JP2007313881A - Metallic foil with adhesive layer, metal clad laminate, printed wiring board, and multi-layered wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metallic foil with an adhesive layer capable of satisfactorily reducing a transmission loss in a high frequency band, showing excellent heat resistance, and enabling manufacture of a printed wiring board hardly causing a separation between layers. <P>SOLUTION: In the preferred embodiment the metallic foil with the adhesive layer includes the metallic foil 10 and the adhesive layer 20 formed on the M surface 12 of the metallic foil 10. The adhesive layer 20 comprises a curable resin composition containing a component (A) of a poly-functional epoxy resin, a component (B) of a poly-functional phenolic resin and a component (C) of a polyamideimide. The weight average molecular weight of the component (C) is from not less than 50,000 to not more than 250,000. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a metal foil with an adhesive layer, a metal-clad laminate, a printed wiring board, and a multilayer wiring board.

  Mobile communication devices such as mobile phones, their base station devices, network-related electronic devices such as servers and routers, or large computers are required to transmit and process large amounts of information with low loss and high speed. ing. In order to meet such demands, the frequency of electric signals handled is increasing in printed wiring boards mounted on the above-described devices. However, since electrical signals have the property of being easily attenuated at higher frequencies, printed wiring boards that handle high-frequency electrical signals are required to have a lower transmission loss than before.

  In order to obtain a printed wiring board with low transmission loss, conventionally, a thermoplastic resin material containing a fluorine-based resin having a low relative dielectric constant and dielectric loss tangent has been used as a substrate material for the printed wiring board. However, since this fluororesin generally has a high melt viscosity and low fluidity, it is not always easy to mold, for example, it is necessary to set high temperature and high pressure conditions during press molding. Moreover, as a printed wiring board material used for the above-mentioned communication apparatus etc., in addition to workability, it had the fault that dimension stability and adhesiveness with metal plating were inadequate.

  Therefore, an attempt has been made to use a thermosetting resin composition having a low relative dielectric constant and dielectric loss tangent instead of the thermoplastic resin material. For example, the following are known as thermosetting resin compositions used as raw materials for dielectric materials such as electronic devices described above. That is, Patent Documents 1 to 3 disclose resin compositions containing triallyl cyanurate or triallyl isocyanurate. Patent Documents 1, 2, 4, or 5 disclose resin compositions containing polybutadiene. Furthermore, Patent Document 6 discloses a resin composition containing a thermosetting polyphenylene ether provided with a radical crosslinkable functional group such as an allyl group, and the above-mentioned triallyl cyanurate and triallyl isocyanurate. Yes. These patent documents generally show that the above thermosetting resin composition does not have a large number of polar groups after curing, so that a low transmission loss can be achieved.

  In the printed wiring board, it is desirable that the adhesiveness between the insulating layer and the conductive layer provided thereon is high. If the adhesiveness between the insulating layer and the conductive layer is low, inconveniences such as separation of the two during use tend to occur. A printed wiring board is often formed by processing a conductive foil of a metal-clad laminate in which a conductive foil is laminated on an insulating layer, but in order to obtain excellent adhesion between the insulating layer and the conductive layer It is also important that the adhesion between the insulating layer and the conductive foil in this metal-clad laminate is high.

From such a viewpoint, a metal-clad laminate obtained by laminating a prepreg sheet with a copper foil coated with polybutadiene modified with epoxy, maleic acid, carboxylic acid or the like is known (see Patent Documents 7 and 8). . A printed wiring board in which a layer containing an epoxy compound or a polyamideimide compound is interposed between an insulating layer and a conductor layer is also known (see Patent Documents 9 and 10).
Japanese Examined Patent Publication No. 6-69746 Japanese Patent Publication No. 7-47689 JP 2002-265777 A Japanese Patent Publication No.58-21925 JP-A-10-117052 Japanese Patent Publication No. 6-92533 JP 54-74883 A JP 55-86744 A JP 2005-167172 A JP 2005-167173 A

  By the way, in recent years, it has been required for electronic devices and the like as described above to cope with higher frequency electrical signals. However, for example, a low dielectric constant, low dielectric loss tangent resin as described in Patent Documents 1 to 6 described above is used as a dielectric material, and only a low transmission loss of an electric signal in an insulating layer (dielectric layer) is achieved. Therefore, it has become difficult to sufficiently cope with such high frequencies. That is, the transmission loss of electrical signals is caused by both the loss due to the insulating layer (dielectric loss) and the loss due to the conductive layer (conductor loss). Therefore, it is necessary to reduce not only the dielectric loss but also the conductor loss by improving the conventional dielectric material.

  In particular, in most printed wiring boards (multilayer wiring boards) that have been put into practical use in recent years, the thickness of the insulating layer disposed between the signal layer, which is a conductive layer, and the ground layer is as thin as 200 μm or less. . Therefore, when a resin having a dielectric constant or a dielectric loss tangent that is somewhat low is employed as the material of the insulating layer, the conductor loss rather than the dielectric loss is dominant as the transmission loss of the entire wiring board.

  Here, as a method for reducing the conductor loss, there is a method using a metal foil having a small surface unevenness on the surface of the conductive layer that is bonded to the insulating layer (roughened surface, hereinafter referred to as “M surface”). Can be mentioned. Specifically, a metal-clad equipped with a metal foil whose surface roughness (ten-point average roughness; Rz) of the M plane is 2 μm or less (hereinafter, such metal foil is referred to as “low-roughened foil”). It is conceivable to use a laminate.

  Therefore, based on the above findings, the present inventors first have a low dielectric constant and low dielectric loss tangent resin that is cured by polymerization of a vinyl group or an allyl group, as described in Patent Documents 1 to 6. The printed wiring board obtained by using together with the low roughening foil mentioned above was produced and examined in detail. As a result, such a printed wiring board has a low polarity of the insulating layer and a low anchoring effect due to the unevenness of the M surface of the metal foil, so that the adhesive force (bonding force) between the insulating layer and the conductive layer is weak. It was confirmed that peeling easily occurred between these layers. In particular, such peeling tends to be prominent when the printed wiring board is heated (particularly when heated after moisture absorption). Thus, when the above-described resin is used as a dielectric material, it is difficult to sufficiently secure the adhesion between the insulating layer and the conductive layer if a low-roughened foil is used to reduce conductor loss. It has been found.

  Further, by applying the means described in Patent Documents 7 and 8, the insulating layer and a low-roughened copper foil having an M-plane Rz of 2 μm or less are bonded together via a modified polybutadiene, and a printed wiring board is obtained. When produced, it was found that a sufficiently high copper foil peel strength could not be obtained, and that heat resistance (particularly heat resistance during moisture absorption) was reduced.

  Furthermore, by applying the means described in Patent Documents 9 and 10, a polyamideimide resin having a thickness of 0.1 to 5 μm was previously provided on the surface of the low-roughened copper foil having an Rz of M surface of 2 μm or less. When a printed wiring board was produced using the copper foil with an adhesive layer, it was confirmed that high copper foil peeling strength was obtained. However, since the anchor effect due to the unevenness of the M surface of the metal foil is low, the adhesive force between the polyamide-imide resin and the insulating layer becomes weak (bonding force), for example when heated (especially after moisture absorption) Etc.), it has been found that peeling easily occurs between these layers.

  Therefore, the present invention has been made in view of such circumstances, and can reduce the transmission loss in the high frequency band, has excellent heat resistance, and does not easily cause delamination between layers. It aims at providing the metal foil with an adhesive layer which can manufacture a board. Another object of the present invention is to provide a metal-clad laminate, a printed wiring board, and a multilayer wiring board obtained using such a metal foil with an adhesive layer.

  In order to achieve the above object, a metal foil with an adhesive layer of the present invention is a metal foil with an adhesive layer comprising a metal foil and an adhesive layer provided on the metal foil, wherein the adhesive layer is (A) Component: Polyfunctional epoxy resin, (B) component: Polyfunctional phenol resin, and (C) component: A curable resin composition containing polyamideimide, and (C) component has a weight average molecular weight of 50,000. It is characterized by being 250,000 or less.

  The adhesive layer in the metal foil with an adhesive layer of the present invention is composed of a curable resin composition containing the components (A) to (C). The cured product of this curable resin composition contains a cured product of a polyfunctional epoxy resin and a polyfunctional phenol resin, and polyamideimide by curing, and therefore has insulation characteristics such as low roughened foil and low dielectric constant. The adhesion to the layer is extremely excellent. Furthermore, since the cured product of the curable resin composition is a cured product of the above three components, it also has excellent heat resistance.

  Therefore, when a metal-clad laminate or a printed wiring board (printed wiring board) is manufactured using such a metal foil with an adhesive layer as described later, the insulating layer and the conductive layer are the adhesive layer of the present invention. The adhesive metal foil is strongly bonded via the cured product of the adhesive layer, and these peelings can be largely prevented. In addition, due to the low dielectric constant and low dielectric loss tangent characteristics of the adhesive hardened layer, a significant reduction in transmission loss can be achieved. Furthermore, due to the adhesive cured layer having excellent heat resistance, excellent heat resistance can be obtained as a whole. In the following description, a layer obtained by curing the adhesive layer of the metal foil with an adhesive layer of the present invention is referred to as an “adhesive cured layer”, and is an insulating material that is a substrate material such as a metal-clad laminate or a printed wiring board (printed wiring board). These layers are classified as “insulating layers” or “insulating resin layers”.

  In the metal foil with an adhesive layer of the present invention, the (A) component and the (B) component in the curable resin composition constituting the adhesive layer have a glass transition temperature of 150 ° C. or higher after curing of the mixture. Is preferred. By satisfying such conditions, the heat resistance of the adhesive hardened layer is further improved, and the printed wiring board obtained using the metal foil with the adhesive layer of the present invention also has excellent heat resistance in a practical temperature range. To have. In addition, this glass transition temperature (Tg) can be measured by differential scanning calorimetry (DSC) based on JIS-K7121-1987.

  In the curable resin composition, the polyfunctional epoxy resin (A) is a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a brominated phenol novolak type epoxy resin, a bisphenol A novolak type epoxy resin, or a biphenyl type epoxy resin. , Naphthalene skeleton-containing epoxy resins, aralkylene skeleton-containing epoxy resins, biphenyl-aralkylene skeleton-containing epoxy resins, phenol salicylaldehyde novolac-type epoxy resins, lower alkyl group-substituted phenol salicylaldehyde novolac-type epoxy resins, dicyclopentadiene skeleton-containing epoxy resins, many It is preferably at least one polyfunctional epoxy resin selected from the group consisting of a functional glycidylamine type epoxy resin and a polyfunctional alicyclic epoxy resin.

  The polyfunctional phenol resin as component (B) is an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a salicylaldehyde type phenol resin, a copolymer type resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, and It is preferable to contain at least one polyfunctional phenol resin selected from the group consisting of novolak type phenol resins.

  These polyfunctional epoxy resins or polyfunctional phenol resins can impart excellent adhesion and heat resistance to the adhesive-cured layer by being combined with other components in the present invention.

  Furthermore, as the polyamideimide as the component (C), those containing a structural unit composed of a saturated hydrocarbon are preferable. When using polyamide imide containing a structural unit consisting of saturated hydrocarbons, adhesion to the metal foil or insulating layer by the adhesive hardened layer will be good, and good adhesion will be maintained even during moisture absorption. Will come to be. As a result, the printed wiring board or the like obtained using the metal foil with the adhesive layer of the present invention has a characteristic that delamination is hardly caused even after moisture absorption.

  In the curable resin composition which comprises an contact bonding layer, it is preferable that the mixture ratio of (C) component is 10-400 mass parts with respect to a total of 100 mass parts of (A) component and (B) component. When the blending ratio of the component (C) is in such a range, good adhesion can be obtained, and the toughness, heat resistance, chemical resistance and the like of the adhesive cured layer tend to be particularly improved.

  The curable resin composition preferably further contains crosslinked rubber particles and / or polyvinyl acetal resin as the component (D). By further including these components, the adhesion to the metal foil or the like by the adhesive hardened layer is further improved.

