows the figure that the local section of the multilayer circuit board of second case forms.

Wherein, 10 ... conductor foil, 11 ... circuit pattern, 12 ... 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 ... plating overlay film, 62 ... insulating barrier, 64 ... bonding cured layer, 66 ... internal layer circuit pattern, 68 ... interlayer insulating film, 70 ... through hole (through hole), 72 ... outer circuit pattern, 74 ... mesoporous (via hole), 76 ... through hole, 80 ... core substrate, 90 ... bonding cured layer, 92 ... insulating resin layer, 94 ... plating overlay film, 96 ... through hole, 100 ... conductor foil with adhesive linkage, 110 ... 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, to of the present invention, be preferred embodiment elaborated.It should be noted that, in figure, for identical element, use same-sign, the repetitive description thereof will be omitted.In addition, waiting up and down position relationship as long as no particularly pointing out, is exactly the position relationship based on shown in figure.In addition, the dimensional ratios of accompanying drawing is not limited to illustrated ratio.

[with the conductor foil of adhesive linkage]

First, the conductor foil with adhesive linkage is preferred embodiment described.Fig. 1 is the partial perspective view of the conductor foil with adhesive linkage preferred embodiment.The formation with adhesive linkage conductor foil 100 shown in Fig. 1 is the adhesive linkage 20 that possesses conductor foil 10, joins and form with the roughening treated side (M face) 12 of this conductor foil 10.

(conductor foil)

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

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

Conductor foil 10 can be both the single layer structure consisting of a kind of metal material, can be also the single layer structure consisting of various metals material, can also be by 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 above-mentioned conductor foil 10, for example as Copper Foil, on market, can buy F1-WS (Furukawa CIRCUIT FOIL company system, trade name, Rz=1.9 μ m), F2-WS (Furukawa CIRCUIT FOIL company system, trade name, Rz=2.0 μ m), F0-WS (Furukawa CIRCUIT FOIL company system, trade name, Rz=1.0 μ m), HLP (day ore deposit metal company system, trade name, Rz=0.7 μ m), T9-SV (Bo Fen industrial group of FUKUDA METAL system, Rz=1.8 μ m) etc., they are all suitable.

(adhesive linkage)

Adhesive linkage 20 with the conductor foil 100 of 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 forms.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, 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, have the tendency of the high-frequency transmission characteristic reduction of the plywood that posts conductor.To forming each composition of the hardening resin composition of adhesive linkage 20, describe below.

First, (A) composition is described.

Polyfunctional epoxy resin as (A) composition is in a molecule, to have the compound of a plurality of epoxy radicals, is in utilizing the compound of the state of a plurality of molecules of reaction bonded between epoxy radicals.As this kind (A) composition, for example can enumerate phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, bromination phenol novolak type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, biphenyl type epoxy resin, epoxy resin containing naphthalene skeleton, epoxy resin containing sub-aralkyl skeleton, epoxy resin containing biphenyl-sub-aralkyl skeleton, phenol salicylide phenolic resin varnish type epoxy resin, low alkyl group substituted phenol salicylide phenolic resin varnish type epoxy resin, epoxy resin containing bicyclopentadiene skeleton, multifunctional glycidyl group amine type epoxy resin and multifunctional alicyclic epoxy resin etc.As (A) composition, both can contain separately a kind of in them, also can combine 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 as (A) composition, just can obtain at an easy rate good cementability and the electrical characteristic of the solidfied material (bonding cured layer) of adhesive linkage 20.

Below, (B) composition is described.

Multifunctional phenolic compound as (B) composition is in a molecule, to have the compound of a plurality of phenol hydroxyls, as the curing agent that belongs to the polyfunctional epoxy resin of (A) composition, plays a role.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 combine contain two or more.

Above-mentioned (A) composition and (B) composition are preferably so that the vitrification point after the solidifying of the mixture that they are obtained by mixing reaches 150 ℃ of above modes selects.By making (A) composition and (B) solidfied material of the mixture of composition meet this kind of condition, the tendency that the heat resistance after the moisture absorption of the bonding cured layer obtaining after solidifying will be improved.Consequently, use printing (printed) wiring board obtaining with the conductor foil 100 of adhesive linkage also can in practical temperature range, there is good heat resistance.

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 more than 20,000 weight average molecular weight below 300,000 (following table is shown " Mw "), more preferably has more than 50,000 Mw below 300,000, further preferably has more than 50,000 Mw below 250,000.Here, in Mw, can apply following value, that is, utilize gel permeation chromatography to measure, the value that the lubber-line made from use polystyrene standard converts.

If (C) molecular weight of composition is less than 20,000, the hardening resin composition that contains this (C) composition in use and in the conductor foil with adhesive linkage that obtains, and then in using this printed wiring board obtaining with the conductor foil of adhesive linkage, the cementability of bonding cured layer and conductor foil (conductor layer) just has the tendency reducing irrelevantly.Especially in the situation that reduced the thickness of conductor foil, it is more obvious that this tendency becomes.On the other hand, because molecular weight surpasses 300,000, the mobility 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 consisting of saturated hydrocarbons in its molecule.By making (C) composition contain saturated hydrocarbons, utilize the cementability to conductor foil etc. that bonding cured layer obtains will become good.In addition, due to the moisture-proof raising of (C) composition, can also maintain well the cementability of the bonding cured layer after moisture absorption.Consequently, use the moisture-proof heat resistance of the printed wiring board obtaining with the conductor foil 100 of adhesive linkage etc. of present embodiment to improve.(C) composition is particularly preferably in having the construction unit consisting of saturated hydrocarbons in main chain.

The construction unit that should consist of saturated hydrocarbons is particularly preferably saturated fat ring type alkyl.In the situation that thering is 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 heat resistance that possesses its printed wiring board etc. further improves.In addition,, in the situation that the Mw of (C) composition is more than 20,000, in particular for more than 50,000, have the tendency that can stably obtain effect as above.

In addition, (C) composition more preferably contains siloxane structure in its main chain.So-called siloxane structure is the construction unit that the substituent silicon atom with regulation is alternatively combined repeatedly with oxygen atom.By making (C) composition contain siloxane structure in main chain, the 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 has the tendency of easy formation adhesive linkage 20.

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

In addition, (C) composition that contains siloxane structure in main chain also can synthesize according to 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 to contain and there are 3 above diamine compounds of aromatic ring and the mixture of siloxane diamine and trimellitic acid anhydride reactants, make to contain method (methods described in 06-No. 116517 communiques of Japanese kokai publication hei) that the mixture of rewarding imidodicarbonic diamide dicarboxylic acids reacts with aromatic diisocyanate etc.If utilize the hardening resin composition of the present embodiment that forms adhesive linkage 20, use with synthetic (C) composition of these known methods, also can obtain sufficiently high conductor foil and draw stripping intensity.

