JP2010037489A - Adhesive film, and metal foil with resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive film having excellent crack resistance and breakage resistance, and performances required for uses such as the multilayer wiring boards, and to provide a metal foil with a resin. <P>SOLUTION: The adhesive film comprises: (a) a polyamideimide resin; (b) an epoxy resin; and (c) a phenoxy resin as essential components, wherein the content of the (c) phenoxy resin component in the adhesive film is 5-30 mass%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an adhesive film and a metal foil with a resin.

  The laminate for a printed wiring board is obtained by stacking a predetermined number of prepregs each having an electrically insulating resin composition as a matrix and then heating and pressing to integrate them. When a printed circuit is formed by a subtractive method, a metal-clad laminate is used. This metal-clad laminate is manufactured by stacking a metal foil such as a copper foil on the surface (one side or both sides) of the prepreg and heating and pressing. As the electrically insulating resin, a thermosetting resin such as a phenol resin, an epoxy resin, a polyimide resin, or a bismaleimide-triazine resin is widely used, and a thermoplastic resin such as a fluorine resin or a polyphenylene ether resin is used. There is also.

  Prepregs based on phenolic resins and epoxy resins are widely used as materials for metal-clad laminates because of the low cost of materials, and prepregs based on epoxy resins are often improved with improved resin. Heat resistance, halogen-free flame retardant, low dielectric constant, low dielectric loss, etc. are progressing. These materials are resin systems having a relatively small molecular weight, and if processing such as cutting is performed on the B-stage prepreg, it is necessary to pay attention to contamination of the laminated copper foil due to generation of dust by resin powder.

  On the other hand, with the widespread use of information terminal devices such as personal computers and mobile phones, printed wiring boards mounted on them are becoming smaller and higher in density. The mounting form has progressed from a pin insertion type to a surface mounting type and further to an area array type represented by BGA (ball grid array) using a plastic substrate. In a substrate on which a bare chip such as a BGA is directly mounted, the connection between the chip and the substrate is generally performed by wire bonding by thermosonic bonding. For this reason, the substrate on which the bare chip is mounted is exposed to a high temperature of 150 ° C. or higher, and the electrically insulating resin needs a certain degree of heat resistance.

  Also, there is a case where so-called repairability is required to remove the chip once mounted, but since this is subject to the same level of heat as chip mounting, the substrate must be chip mounted again afterwards. Then, heat treatment will be added. Along with this, substrates requiring repairability are also required to have cyclic thermal shock resistance at high temperatures, and conventional multilayer wiring boards using an insulating resin system are between the core substrate and the resin of the multilayered layer or the inner layer. Separation may occur between the circuit and the resin of the multilayered layer.

  Furthermore, with the miniaturization and high performance of electronic devices, it has become necessary to accommodate printed circuit boards with component mounting in a limited space. In this method, a plurality of printed circuit boards are arranged in multiple stages and connected to each other by a wire harness or a flexible wiring board. In addition, a rigid-flex substrate in which a flexible substrate based on polyimide and a conventional rigid substrate are multilayered is used.

Under such circumstances, a prepreg impregnated with a resin composition containing a polyamide-imide resin as an essential component on a fiber base has been proposed in order to improve the formation of fine wiring with excellent thermal shock resistance, reflow resistance, and crack resistance. (For example, refer to Patent Document 1).
JP 2003-55486 A

  However, the prepregs of Patent Document 1 and the like have room for improvement with respect to crack resistance and rupture resistance.

  Therefore, an object of the present invention is to provide an adhesive film and a resin-coated metal foil that are excellent in crack resistance and rupture resistance and have performances required for uses such as the multilayer wiring board described above.

  In order to achieve the above object, the present invention provides an adhesive film comprising a) a polyamideimide resin, b) an epoxy resin, and c) a phenoxy resin as essential components, and c) a phenoxy resin component in the adhesive film. The content rate of 5-30 mass% provides the adhesive film characterized by the above-mentioned.