  Among these, from the viewpoint of obtaining the above characteristics particularly well, the component (D) includes acrylonitrile butadiene rubber particles, carboxylic acid modified acrylonitrile butadiene rubber particles, carboxylic acid modified acrylonitrile butadiene rubber particles, butadiene rubber-acrylic resin core shell. At least one crosslinked rubber particle selected from the group consisting of particles is preferred.

  In the metal foil with an adhesive layer of the present invention, the adhesive layer is formed by applying a resin varnish containing a curable resin composition and a solvent on the surface of the metal foil to form a resin varnish layer, and then from the resin varnish layer. It is preferable that it is obtained by removing the solvent. The adhesive layer thus formed becomes a layer having a uniform thickness and characteristics, and easily exhibits excellent adhesiveness with a metal foil or the like after curing.

  Moreover, it is preferable that the film thickness of the contact bonding layer in metal foil with a contact bonding layer is 0.1-5 micrometers. According to the adhesive layer having such a thickness, sufficient adhesion to the metal foil can be obtained, and dielectric loss can be reduced well.

  Furthermore, the ten-point average roughness (Rz) of the surface on the adhesive layer side in the metal foil is preferably 2 μm or less. When the surface roughness of the M surface is 2 μm or less, the conductor loss due to the conductive layer formed from this metal foil is reduced, and the printed wiring board obtained using the metal foil with the adhesive layer of the present invention has a dielectric loss. In addition to the above, the conductor loss is also well reduced. Here, the ten-point average roughness (Rz) refers to the ten-point average roughness defined in JIS B0601-1994.

  The metal-clad laminate according to the present invention is preferably obtained by using the metal foil with an adhesive layer of the present invention, and a metal laminated on the insulating resin layer via an adhesive hardened layer. The adhesive cured layer and the metal foil are formed from the metal foil with an adhesive layer of the present invention, and the adhesive cured layer is a cured product of the adhesive layer in the metal foil with an adhesive layer, and the metal foil Is made of a metal foil in a metal foil with an adhesive layer.

  In such a metal-clad laminate, the metal foil with an adhesive layer of the present invention is in contact with the adhesive layer in the metal foil with an adhesive layer on at least one surface of an insulating resin film containing an insulating resin. After obtaining a laminated body by laminating, it is preferable that the laminated body is obtained by heating and pressing.

  In the metal-clad laminate of the present invention, an insulating resin layer (insulating layer) and a metal foil are bonded via a cured product (adhesive cured layer) of an adhesive layer in the metal foil with an adhesive layer of the present invention. Therefore, the adhesion between the metal foil and the insulating layer is excellent. Therefore, even when a low-roughened foil is used as the metal foil, peeling between the layers hardly occurs. Further, the adhesive hardened layer has a characteristic that it has a low dielectric constant and a low dielectric loss tangent. As a result, the printed wiring board obtained from such a metal-clad laminate is extremely unlikely to delaminate.

  Furthermore, the printed wiring board according to the present invention can be applied as a printed wiring board, and is obtained by processing the metal foil in the metal-clad laminate of the present invention so as to have a predetermined circuit pattern. It is. Even if such a printed wiring board uses a low-roughened foil, the circuit pattern made of the metal foil and the insulating resin layer hardly peel off, and the adhesive hardened layer has excellent heat resistance. As a whole, it has excellent heat resistance.

  Furthermore, this invention can provide the multilayer wiring board which is hard to produce peeling between layers and has high heat resistance by providing the printed wiring board of the said invention. That is, the multilayer wiring board of the present invention includes a core substrate having at least one printed wiring board and an outer wiring board having at least one printed wiring board disposed on at least one surface of the core substrate. Then, at least one of the printed wiring boards in the core substrate is the printed wiring board of the present invention.

  Note that high-frequency compatible printed wiring boards applied to electronic devices as described above are required to have good impedance control as well as low transmission loss. In order to realize this, it is important to improve the accuracy for forming a good pattern width of the conductive layer during the production of the printed wiring board. Here, in the case of using a metal foil having a small surface roughness such as a low profile foil, there is a tendency that it is advantageous for improving the accuracy in forming a conductor pattern and for further fine patterning.

  Under such circumstances, according to the metal foil with an adhesive layer of the present invention, a low-roughened foil is used, and an insulating resin material having a low dielectric constant and a low dielectric loss tangent is used for the insulating layer. However, sufficient adhesion between the insulating layer and the metal foil can be obtained. Therefore, according to the printed wiring board using the metal foil with an adhesive layer of the present invention, not only low transmission loss but also good impedance control can be realized.

  The reason why the excellent adhesiveness as described above can be obtained by the metal foil with the adhesive layer of the present invention is not clear in detail at present, but the present inventors speculate as follows. Yes. For example, when using a low-roughened foil as the metal foil, in addition to lowering the adhesiveness of the low-roughened foil to the insulating layer, etc., multilayering is performed using a metal-clad laminate provided with this low-roughened foil. Even in such a case, delamination may easily occur. That is, by removing the metal foil of the metal-clad laminate in which the low-roughened foil having Mz Rz of 2 μm or less is laminated on both surfaces of the insulating resin layer, the prepreg and the metal foil are sequentially stacked on the surface. When producing a multilayer laminated board and also a printed wiring board, the roughness transferred to the inner insulating resin layer by the low-roughening foil is also small.

  In the multilayer laminate obtained in this manner, the anchor effect between the insulating resin layer and the prepreg is also greater in the metal-clad laminate than when a general copper foil (Rz is 6 μm or more) is used. Accordingly, the adhesive force (bonding force) between the insulating resin layer and the prepreg is reduced. Therefore, as a result, the metal foil disposed on the surface of the prepreg is easily peeled from the insulating resin layer. In particular, such a tendency is remarkable when heating (especially heating after moisture absorption) is performed.

  In such a case, by using a metal-clad laminate obtained by laminating a metal foil with an adhesive layer on the surface of the insulating resin layer, it is possible to reduce the decrease in the adhesive strength as described above. That is, when a multilayer laminate is formed using this metal-clad laminate, an adhesive layer derived from the metal foil with an adhesive layer is interposed between the insulating resin layer and the prepreg. The adhesion of the layer is improved to some extent.

  However, in this case, when only a polyamideimide or a resin material in which a polyamideimide and an epoxy resin are combined is applied to the adhesive layer, the heat resistance is insufficient for application as a printed wiring board. Although this resin material can show favorable adhesiveness, it is thought that it is because heat resistance after moisture absorption is not so good because it tends to cause hydrogen bonding with water and the like.

  On the other hand, in the metal foil with an adhesive layer of the present invention, the components (A) and (B) contained in the adhesive layer are excellent in heat resistance after curing (particularly heat resistance after moisture absorption). Therefore, the multilayer laminated board and printed wiring board obtained using this metal foil with an adhesive layer have excellent heat resistance as a whole. In addition, since the components (A) and (B) are excellent in adhesiveness to the insulating resin layer and the metal foil, even if the amount of the polyamideimide as the component (C) is reduced, Sufficient adhesion can be maintained. In general, polyamideimide tends to lower the heat resistance of the adhesive hardened layer. Therefore, according to the metal foil with an adhesive layer of the present invention, it is possible to further increase the amount of polyamideimide added to the necessary minimum. Improvement of the heat resistance will be achieved.

  In particular, in the metal foil with an adhesive layer of the present invention, the component (C) (polyamideimide) contained in the curable resin composition constituting the adhesive layer has a weight average molecular weight of 50,000 to 250,000. Therefore, in addition to the improvement in heat resistance, good adhesion strength with the metal foil and the insulating layer can be obtained. Although such factors are not always clear, the following reasons can be considered. That is, according to the adhesive layer in the metal foil with an adhesive layer of the present invention, a sea-island structure is formed by the components (A), (B), and (C) after curing. Specifically, a sea layer composed of the (C) component region and an island layer composed of the (A) and (B) component regions are formed. In the adhesive hardened layer, it is considered that both the excellent adhesiveness due to the component (C) and the high heat resistance due to the components (A) and (B) are satisfactorily exhibited by such a sea-island structure. In particular, when the weight average molecular weight of the component (C) is 50,000 or more, the above-described sea-island structure is clearly formed, and when it is 250,000 or less, the component (C) is excellent in the adhesive layer. Fluidity is maintained, and this allows good adhesion to the metal foil and insulating properties. As a result, by using the metal foil with an adhesive layer of the present invention, it is considered that the heat resistance of the adhesive hardened layer and the adhesiveness to the metal foil or the like can be obtained extremely well.

  Therefore, a printed wiring board or a multilayer wiring board obtained using the metal foil with an adhesive layer of the present invention has a specific adhesive hardened layer between the conductive layer (circuit pattern) and the insulating layer. Even when a smooth conductive layer and an insulating layer with low dielectric loss are provided, the adhesiveness between the conductive layer and the insulating layer is good and the heat resistance is also excellent.

  According to the present invention, it is possible to provide a metal foil with an adhesive layer that can satisfactorily reduce transmission loss in a high-frequency band and that can produce a printed wiring board that hardly causes delamination between layers. It becomes possible. Moreover, it becomes possible to provide a metal-clad laminate, a printed wiring board, and a multilayer wiring board obtained using such a metal foil with an adhesive layer.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant descriptions are omitted.
[Metal foil with adhesive layer]

  First, the metal foil with an adhesive layer according to a preferred embodiment will be described. FIG. 1 is a partial perspective view of a metal foil with an adhesive layer according to a preferred embodiment. The metal foil 1 with an adhesive layer shown in FIG. 1 has a configuration including a metal foil 10 and an adhesive layer 20 formed so as to be in contact with the roughened surface (M surface) 12 of the metal foil 10. Yes.

(Metal foil)
The metal foil 10 is not particularly limited as long as it is conventionally applied to a conductive layer such as a printed wiring board, and for example, a copper foil, a nickel foil, an aluminum foil, or the like can be applied. Of these, electrolytic copper foil or rolled copper foil is preferable. Moreover, it is preferable that the metal foil 10 is subjected to a barrier layer forming treatment with nickel, tin, zinc, chromium, molybdenum, cobalt, or the like from the viewpoint of improving its rust prevention property, chemical resistance, heat resistance, and the like. Further, from the viewpoint of improving the adhesion with the insulating layer, it is preferable that surface treatment such as surface roughening treatment or treatment with a silane coupling agent is performed.

  Among these surface treatments, regarding the surface roughening treatment, if the surface roughness (Rz) on the M plane 12 is preferably 4 μm or less, more preferably 2 μm or less, high frequency There is a tendency that transmission characteristics can be further improved. The silane coupling agent used for the silane coupling agent treatment is not particularly limited, but epoxy silane, amino silane, cationic silane, vinyl silane, acryloxy silane, methacryloxy silane, ureido silane, mercapto silane, sulfide silane, An isocyanate silane etc. are mentioned.

  The metal foil 10 may have a single-layer structure made of one kind of metal material, may have a single-layer structure made of a plurality of metal materials, or a laminated structure in which a plurality of metal layers made of different materials are laminated. There may be. Moreover, the thickness of the metal foil 10 is not specifically limited. Among the metal foils 10 described above, for example, as copper foil, F1-WS (Furukawa Circuit Foil, Rz = 1.9), F0-WS (Furukawa Circuit Foil, trade name, Rz = 1.0 μm) T9-SV (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., Rz = 1.8) is commercially available and suitable.

(Adhesive layer)
The adhesive layer 20 in the metal foil 1 with an adhesive layer is made of a curable resin composition containing (A) component; polyfunctional epoxy resin, (B) component; polyfunctional phenol resin, and (C) component; polyamideimide. It is a layer. The thickness of the adhesive layer 20 is preferably 0.1 to 5 μm. If the thickness is less than 0.1 μm, it tends to be difficult to obtain sufficient peel strength of a metal foil or the like in a metal-clad laminate and the like to be described later. On the other hand, if it exceeds 5 μm, the high-frequency transmission characteristics of the metal-clad laminate tend to be reduced. Hereinafter, each component of the curable resin composition constituting the adhesive layer 20 will be described.