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

This kind of polyamidoimide for example can obtain by following operation,, make to have diamine compound and the trimellitic acid anhydride reactant of saturated hydrocarbyl, at the dicarboxylic acids containing imide that makes gained, derive and become after sour halide, or use condensing agent to react with diamine compound.Or, also can obtain by following operation, that is, make to have diamine compound and the trimellitic acid anhydride reactant of saturated hydrocarbyl, vulcabond is reacted with the dicarboxylic acids containing imide of gained.And the polyamidoimide with saturated fat ring type alkyl can obtain by following operation, that is, in these methods, the diamine compound as saturated hydrocarbyl with saturated fat ring type alkyl is used as raw material.

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

[changing 1]

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

[changing 2]

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

As with above-mentioned formula (1a) or the diamine compound with saturated hydrocarbyl (1b) representing, specifically, can exemplify compound as follows.That is, for example can exemplify 2,2-bis-[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-bis-[4-(4-aminocyclohexyl oxygen base) cyclohexyl] HFC-236fas, two [4-(4-aminocyclohexyl oxygen base) cyclohexyl] methane, 4,4 '-bis-(4-aminocyclohexyl oxygen base) bicyclohexane, two [4-(4-aminocyclohexyl oxygen base) cyclohexyl] ether, two [4-(4-aminocyclohexyl oxygen base) cyclohexyl] ketone, 1,3-bis-(4-aminocyclohexyl oxygen base) benzene, Isosorbide-5-Nitrae-bis-(4-aminocyclohexyl oxygen base) benzene, 2,2 '-dimethyl dicyclohexyl-4,4 '-diamines, 2,2 '-bis-(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 '-dihydroxyl 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-bis-(4-aminocyclohexyl) propane etc.Diamine compound both can have been used a kind of in these compounds individually, also can be used in combination two or more.And, in the manufacture of the polyamidoimide of present embodiment, as described later, also can be used together other diamine compound, do not there is the diamine compound of saturated hydrocarbyl.

The diamine compound with saturated hydrocarbyl for example can be by easily obtaining its aromatic rings hydrogenating reduction having the aromatic diamine compound of the aromatic rings of the structure corresponding with saturated hydrocarbyl.As this kind of aromatic diamine compound, for example, can exemplify 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane and (be expressed as below " BAPP ".), two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fas, two [4-(4-amino-benzene oxygen) phenyl] methane, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] ether, two [4-(4-amino-benzene oxygen) phenyl] ketone, 1,3-bis-(4-amino-benzene oxygen) benzene, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 2,2 '-dimethyl diphenyl base-4,4 '-diamines, 2,2 '-bis-(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, such as enumerating, drawing 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.

In the situation that be to use the material that there is the diamine compound of saturated hydrocarbyl and obtain as above as the polyamidoimide of (C) composition, in the main chain of polyamidoimide, will comprise the construction unit being formed by saturated hydrocarbyl.This kind of polyamidoimide derives from the construction unit consisting 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 with adhesive linkage that has used the hardening resin composition that comprises the polyamidoimide with the construction unit being formed by saturated hydrocarbyl in adhesive linkage 20, compare with for example having used the situation of the resin combination that comprises the polyamidoimide with aromatic rings, when the plywood of conductor is posted in manufacture, in the time of can suppressing significantly its moisture absorption and conductor foil (conductor layer) and insulating barrier etc. between the reduction of cementability.And the diamine compound as having saturated hydrocarbyl, has been used in the situation of the diamine compound with ester ring type saturated hydrocarbyl, this kind of effect will become obvious especially.

As the polyamidoimide of (C) composition, can be also 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 can import the structure that consists of saturated hydrocarbyl construction unit in addition in polyamidoimide, more easily obtain required characteristic.

As the diamine compound having beyond the diamine compound of saturated hydrocarbyl, first can enumerate the compound representing with following general formula (3).

[changing 3]

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

In the diamine compound representing with above-mentioned formula (3), best R ⁸and R ⁹independently of one another for hydrogen atom, the carbon number alkyl that is 1～3 or also can there is substituent phenyl.As the substituting group that also can be combined with this phenyl, can exemplify carbon number and be 1～3 alkyl, halogen atom etc.In the diamine compound representing with general formula (3), from realize the viewpoint of low elastic modulus and high Tg simultaneously, consider L ⁴be particularly preferably oxygen base.As this kind of diamine compound, specifically, can exemplify Jeffermine D-400, Jeffermine D-2000 (being Suntechno Chemical company system, trade name above) etc.

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

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

[changing 4]

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

[changing 5]

As aromatic diamine, specifically, can enumerate 2,2-bis-[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-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fas, two [4-(4-amino-benzene oxygen) phenyl] methane, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] ether, two [4-(4-amino-benzene oxygen) phenyl] ketone, 1,3-bis-(4-amino-benzene oxygen) benzene, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 2,2 '-dimethyl diphenyl base-4,4 '-diamines, 2,2 '-bis-(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 have been used separately a kind of in above-mentioned compound, also can be used in combination two or more.

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

In addition, as with there is the diamine compound of saturated hydrocarbyl the diamine compound of use, the siloxane diamine preferably representing with following general formula (6).

[changing 6]

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

As this kind of siloxane diamine, particularly preferably R ¹³～R ¹⁸for the compound of methyl, that is, particularly preferably there is the compound that combines amino structure at two ends of dimethyl siloxane.And, as siloxane diamine, both can use separately a kind of compound, also two or more compound combinations can be used.

As the siloxane diamine representing with above-mentioned general formula (6), 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) (being chemical industry society of SHIN-ETSU HANTOTAI system, trade name above), BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200) (above, Dow Corning Corporation's system: Toray Dowconing Silicone company system, trade name) etc. can buy on market.

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

In the manufacture of polyamidoimide with the construction unit being formed by saturated hydrocarbons, first, as diamine compound, prepare the diamine compound that contains the diamine compound at least with saturated hydrocarbyl.Then, make these diamine compounds and trimellitic acid anhydride reactant.Now, between the carboxyl that the amino having, trimellitic anhydride have or acid anhydride, produce reaction at diamine compound, generate amide groups.In this reaction, particularly preferably produce reacting of the amino of diamine compound and the acid anhydride of trimellitic anhydride.

This reaction is preferably dissolved or dispersed in diamine compound, trimellitic anhydride in non-proton property polar solvent, at 70～100 ℃, carries out.As non-proton property polar solvent, can exemplify N-methyl-2-pyrrolidones (NMP), γ-butyrolactone, N, N-dimethyl formamide, N, N-dimethyl acetamide, methyl-sulfoxide, sulfolane, cyclohexanone etc.Wherein, NMP particularly preferably.These non-proton property polar solvents both can have been used separately a kind of, 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 %.When the solid constituent in this solution is less than 10 quality %, 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 %, the dissolubility of trimellitic anhydride reduces, and has and is difficult to carry out the tendency of reaction fully.

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

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

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

[changing 7]

In formula (7), L ⁸the diamine compound that expression represents with above-mentioned general formula (1a), (1b), (3), (4a), (4b) or (6) removed amino residue.Like this, as the diacid containing imide, can obtain having the L of the structure corresponding with the diamine compound using as raw material ⁸various compounds.

As carrying out the imido method of synthesizing polyamides with the diacid containing imide so obtaining, can enumerate method as follows.That is, first, as the first method, can enumerate after the diacid containing imide as above is derived as sour halide, by the method for itself and diamine compound copolymerization as above.