Such an adhesive film has the above-described configuration, and thus has excellent crack resistance and rupture resistance, and has performance required for applications such as multilayer wiring boards. The reason why such an effect is obtained by the adhesive film of the present invention is not necessarily clear, but it is thought to be caused at least by the fact that c) the content of the phenoxy resin component is in the specific range.
That is, the c) phenoxy resin is inherently low in compatibility with the a) polyamideimide resin, and it is considered difficult to obtain a uniform blend or coating film. However, the content of the c) phenoxy resin component is within the above specific range. Thus, it is considered that the above-described effects can be obtained by solving this problem and sufficiently exhibiting the characteristics of the phenoxy resin.

  In the adhesive film of the present invention, it is preferable that a) the polyamideimide resin has at least a structure of any one of the following general formulas (1), (2), (3a), (3b), and (4). Thereby, heat resistance, crack resistance, and rupture resistance are further improved.

［式（１）中、Ｒ^１，Ｒ^２は２価のアルキル基、Ｒ^３，Ｒ^４，Ｒ^７，Ｒ^８は１価のアルキル基又は置換基を有するアルキル基、Ｒ^５，Ｒ^６は１価の芳香族基又は置換基を有する芳香族基を示し、ｍ，ｎはそれぞれ０から４０の整数であり、１≦ｎ＋ｍ≦５０である。］

[In the formula (1), R ¹ and R ² are divalent alkyl groups, R ³ , R ⁴ , R ⁷ and R ⁸ are monovalent alkyl groups or alkyl groups having a substituent, and R ⁵ and R ⁶ are A monovalent aromatic group or an aromatic group having a substituent is shown, and m and n are each an integer of 0 to 40, and 1 ≦ n + m ≦ 50. ]

［式（３ａ）及び（３ｂ）中、Ｘ^１は炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基、単結合又は下記一般式（３１ａ）若しくは（３１ｂ）で表される２価の基を示し、Ｘ^２は炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基又はカルボニル基を示し、Ｒ^１１，Ｒ^１２，及びＲ^１３はそれぞれ独立に水素原子、水酸基、メトキシ基、メチル基又はハロゲン化メチル基を示す。］

[In the formulas (3a) and (3b), X ¹ represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether. A divalent group represented by a group, a carbonyl group, a single bond or the following general formula (31a) or (31b), wherein X ² is a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms; To 3 divalent halogenated aliphatic hydrocarbon groups, sulfonyl groups, ether groups or carbonyl groups, wherein R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogen atom. Represents a methylated group. ]

［式（３１ａ）中、Ｚは炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基又は単結合を示す。］

[In the formula (31a), Z is a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, a carbonyl group, or Indicates a single bond. ]

［式（４）中、Ｘはメチレン基、スルホニル基、エーテル基、カルボニル基又は単結合、Ｒ^２１及びＲ^２２はそれぞれ水素原子、アルキル基、フェニル基又は置換フェニル基を示し、ｐは１〜５０の整数を示す。］

[In Formula (4), X represents a methylene group, a sulfonyl group, an ether group, a carbonyl group or a single bond, R ²¹ and R ²² represent a hydrogen atom, an alkyl group, a phenyl group or a substituted phenyl group, respectively; An integer of 50 is shown. ]

  Further, the present invention is a metal foil with a resin in which a resin layer is provided on a metal foil, and the resin layer contains a) a polyamideimide resin, b) an epoxy resin, and c) a phenoxy resin as essential components. The content of c) phenoxy resin component in the resin layer is 5 to 30% by mass.

  Such a metal foil with a resin is excellent in crack resistance and fracture resistance as in the above-described adhesive film, and has performance necessary for uses such as a multilayer wiring board.