  First, the component (A) will be described.

  The polyfunctional epoxy resin as the component (A) is a compound having a plurality of epoxy groups in one molecule, and is a compound in which a plurality of molecules can be bonded by reaction between epoxy groups. Examples of such component (A) include phenol novolac type epoxy resins, cresol novolac type epoxy resins, brominated phenol novolac type epoxy resins, bisphenol A novolak type epoxy resins, biphenyl type epoxy resins, naphthalene skeleton-containing epoxy resins, Aralkylene skeleton-containing epoxy resin, biphenyl-aralkylene skeleton epoxy resin, phenol salicylaldehyde novolak type epoxy resin, lower alkyl group-substituted phenol salicylaldehyde novolak type epoxy resin, dicyclopentadiene skeleton containing epoxy resin, polyfunctional glycidylamine type epoxy resin and many A functional alicyclic epoxy resin etc. are mentioned. As the component (A), one of these may be contained alone, or two or more may be contained in combination.

  Especially, as (A) component, a cresol novolak type epoxy resin, a biphenyl type epoxy resin, or a phenol novolak type epoxy resin is preferable. By including these polyfunctional epoxy resins as the component (A), excellent adhesion and electrical characteristics due to the cured product (adhesive cured layer) of the adhesive layer 20 are easily obtained.

  Next, the component (B) will be described.

  The polyfunctional phenol compound (B) is a compound having a plurality of phenolic hydroxyl groups in one molecule, and functions as a curing agent for the polyfunctional epoxy resin (A). Examples of the component (B) include aralkyl type phenol resins, dicyclopentadiene type phenol resins, salicylaldehyde type phenol resins, benzaldehyde type phenol resins and aralkyl type phenol resins, and novolac type phenol resins. It is done. (B) As a component, these compounds may be contained independently and may be contained in combination of 2 or more type. The component (A) and (B) described above are particularly selected from the viewpoint of improving the heat resistance after moisture absorption of the adhesive-cured layer by selecting the glass transition temperature after curing of these mixtures to be 150 ° C. or higher. preferable.

  Next, the component (C) will be described.

  The polyamideimide as the component (C) is a polymer having a repeating unit including an amide structure and an imide structure. (C) component in this embodiment has a weight average molecular weight (henceforth "Mw") of 50,000-250,000. Here, Mw can be measured by gel permeation chromatography, and a value converted by a calibration curve created using standard polystyrene can be applied.

  When the molecular weight of the component (C) is less than 50,000, the metal foil with an adhesive layer obtained by using the curable resin composition containing the component (C), and further using the metal foil with an adhesive layer are obtained. In the printed wiring board thus obtained, the adhesion between the adhesive hardened layer and the metal foil (conductive layer) tends to be disadvantageously lowered. In particular, this tendency becomes more prominent when the thickness of the metal foil is reduced. On the other hand, even if the molecular weight exceeds 250,000, the fluidity of the polyamideimide is deteriorated, so that the adhesiveness between the adhesive cured layer and the metal foil (conductive layer) tends to be lowered. This tendency is also remarkable when the thickness of the metal foil is reduced.

  (C) It is preferable that the component contains the structural unit which consists of a saturated hydrocarbon in the molecule | numerator. When the component (C) contains a saturated hydrocarbon, the adhesion to the metal foil or the like by the adhesive hardened layer becomes good. In addition, since the moisture resistance of the component (C) is improved, the adhesion by the adhesive cured layer after moisture absorption is also maintained well. As a result, moisture and heat resistance of a printed wiring board or the like obtained using the metal foil 1 with an adhesive layer of the present embodiment is improved. The component (C) particularly preferably has a structural unit composed of a saturated hydrocarbon in the main chain.

  The structural unit consisting of this saturated hydrocarbon is particularly preferably a saturated alicyclic hydrocarbon group. In the case of having a saturated alicyclic hydrocarbon group, the adhesiveness at the time of moisture absorption by the adhesive hardened layer is particularly good, and the adhesive hardened layer has a high Tg, and the heat resistance of a printed wiring board provided with the same Is further improved. And the effect as mentioned above exists in the tendency which is acquired stably especially when Mw of (C) component is 50,000 or more.

  The component (C) more preferably contains a siloxane structure in the main chain. A siloxane structure is a structural unit in which silicon atoms and oxygen atoms having a predetermined substituent are alternately and repeatedly bonded. When the component (C) contains a siloxane structure in the main chain, the properties such as the elastic modulus and flexibility of the cured layer of the adhesive layer 20 can be improved, and the durability of the resulting printed wiring board can be improved. In addition, the drying efficiency of the curable resin composition tends to be good and the adhesive layer 20 tends to be easily formed.

  Examples of the polyamideimide as component (C) include polyamideimide synthesized by a so-called isocyanate method by reaction of trimellitic anhydride and aromatic diisocyanate. As a specific example of this isocyanate method, a method in which an aromatic tricarboxylic acid anhydride and a diamine compound having an ether bond are reacted in the presence of excess diamine compound and then reacted with diisocyanate (see, for example, Japanese Patent No. 2897186). And a method of reacting an aromatic diamine compound and trimellitic anhydride (for example, a method described in JP-A No. 04-182466).

  Further, the component (C) containing a siloxane structure in the main chain can also be synthesized according to the isocyanate method. Specific examples of the synthesis method include a method of polycondensing an aromatic tricarboxylic acid anhydride, an aromatic diisocyanate and a siloxane diamine compound (for example, a method described in JP-A No. 05-009254), an aromatic dicarboxylic acid or A method of polycondensing an aromatic tricarboxylic acid and a siloxane diamine compound (for example, a method described in JP-A-06-116517), a diamine compound having three or more aromatic rings and a mixture containing siloxane diamine and trimellitic anhydride Examples include a method of reacting a mixture containing diimide dicarboxylic acid obtained by reacting with an acid with an aromatic diisocyanate (for example, a method described in JP-A-06-116517). According to the curable resin composition of the present embodiment constituting the adhesive layer 20, sufficiently high metal foil peeling strength can be obtained even when the component (C) synthesized by these known methods is used.

  Hereinafter, an example of a method for producing a polyamideimide having a structural unit (particularly a saturated alicyclic hydrocarbon group) composed of a saturated hydrocarbon suitable as the component (C) in the main chain will be described in detail.

  Such a polyamideimide is, for example, after derivatizing an imide group-containing dicarboxylic acid obtained by reacting a diamine compound having a saturated hydrocarbon group with trimellitic anhydride into an acid halide, or using a condensing agent. It can be obtained by reacting with a diamine compound. Alternatively, it can also be obtained by reacting a diisocyanate with an imide group-containing dicarboxylic acid obtained by reacting a diamine compound having a saturated hydrocarbon group with trimellitic anhydride. A polyamide having a saturated alicyclic hydrocarbon group can be obtained by using a diamine compound having a saturated alicyclic hydrocarbon group as a saturated hydrocarbon group in these methods.

［式（１ａ）及び（１ｂ）中、Ｌ^１は、ハロゲン置換されていてもよい炭素数１〜３の２価の脂肪族炭化水素基、スルホニル基、オキシ基、カルボニル基、単結合又は下記式（２ａ）又は（２ｂ）で表される２価の基を示し、Ｌ^２はハロゲン置換されていてもよい炭素数１〜３の２価の脂肪族炭化水素基、スルホニル基、オキシ基又はカルボニル基を示し、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子、水酸基、メトキシ基、ハロゲン置換されていてもよいメチル基を示す。

ただし、式（２ａ）中、Ｌ^３は、ハロゲン置換されていてもよい炭素数１〜３の２価の脂肪族炭化水素基、スルホニル基、オキシ基、カルボニル基又は単結合を示す。］ Specific examples of the diamine compound having a saturated hydrocarbon group include compounds represented by the following general formula (1a) or (1b).

[In the formulas (1a) and (1b), L ¹ is an optionally halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, a single bond, or A divalent group represented by the formula (2a) or (2b), wherein L ² is a halogenated halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, or Represents a carbonyl group, and R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group or a halogen-substituted methyl group.

However, in the formula (2a), L ³ represents a C 1-3 divalent aliphatic hydrocarbon group, sulfonyl group, oxy group, carbonyl group or single bond which may be halogen-substituted. ]

  Specific examples of the diamine compound having a saturated hydrocarbon group as represented by the above formulas (1a) and (1b) include the following compounds. That is, for example, 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] propane, bis [4- (3-aminocyclohexyloxy) cyclohexyl] sulfone, bis [4- (4-aminocyclohexyloxy) cyclohexyl ] Sulfone, 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] hexafluoropropane, bis [4- (4-aminocyclohexyloxy) cyclohexyl] methane, 4,4′-bis (4-aminocyclohexyl) Oxy) dicyclohexyl, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ether, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ketone, 1,3-bis (4-aminocyclohexyloxy) benzene, 1, 4-bi (4-aminocyclohexyloxy) benzene, 2,2′-dimethylbicyclohexyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) dicyclohexyl-4,4′-diamine, 2,6,2 ', 6'-tetramethyl-4,4'-diamine, 5,5'-dimethyl-2,2'-sulfonyldicyclohexyl-4,4'-diamine, 3,3'-dihydroxydicyclohexyl-4,4'- Diamine, (4,4'-diamino) dicyclohexyl ether, (4,4'-diamino) dicyclohexylsulfone, (4,4'-diaminocyclohexyl) ketone, (3,3'-diamino) benzophenone, (4,4 ' -Diamino) dicyclohexylmethane, (4,4'-diamino) dicyclohexyl ether, (3,3'-diamino) di Black hexyl ether, (4,4'-diamino) dicyclohexylmethane, (3,3'-diamino) dicyclohexylmethane ether, 2,2-bis (4-aminocyclohexyl) propane and the like. A diamine compound may be used individually by 1 type in these compounds, and may be used in combination of 2 or more type. In the production of the polyamideimide of the present embodiment, as will be described later, other diamine compounds, that is, diamine compounds having no saturated hydrocarbon group may be used in combination.

  A diamine compound having a saturated hydrocarbon group can be easily obtained, for example, by subjecting an aromatic diamine compound having an aromatic ring structure corresponding to the saturated hydrocarbon group to hydrogen reduction. Examples of such aromatic diamine compounds include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as “BAPP”), bis [4- (3-aminophenoxy). ) Phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl ] Methane, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethylbiphenyl-4, 4 ′ Diamine, 2,2′-bis (trifluoromethyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethyl-4,4′-diamine, 5,5′-dimethyl-2 2′-sulfonylbiphenyl-4, 4′-diamine, 3,3′-dihydroxybiphenyl-4, 4′-diamine, (4,4′-diamino) diphenyl ether, (4,4′-diamino) diphenylsulfone, (4,4′-diamino) benzophenone, (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, etc. Can be illustrated.

  Hydrogen reduction of an aromatic diamine compound can be performed by a general method for reducing an aromatic ring. Examples of this reduction method include Raney nickel catalyst and platinum oxide catalyst (D. Varech et al., Tetrahedron Letter, 26, 61 (1985); RHBaker et al., J. Am. Chem. Soc., 69, 1250 (1947)). Rhodium-aluminum oxide catalyst (JCSircar et al., J. Org. Chem., 30, 3206 (1965); AIMeyers et al., Organic Synthesis Collective Volume VI, 371 (1988); AWBurgstahler, Organic Synthesis Collective Volume V, 591 ( 1973); AJBriggs, Synthesis, 1988, 66), rhodium oxide-platinum oxide catalyst (S. Nishimura, Bull. Chem. Soc. Jpn., 34, 32 (1961); EJCorey et al., J. Am. Chem. Soc. 101, 1608 (1979)), charcoal-supported rhodium catalyst (K. Chebaane et al., Bull. Soc. Chim. Fr., 1975, 244), sodium borohydride-rhodium chloride catalyst (PG Gassman et al., Organic Synthesis) Collective Volume VI, 581 (1988); PG Gassman et al., Organic Synthesis Collective Volume VI, 601 (1988)), and the like.