Containing the diacid of imide, can utilization derive at an easy rate as sour halide with thionyl chloride or phosphorus trichloride, phosphorus pentachloride, reacting of dichloromethyl ether.In addition the halide containing the diacid of imide so obtaining, can be under room temperature or heating condition at an easy rate with diamine compound copolymerization.

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

As third method, can enumerate and make containing the diacid of imide and the method for di-isocyanate reaction.Via this reaction in the situation that, as diamine compound and the trimellitic anhydride of the raw material containing the diacid of imide, preferably set as shown below with the ratio of vulcabond.; (diamine compound: trimellitic anhydride: vulcabond) calculate and preferably reach 1.0:(2.0～2.2 with mol ratio): the scope of (1.0～1.5), more preferably reaches 1.0:(2.0～2.2): the scope of (1.0～1.3).By adjustment, be this kind of mol ratio, just can obtain HMW more and be conducive to the polyamidoimide that film forms.

As vulcabond used in third method, can exemplify the compound representing with following general formula (8).

[changing 8]

OCN—L ⁹—NCO (8)

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

[changing 9]

As the vulcabond representing with above-mentioned general formula (8), can enumerate aliphatic diisocyanate or aromatic diisocyanate, preferred fragrance (cyclo) aliphatic diisocyanates, particularly preferably by both and use.As aromatic diisocyanate, can exemplify 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, MDI particularly preferably.By using MDI as aromatic diisocyanate, can improve the flexibility of the polyamidoimide of gained, and reduce crystallinity.The film-shaped that consequently, can improve polyamidoimide becomes second nature.On the other hand, as aliphatic diisocyanate, can exemplify hexylidene diisocyanate, 2,2,4-trimethyl hexylidene diisocyanate, IPDI etc.

By aromatic diisocyanate and aliphatic diisocyanate use in the situation that, preferably with respect to aromatic diisocyanate 100 molar part, add the aliphatic diisocyanate of 5～10 molar part left and right.So just can further improve the heat resistance of the polyamidoimide of gained.

Can, by adding vulcabond in the solution to containing containing the diacid of imide, make it to react and carry out under the reaction temperature of 130～200 ℃ containing reacting of the diacid of imide and vulcabond in third method.In addition, this reaction also can be carried out with base catalyst.In this situation, preferably reaction temperature is made as to 70～180 ℃, is more preferably made as 120～150 ℃.Owing to carrying out this reaction under the existence when at base catalyst, with do not having the situation of reacting under the condition of base catalyst to compare, therefore can under lower temperature, make reaction carry out, can suppress the carrying out of the side reaction of reaction between the vulcabond under hot conditions and so on.Consequently, can obtain the more polyamidoimide compound of HMW.

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

The polyamidoimide obtaining as utilizing above-mentioned the whole bag of tricks, for example, can enumerate the material with the construction unit representing with following general formula (10).And, in following formula (10), L ⁸and L ⁹with above-mentioned L ⁸and L ⁹synonym.

[changing 10]

Hardening resin composition is preferred embodiment to contain (A) as above～(C) composition of composition.In addition,, in this kind of hardening resin composition, preferably to meet the mixing ratio of condition as follows, comprise (A)～(C) composition.

First, for the mixing ratio of (B) composition in hardening resin composition, with respect to (A) composition 100 mass parts, be preferably 0.5～200 mass parts, more preferably 10～150 mass parts.If (B) mixing ratio of composition is less than 0.5 mass parts, at the conductor foil 100 with adhesive linkage or use in the printed wiring board that it obtains, have the toughness of bonding cured layer or the tendency reducing with the cementability of conductor foil (conductor layer).On the other hand, if surpass 200 mass parts, not only the Thermocurable of adhesive linkage 20 reduces, and because the reactivity of bonding cured layer and insulating resin layer etc. reduces, therefore in the situation that formed the plywood that posts conductor or printed wiring board as described later, heat 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. is with regard to likely reduction.

In addition, for the mixing ratio of (C) composition, with respect to (A) composition and (B) total 100 mass parts of composition, be preferably made as 10～400 mass parts.If mixing ratio that should (C) composition is less than 10 mass parts, at the conductor foil 100 with adhesive linkage or use it and in the printed wiring board that obtains, have the toughness of bonding cured layer or the tendency reducing with the cementability of its conductor foil (conductor layer).On the other hand, if surpass 400 mass parts, heat 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 likely reduce.

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

The mixing ratio of the curing accelerator in hardening resin composition preferably decides according to the mixing ratio of (A) composition.Specifically, with respect to (A) composition 100 mass parts, be preferably made as 0.05～10 mass parts.If coordinate curing accelerator within the scope of this, 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 reactivity and curability.Consequently, the cured layer being obtained by adhesive linkage 20 (bonding cured layer) will have more good resistance to chemical reagents, heat resistance or moisture-proof heat 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.

First, as (D) composition, particularly preferably contain (D1) cross-linked rubber particle.As cross-linked rubber particle, be preferably selected from least one 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 by acrylonitrile and butadiene copolymer, and in the stage of copolymerization, it is crosslinked partly, makes emboliform material.In addition, carboxyl acid modified acrylonitrile butadiene rubber particle is by above-mentioned copolymerization, the carboxylic acids such as simultaneously co-polypropylene acid, methacrylic acid and must 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, then adds the monomers such as acrylate or acrylic acid and continues polymerization.The size of these cross-linked rubber particles is calculated with an average grain diameter, is preferably made as 50nm～1 μ m.As cross-linked rubber particle, the above-mentioned material of interpolation that both can be independent, also can combine add two or more.

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

In addition, as (D) composition, more preferably contain (D2) polyvinyl acetal resin.Particularly, when conduct (D) composition is by (D1) cross-linked rubber particle, (D2) polyvinyl acetal resin used time, due to the drawing stripping intensity, the stripping intensity of drawing of the electroless plating after chemical roughening improved, therefore particularly preferably conductor foil of utilizing that bonding cured layer obtains.

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 without particular limitation the various resins with various amount of hydroxyl groups or acetyl base unit weight, however the resin that particularly preferably degree of polymerization is 1000～2500.If the degree of polymerization of polyvinyl acetal resin is this scope, can guarantee fully the scolding tin heat resistance of bonding cured layer.In addition, the viscosity of the varnish that contains hardening resin composition, the property disposed can become good, thereby there is the manufacture making with the conductor foil 20 of adhesive linkage to become, are easy to tendency.

Here the number-average degree of polymerization of said polyvinyl acetal resin for example can adopt the value by number-average molecular weight (using the lubber-line of the polystyrene standard of (gel permeation chromatography) to measure) decision of the polyvinyl acetate as 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 meet the condition identical with polyvinyl acetal resin.

As polyvinyl acetal resin, commodity electrochemical Butyral4000-2 by name of making such as commodity S-Lec by name BX-1, BX-2, BX-5, BX-55, BX-7, BH-3, BH-S, KS-3Z, KS-5, KS-5Z, KS-8, KS-23Z, the electrochemical industry (strain) that can enumerate ponding chemical industry (strain) system, 5000A, 6000C, 6000EP etc.As polyvinyl acetal resin, above-mentioned material can be used separately, or it is two or more to mix use.