  In the metal foil with resin of the present invention, it is preferable that a) the polyamideimide resin has at least one of the structures of the above general formulas (1), (2), (3a), (3b), and (4). . Thereby, heat resistance, crack resistance, and rupture resistance are further improved.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive film and resin-added metal foil which are excellent in heat resistance, crack resistance, and fracture resistance, and have the performance required for uses, such as the above-mentioned multilayer wiring board, can be provided.

The adhesive film of the present invention comprises a) polyamideimide resin, b) epoxy resin, and c) phenoxy resin as essential components.
The metal foil with resin of the present invention is a metal foil with resin in which a resin layer is provided on the metal foil, and the resin layer is required to have a) a polyamideimide resin, b) an epoxy resin, and c) a phenoxy resin. It is contained as a component.
Hereinafter, preferred embodiments of the adhesive film and the resin-coated metal foil of the present invention will be described in detail.

[A) Polyamideimide resin]
a) The polyamideimide resin preferably has at least one of the structures represented by the general formulas (1), (2), (3a), (3b), and (4). Polyamideimide resin having such a structure is obtained by reacting diamines represented by general formulas (5), (6), (7a), (7b), and (8) with trimellitic anhydride. It is preferable that it is a thing obtained by making the mixture containing an acid and aromatic diisocyanate react.

［式（５）中、Ｒ^１，Ｒ^２は２価のアルキル基、Ｒ^３，Ｒ^４，Ｒ^７，Ｒ^８は１価のアルキル基又は置換基を有するアルキル基、Ｒ^５，Ｒ^６は１価の芳香族基又は置換基を有する芳香族基を示し、ｍ，ｎはそれぞれ０から４０の整数であり、１≦ｎ＋ｍ≦５０である。］

[In the formula (5), R ¹ and R ² are divalent alkyl groups, R ³ , R ⁴ , R ⁷ and R ⁸ are monovalent alkyl groups or alkyl groups having a substituent, and R ⁵ and R ⁶ are A monovalent aromatic group or an aromatic group having a substituent is shown, and m and n are each an integer of 0 to 40, and 1 ≦ n + m ≦ 50. ]

［式（７ａ）及び（７ｂ）中、Ｘ^１は炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基、単結合又は下記一般式（７１ａ）若しくは（７１ｂ）で表される２価の基を示し、Ｘ^２は炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基又はカルボニル基を示し、Ｒ^１１，Ｒ^１２，及びＲ^１３はそれぞれ独立に水素原子、水酸基、メトキシ基、メチル基又はハロゲン化メチル基を示す。］

[In the formulas (7a) and (7b), X ¹ represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether. A divalent group represented by a group, a carbonyl group, a single bond or the following general formula (71a) or (71b), wherein X ² is a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, 1 carbon atom To 3 divalent halogenated aliphatic hydrocarbon groups, sulfonyl groups, ether groups or carbonyl groups, wherein R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogen atom. Represents a methylated group. ]

［式（７１ａ）中、Ｚは炭素数１〜３の２価の脂肪族炭化水素基、炭素数１〜３の２価のハロゲン化脂肪族炭化水素基、スルホニル基、エーテル基、カルボニル基又は単結合を示す。］

[In the formula (71a), Z represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, a carbonyl group, or Indicates a single bond. ]

［式（８）中、Ｘはメチレン基、スルホニル基、エーテル基、カルボニル基又は単結合、Ｒ^２１及びＲ^２２はそれぞれ水素原子、アルキル基、フェニル基又は置換フェニル基を示し、ｐは１〜５０の整数を示す。］

[In Formula (8), X represents a methylene group, a sulfonyl group, an ether group, a carbonyl group or a single bond, R ²¹ and R ²² represent a hydrogen atom, an alkyl group, a phenyl group or a substituted phenyl group, respectively, and p represents 1 to An integer of 50 is shown. ]

  Examples of the siloxane diamine represented by the general formula (5) include X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 900), X-22-161B (amine equivalent 1500) X-22. -9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200), reactive silicon oil KF8010 (amine equivalent 430) (above, Shin-Etsu Chemical Co., Ltd., trade name), BY16-853 (amine equivalent) 650), BY16-853B (amine equivalent 2200), (above, trade name manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like.