  When the polyamideimide as component (C) is obtained using a diamine compound having a saturated hydrocarbon group as described above, the main chain of the polyamideimide contains a structural unit composed of saturated hydrocarbons. It becomes like this. Such a polyamideimide has an extremely high water absorption resistance or water repellency compared to a conventional polyamideimide due to such a structural unit comprising a saturated hydrocarbon. And according to the metal foil 1 with an adhesive layer using the curable resin composition containing a polyamideimide having a structural unit composed of a saturated hydrocarbon for the adhesive layer 20, for example, a resin composition containing a polyamideimide having an aromatic ring Compared with the case where it is used, when a metal-clad laminate is manufactured, it is possible to greatly suppress a decrease in adhesiveness between the metal foil (conductive layer) and the insulating layer during moisture absorption. Such an effect is particularly prominent when a diamine compound having an alicyclic saturated hydrocarbon group is used as the diamine compound having a saturated hydrocarbon group.

  (C) Polyamideimide which is a component may further add a diamine compound other than the diamine compound having an alicyclic saturated hydrocarbon group in the production stage. If it carries out like this, structural units other than the structure which consists of saturated hydrocarbons will be introduce | transduced in the obtained polyamideimide, and also it will become easy to obtain the desired characteristic.

［式（３）中、Ｌ^４はメチレン基、スルホニル基、オキソ基、カルボニル基又は単結合を示し、Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、アルキル基又は置換基を有していてもよいフェニル基を示し、ｋは１〜５０の整数を示す。］ Examples of the diamine compound other than the diamine compound having a saturated hydrocarbon group include compounds represented by the following general formula (3).

[In Formula (3), L ⁴ represents a methylene group, a sulfonyl group, an oxo group, a carbonyl group or a single bond, and R ⁸ and R ⁹ each independently have a hydrogen atom, an alkyl group or a substituent. And k represents an integer of 1 to 50. ]

In the diamine compound represented by the above formula (3), R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group which may have a substituent. It is preferable. Examples of the substituent that may be bonded to the phenyl group include an alkyl group having 1 to 3 carbon atoms and a halogen atom. In the diamine compound represented by the general formula (3), L ⁴ is particularly preferably an oxy group from the viewpoint of achieving both a low elastic modulus and a high Tg. Specific examples of such a diamine compound include Jeffamine D-400 and Jeffamine D-2000 (manufactured by Sun Techno Chemical Co., Ltd., trade name).

  An aromatic diamine having an aromatic ring is also suitable as a diamine compound to be combined with a diamine having a saturated hydrocarbon group. As the aromatic diamine, a compound in which two amino groups are directly bonded to an aromatic ring, or two or more aromatic rings are bonded directly or via a specific group, at least of these aromatic rings A compound in which an amino group is bonded to each of the two is exemplified, and the compound is not particularly limited as long as it has such a structure.

As the aromatic diamine compound, for example, a compound represented by the following general formula (4a) or (4b) is preferable.

In formulas (4a) and (4b), L ⁵ is an optionally halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, a carbonyl group, a single bond, or A divalent group represented by the formula (5a) or (5b), wherein L ⁶ is a halogenated halogenated divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an oxy group, or R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, a hydroxyl group, a methoxy group or a halogen-substituted methyl group. In the following formula (5a), L ⁷ represents a C 1-3 divalent aliphatic hydrocarbon group, a sulfonyl group, an oxy group, a carbonyl group or a single bond which may be halogen-substituted.

  Specific examples of the aromatic diamine include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone, and bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1 , 4-bis (4-aminophenoxy) benzene, 2,2′-dimethylbiphenyl-4,4′-diamine, 2,2′-bis (trif Oromethyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethyl-4,4′-diamine, 5,5′-dimethyl-2,2′-sulfonylbiphenyl-4,4 ′ -Diamine, 3,3'-dihydroxybiphenyl-4,4'-diamine, (4,4'-diamino) diphenyl ether, (4,4'-diamino) diphenylsulfone, (4,4'-diamino) benzophenone, 3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, and the like. An aromatic diamine compound may be used individually by 1 type in the compound mentioned above, and may be used in combination of 2 or more type.

  By using these aromatic diamines in combination, an aromatic ring structure is introduced into the polyamideimide in addition to the structural units composed of saturated hydrocarbons. The curable resin composition containing such a polyamideimide can further improve the Tg of the cured product (further, the cured layer of the adhesive layer), and can further improve the heat resistance.

Furthermore, as a diamine compound used in combination with a diamine compound having a saturated hydrocarbon group, a siloxane diamine represented by the following general formula (6) is suitable.

In the formula (6), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ (hereinafter referred to as “R ^{13 to} R ¹⁸ ”) each independently represent 1 to 1 carbon atoms. It is preferable that it is the phenyl group which may have 3 alkyl groups or a substituent. The substituent that may be bonded to the phenyl group is preferably an alkyl group having 1 to 3 carbon atoms or a halogen atom. R ¹⁹ and R ²⁰ are each independently preferably an alkylene group having 1 to 6 carbon atoms or an arylene group which may have a substituent. As this arylene group, a phenylene group which may have a substituent or a naphthalene group which may have a substituent is preferable. Furthermore, as a substituent which may be couple | bonded with this arylene group, a C1-C3 alkyl group or a halogen atom is preferable. Furthermore, in Formula (6), a and b are integers of 1-15, respectively.

As such a siloxane diamine, a compound in which R ^{13 to} R ¹⁸ are methyl groups, that is, a compound having a structure in which amino groups are bonded to both ends of dimethylsiloxane is particularly preferable. As the siloxane diamine, one type of compound may be used alone, or two or more types of compounds may be used in combination.

  Specific examples of the siloxane diamine represented by the general formula (6) include silicone oil X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B ( Amine equivalent 1500), X-22-9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd., trade name), BY16-853 (amine equivalent 650), What is commercially available as BY16-853B (amine equivalent 2200) (above, manufactured by Toray Dow Corning Silicone Co., Ltd.) is suitable.

  By using the siloxane diamine described above as the diamine compound, the polyamideimide as the component (C) has a siloxane structure in the main chain. Further, the curable resin composition containing such a polyamideimide having a siloxane structure can form a cured product that is excellent in flexibility and hardly generates swelling under high temperature conditions. The durability and heat resistance of a printed wiring board or the like obtained using the metal foil 1 with an adhesive layer can be further improved.

  In the production of a polyamideimide having a structural unit composed of a saturated hydrocarbon, first, a diamine compound containing at least a diamine compound having a saturated hydrocarbon group is prepared as a diamine compound. Subsequently, these diamine compounds are reacted with trimellitic anhydride. At this time, a reaction occurs between the amino group of the diamine compound and the carboxyl group or the anhydrous carboxyl group of trimellitic anhydride to produce an amide group. In such a reaction, it is particularly preferable to cause a reaction between the amino group of the diamine compound and the anhydrous carboxyl group of trimellitic anhydride.

  This reaction is preferably performed at 70 to 100 ° C. by dissolving or dispersing the diamine compound and trimellitic anhydride in an aprotic polar solvent. Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, and cyclohexanone. Of these, NMP is particularly preferable. These aprotic polar solvents may be used alone or in combination of two or more.

  The aprotic polar solvent is preferably an amount such that the solid content is 10 to 70% by mass with respect to the total mass of the aprotic polar solvent, the diamine compound and trimellitic anhydride, and is 20 to 60% by mass. Is more preferable. When the solid content in the solution is less than 10% by mass, the amount of the solvent used is too large and tends to be industrially disadvantageous. On the other hand, when it exceeds 70% by mass, the solubility of trimellitic anhydride is lowered, and it tends to be difficult to perform a sufficient reaction.

  Next, an aromatic hydrocarbon which can be azeotroped with water is added to the solution after the above reaction, and further reacted at 150 to 200 ° C. Thereby, a dehydration ring-closing reaction occurs between the adjacent carboxyl group and amide group, and as a result, an imide group-containing dicarboxylic acid is obtained. Here, examples of the aromatic hydrocarbon that can be azeotroped with water include toluene, benzene, xylene, and ethylbenzene. Of these, toluene is preferable. The aromatic hydrocarbon is preferably added in an amount corresponding to 10 to 50 parts by mass with respect to 100 parts by mass of the aprotic polar solvent. When the addition amount of the aromatic hydrocarbon is less than 10 parts by mass with respect to 100 parts by mass of the aprotic polar solvent, the water removal effect tends to be insufficient, and generation of an imide group-containing dicarboxylic acid The amount may be reduced. On the other hand, if the amount exceeds 50 parts by mass, the reaction temperature in the solution decreases, and the amount of imide group-containing dicarboxylic acid produced tends to decrease.

  During this dehydration ring closure reaction, the aromatic hydrocarbon in the solution is distilled off together with water, so that the amount of the aromatic hydrocarbon in the reaction solution may be less than the above-mentioned preferred range. Thus, for example, by performing operations such as distilling water and aromatic hydrocarbons into a moisture determination receiver with a cock, separating the aromatic hydrocarbons, and then returning them to the reaction solution. The amount of the group hydrocarbon may be kept at a certain ratio. In addition, after completion | finish of a spin-drying | dehydration ring-closing reaction, it is preferable to remove the aromatic hydrocarbon which can azeotrope with water, keeping the temperature of a solution at about 150-200 degreeC.

The imide group-containing dicarboxylic acid obtained by the reaction so far has, for example, a structure represented by the following general formula (7).

In the formula (7), L ⁸ is a residue obtained by removing the amino group of the diamine compound represented by the general formula (1a), (1b), (3), (4a), (4b) or (6). Indicates. The imide-containing dicarboxylic acid, various compounds having the L ⁸ of structure corresponding to the diamine compound used as the starting material can be obtained.

  Examples of a method for synthesizing polyamideimide using the imide group-containing dicarboxylic acid thus obtained include the following methods. That is, first, as the first method, there is a method in which an imide group-containing dicarboxylic acid as described above is derived into an acid halide and then copolymerized with the diamine compound as described above.

  The imide group-containing dicarboxylic acid is easily derived into an acid halide by reaction with thionyl chloride, phosphorus trichloride, phosphorus pentachloride, or dichloromethyl methyl ether. The imide group-containing dicarboxylic acid halide thus obtained can be easily copolymerized with a diamine compound at room temperature or under heating conditions.

  The second method includes a method in which an imide group-containing dicarboxylic acid is copolymerized with the diamine compound as described above in the presence of a condensing agent. In such a reaction, a general condensing agent that forms an amide bond can be used as the condensing agent. Among these, it is preferable to use dicyclohexylcarbodiimide, diisopropylcarbodiimide or N-ethyl-N′-3-dimethylaminopropylcarbodiimide alone, or to use these in combination with N-hydroxysuccinimide or 1-hydroxybenzotriazole.

  As a third method, a method of reacting an imide group-containing dicarboxylic acid with a diisocyanate can be mentioned. When going through such a reaction, the ratio of the diamine compound and trimellitic anhydride, which are raw materials of the imide group-containing dicarboxylic acid, and the diisocyanate is preferably set as follows. That is, (diamine compound: trimellitic anhydride: diisocyanate) is in a molar ratio of 1.0: (2.0 to 2.2): (1.0 to 1.5). Preferably, 1.0: (2.0 to 2.2) :( 1.0 to 1.3) is more preferable. By adjusting to such a molar ratio, it is possible to obtain a polyamideimide having a higher molecular weight and advantageous for film formation.

Examples of the diisocyanate used in the third method include compounds represented by the following general formula (8).

In formula (8), L ⁹ is a divalent organic group or divalent aliphatic hydrocarbon group having one or more aromatic rings. In particular, it is selected from the group consisting of a group represented by the following formula (9a), a group represented by the following formula (9b), a tolylene group, a naphthylene group, a hexamethylene group, and a 2,2,4-trimethylhexamethylene group. It is preferably at least one group.