In hardening resin composition, with respect to (A) composition and (B) total 100 mass parts of composition, preferably the mixing ratio of (D) composition is made as to the scope of 0.5～100 mass parts, be more preferably made as 1～50 mass parts.If (D) mixing ratio of composition is less than 0.5 mass parts, at the conductor foil 100 with adhesive linkage or use in the printed wiring board that it obtains, have the tendency that the toughness of bonding cured layer or the cementability of this bonding cured layer and conductor foil (conductor layer) reduce.On the other hand, if surpass 100 mass parts, heat 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 likely reduce.And in the situation that containing Multiple components as (D) composition, preferably the total of each composition meets above-mentioned mixing ratio.

In addition, hardening resin composition also can be according to required characteristic, and the degree of the characteristic degradation such as the heat resistance that the cured layer consisting of adhesive linkage 20 with the utilization that can not make to form in printed wiring board etc. obtains, cementability, resistance to hygroscopicity contains the various additives such as fire retardant, filler, coupling agent.

As fire retardant, be not particularly limited, however the preferred fire retardant such as bromine system, phosphorus system, metal hydroxides.More particularly, as bromide fire retardant, can enumerate the 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, the bromination additive flame retardants such as 3,5-triazine; The bromination reaction type fire retardant that tribromo phenyl maleimide, tribromo phenyl acrylate, tribromo-benzene ylmethyl acrylate, tetrabromobisphenol A type dimethylacrylate, pentabromobenzyl acrylate, brominated styrene etc. contain unsaturated double-bond etc.

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

In the situation that adding fire retardant, its mixing ratio is not particularly limited, yet with respect to (A) composition and (B) total amount 100 mass parts of composition, is preferably made as 5～150 mass parts, more preferably be made as 5～80 mass parts, be further preferably made as 5～60 mass parts.If the mixing ratio of fire retardant is less than 5 mass parts, the anti-flammability that has adhesive linkage 20 or a bonding cured layer inadequate tendency that becomes.On the other hand, if surpass 100 mass parts, have the tendency of the heat 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, such as enumerating 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 the clays such as clay, talcum, aluminium borate, aluminium borate, carborundum etc.

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

In addition, as coupling agent, be not particularly limited, yet such as can enumerate silane series coupling agent, titanate esters is coupling agent etc.As silane series coupling agent, can exemplify carbon functional silanes.Specifically, can enumerate 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group (methyl) dimethoxy silane, 2-(2,3-ethyoxyl cyclohexyl) ethyl trimethoxy silanes etc. containing 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. are containing amino silane; The cationic silane such as 3-(trimethoxysilyl) propyl group tetramethyl ammonium chlorides; VTESs etc. are containing the silane of vinyl; 3-methacryloxypropyl trimethoxy silane etc. are containing the silane of acryloyl group; 3-sulfydryl propyl trimethoxies etc. contain the silane of sulfydryl etc.On the other hand, as titanate esters, be coupling agent, such as enumerating the phthalandione Arrcostabs such as titanium propanolate, butanols titanium.As these coupling agents, both can use separately a kind ofly, also can be used in combination two or more.

The mixing ratio of the coupling agent in hardening resin composition is not particularly limited, yet with respect to (A) composition and (B) total amount 100 mass parts of composition, is 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 by utilizing (A) composition, (B) composition, (C) composition and other adding ingredient known method to coordinate, mix and prepare.

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

Below, to thering is the preferred manufacture method of the conductor foil 100 with adhesive linkage of above-mentioned formation, describe.Conductor foil 100 with adhesive linkage for example can obtain by following operation,, first, prepare above-mentioned hardening resin composition, by it directly or by after dissolving in solvent or having disperseed the varnish of this resin combination to coat on the M face 12 of conductor foil 10 as above, be dried etc. and formation adhesive linkage 20.Now, also can make hardening resin composition semi-solid preparation (B stage).

The coating of hardening resin composition or its varnish can utilize known method to carry out, and such as using, licks painting machine (kiss coater), roll coater (roll coater), knife type coater (commacoater), intaglio plate (gravure) coating machine etc. and carries out.In addition, dry can profit enforcement with the following method, that is, in heat drying stove etc., for example, at 70～250 ℃, preferably, at the temperature of 100～200 ℃, carry out 1～30 minute, preferably within 3～15 minutes, processes.For by hardening resin composition dissolving etc. and used solvent in the situation that, more than baking temperature is preferably made as the temperature that solvent can volatilize.

Solvent as used when by hardening resin composition varnish, is not particularly limited, yet such as enumerating the alcohols such as methyl alcohol, ethanol, butanols; The ethers such as ethyl cellosolve, butyl cellosolve, glycol monoethyl ether, carbitol, BC; The ketones such as acetone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone; Toluene, dimethylbenzene, mesitylene etc. are aromatic hydrocarbon based; The 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, the nitrogenous class equal solvents such as N-dimethyl acetamide, N-methyl-2-pyrrolidones.In varnish, solvent both can have been used separately a kind of, also can be used in combination two or more.

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

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

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

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

[posting plywood and the manufacture method thereof of conductor]

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

(first case)

Fig. 2 means the figure that the local section of the plywood that posts conductor of first case forms.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, as insulating barrier 22, for example, can adopt known prepreg has been fitted after the sheet number of regulation, heat and/or pressurize and must material.As this prepreg, can use prepared resin varnish be impregnated in weaving cotton cloth of the fiber made by least one material being selected from glass, paper wood and organic high molecular compound or nonwoven and the material that utilizes known method to make.As the fiber of being made by glass (glass fibre), can exemplify E glass, S glass, NE glass, D glass, Q glass.In addition, as the fiber of being made by organic high molecular compound (organic fiber), can exemplify aramid fiber, fluorine resin, polyester, liquid crystal liquid crystal property macromolecule etc.They both can use separately a kind of, also can be used in combination two or more.

As resin contained in resin varnish, preferably there is the resin (insulative resin) of insulating properties, more preferably there is the resin of ethene unsaturated bond.As this kind of insulative resin, can enumerate polybutadiene, poly-triallylcyanurate, poly-cyanacrylate, the polyphenylene oxide containing unsaturated group with the construction unit that comprises ethene unsaturated bond, maleimide compound etc.These insulative resins due to relative dielectric constant and dielectric loss angle tangent low, therefore can reduce the loss of the wiring board being obtained by the plywood 200 that posts conductor.They both can use separately a kind of, also can be used in combination two or more.

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

Maleimide compound (poly maleimide) as insulative resin can be both the resin in main chain with maleimide skeleton, can be also at side chain and/or end, to have the resin of 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 reducing the loss of the wiring board being obtained by the plywood 200 that posts conductor, and can improve curability, so the coefficient of thermal expansion of resin or heat resistance will become more good.

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

In addition, as conductor layer 26, can use without particular limitation the material in the conductor layer that is generally used for printed wiring board etc.As this kind of conductor layer 26, can exemplify conductor foil, can exemplify the material of being made by metal forming specifically.As metal forming, can use above-mentioned with in the conductor foil 100 of adhesive linkage as the illustrative material of conductor foil 10.