  Moreover, as a diamine represented by the said General formula (6), Wandamine (New Nippon Rika Co., Ltd. brand name) etc. can be illustrated.

  Examples of the aromatic diamine represented by the general formula (7a) or (7b) include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) and bis [4- (3-amino). Phenoxy) 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′-sulfonyl-biphenyl-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.

Preferable specific examples of R ²¹ and R ^{22 in} the general formula (8) include a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, and a substituted phenyl group, and may be bonded to the phenyl group. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms and a halogen atom.

  Moreover, as for the diamine shown by General formula (8), it is preferable that X is an ether group from a viewpoint of coexistence of a low elasticity modulus and high Tg. Examples of such aliphatic diamines include Jeffamine D-400 (amine equivalent 200), Jeffamine D-2000 (amine equivalent 1000), etc. (trade name, manufactured by Mitsui Chemicals Fine Co., Ltd.).

  a) As a diisocyanate compound used for manufacture of a polyamideimide resin, it is preferable to use the compound represented by following General formula (9).

In the general formula (9), D is a divalent organic group having at least one aromatic ring or a divalent aliphatic hydrocarbon group, and —C ₆ H ₄ —CH ₂ —C ₆ H ₄ — And at least one group selected from the group consisting of a tolylene group, a naphthylene group, a hexamethylene group, a 2,2,4-trimethylhexamethylene group and an isophorone group.

  As the diisocyanate compound represented by the general formula (9), aliphatic diisocyanate or aromatic diisocyanate can be used, but aromatic diisocyanate is preferably used.

  Examples of aromatic diisocyanates include 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, 2,4-tolylene dimer, and the like. As an example, it is particularly preferable to use MDI. By using MDI as the aromatic diisocyanate, the flexibility of the obtained polyamideimide resin can be improved.

  Examples of the aliphatic diisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate.

  The content of the a) polyamideimide resin in the adhesive film or resin layer is preferably 40 to 90% by mass, and more preferably 60 to 80% by mass.

[B) Epoxy resin]
b) The epoxy resin is not particularly limited, but preferably has two or more glycidyl groups. b) As an epoxy resin, polyglycidyl ether obtained by reacting a polyhydric phenol such as bisphenol A, a novolak type phenol resin, an orthocresol novolac type phenol resin or a polyhydric alcohol such as 1,4-butanediol with epichlorohydrin, Examples thereof include polyglycidyl esters obtained by reacting polybasic acids such as phthalic acid and hexahydrophthalic acid with epichlorohydrin, N-glycidyl derivatives of amines, amides or compounds having a heterocyclic nitrogen base, alicyclic epoxy resins, etc. It is done.

  The content of b) epoxy resin in the adhesive film or resin layer is preferably 10 to 60% by mass, and more preferably 20 to 40% by mass.

  b) It is preferable to add a curing agent and / or a curing accelerator to the epoxy resin in order to improve thermal, mechanical and electrical properties.

  Curing agents and curing accelerators are not limited as long as they can react with epoxy resins or accelerate curing. For example, amines, imidazoles, polyfunctional phenols, acid anhydrides, etc. are used. it can. As the amines, dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used. As the polyfunctional phenols, hydroquinone, resorcinol, bisphenol A and their halogen compounds, and a novolac type phenol resin which is a condensate with formaldehyde, a resol type A phenol resin or the like can be used. As the acid anhydrides, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, or the like can be used. As the curing accelerator, alkyl group-substituted imidazole, benzimidazole and the like can be used as imidazoles.