  Examples of the diisocyanate represented by the general formula (8) include aliphatic diisocyanates and aromatic diisocyanates, and aromatic diisocyanates are preferable, and it is particularly preferable to use both in combination. Examples of aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and 2,4-tolylene dimer. It can be illustrated. Of these, MDI is particularly preferable. By using MDI as the aromatic diisocyanate, the flexibility of the polyamideimide obtained can be improved and the crystallinity can be further reduced. As a result, the film-formability of polyamideimide can be improved. On the other hand, examples of the aliphatic diisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate.

  When the aromatic diisocyanate and the aliphatic diisocyanate are used in combination, it is preferable to add the aliphatic diisocyanate in an amount of about 5 to 10 parts by mole with respect to 100 parts by mole of the aromatic diisocyanate. Thereby, the heat resistance of the polyamideimide obtained can be further improved.

  The reaction of the imide group-containing dicarboxylic acid and the diisocyanate in the third method can be performed by adding the diisocyanate to a solution containing the imide group-containing dicarboxylic acid and reacting at a reaction temperature of 130 to 200 ° C. Moreover, you may perform this reaction using a basic catalyst. In this case, the reaction temperature is preferably 70 to 180 ° C, more preferably 120 to 150 ° C. When this reaction is performed in the presence of a basic catalyst, the reaction can proceed at a lower temperature than when the reaction is performed in the absence of a basic catalyst. The progress of side reactions such as reactions can be suppressed. As a result, a higher molecular weight polyamideimide compound can be obtained.

  Examples of the basic catalyst include trialkylamines such as trimethylamine, triethylamine, tripropylamine, tri (2-ethylhexyl) amine, and trioctylamine. Among these, triethylamine is particularly preferable because it is a suitable basic catalyst that can promote the above-described reaction and is easily removed from the system after the reaction.

Examples of the polyamideimide obtained by the various methods described above include those having a structural unit represented by the following general formula (10). In the following formulas (10), ^{L 8} and ^{L 9} has the same meaning as ^{L 8} and ^{L 9} above.

  The curable resin composition in a preferred embodiment contains the components (A) to (C) as described above. And in such a curable resin composition, it is preferable that (A)-(C) component is contained in the mixture ratio which satisfy | fills the conditions as shown below.

  First, the blending ratio of the component (B) in the curable resin composition is preferably 0.5 to 200 parts by mass and more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the component (A). preferable. When the blending ratio of the component (B) is less than 0.5 parts by mass, in the metal foil 1 with an adhesive layer and a printed wiring board obtained using the same, the toughness of the adhesive hardened layer and the metal foil (conductive layer) There exists a tendency for adhesiveness to fall. On the other hand, if it exceeds 200 parts by mass, the thermosetting property of the adhesive layer 20 is lowered, and the reactivity between the adhesive cured layer and the insulating resin layer is lowered. When the film is formed, the heat resistance, chemical resistance and breaking strength in the vicinity of the adhesive hardened layer itself or the interface between the adhesive hardened layer and the insulating resin layer tend to be lowered.

  Moreover, it is preferable that the mixture ratio of (C) component shall be 10-400 mass parts with respect to 100 mass parts of total of (A) component and (B) component. When the blending ratio of the component (C) is less than 10 parts by mass, the toughness of the adhesive hardened layer and the metal foil (conductive layer) in the metal foil 1 with an adhesive layer and the printed wiring board obtained using the same. There is a tendency for the adhesiveness to decrease. On the other hand, if it exceeds 400 parts by mass, the heat resistance, chemical resistance and breaking strength in the vicinity of the adhesive hardened layer itself or in the vicinity of the interface between the adhesive hardened layer and the insulating resin layer tend to be lowered.

  The curable resin composition constituting the adhesive layer 20 may further include a desired component as necessary in addition to the components (A) to (C) described above. As components other than the components (A) to (C), first, curing acceleration having a catalytic function for promoting the reaction between the polyfunctional epoxy resin as the component (A) and the polyfunctional phenol resin as the component (B). Agents. Although it does not restrict | limit especially as a hardening accelerator, For example, an amine compound, an imidazole compound, an organic phosphorus compound, an alkali metal compound, an alkaline-earth metal compound, a quaternary ammonium salt etc. are mentioned. As a hardening accelerator, 1 type may be used independently and 2 or more types may be used in combination.

  The blending ratio of the curing accelerator in the curable resin composition is preferably determined according to the blending ratio of the component (A). Specifically, it is preferable to set it as 0.05-10 mass parts with respect to 100 mass parts of (A) component. When a curing accelerator is blended within this range, a good reaction rate between the component (A) and the component (B) is obtained, and the curable resin composition of the adhesive layer 20 is further excellent in reactivity and curability. It becomes like this. As a result, the hardened layer (adhesive hardened layer) obtained from the adhesive layer 20 has more excellent chemical resistance, heat resistance and moisture heat resistance.

  Moreover, as components other than (A)-(C) component, it is preferable to contain (D1) crosslinked rubber particle and / or (D2) polyvinyl acetal resin as (D) component.

  First, the component (D) particularly preferably includes (D1) crosslinked rubber particles. As the crosslinked rubber particles, at least one selected from acrylonitrile butadiene rubber particles, carboxylic acid-modified acrylonitrile butadiene rubber particles, and core-shell particles of butadiene rubber-acrylic resin is preferable.

  Here, the acrylonitrile butadiene rubber particles are particles obtained by copolymerizing acrylonitrile and butadiene and partially crosslinking in the copolymerization stage. The carboxylic acid-modified acrylonitrile butadiene rubber particles are obtained by copolymerizing together carboxylic acids such as acrylic acid and methacrylic acid in the above copolymerization. Further, the core-shell particles of butadiene rubber-acrylic resin are obtained by a two-stage polymerization method in which butadiene particles are polymerized by emulsion polymerization, and a monomer such as acrylic acid ester or acrylic acid is further added to continue polymerization. The size of these crosslinked rubber particles is preferably a primary average particle diameter of 50 nm to 1 μm. As the crosslinked rubber particles, those described above may be added alone or in combination of two or more.

  More specific examples of such crosslinked rubber particles include, for example, XER-91 manufactured by Nippon Synthetic Rubber Co., Ltd. as carboxylic acid-modified acrylonitrile butadiene rubber particles. Examples of the core-shell particles of butadiene rubber-acrylic resin include EXL-2655 manufactured by Kureha Chemical Industry Co., Ltd. and AC-3832 manufactured by Takeda Pharmaceutical Company Limited.

  Moreover, as (D) component, it is more preferable when (D2) polyvinyl acetal resin is included. In particular, when (D1) crosslinked rubber particles and (D2) polyvinyl acetal resin are used in combination as the component (D), the peel strength against the metal foil by the adhesive hardened layer and the peel strength against electroless plating after chemical roughening Is particularly preferable.

  Examples of the polyvinyl acetal resin as component (D2) include polyvinyl acetal and carboxylic acid-modified polyacetal resins that are carboxylic acid-modified products thereof. As the polyvinyl acetal resin, various resins having various amounts of hydroxyl groups and acetyl groups can be applied without particular limitation, and those having a polymerization degree of 1000 to 2500 are particularly preferable. When the polymerization degree of the polyvinyl acetal resin is within this range, the solder heat resistance of the adhesive hardened layer can be sufficiently secured. Moreover, the viscosity and handleability of the varnish containing the curable resin composition are improved, and the production of the metal foil 20 with an adhesive layer tends to be easy.

  Here, the number average degree of polymerization of the polyvinyl acetal resin is, for example, a value determined from a standard polystyrene calibration curve based on the number average molecular weight (gel permeation chromatography) of polyvinyl acetate as a raw material. Can be adopted. The carboxylic acid-modified polyvinyl acetal resin is a carboxylic acid-modified product of the above-mentioned polyvinyl acetal resin, and preferably satisfies the same conditions as the polyvinyl acetal resin.

  Examples of the polyvinyl acetal resin include trade names manufactured by Sekisui Chemical Co., Ltd., ESREC BX-1, BX-2, BX-5, BX-55, BX-7, BH-3, BH-S, and KS-. Examples include 3Z, KS-5, KS-5Z, KS-8, KS-23Z, trade names manufactured by Denki Kagaku Kogyo Co., Ltd., and electrified butyral 4000-2, 5000A, 6000C, 6000EP, and the like. As a polyvinyl acetal resin, what was mentioned above can also be used individually or in mixture of 2 or more types.

  In the curable resin composition, the blending ratio of the component (D) is preferably in the range of 0.5 to 100 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B), and 1 to 50 masses. It is more preferable to use parts. When the blending ratio of the component (D) is less than 0.5 parts by mass, the toughness of the adhesive hardened layer, the adhesive hardened layer and the metal foil in the metal foil 1 with an adhesive layer and a printed wiring board obtained using the same There exists a tendency for adhesiveness with (conductive layer) to fall. On the other hand, when it exceeds 100 parts by mass, the heat resistance, chemical resistance and breaking strength in the vicinity of the adhesive cured layer itself or the interface between the adhesive cured layer and the insulating resin layer tend to be lowered. In addition, when several types of component is included as (D) component, it is preferable that those sum totals satisfy | fill the mixing | blending ratio mentioned above.

  Furthermore, the curable resin composition has various heat-resistant additives such as a flame retardant, a filler, a coupling agent, and the like according to desired characteristics. It may be included to such an extent that properties such as property, adhesiveness and moisture absorption resistance are not deteriorated.

  Although it does not specifically limit as a flame retardant, Flame retardants, such as a bromine type, a phosphorus type, and a metal hydroxide, are suitable. More specifically, brominated flame retardants include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl) , Ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated Brominated flame retardants such as polystyrene, 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobi Phenol A type dimethacrylate, pentabromobenzyl acrylate, brominated reactive flame retardant containing an unsaturated double bond of the brominated styrene.

  Phosphorus flame retardants include aromatics such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2, 6-xylenyl phosphate, resorcinol bis (diphenyl phosphate) Phosphoric acid esters, phosphonic acid esters such as diphenyl phenylphosphonate, diallyl phenylphosphonate, bis (1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa- Phosphinic acid esters such as 10-phosphaphenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, Li Lin melamine, melam polyphosphate, ammonium polyphosphate, phosphorus-based flame retardant of red phosphorus and the like. Further, examples of the metal hydroxide flame retardant include magnesium hydroxide and aluminum hydroxide. These flame retardants may be used individually by 1 type, and may be used in combination of multiple types.

  When the flame retardant is added, the blending ratio is not particularly limited, but is preferably 5 to 150 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), and 5 to 80 It is more preferable to set it as a mass part, and it is still more preferable to set it as 5-60 mass parts. When the blending ratio of the flame retardant is less than 5 parts by mass, the flame resistance of the adhesive layer 20 and the adhesive hardened layer tends to be insufficient. On the other hand, if it exceeds 100 parts by mass, the heat resistance of the adhesive hardened layer tends to decrease.

  Moreover, it does not specifically limit as a filler which is an additive, However, An inorganic filler is suitable. Examples of inorganic fillers include alumina, titanium oxide, mica, silica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, Examples thereof include calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate, aluminum borate, silicon carbide and the like.

  These fillers may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, there is no restriction | limiting in particular about the shape of a filler, and a particle size, However, When a particle size is 0.01-50 micrometers, it is more preferable that it is 0.1-15 micrometers. The blending ratio of the filler in the curable resin composition is, for example, preferably 1 to 1000 parts by mass and 1 to 800 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). More preferably.

  Furthermore, although it does not specifically limit as a coupling agent, For example, a silane coupling agent, a titanate coupling agent, etc. are mentioned. Examples of the silane coupling agent include carbon functional silane. Specifically, epoxy group-containing silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 2- (2,3-epoxycyclohexyl) ethyltrimethoxysilane; Amino group-containing silanes such as aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl (methyl) dimethoxysilane; Cationic silanes such as (trimethoxylyl) propyltetramethylammonium chloride; vinyl group-containing silanes such as vinyltriethoxysilane; acrylic group-containing silanes such as 3-methacryloxypropyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane Of mercapto group-containing silanes It is below. On the other hand, examples of titanate coupling agents include alkyl titanates such as titanium propoxide and titanium butoxide. As these coupling agents, one kind may be used alone, or two or more kinds may be used in combination.