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 forms.Hardening resin composition (material before solidifying) as forming this bonding cured layer 24, can be used the composition identical with the above-mentioned hardening resin composition with the formation adhesive linkage 20 in the conductor foil 100 of adhesive linkage.

In the situation that there is the plywood that posts conductor 200 of above-mentioned formation, used above-mentionedly with adhesive linkage conductor foil 100, for example, can utilize manufacture method as follows to manufacture.

That is, first, prepare in the same manner as described above the conductor foil 100 with adhesive linkage.In the conductor foil 100 of this kind with adhesive linkage, adhesive linkage 20 is equivalent to solidify front bonding cured layer 24.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 makes the known methods such as resin semi-solid preparation make such as utilization.

Then, the sheet number of the overlapping regulation of this prepreg is formed to insulative resin film.In addition, in the one side of this insulative resin film, so that the mode that the adhesive linkage 20 of the above-mentioned conductor foil 100 with adhesive linkage and insulating resin film join, the stacked above-mentioned conductor foil 100 with adhesive linkage.By by 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, by insulative resin film, form insulating barrier 22, by adhesive linkage 20, form bonding cured layer 24.

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

(second case)

Fig. 3 means the figure that the local section of the plywood that posts conductor of second case forms.The plywood that posts conductor 300 of second case is different from 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 Fig. 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 the contrary side of insulating resin layer 40 10 of these bonding cured layers 30.

Insulating resin layer 40 has a plurality of layer by layer folded and integrated 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 above-mentioned first case.In posting the plywood 300 of conductor, this insulating resin layer 40 is integrated with bonding cured layer 30, forms thus insulating barrier 50.

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

The plywood that posts conductor 300 of second case for example can obtain as shown below.First, prepare in the same manner insulative resin film with the situation of first case.Then, on the two sides of this insulative resin film, so that the mode of joining with the adhesive linkage 20 of the conductor foil 100 of adhesive linkage and insulating resin film, the overlapping a pair of conductor foil 100. with adhesive linkage thereafter respectively, by by 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, by insulative resin film, form insulating resin layer 40, by adhesive linkage 20, form bonding cured layer 30.

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

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

[printed wiring board and manufacture method thereof]

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

(first case)

Fig. 4 means the figure that the local section of the printed wiring board of first case forms.Printed wiring board 400 shown in Fig. 4 has and possesses successively insulating barrier 32, the formation of bonding cured layer 34, circuit pattern 36.This printed wiring board 400 is the wiring boards that use the plywood that posts conductor 200 in above-mentioned first case to obtain rightly.That is, insulating barrier 32, bonding cured layer 34 and circuit pattern 36 consist of the identical material of insulating barrier 22, bonding cured layer 24 and conductor layer 26 with posting the plywood 200 of conductor respectively.

The printed wiring board 400 with this kind of formation for example can be manufactured 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 case)

Fig. 5 means the figure that the local section of the printed wiring board of second case forms.Printed wiring board 500 shown in Fig. 5 is wiring boards that the plywood that posts conductor 300 of the above-mentioned second case of use obtains rightly, has the formation that possesses circuit pattern on 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 the contrary side of insulating resin layer 40 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 running 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 by conducting between the circuit pattern 11 at the table 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 is integrated with insulating resin layer 40, forms the insulating barrier 50 playing a role as substrate.

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

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

In addition, even as the resin material of insulating resin layer 40, used the resin with high-insulativity and high-fire resistance, also can reduce fully peeling off of circuit pattern 11.In addition, even under high humidity, bonding cured layer 30 also can maintain 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 heat resistance, particularly has the good heat resistance under super-humid conditions.

[multilayer circuit board and manufacture method thereof]

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

(first case)

Fig. 6 schematically shows the figure that the local section of the multilayer circuit board of first case forms.Multilayer circuit board 600 shown in Fig. 6 has following structure,, by thering is successively 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, 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 interlayer insulating film 68 with outer circuit pattern 72.In addition, between the internal layer circuit pattern 66 of one group of wiring board, by through hole 76, connected.

In multilayer circuit board 600, insulating barrier 62, bonding cured layer 64 and internal layer circuit pattern 66 consist of the insulating barrier 32 with printed wiring board 400, bonding cured layer 34 and the identical material of circuit pattern 36 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 for example, being formed by the known resin material (contained resin material in the insulating barrier 32 of printed wiring board 400) with insulating properties; Or the layer being formed by the prepreg that has coordinated the strengthening base material of regulation in the resin material of this insulating properties etc.

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

The multilayer circuit board 600 with this kind of formation can utilize method manufacture as follows.That is, 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 to perforate as required, implement metal-plated etc., form through hole 76.Then, upper at the circuit pattern 36 (internal layer circuit pattern 66) of printed wiring board 400, the prepreg that should form interlayer insulating film 68 of the sheet number of overlapping regulation etc.

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

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

Like this at the multilayer circuit board of formation between interlayer insulating film 68 and outer circuit pattern 72 with bonding cured layer except utilizing the method that stacks gradually interlayer insulating film 68 and outer circuit pattern 72 as above obtains, can also obtain by the stacked conductor foil 100 with adhesive linkage as used in the manufacture of wiring board 400.In addition, this kind of multilayer circuit board 600 also can be manufactured 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 and have required stacked number.This kind of multilayer circuit board 600 can be manufactured 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 case)

Fig. 7 schematically shows the figure that the local section of the multilayer circuit board of second case forms.Multilayer circuit board 700 shown in Fig. 2 possesses: insulating resin layer 92, the bonding cured layer 90 on the face of the contrary side of core substrate 510 that is formed at these insulating resin layers 92 consisting of the solidfied material (base material) of prepreg that is laminated in the two sides of core substrate 510, the lip-deep outer circuit pattern 110 more in the outer part 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.

The multilayer circuit board 700 with this kind of formation can use printed wiring board 500 to manufacture rightly.That is, first, prepare printed wiring board 500, using it as internal layer core substrate 510.Overlapping one or more layers prepreg used during as the manufacture of plywood 300 posting conductor on the two sides of this internal layer core substrate 510.Then, on two surfaces in the outside of this prepreg, so that the mode that the adhesive linkage 20 of the above-mentioned conductor foil 100 with adhesive linkage contacts with it, more overlapping this conductor foil 100 with adhesive linkage.

Then, by the duplexer heating press molding of gained, by bonding between each layer.So just by the prepreg being laminated on internal layer core substrate 510, form insulating resin layer 92, by the adhesive linkage 20 of the conductor foil 100 with adhesive linkage, form bonding cured layer 90.Afterwards, identical during with the manufacture of printed wiring board 500, suitably implement perforate processing and plating overlay film, form through hole 96 and plating overlay film 94.Now, perforate processing both can only be carried out the part being laminated on 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 thus multilayer circuit board 700.

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

Above, although the conductor foil with adhesive linkage, the plywood that posts conductor, printed wiring board and multilayer circuit board preferred embodiment of the present invention is 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 depart from its purport.