When the curing agent and / or curing accelerator is an amine, the amount of the curing agent and / or curing accelerator is such that the equivalent of the active hydrogen of the amine and the epoxy equivalent of the epoxy resin are approximately equal. It is preferable to do. When the curing accelerator is imidazole, the amount of the curing accelerator is not simply an equivalent ratio with active hydrogen, and b) 0.001 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. Necessary. When the curing agent and / or curing accelerator is a polyfunctional phenol or acid anhydride, b) 0.6 to 1.2 equivalent of phenolic hydroxyl group or carboxyl group is required for 1 equivalent of epoxy resin. .
If the amount of these curing agents and / or curing accelerators is small, uncured epoxy resin remains, and Tg (glass transition temperature) becomes low. If too large, unreacted curing agents and curing accelerators remain, Insulation properties are reduced. b) The epoxy equivalent of the epoxy resin is preferably taken into account since it can also react with the amide group of the polyamideimide resin.

[C) Phenoxy resin]
c) The phenoxy resin is not particularly limited, but in order for the cured product to exhibit excellent properties such as flexibility, toughness, and film-forming property, an average molecular weight (weight average polystyrene equivalent by gel permeation chromatography) is used. The molecular weight is preferably 20000 or more, more preferably 30000 or more.

  c) Examples of commercially available phenoxy resins include PKHH, PAHJ (manufactured by Union Carbide), YPB-43C, YPB-43D, YPB-43G, YPB-43M, YP-50, or YPB-40ASB25, YPB-40AM40 ( Toto Kasei Co., Ltd.).

  The content of c) phenoxy resin in the adhesive film or resin layer is 5 to 30% by mass, and preferably 10 to 25% by mass. When the content is less than 5% by mass, the flexibility of the cured product is insufficient, and when it is greater than 30% by mass, the flexibility and heat resistance of the cured product are deteriorated.

  Moreover, it is preferable that the adhesive film or resin layer of this invention contains a flame retardant as an additive for the purpose of an improvement of a flame retardance. As additive type flame retardants used in the present invention, OP930 (trade name, manufactured by Clariant), HP-360 (trade name, manufactured by Showa Denko KK), HCA-HQ (trade name, manufactured by Sanko), melamine polyphosphate PMP -100, PMP-200, PMP-300 (Nissan Chemical Co., Ltd. product name) and the like.

  When the adhesive film or resin layer of this invention contains a flame retardant, the content rate of the flame retardant in the said adhesive film or resin layer is preferable in it being 5-30 mass%, and it is more preferable in it being 10-25 mass%.

  The adhesive film of the present invention, the metal foil with resin, and the varnish obtained by mixing, dissolving, and dispersing the above-described components in an organic solvent can be produced by coating and drying on a substrate or metal foil. The organic solvent used in these productions is not limited as long as solubility is obtained. Methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl- Examples include 2-pyrrolidone, γ-butyrolactone, sulfolane, and cyclohexanone.

  The drying temperature is preferably 80 ° C. to 180 ° C., and the drying time is not particularly limited in consideration of the gelling time of the varnish. At the time of drying, it is preferable that 80% by weight or more of the organic solvent used in the varnish is volatilized.

  The thickness of the adhesive film and the resin layer of the metal foil with resin is preferably 10 to 100 μm, and more preferably 20 to 80 μm. When the thickness of the adhesive film or the resin layer is less than 10 μm, the embedding property of the circuit pattern applied to the inner layer substrate tends to be lowered when it is multilayered. On the other hand, when the thickness exceeds 100 μm, the heat resistance of the wiring board tends to be lowered or the bendability tends to be lowered when a multilayer wiring board is formed by a volatile component in the resin.

  The metal foil with resin and the adhesive film of the present invention are used in a multilayered manner on a foldable wiring board. As a wiring board that can be bent, flexible wiring boards using polyimide film base materials such as Upilex (trade name, manufactured by Ube Industries Co., Ltd.) and Espanex (trade name, manufactured by Nippon Steel Chemical Co., Ltd.), and low elastic resin Examples thereof include a flexible wiring board combined with a glass cloth. Further, it may be used in a multilayer on a general rigid wiring board.