  The blending ratio of the coupling agent in the curable resin composition is not particularly limited, but is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is more preferable in it being 0.1-10 mass parts.

And the curable resin composition containing each component mentioned above prepares by mix | blending (A) component, (B) component, (C) component, and another additive component by a well-known method, and mixing. Can do.
[Method for producing metal foil with adhesive layer]

  Next, the suitable manufacturing method of the metal foil 1 with the contact bonding layer which has the structure mentioned above is demonstrated. The metal foil 1 with an adhesive layer is prepared, for example, by first preparing the above-described curable resin composition and using the varnish prepared by dissolving or dispersing the curable resin composition in a solvent as it is, as described above. It can obtain by making it the adhesive layer 20 by drying etc. after apply | coating to. At this time, the curable resin composition may be semi-cured (B-staged).

  The curable resin composition and its varnish can be applied by a known method, for example, using a kiss coater, a roll coater, a comma coater, or the like. Moreover, drying can be implemented by the method of processing in a heat drying oven etc. at the temperature of 70-250 degreeC, for example, Preferably it is 100-200 degreeC for 1 to 30 minutes, Preferably it is 3 to 15 minutes. When a solvent is used to dissolve the curable resin composition, the drying temperature is preferably equal to or higher than the temperature at which the solvent can be volatilized.

  The solvent used for varnishing the curable resin composition is not particularly limited. For example, alcohols such as methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol, etc. Ethers, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene, xylene, mesitylene, esters such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate, Examples thereof include solvents such as nitrogen-containing compounds such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone. In varnishing, only one solvent may be used alone, or two or more solvents may be used in combination.

  Among these solvents, when nitrogen-containing compounds and ketones are used in combination, the blending ratio is preferably 1 to 500 parts by mass of ketones with respect to 100 parts by mass of nitrogen-containing compounds. Is preferably 3 to 300 parts by mass, and more preferably 5 to 250 parts by mass of ketones.

  In addition, when the curable resin composition is varnished, it is preferable to adjust the amount of the solvent so that the solid content (nonvolatile content) concentration in the varnish is 3 to 80% by mass. When manufacturing the metal foil 1 with an adhesive layer, the solid content concentration and the varnish viscosity can be adjusted so that the adhesive layer 20 having a preferable film thickness as described above can be obtained by appropriately adjusting the amount of the solvent. It becomes easy.

  The metal foil 1 with an adhesive layer having the above-described configuration can be easily formed on a metal-clad laminate or the like by being laminated on an insulating resin layer or the like via the adhesive layer 20. And since the metal-clad laminated board etc. which were obtained in this way have adhered the metal foil 1 and the insulating resin layer through the hardened | cured material (adhesion hardening layer) of the contact bonding layer 20, for example, insulation Even when a low dielectric constant resin such as polybutadiene, triallyl cyanurate, triallyl isocyanurate, or functionalized polyphenylene ether is used as the material for the resin layer, it has excellent conductor (metal foil) peel strength. It can be expressed. Moreover, the peel strength is sufficiently maintained even during moisture absorption. As a result, the metal-clad laminate is extremely difficult to cause delamination between layers, and can sufficiently maintain its characteristics even during moisture absorption.

In addition, these characteristics can be sufficiently obtained even when the metal foil 1 with an adhesive layer has the metal foil 10 having a relatively small roughness on the M surface. Therefore, a printed wiring board or the like obtained using a metal-clad laminate has excellent high frequency characteristics, conductive layer adhesiveness, and heat resistance. Therefore, the metal foil 1 with an adhesive layer of the present embodiment is used as a member or a raw material for a metal-clad laminate for forming printed wiring boards (printed wiring boards) and the like provided in various electric machines and electronic devices that handle high-frequency signals. Is preferred.
[Metal-clad laminate]

  Next, the metal-clad laminate suitably obtained using the metal foil 1 with an adhesive layer described above will be described. This metal-clad laminate is obtained by using the above-described metal foil with an adhesive layer, and its formation method, shape, laminated structure and the like are not particularly limited.

  FIG. 2 is a partial cross-sectional view of a metal-clad laminate according to a preferred embodiment. This FIG. 2 has shown typically the cross-sectional structure of the metal-clad laminated board of suitable embodiment. The metal-clad laminate 100 shown in FIG. 2 includes an insulating resin layer 40, an adhesive cured layer 30 laminated on both surfaces of the insulating resin layer 40, and the opposite side of the adhesive cured layer 30 with respect to the insulating resin layer 40. And a metal foil 10 laminated on the surface.

  The insulating resin layer 40 has a configuration in which a plurality of layers are laminated and integrated. Further, the insulating resin layer 40 and the adhesive hardened layer 30 are integrated, and the insulating layer 50 is formed by these. The metal foil 10 and the adhesive hardened layer 30 in the metal-clad laminate 100 are formed from the metal foil 1 with an adhesive layer of the above-described embodiment. That is, the adhesive cured layer 30 is a cured layer obtained by curing the adhesive layer 20 in the metal foil 1 with an adhesive layer, and the metal foil 10 is formed from the metal foil 10 in the metal foil 1 with an adhesive layer.

  The metal-clad laminate 100 having such a configuration can be obtained as follows. First, a prepreg for forming the insulating resin layer 40 is prepared. As a prepreg, a resin having insulation properties such as polybutadiene, triallyl cyanurate, triallyl isocyanurate, functionalized polyphenylene ether is impregnated into a reinforcing fiber such as glass fiber or organic fiber, for example, semi-curing the resin, etc. And those prepared by known methods.

  Next, a plurality of the prepregs are stacked to form an insulating resin film, and a pair of metal foils 1 with an adhesive layer is placed on both surfaces of the insulating resin film so that the adhesive layers 20 are in contact with the insulating resin film. Overlapping each other. Then, the metal-clad laminated board 100 is obtained by heating and / or pressurizing these. By this heating and pressurization, the insulating resin in the insulating resin film is cured, and the curable resin composition constituting the adhesive layer 20 is cured. As a result, the insulating resin layer 40 is formed from the insulating resin film, and the adhesive hardened layer 30 is formed from the adhesive layer 20.

  The heating is preferably performed at a temperature of 150 to 250 ° C., and the pressing is preferably performed at a pressure of 0.5 to 10.0 MPa. This heating and pressurization can be performed simultaneously by using a vacuum press. In this case, the vacuum press is preferably performed for 30 minutes to 10 hours. As a result, the curing of the adhesive layer 20 and the insulating resin film is sufficiently advanced, the adhesive layer between the metal foil 10 and the insulating layer 50 is excellent, and the chemical resistance, heat resistance and moisture heat resistance are excellent. The metal-clad laminate 100 can be obtained.

  The metal-clad laminate 100 of the preferred embodiment has the above-described configuration. In other words, the insulating resin layer 40 and the adhesive hardened layer 30 are integrated between the pair of metal foils 10. The layer 50 is sandwiched. Since such a metal-clad laminate 100 is formed using the metal foil 1 with an adhesive layer, it is advantageous for producing a printed wiring board that can sufficiently suppress transmission loss in a high frequency band. In addition, the adhesion between the insulating layer 50 and the metal foil 10 is sufficiently excellent.

In the above-described example, the metal-clad laminate 100 is exemplified by the one in which the metal foil 100 with the adhesive layer is laminated on both surfaces of the insulating resin film. However, the metal-clad laminate of the present invention is not limited to this. The metal foil with an adhesive layer may be laminated only on one side of the insulating resin film. Moreover, although the insulating resin layer 40 has a laminated structure including a plurality of layers, the insulating resin layer 40 is not limited to this, and may have a single layer structure.
[Printed wiring board]

  Next, a printed wiring board (printed wiring board) according to a preferred embodiment will be described. The printed wiring board of the present invention is obtained by using the above-described metal foil with an adhesive layer, preferably a metal-clad laminate, and its formation method, shape, laminated structure and the like are not particularly limited.

  FIG. 3 is a diagram showing a partial cross-sectional configuration of a printed wiring board according to a preferred embodiment. As shown in the drawing, the printed wiring board 200 is opposite to the insulating resin layer 40, the adhesive cured layer 30 laminated on both surfaces of the insulating resin layer 40, and the insulating resin layer 40 in these adhesive cured layers 30. And a conductive layer 11 formed on the side surface. In addition, a through hole 70 penetrating in the stacking direction is formed at a predetermined position of the printed wiring board 200, and on the wall surface and the surface of the conductive layer 11 around the opening of the through hole 70. A plating film 60 is formed. By the plating film 60, the conductive layers 11 on the front and back surfaces are connected to each other.

  In this printed wiring board 200, the adhesive hardened layer 30 and the insulating resin layer 40 have the same configuration as the metal-clad laminate 100 described above. The adhesive cured layer 30 and the insulating resin layer 40 are integrated to form an insulating layer 50 that functions as a substrate.

  The printed wiring board 200 having such a configuration is preferably manufactured as follows, for example. That is, first, the metal-clad laminate 100 of the above-described embodiment is prepared. Next, the metal-clad laminate 100 is subjected to drilling by a known method and then plated. Thereby, the through hole 70 and the plating film 60 are formed. Further, the metal foil 10 on the surface of the metal-clad laminate 100 is processed into a predetermined circuit shape by a known method such as etching. Thereby, the conductive layer 11 is formed from the metal foil 10. In this way, the printed wiring board 200 is obtained.

  Thus, the printed wiring board 200 is formed from the metal-clad laminate 100 obtained by using the metal foil 1 with an adhesive layer. For this reason, in the printed wiring board 200, the conductive layer 11 obtained from the conductor foil 10 is strongly bonded to the insulating resin layer 40 through the adhesive hardened layer 30. That is, the adhesion between the conductive layer 11 and the insulating layer 50 is extremely good. Therefore, even when a low-roughened foil is used as the metal foil 10 for forming the conductive layer 11, the conductive layer 11 is unlikely to peel from the insulating layer 50. Such a printed wiring board 200 can have a small transmission loss in a high frequency band.

Further, even when a resin having high insulation and high heat resistance is applied as the resin material of the insulating resin layer 40, peeling of the conductive layer 11 can be sufficiently reduced. Furthermore, the adhesive hardened layer 30 can maintain excellent adhesiveness even under high humidity conditions. Therefore, the printed wiring board 200 can have a higher frequency response because the insulating layer 50 has excellent insulating properties, and has excellent heat resistance, particularly excellent heat resistance under high humidity conditions. .
[Multilayer wiring board]

  Furthermore, the multilayer wiring board according to a preferred embodiment includes the above-described printed wiring board 200 as an inner core board. FIG. 4 is a diagram showing a partial cross-sectional configuration of a multilayer printed wiring board according to a preferred embodiment.

  As illustrated, the multilayer printed wiring board 300 includes an insulating resin layer 42 made of a cured product (base material) of a prepreg laminated on both surfaces of the inner layer core substrate 210, and the inner layer core substrate 210 of these insulating resin layers 42. The adhesive hardened layer 32 is formed on the surface opposite to the adhesive hardened layer 32, and the conductive layer 110 is further provided on the outer surface of the adhesive hardened layer 32. Here, the inner core substrate 210 has the same configuration as the printed wiring board 200 described above.

  The multilayer printed wiring board 300 having such a configuration is formed using the printed wiring board 200. That is, first, the printed wiring board 200 is prepared, and this is used as the inner layer core substrate 210. One or more prepregs as used in manufacturing the metal-clad laminate 100 are stacked on both surfaces of the inner layer core substrate 210. Next, the metal foil 1 with an adhesive layer described above is further stacked on both outer surfaces of the prepreg so that the adhesive layer 20 is in contact therewith.