Embodiment

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

[synthesizing of polyamidoimide]

(synthesis example 1A)

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

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

Solution in flask is being returned to after room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 60mmol, temperature in flask is elevated to 190 ℃, react after 2 hours, with 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)

First, to possessing in the separable flask of 1L of Dean-Stark reflux cooler, thermometer, agitator, add as thering is Jeffermine D-2000 (Suntechno Chemical company system, the trade name) 30mmol of the diamine compound of representative examples of saturated aliphatic alkyl, 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 Setting in flask is 80 ℃ and stirs 30 minutes.

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

Solution in flask is being returned to after room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 180mmol, temperature in flask is elevated to 190 ℃, react after 2 hours, with 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.

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

(formulation example 1A)

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

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in YDCN-500 and MEH7500, 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 phenol novolak type epoxy resin (N-770 of (A) composition, large Japanese ink chemical industrial company system, trade name) 5.0g, cresols novolaks phenolic resins (KA-1163 as (B) composition, large Japanese ink chemical industrial company system, trade name) 3.9g, carboxyl acid modified acrylonitrile butadiene rubber particle (XER-91SE-15 of the polyamidoimide nmp solution 55g obtaining in the synthesis example 2A as (C) composition and conduct (D) composition, JSR (strain) system, trade name, solid component concentration is 15 quality %) 8.5g cooperation, then as curing accelerator, added 2-ethyl-4-methylimidazole (2E4MZ, four countries change into industrial group's system, trade name) after 0.025g, coordinate N-methyl-2-pyrrolidones 39g and MEK 20g, be mixed with the resin varnish for adhesive linkage (solid component concentration is about 20 quality %) of formulation example 2A.

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in N-770 and KA-1163, be 190 ℃.

(formulation example 3A)

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

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in NC-3000H and YLH129, be 170 ℃.

(formulation example 4A)

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

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in DER-331L and KA1163, be 135 ℃.

(relatively formulation example 1A)

In the polyamidoimide nmp solution 50g obtaining in synthesis example 1A, coordinate N-methyl-2-pyrrolidones 50g, be mixed with the resin varnish for adhesive linkage (solid component concentration is 15 quality %) of comparison formulation example 1A.

(relatively formulation example 2A)

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

[making of prepreg for insulating resin layer]

(production example 1)

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

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

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

(production example 2)

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

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

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

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

(production example 3)

First, to possessing in the separable flask of 10L of cooling tube, thermometer, agitator, add oxolane (THF) 5000mL, polyphenylene oxide resin (NORYL PPO646-111, Japanese GEPlastics company system, trade name) 100g, stirring and dissolving when the temperature in flask is heated to be to 60 ℃.Returned to after room temperature, under stream of nitrogen gas, added n-BuLi (1.55mol/L, hexane solution) 540mL, stirred 1 hour.Then, add bromination allyl ester 100g and stir after 30 minutes, coordinate appropriate methyl alcohol, by the polymer segregation having precipitated and obtain allylation polyphenylene oxide.

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

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

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

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

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

(with the making of the conductor foil of adhesive linkage)

By the adhesive linkage obtaining in formulation example 1A～4A and comparison formulation example 1A～2A with resin varnish respectively natural curtain coating be coated on the M face [surface roughness (Rz): 0.8 μ m] of electrolytic copper foil (F0-WS-18, slim Copper Foil, Furukawa Electric Industrial Co., Ltd system) of thick 18 μ m upper after, at 170 ℃, be dried 5 minutes, made embodiment 1A, 2A, 3A and 4A; And the conductor foil with adhesive linkage of comparative example 1A and 2A.The thickness of dried adhesive linkage is 2 μ m.And, used the adhesive linkage of formulation example 1A, 2A, 3A and 4A to be equivalent to embodiment 1A, 2A, 3A and 4A by the situation of resin varnish, used the adhesive linkage obtaining in comparison formulation example 1A and 2A to be equivalent to comparative example 1A and 2A by the situation of resin varnish.

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

Respectively with the conductor foil with adhesive linkage that is used in combination embodiment 1A～4A and comparative example 1A～2A of regulation, the insulating resin layer prepreg of production example 1～3, according to method shown below, manufactured the two-sided plywood and the multilager base plate that are covered with copper corresponding with the situation of the prepreg with adhesive linkage of using each embodiment and comparative example.And the prepreg with 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)

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

(making of multilager base plate)

First, made the various two-sided plywood that is covered with copper same as described above.Then, after by each, the two-sided Copper Foil that is covered with the plywood of copper partly utilizes etching to remove completely, when making with the plywood that is respectively covered with copper insulating resin layer used with the identical prepreg of prepreg respectively two-sided after removing Copper Foil be covered with 1 of the two sides configuration of the plywood of copper 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 outside it., 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, two sides at the insulating resin layer of overlapping 4 production examples 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, the punching press condition of 70 minute heated to press molding thereafter.Made like this, respectively that on surface, to possess the two-sided plywood that is covered with copper of two kinds of different electrolytic copper foils (thick: 0.55mm).The two-sided plywood that is covered with copper that possesses the former electrolytic copper foil is made as to comparative example 3A, the two-sided plywood that is covered with copper that possesses the latter's electrolytic copper foil is made as to comparative example 4A.In addition, use these two-sided plywoods that is covered with copper, made in the same manner as described above multilager base plate.

[evaluating characteristics]

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

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, first, to the two-sided Copper Foil that is covered with the plywood of copper, implement to utilize and to be etched with the processing that the mode of the circuitry shapes with live width 5mm is partly removed unwanted Copper Foil, made the plywood sample of the flat shape with 2.5cm * 10cm.The sample of so making is kept respectively 5 hours in normality and device for pressure cooker testing (PCT) (condition: 121 ℃, 2.2 atmospheric pressure, 100%RH).In addition the two-sided Copper Foil that is covered with the plywood of copper of having measured under following condition after 5 hours, draws stripping intensity (unit: kN/m).The result of gained is shown in table 1.

Test method: 90 ° of direction tension tests

Draw speed: 50mm/ minute

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

And, for Copper Foil, draw stripping intensity, in table with "-", represent refer to, after keeping in PCT, Copper Foil is peeled off, therefore cannot measure Copper Foil draws stripping intensity.

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

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

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

And the numeral in table is being carried out in the middle of 3 sample for evaluations of identical test, between insulating barrier and Copper Foil (conductive layer), do not see the sheet number of sample that expands or peel off the generation of (ミ-ズ リ Application グ).That is to say, this number is larger, represents that the heat resistance of corresponding sample for evaluation is better.

(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, insulating barrier distance: 1.04mm between upper and lower earth conductor, line length: 200mm, characteristic impedance 50 Ω, frequency: 3GHz, measures temperature: 25 ℃.The result of gained is shown in table 1.

[table 1]

According to table 1, distinguish, in the situation that used the conductor foil with adhesive linkage of embodiment 1A～4A, can obtain and there is good Copper Foil and draw stripping intensity and scolding tin heat resistance, but also loss can be maintained to obtain to enough low two-sided plywood and multilager base plates that is covered with copper.On the other hand, the in the situation that of comparative example 1A～4A, confirm, the Copper Foil after PCT draws the reduction of stripping intensity obvious, and scolding tin heat resistance is abundant not, and it is large that loss becomes irrelevantly.