  As the metal foil in the metal foil with resin of the present invention, copper foil and aluminum foil are generally used, but those having a thickness of 5 to 200 μm which are usually used for printed wiring boards can be used. Also, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as intermediate layers, and a 0.5-15 μm copper layer and a 10-300 μm copper layer are provided on both sides. Alternatively, a three-layer composite foil or a two-layer composite foil in which aluminum and copper foil are combined can also be used.

When the metal foil is subjected to surface roughening treatment, the ten-point average roughness (Rz) on the roughened surface is preferably 10 μm or less, and more preferably 5 μm or less. The 10-point average roughness (Rz) refers to the 10-point average roughness (Rz) defined in JIS B0601-1994.
According to the resin-coated metal foil provided with a metal foil having such a surface roughness as a base material, the high-frequency transmission characteristics of the obtained printed wiring board are further improved while maintaining a sufficient level of adhesion between the conductive layer and the insulating layer. can do.

  As a base material used when producing the adhesive film of the present invention, a resin base material subjected to a release treatment can be used. Although there is no restriction | limiting in particular as a resin base material which performed the mold release process, Polyolefin, such as PET (polyethylene terephthalate), PP (polypropylene), PE (polyethylene), polyvinyl chloride, polycarbonate, polyimide, polyamide, aramid, etc. A resin film is mentioned. Among these, it is particularly preferable to use a PET film in terms of price, heat resistance, and dimensional stability. The thickness of the resin substrate is preferably 10 to 150 μm.

  The manufacturing method of the multilayer wiring board is as follows. The metal foil with resin in the present invention is stacked on a wiring board having an inner layer circuit, and is usually in the range of 150 to 280 ° C, preferably in the range of 170 ° C to 240 ° C, and usually in the range of 0.5 to 20 MPa, preferably in the range of 1 to 8 MPa. Then, through-holes and via connections are formed as necessary. The via can be formed by laser processing or drilling using a conformal mask method or a large window method. The through hole can be processed by a normal drill or a laser. After performing interlayer connection by plating, circuit processing can be performed to obtain a printed circuit board (multilayer wiring board).

  In the case of producing a multilayer wiring board using the adhesive film of the present invention, the adhesive film and the copper foil are stacked on the wiring board having the inner layer circuit, and the temperature is usually in the range of 150 to 280 ° C, preferably 170 to 240 ° C. In general, the lamination is performed at a pressure in the range of 0.5 to 20 MPa, preferably 1 to 8 MPa.

  In addition, an adhesive film may be sandwiched between two or more wiring boards having an inner layer circuit to form a multilayer. When it is necessary to connect the layers, it is preferable to align each wiring board, and to use a plurality of adhesive films between the layers as necessary. Stacked wiring boards, adhesive films and optionally copper foils are usually in the range of 150-280 ° C, preferably in the range of 170 ° C-240 ° C, usually in the range of 0.5-20 MPa, preferably in the range of 1-8 MPa. It can be heated and pressed at a pressure of

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Synthesis of polyamide-imide resin]
(Synthesis Example 1)
BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) in a 5-liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer 287.4 g (0.70 mol), reactive silicon oil KF-8010 (trade name, amine equivalent 415, manufactured by Shin-Etsu Chemical Co., Ltd.) 249.0 g (0.30 mol), TMA (trimellitic anhydride) 385.2 g ( 2.005 mol) and 2400 g of NMP (N-methyl-2-pyrrolidone) as an aprotic polar solvent were charged and stirred at 80 ° C. for 30 minutes. Then, 600 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 4 hours. After confirming that water was no longer distilled in the moisture determination receiver, toluene was removed by raising the temperature to about 180 ° C. while removing the distillate accumulated in the moisture determination receiver. Thereafter, the solution was cooled to 80 ° C. or lower, and 252.8 g (1.01 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, followed by reaction at 150 ° C. for 3 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin solid content 32.9%) was obtained.