  Next, the obtained laminate is heated and pressed to adhere the layers to each other. Thereby, the insulating resin layer 42 is formed from the prepreg laminated | stacked on the inner layer core board | substrate 210, and the adhesion hardening layer 32 is formed from the adhesive layer 20 in the metal foil 1 with an adhesive layer. Then, in the same manner as when the printed wiring board 200 is manufactured, a perforation process and a plating film are appropriately performed to form the through hole 72 and the plating film 62. At this time, the drilling process may be performed only on a portion laminated on the inner layer core substrate 210 as illustrated, or may be performed so as to penetrate the inner layer core substrate 210. Then, the outermost metal foil (metal foil 10) is processed into a predetermined circuit shape by a known method to form the conductive layer 110, whereby the multilayer printed wiring board 300 is obtained.

  The multilayer printed wiring board is not limited to the form described above, and may have a configuration other than the above as long as at least the printed wiring board 200 is used as the inner layer core substrate. For example, the multilayer printed wiring board is obtained by alternately laminating the prepreg and the printed wiring board 200 on the surface of the printed wiring board 200 that is the inner layer core substrate, and heating and pressing the obtained laminate. It may be obtained. In such a multilayer printed wiring board, the outermost conductive layer may be a processed metal foil bonded via a prepreg, and the metal foil 1 with an adhesive layer laminated on the outermost surface. The metal foil 10 may be processed, or the conductive layer 11 of the printed wiring board 200 laminated on the outermost layer.

  As described above, the metal foil with an adhesive layer, the metal-clad laminate, the printed wiring board, and the multilayer printed wiring board according to the preferred embodiment of the present invention have been described, but the present invention is not limited to the above-described embodiment, It may be appropriately modified without departing from the spirit.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

  [Synthesis of Polyamideimide]

(Synthesis Example 1)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, (4,4′-diamino) dicyclohexylmethane (Wandamine HM (as diamine compound A having a saturated alicyclic hydrocarbon group) was added. WHM), manufactured by Shin Nippon Chemical Co., Ltd., trade name) 45 mmol, reactive silicone oil as siloxane diamine compound B (X-22-161-B, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent: 1500, trade name) 5 mmol, anhydrous tri 105 mmol of merit acid (TMA) and 145 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent were added, and the temperature in the flask was set at 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 60 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C. and reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 1 (solid content concentration of 30% by mass) was obtained. It was 53000 when the weight average molecular weight (Mw) of this NMP solution was measured by the gel permeation chromatography.

(Synthesis Example 2)
First, in a 1 L separable flask equipped with a Dean-Stark reflux condenser, a thermometer, and a stirrer, Jeffamine D-2000 (trade name, manufactured by Sun Techno Chemical Co., Ltd.) 30 mmol as a diamine compound C having a saturated aliphatic hydrocarbon group. , 120 mmol of (4,4′-diamino) diphenylmethane (DDM) as aromatic diamine compound D, 315 mmol of trimellitic anhydride (TMA), 442 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent, The temperature in the flask was set to 80 ° C. and stirred for 30 minutes.

  After completion of the stirring, 100 mL of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for about 2 hours. After confirming that the theoretical amount of water was stored in the moisture meter and no water distilling was observed, the temperature in the flask was increased to 190 ° C while removing the water in the meter. The toluene in the reaction solution was removed.

  After returning the solution in the flask to room temperature, 180 mmol of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, the temperature in the flask was raised to 190 ° C., and the mixture was reacted for 2 hours, and then diluted with NMP. Thus, an NMP solution of polyamideimide of Synthesis Example 2 (solid content concentration of 30% by mass) was obtained. It was 74000 when Mw of this NMP solution was measured by the gel permeation chromatography.

(Comparative Synthesis Example 1)
An NMP solution of polyamideimide was obtained in the same manner as in Synthesis Example 1 except that the amount of MDI was changed to 50 mmol. In addition, it was 23000 when Mw of this NMP solution was measured by the gel permeation chromatography.

(Comparative Synthesis Example 2)
An NMP solution of polyamideimide was obtained in the same manner as in Synthesis Example 2 except that the amount of MDI was changed to 190 mmol and the reaction time was changed to 3 hours. It was 270000 when Mw of this NMP solution was measured by the gel permeation chromatography.
[Preparation of resin varnish for adhesive layer (curable resin composition)]

(Preparation Example 1)
(A) Component cresol novolac type epoxy resin (YDCN-500, manufactured by Tohto Kasei Co., Ltd., trade name) 5.0B, component (B) novolac type phenol resin (MEH7500, manufactured by Meiwa Kasei Co., Ltd., trade name) 3.1 g and 18 g of the polyamideimide NMP solution obtained in Synthesis Example 1 as the component (C) were blended, and further, 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd. (Product name) After adding 0.025 g, 28 g of N-methyl-2-pyrrolidone and 13 g of methyl ethyl ketone were blended to prepare a resin varnish for the adhesive layer of Preparation Example 1 (solid content concentration of about 20% by mass).

  In addition, the glass transition temperature (Tg) of the resin composition obtained by hardening | curing resin which added 2E4MZ to YDCN-500 and MEH7500 was 190 degreeC. Here, the glass transition temperature Tg is a value measured by differential scanning calorimetry (DSC) in accordance with JIS-K7121-1987.

(Preparation Example 2)
(B) component bisphenol A novolak resin (YLH129, Japan Epoxy Resin Co., Ltd.) to 5.0 g of novolak type epoxy resin (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., trade name) having a biphenyl structure as component (A) Manufactured, trade name) 2.0 g, 38 g of polyamideimide NMP solution obtained in Synthesis Example 2 as component (C), and carboxylic acid-modified polyvinyl acetal resin (KS-23Z, component S) as component (D) Kogyo Co., Ltd., trade name) 0.8 g was added, and after further adding 0.025 g of 2-ethyl-4-methylimidazole (2E4MZ, Shikoku Kasei Kogyo Co., trade name) as a curing accelerator, N- Blending 35 g of methyl-2-pyrrolidone and 13 g of methyl ethyl ketone, the resin varnish for the adhesive layer of Preparation Example 2 (solid content concentration of about 20% by mass) It was prepared.

  In addition, the glass transition temperature (Tg) of the resin composition obtained by hardening | curing resin which added 2E4MZ to NC-3000H and YLH129 was 170 degreeC.

(Preparation Example 3)
(A) Phenol novolak type epoxy resin (N-770, manufactured by Dainippon Ink & Chemicals, Inc., trade name) 5.0 g, (B) component cresol novolak type phenol resin (KA-1163, Dainippon) Ink Chemical Industries, Ltd., trade name) 3.9 g, 55 g of polyamideimide NMP solution obtained in Synthesis Example 2 as component (C), and carboxylic acid-modified acrylonitrile butadiene rubber particles (XER) as component (D) -91SE-15, manufactured by JSR Corporation, trade name, solid content concentration of 15% by mass), and 8.5 g as a curing accelerator was further added, and 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., product) Name) After adding 0.025 g, N-methyl-2-pyrrolidone 39 g and methyl ethyl ketone 20 g were blended to prepare the adhesive layer of Preparation Example 3. Fat varnish (solid content concentration of about 20 wt%) was prepared.

  In addition, the glass transition temperature (Tg) of the resin composition obtained by hardening | curing resin which added 2E4MZ to N-770 and KA-1163 was 190 degreeC.

(Preparation Example 4)
Bisphenol A type epoxy resin (DER-331L, manufactured by Dow Chemical Japan Co., Ltd., trade name) 5.0 g, cresol novolac type phenol resin (KA-1163, manufactured by Dainippon Ink and Chemicals, trade name) 3.2 g, and After blending 50 g of the NMP solution of polyamideimide obtained in Synthesis Example 2 and further adding 0.025 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) as a curing accelerator. Then, 46 g of N-methyl-2-pyrrolidone and 15 g of methyl ethyl ketone were blended to prepare an adhesive layer resin varnish (solid content concentration of about 20% by mass) of Preparation Example 4.

  In addition, the glass transition temperature (Tg) of the resin composition obtained by hardening | curing resin which added 2E4MZ to DER-331L and KA1163 was 135 degreeC.

(Comparative Preparation Example 1)
A resin varnish for the adhesive layer was prepared in the same manner as in Preparation Example 2 except that the polyamideimide NMP solution was replaced with the one obtained in Synthesis Example 2 instead of the one obtained in Synthesis Example 2.

(Comparative Preparation Example 2)
A resin varnish for an adhesive layer was prepared in the same manner as in Preparation Example 2 except that the polyamideimide NMP solution was replaced with that obtained in Synthesis Example 2 and that obtained in Comparative Synthesis Example 2 was used.
[Preparation of insulating resin layer prepreg]
(Production Example 1)

  First, in a 2 L separable flask equipped with a cooling tube, a thermometer, and a stirrer, 400 g of toluene and 120 g of a polyphenylene ether resin (modified PPO-noryl PKN4752, manufactured by Nippon GE Plastics Co., Ltd., trade name) were placed. The solution was stirred and dissolved while heating the temperature to 90 ° C.

  Next, 80 g of triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Kogyo Co., Ltd., trade name) was added to the flask while stirring, and the solution was cooled to room temperature after confirming that it was dissolved or uniformly dispersed. Next, after adding 2.0 g of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator, 70 g of toluene was further blended. A varnish for an insulating resin layer having a solid content concentration of about 30% by mass was obtained.

The impregnated varnish for insulating resin layer was impregnated into a glass fiber having a thickness of 0.1 mm (E glass, manufactured by Nitto Boseki Co., Ltd.) and then dried by heating at 120 ° C. for 5 minutes. A prepreg for an insulating resin layer of a certain production example 1 was obtained.
(Production Example 2)

  First, in a 10 L separable flask equipped with a condenser, a thermometer, and a stirrer, 5000 mL of tetrahydrofuran (THF) and 100 g of a polyphenylene ether resin (Noryl PPO646-111, manufactured by Nippon GE Plastics, Inc., trade name) The temperature in the flask was stirred and dissolved while heating to 60 ° C. After returning this to room temperature, 540 mL of n-butyllithium (1.55 mol / L, hexane solution) was added under a nitrogen stream and stirred for 1 hour. Furthermore, after adding 100 g of allyl bromide and stirring for 30 minutes, an appropriate amount of methanol was blended, and the precipitated polymer was isolated to obtain an allylated polyphenylene ether.

  Next, in a 2 L separable flask equipped with a cooling tube, a thermometer, and a stirrer, 400 g of toluene and 100 g of the allylated polyphenylene ether were put and dissolved while stirring while heating the temperature in the flask to 90 ° C. Next, 100 g of triallyl isocyanurate (TAIC, manufactured by Nippon Kasei Kogyo Co., Ltd., trade name) was added to the flask while stirring, and the mixture was cooled to room temperature after confirming that it was dissolved or uniformly dispersed. Next, after adding 2.5 g of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, trade name, manufactured by NOF Corporation) as a radical polymerization initiator, 70 g of toluene was further blended, A varnish for an insulating resin layer having a solid content concentration of about 30% by mass was obtained.

The obtained insulating resin layer varnish was impregnated into a 0.1 mm thick glass fiber (E glass, manufactured by Nitto Boseki Co., Ltd.) and then dried by heating at 120 ° C. for 5 minutes to produce a resin content of 50% by mass. The prepreg for insulating resin layers of Example 2 was obtained.
(Production Example 3)

  First, in a 2 L separable flask equipped with a cooling tube, a thermometer, and a stirrer, 400 g of toluene and 120 g of a polyphenylene ether resin (modified PPO-noryl PKN4752, manufactured by Nippon GE Plastics Co., Ltd., trade name) were placed. The solution was stirred and dissolved while heating the temperature to 90 ° C. Next, 80 g of 1,2-polybutadiene (B-1000, manufactured by Nippon Soda Co., Ltd., trade name) and 10 g of divinylbenzene (DVB) as a crosslinking aid were added to the flask while stirring and dissolved or uniformly dispersed. After confirmation, it was cooled to room temperature. Next, after adding 2.0 g of α, α′-bis (t-butylperoxy) diisopropylbenzene (Perbutyl P, product name, manufactured by NOF Corporation) as a radical polymerization initiator, 70 g of toluene was further blended. A varnish for an insulating resin layer having a solid content concentration of about 30% by mass was obtained.