[synthesizing of polyamidoimide]

(synthesis example 1B)

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

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

Solution in flask is being returned to after room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 60mmol, temperature in flask is elevated to 190 ℃, react after 2 hours, with 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)

First, to possessing in the separable flask of 1L of Dean-Stark reflux cooler, thermometer, agitator, add as thering is Jeffermine D-2000 (Suntechno Chemical company system, the trade name) 30mmol of the diamine compound of representative examples of saturated aliphatic alkyl, 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 Setting in flask is 80 ℃ and stirs 30 minutes.

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

Solution in flask is being returned to after room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 180mmol, temperature in flask is elevated to 190 ℃, react after 2 hours, with 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 by MDI quantitative change more 50mmol, obtained in the same manner the nmp solution of polyamidoimide with synthesis example 1B.And, the Mw of this nmp solution that utilized gel permeation chromatography, consequently 23000.

(synthesis example 4B)

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

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

(formulation example 1B)

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

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in YDCN-500 and MEH7500, be 190 ℃.

(formulation example 2B)

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

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in NC-3000H and YLH129, be 170 ℃.

(formulation example 3B)

In phenol novolak type epoxy resin (N-770 as (A) composition, large Japanese ink chemical industrial company system, trade name) in 5.0g, coordinate cresols novolaks phenolic resins (KA-1163 as (B) composition, large Japanese ink chemical industrial company system, trade name) 3.9g, carboxyl acid modified acrylonitrile butadiene rubber particle (XER-91SE-15 of the polyamidoimide nmp solution 55g obtaining in 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 as curing accelerator, added 2-ethyl-4-methylimidazole (2E4MZ, four countries change into industrial group's system, trade name) after 0.025g, coordinate N-methyl-2-pyrrolidones 39g and MEK 20g, be mixed with the resin varnish for adhesive linkage (solid component concentration is about 20 quality %) of formulation example 3B.

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in N-770 and KA-1163, be 190 ℃.

(formulation example 4B)

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

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in DER-331L and KA1163, be 135 ℃.

(formulation example 5B)

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

(formulation example 6B)

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

[making of prepreg for insulating resin layer]

Manufactured respectively the insulating resin layer prepreg of production example 1～3 same as the above-mentioned methodly.

[embodiment 1B～6B]

(with the making of the conductor foil of adhesive linkage)

By the adhesive linkage obtaining in formulation example 1B～6B with resin varnish respectively natural curtain coating be coated on the M face (surface roughness (Rz): 0.8 μ m) after upper of the electrolytic copper foil (F0-WS-12, slim Copper Foil, Furukawa Electric Industrial Co., Ltd system) of thick 12 μ m, at 150 ℃, be dried 5 minutes, made the conductor foil with 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)

Overlapping in 4 above-mentioned production examples 1～3 arbitrarily-individual insulating resin layer is with the two sides of the base material of prepreg, so that the mode that the adhesive linkage separately of the conductor foil with adhesive linkage of embodiment 1B～6B contacts has with it adhered to after the conductor foil with adhesive linkage, under 200 ℃, 3.0MPa, the punching press condition of 70 minutes, heat press molding, made respectively the plywood that uses the conductor foil with adhesive linkage two-sided of embodiment 1B～6B to be covered with copper (thick: 0.55mm).The conductor foil with 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)

First, same as described above, the two-sided plywood that is covered with copper of the conductor foil with adhesive linkage of embodiment 1B～6B has been used respectively in formation, partly utilizes etching to remove completely their Copper Foil.Thereafter, the two-sided two sides that is covered with the plywood of copper that insulating resin layer with used when the plywood that is covered with copper the is made prepreg identical with prepreg removed after Copper Foil respectively configures 1, so that having adhered in its outside, the mode that the M face of electrolytic copper foil contacts with it does not arrange after 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, the punching press condition of 70 minutes, heat press molding, made multilager base plate.And, for the combination of the conductor foil with adhesive linkage of embodiment 1B～6B and the insulating resin layer of production example 1～3 use prepreg, as shown in table 2.

[comparative example 1B～2B]

In order to compare, two sides at the insulating resin layer of overlapping 4 production 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 electrolytic copper foil (GTS-12 of the thick 12 μ m of adhesive linkage are 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, under the punching press condition of 70 minutes, heat press molding, made respectively the two-sided plywood that is covered with copper (thick: 0.55mm).In addition, by this two-sided plywood that is covered with copper, made respectively in the same manner as described above multilager base plate.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 obtaining in embodiment 1B～6B, 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 table 2.

And, for this Copper Foil, draw stripping intensity, in table with "-", represent refer to, after keeping in PCT, Copper Foil is peeled off, therefore cannot measure Copper Foil draws stripping intensity.

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

Use two-sided plywood and the multilager base plate that is covered with copper obtaining in embodiment 1B～6B and 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 table 2.

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

Measured respectively the two-sided loss (unit: dB/m) that is covered with the plywood of copper of embodiment 1B～6B and comparative example 1B～2B same as the above-mentioned methodly.The result of gained is shown in table 2.

[table 2]

According to table 2, distinguish, in embodiment 1B～6B, 1B～2B compares with comparative example, can obtain more good Copper Foil and draw stripping intensity and scolding tin heat resistance, in addition, can realize enough low transmission losses.Confirm in addition, in embodiment 1B～4B, compare with embodiment 5B and 6B, can obtain higher Copper Foil and draw stripping intensity and scolding tin heat resistance.

[synthesizing of polyamidoimide]

(synthesis example 1C)

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

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

Solution in flask is being returned to after room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 60mmol, temperature in flask is elevated to 190 ℃, react after 2 hours, with 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)

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

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

Solution in flask is being returned to after room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 180mmol, temperature in flask is elevated to 190 ℃, react after 2 hours, with 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)

First, to possessing in the separable flask of 1L of Dean-Stark reflux cooler, thermometer, agitator, add as thering is Jeffermine D-2000 (Suntechno Chemical company system, the trade name) 30mmol of the diamine compound of representative examples of saturated aliphatic alkyl, 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 Setting in flask is 80 ℃ and stirs 30 minutes.

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

Solution in flask is being returned to after room temperature, interpolation is as 4 of vulcabond, 4 '-methyl diphenylene diisocyanate (MDI) 180mmol, temperature in flask is elevated to 190 ℃, react after 2 hours, with 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.

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

(formulation example 1C)

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

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in YDCN-500 and MEH7500, be 190 ℃.

(formulation example 2C)

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

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in N-770 and KA-1165, be 190 ℃.

(formulation example 3C)

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

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in NC-3000H and YLH129, be 170 ℃.

(formulation example 4C)

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

And, by the vitrification point (Tg) of the resin combination that has added the resin solidification of 2E4MZ and obtain in DER-331L and KA1163, be 135 ℃.

(relatively formulation example 1C)

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

(relatively formulation example 2C)

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

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

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

(production example 4)

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

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

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

(with the making of the conductor foil of adhesive linkage)

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

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

On two interareas at certain insulating resin layer of overlapping 4 production examples 1,3 and 4 with the base material of prepreg, so that the mode that the adhesive linkage separately of the above-mentioned conductor foil with adhesive linkage contacts has with it adhered to after any one of the above-mentioned conductor foil with adhesive linkage, by by duplexer under 200 ℃, 3.0MPa, the punching press condition of 70 minutes along stacked direction heating press molding, the two-sided plywood that is covered with copper of having made respectively embodiment 1C, 2C, 3C and 4C and comparative example 1C and 2C 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, by on two interareas of the insulating resin layer of 4 production examples 1 overlapping base material forming 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 under 200 ℃, 3.0MPa, the punching press condition of 70 minutes to the heating press molding of stacked direction, 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 to copper is (thick: 0.55mm).

(making of multilager base plate)

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 completely.Then, the insulating resin layer using when being covered with the plywood of copper with making is disposed at the two-sided two sides that is covered with plywood of removing after 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 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, by duplexer at 200 ℃, 3.0MPa, under the punching press condition of 70 minutes, utilize the heating press molding of stacked direction, made the multilager base plate corresponding with embodiment 1C～4C and 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)

First, use the two-sided plywood that is covered with copper obtaining in embodiment 1C～4C, 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 table 3.

And, for this Copper Foil, draw stripping intensity, in table with "-", represent refer to, after keeping in PCT, Copper Foil is peeled off, therefore cannot measure Copper Foil draws stripping intensity.

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

Use two-sided plywood and the multilager base plate that is covered with copper obtaining in embodiment 1C～4C and comparative example 1C～4C, their the scolding tin heat resistance of having utilized method evaluation same as described above.The result of gained is shown in table 3.

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

Measured respectively the two-sided loss (unit: dB/m) that is covered with the plywood of copper of embodiment 1C～4C and comparative example 1C～4C same as the above-mentioned methodly.

[table 3]

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

Claims (19)

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

Described adhesive linkage is by containing

(A) composition: polyfunctional epoxy resin,

(B) composition: multifunctional phenolic resins, (C) composition: polyamidoimide and

(D) composition: polyvinyl acetal resin

Hardening resin composition form,

The vitrification point of the mixture of described (A) composition and described (B) composition after solidifying reaches more than 150 ℃.

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

3. the conductor foil with adhesive linkage according to claim 1 and 2, it is characterized in that, described (A) composition contains from by phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, bromination phenol novolak type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, biphenyl type epoxy resin, epoxy resin containing naphthalene skeleton, epoxy resin containing sub-aralkyl skeleton, epoxy resin containing biphenyl-Ya aralkyl skeleton, phenol salicylide phenolic resin varnish type epoxy resin, low alkyl group substituted phenol salicylide phenolic resin varnish type epoxy resin, epoxy resin containing bicyclopentadiene skeleton, at least one epoxy resin of selecting in the group that multifunctional glycidyl group amine type epoxy resin and multifunctional alicyclic epoxy resin form.

4. according to the conductor foil with adhesive linkage described in any one in claim 1～3, it is characterized in that, described (B) composition contains at least one multifunctional phenolic resins of selecting from the copoly type resin by aralkyl-type phenol resin, dicyclopentadiene-type phenolic resins, salicylide type phenolic resins, benzaldehyde type phenolic resins and aralkyl-type phenol resin and group that phenolic varnish type phenolic resins forms.

5. according to the conductor foil with adhesive linkage described in any one in claim 1～4, it is characterized in that, described (C) composition contains the construction unit consisting of saturated hydrocarbons.

6. according to the conductor foil with adhesive linkage described in any one in claim 1～5, it is characterized in that, with respect to total 100 mass parts of described (A) composition and described (B) composition, the mixing ratio of described (C) composition is 0.5～500 mass parts.

7. according to the conductor foil with adhesive linkage described in any one in claim 1～6, it is characterized in that, described adhesive linkage is to form after resin varnish layer by the resin varnish that contains described hardening resin composition and solvent being coated on the surface of described conductor foil, from described resin varnish layer, removes described solvent and obtains.

8. according to the conductor foil with adhesive linkage described in any one in claim 1～7, it is characterized in that, described adhesive linkage has the thickness of 0.1～10 μ m.

9. according to the conductor foil with adhesive linkage described in any one in claim 1～8, it 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 4 μ m.

10. a plywood that posts conductor, it is characterized in that, by following operation, obtain, described being operating as: at least one side of the insulative resin film that contains the resin with insulating properties, so that the mode contacting with it with the adhesive linkage of the conductor foil of adhesive linkage, obtaining with the conductor foil of adhesive linkage after laminated body described in any one in stacked claim 1～9, to described laminated body heating and pressurization.

11. 1 kinds of plywoods that post conductor,

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

Described bonding cured layer and described conductor layer are formed by the conductor foil with adhesive linkage described in any one in claim 1～9,

Described bonding cured layer consists of the solidfied material of the described adhesive linkage of the described conductor foil with adhesive linkage, and described conductor layer consists of the described conductor foil of the described conductor foil with adhesive linkage.

12. 1 kinds of plywoods that post conductor,

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

Described bonding cured layer is by containing

(A) composition: polyfunctional epoxy resin,

(B) composition: multifunctional phenolic resins, (C) composition: polyamide and

(D) composition: polyvinyl acetal resin

The solidfied material of resin combination form,

The vitrification point of the mixture of described (A) composition and described (B) composition after solidifying reaches more than 150 ℃.

13. according to the plywood that posts conductor described in claim 11 or 12, it is characterized in that,

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

As described base material, possess weaving cotton cloth or nonwoven of fiber that at least one material of selecting makes in the group from consisting of glass, paper wood and organic high molecular compound.

14. plywoods that post conductor according to claim 13, is characterized in that, described insulating barrier contain there is ethene unsaturated bond resin as described insulative resin.

15. according to the plywood that posts conductor described in claim 13 or 14, it is characterized in that, described insulative resin contains from by polybutadiene, poly-triallylcyanurate, poly-cyanacrylate, containing at least one resin of selecting in the polyphenylene oxide of unsaturated group and group that maleimide compound forms.

16. according to the plywood that posts conductor described in any one in claim 13～15, it is characterized in that, described insulative resin contains at least one resin of selecting in the group from consisting of polyphenylene oxide and thermoplastic elastomer (TPE).

17. according to the plywood that posts conductor described in any one in claim 11～16, it is characterized in that, described insulating barrier has the relative dielectric constant below 4.0 under 1GHz.

18. 1 kinds of printed wiring boards, is characterized in that, the circuit pattern by the described conductor layer in the plywood that posts conductor described in any one in claim 11～17 is processed into regulation obtains.

19. 1 kinds of multilayer circuit boards, it is to possess: there is the core substrate of one deck printed wiring board at least, at least one side that is disposed at described core substrate goes up and has at least multilayer circuit board of the outer-layer circuit plate of one deck printed wiring board, it is characterized in that,

At least one deck in the printed wiring board of described core substrate is the printed wiring board described in claim 18.

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