The obtained insulating resin layer varnish was impregnated into a 0.1 mm thick glass fiber (E glass, manufactured by Nitto Boseki Co., Ltd.) and then dried by heating at 120 ° C. for 5 minutes to produce a resin content of 50% by mass. The prepreg for insulating resin layers of Example 3 was obtained.
[Examples 1-4, Comparative Examples 1-2]

(Production of metal foil with adhesive layer)
M of the adhesive copper resin varnish obtained in Preparation Examples 1 to 4 and Comparative Preparation Examples 1 and 2 having a thickness of 12 μm (F0-WS-12, low profile copper foil, manufactured by Furukawa Electric Co., Ltd.) After each surface was naturally cast on the surface (surface roughness (Rz) = 0.8 μm), it was dried at 150 ° C. for 5 minutes to produce metal foils with adhesive layers of Examples 1-4 and Comparative Examples 1-2. did. The thickness of the adhesive layer after drying was 3 μm. In addition, the case where the varnish of Preparation Examples 1-4 corresponds to Examples 1-4, respectively, The case where the varnish of Comparative adjustment examples 1-2 is used corresponds to Comparative Examples 1-2, respectively.

(Production of double-sided copper-clad laminate)
The metal foils with adhesive layers of Examples 1 to 4 and Comparative Examples 1 and 2 are bonded to both surfaces of the base material formed by stacking the four prepregs for the insulating resin layer of any of Preparation Examples 1 to 3 described above. After making it adhere so that a layer may touch, it is heat-press-molded on the press conditions of 200 ° C, 3.0 MPa, 70 minutes, and uses metal foil with an adhesion layer of Examples 1-4 and comparative examples 1-2. Double-sided copper-clad laminates (thickness: 0.55 mm) were prepared. The combinations of the metal foil with an adhesive layer and the prepreg for insulating layer in each example or comparative example were as shown in Table 1.

(Production of multilayer substrate)
First, similarly to the above, double-sided copper-clad laminates using the metal foils with adhesive layers of Examples 1 to 4 and Comparative Examples 1 to 2 were formed, respectively, and these copper foil portions were completely removed by etching. After that, the same prepreg as the insulating resin layer prepreg used in the production of the copper clad laminate was placed on each side of the double-sided copper clad laminate after removing the copper foil, and no adhesive layer was provided on the outside. After depositing an electrolytic copper foil of 12 μm thickness (GTS-12, general copper foil, manufactured by Furukawa Electric Co., Ltd., M surface roughness (Rz) = 8 μm, trade name) so that the M surface is in contact , 200 ° C., 3.0 MPa, and press-molding under a press condition of 70 minutes to produce a multilayer substrate. In addition, it shows in Table 1 about the combination of the metal foil with an adhesive layer of Examples 1-4 and Comparative Examples 1-2, and the prepreg for insulation resin layers of Preparation Examples 1-3.
[Comparative Examples 3 to 4]

For comparison, an electrolytic copper foil (F0-WS-12, manufactured by Furukawa Electric Co., Ltd.) having a thickness of 12 μm and not provided with an adhesive layer on both surfaces of the base material formed by stacking the four prepregs for insulating resin layer of Production Example 1 , Product name) or 12 μm thick electrolytic copper foil (GTS-12, general copper foil, manufactured by Furukawa Electric Co., Ltd., surface roughness (Rz): 8 μm, product name) without an adhesive layer Then, after making these M faces come into contact with each other, they were heated and pressed under the press conditions of 200 ° C., 3.0 MPa, and 70 minutes to obtain double-sided copper-clad laminates (thickness: 0.55 mm), respectively. Produced. In addition, multilayer substrates were respectively produced from this double-sided copper-clad laminate in the same manner as described above. Among these, the case where the former electrolytic copper foil is used corresponds to Comparative Example 3, and the case where the latter electrolytic copper foil is used corresponds to Comparative Example 4.
[Measurement of peel strength of copper foil in copper-clad laminate]

The double-sided copper-clad laminate obtained in Examples 1 to 4 and Comparative Examples 1 to 4 is subjected to a process of removing unnecessary copper foil portions by etching so that the copper foil has a circuit shape with a line width of 5 mm. A laminate sample having a planar shape of 2.5 cm × 10 cm was produced. The sample thus prepared was held in an apparatus for normal and pressure cooker test (PCT) (conditions: 121 ° C., 2.2 atm, 100% RH) for 5 hours, and then peeled off with copper foil (unit: kN / m) was measured under the following conditions. The obtained results are shown in Table 1.
Test method: 90 ° C direction tensile test Tensile speed: 50 mm / min Measuring device: Shimadzu Autograph AG-100C
In addition, about this copper foil peeling strength, what was shown by "-" in a table | surface was that copper foil had already peeled after hold | maintaining in PCT, Therefore The copper foil peeling strength was not able to be measured Means.
[Evaluation of solder heat resistance of copper-clad laminates and multilayer boards]

After cutting the double-sided copper-clad laminate and the multilayer substrate obtained in Examples 1 to 4 and Comparative Examples 1 to 4 into 50 mm squares, the double-sided copper-clad laminate is obtained by etching the copper foil on one side into a predetermined shape. In addition, after removing the copper foil of the outer layer completely by etching, the multilayer substrate is subjected to a normal time and an apparatus for pressure cooker test (PCT) (conditions: 121 ° C., 2.2 atm) for a predetermined time (1 to 5 hours). Retained. Thereafter, these were immersed in a molten solder at 260 ° C. for 20 seconds, and the appearance of each of the double-sided copper-clad laminate and the multilayer board after the treatment was visually examined. The obtained results are shown in Table 1. In addition, the number in a table | surface means the number of sheets which did not swell and generation | occurrence | production of a mesling between an insulating layer and copper foil (electroconductive layer) among three copper clad laminated boards after a solder immersion. It means that it is excellent in solder heat resistance, so that this number is large.
[Evaluation of transmission loss of copper-clad laminate]

The transmission loss (unit: dB / m) of the double-sided copper-clad laminates of Examples 1 to 4 and Comparative Examples 1 to 4 was measured by a triplate line resonator method using a vector network analyzer. Measurement conditions were as follows: line width: 0.6 mm, insulating layer distance between upper and lower ground conductors: about 1.04 mm, line length: 200 mm, characteristic impedance: about 50Ω, frequency: 3 GHz, measurement temperature: 25 ° C. The obtained results are shown in Table 1.

  From Table 1, in Examples 1-4, it turned out that the copper foil peeling strength and solder heat resistance which were excellent compared with Comparative Examples 1-4 were obtained, and also low transmission loss was possible. did.

  As a result, according to the present invention, the metal with an adhesive layer capable of sufficiently reducing transmission loss particularly in a high frequency band and capable of forming a printed wiring board with sufficiently strong adhesive force between the insulating layer and the conductive layer. It was confirmed that foil could be provided. Therefore, the metal-clad laminate, printed wiring board, and multilayer wiring board obtained by using this metal foil also have low transmission loss and can have good heat resistance (particularly, good heat resistance even after moisture absorption).

It is a fragmentary perspective view of the metal foil with the contact bonding layer which concerns on suitable embodiment. It is a fragmentary sectional view of the metal-clad laminate of a preferred embodiment. It is a fragmentary sectional view of the printed wiring board of preferred embodiment. It is a fragmentary sectional view of the multilayer printed wiring board of preferred embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Metal foil with an adhesive layer, 10 ... Metal foil, 11 ... Conductive layer, 12 ... M surface, 20 ... Adhesive layer, 30, 32 ... Adhesion hardening layer, 40, 42 ... Insulating resin layer, 50 ... Insulating layer, 60 , 62 ... plating film, 70, 72 ... through hole, 100 ... metal-clad laminate, 110 ... conductive layer, 200 ... printed wiring board, 210 ... inner core board, 300 ... multilayer printed wiring board.

Claims (15)

A metal foil with an adhesive layer comprising a metal foil and an adhesive layer provided on the metal foil,
The adhesive layer is composed of a curable resin composition containing (A) component; polyfunctional epoxy resin, (B) component; polyfunctional phenol resin, and (C) component; polyamideimide;
The component (C) is a metal foil with an adhesive layer having a weight average molecular weight of 50,000 to 250,000.   The metal foil with an adhesive layer according to claim 1, wherein the component (A) and the component (B) have a glass transition temperature of 150 ° C or higher after curing of the mixture.   The component (A) is a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a brominated phenol novolak type epoxy resin, a bisphenol A novolak type epoxy resin, a biphenyl type epoxy resin, a naphthalene skeleton-containing epoxy resin, an aralkylene skeleton-containing epoxy resin. , Biphenyl-aralkylene skeleton-containing epoxy resin, phenol salicylaldehyde novolak type epoxy resin, lower alkyl group-substituted phenol salicylaldehyde novolak type epoxy resin, dicyclopentadiene skeleton containing epoxy resin, polyfunctional glycidylamine type epoxy resin and polyfunctional alicyclic type The metal foil with an adhesive layer according to claim 1 or 2, comprising at least one polyfunctional epoxy resin selected from the group consisting of epoxy resins.   The component (B) is composed of an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a salicylaldehyde type phenol resin, a copolymer type resin of a benzaldehyde type phenol resin and an aralkyl type phenol resin, and a novolac type phenol resin. The metal foil with an adhesive layer according to any one of claims 1 to 3, comprising at least one polyfunctional phenol resin selected from the above.   The metal foil with an adhesive layer according to any one of claims 1 to 4, wherein the component (C) includes a structural unit composed of a saturated hydrocarbon.   The blending ratio of the component (C) is 10 to 400 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B), according to any one of claims 1 to 5. Metal foil with adhesive layer.   The metal foil with an adhesive layer according to any one of claims 1 to 6, wherein the curable resin composition further contains a crosslinked rubber particle and / or a polyvinyl acetal resin as the component (D).   The component (D) is at least one crosslinked rubber particle selected from the group consisting of acrylonitrile butadiene rubber particles, carboxylic acid-modified acrylonitrile butadiene rubber particles, carboxylic acid-modified acrylonitrile butadiene rubber particles, and core-shell particles of butadiene rubber-acrylic resin. The metal foil with an adhesive layer according to claim 7.   The adhesive layer is formed by applying a resin varnish containing the curable resin composition and the solvent on the surface of the metal foil to form a resin varnish layer, and then removing the solvent from the resin varnish layer. The metal foil with an adhesive layer according to any one of claims 1 to 8, which is obtained by the following.   The metal foil with an adhesive layer according to claim 1, wherein the adhesive layer has a thickness of 0.1 to 5 μm.   The metal foil with an adhesive layer according to any one of claims 1 to 10, wherein a ten-point average roughness (Rz) of a surface of the metal foil on which the adhesive layer is formed is 2 µm or less. An insulating resin layer, and a metal foil laminated on the insulating resin layer via an adhesive hardened layer,
The said adhesive hardening layer and said metal foil are formed from the metal foil with an adhesive layer as described in any one of Claims 1-11,
The metal-clad laminate, wherein the adhesive hardened layer is made of a cured product of the adhesive layer in the metal foil with the adhesive layer, and the metal foil is made of the metal foil in the metal foil with the adhesive layer.   The metal foil with an adhesive layer according to any one of claims 1 to 11 is in contact with the adhesive layer in the metal foil with an adhesive layer on at least one surface of an insulating resin film containing an insulating resin. A metal-clad laminate obtained by laminating to obtain a laminate, and then heating and pressing the laminate.   A printed wiring board obtained by processing the metal foil in the metal-clad laminate according to claim 12 or 13 so as to have a predetermined circuit pattern. A multilayer wiring board comprising: a core substrate having at least one printed wiring board; and an outer wiring board disposed on at least one side of the core substrate and having at least one printed wiring board,
The multilayer wiring board according to claim 14, wherein at least one of the printed wiring boards in the core substrate is the printed wiring board according to claim 14.

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