(Synthesis Example 2)
BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane) in a 5-liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer 110.8 g (0.27 mol), KF-8010 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 415) 373.5 g (0.45 mol), Wandamine (trade name of Shin Nippon Chemical Co., Ltd.) 37.9 g (0 .18 mol), 346.6 g (1.805 mol) of TMA (trimellitic anhydride) and 2400 g of NMP (N-methyl-2-pyrrolidone) were charged and stirred at 80 ° C. for 30 minutes. Then, 600 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 4 hours. After confirming that water was no longer distilled in the moisture determination receiver, toluene was removed by raising the temperature to about 180 ° C. while removing the distillate accumulated in the moisture determination receiver. Thereafter, the solution was cooled to 80 ° C. or lower, and 227.5 g (0.909 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate and reacted at 150 ° C. for 3 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin solid content 31.4%) was obtained.

(Synthesis Example 3)
A 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a 5 L separable flask equipped with a stirrer, KF-8010 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 415) 365.2 g (0.440 mol), 65.6 g (0.264 mol) of DDS (diaminodiphenylsulfone), 37.0 g (0.176 mol) of Wandamine (New Nippon Rika Co., Ltd.), 338.9 g of TMA (trimellitic anhydride) (1.764 mol) and 2400 g of NMP (N-methyl-2-pyrrolidone) were charged and stirred at 80 ° C. for 30 minutes. Then, 600 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 4 hours. After confirming that water was no longer distilled in the moisture determination receiver, toluene was removed by raising the temperature to about 180 ° C. while removing the distillate accumulated in the moisture determination receiver. Thereafter, the solution was cooled to 80 ° C. or lower, and 222.5 g (0.889 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate and reacted at 150 ° C. for 3 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin solid content 30.0%) was obtained.

(Synthesis Example 4)
In a 5 liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer, 77.0 g (0.310 mol) of DDS (diaminodiphenylsulfone), Wandamine (New Japan) Rika Co., Ltd. trade name) 48.9 g (0.233 mol), Jeffamine D2000 (Mitsui Chemical Fine Co., Ltd. trade name, amine equivalent 1000) 465.0 g (0.233 mol), TMA (trimellitic anhydride) 298. 5 g (1.554 mol) and 2400 g of NMP (N-methyl-2-pyrrolidone) were charged and stirred at 80 ° C. for 30 minutes. Then, 600 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 4 hours. After confirming that water was no longer distilled in the moisture determination receiver, toluene was removed by raising the temperature to about 180 ° C. while removing the distillate accumulated in the moisture determination receiver. Thereafter, the solution was cooled to 80 ° C. or lower, and 195.9 g (0.783 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, followed by reaction at 150 ° C. for 3 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin solid content 31.1%) was obtained.

[Preparation of varnish]
Example 1
93.3 g of CSD-40 (trade name, manufactured by Hitachi Chemical Coated Sand Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content: 30.0%), and NC-3000H (product manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin Name) 12.0 g, YP-50ME35 (trade name, manufactured by Tohto Kasei Co., Ltd., methyl ethyl ketone solution having a solid content of 35% by mass) as a phenoxy resin, 34.3 g, and 1-cyanoethyl-2-ethyl-4-methylimidazole 0.06 g Were mixed and stirred for about 1 hour until the resin became uniform to obtain a resin varnish.

(Example 2)
85.1 g of NMP solution of polyamideimide resin (resin solid content 32.9%) of Synthesis Example 1 and 12.0 g of NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.), YP-50ME35 (manufactured by Tohto Kasei Co., Ltd.) (Trade name, methyl ethyl ketone solution with a solid content of 35% by mass) 34.3 g and 0.06 g of 1-cyanoethyl-2-ethyl-4-methylimidazole as a curing accelerator are mixed and stirred for about 1 hour until the resin is uniform. Thus, a resin varnish was obtained.

(Example 3)
89.2 g of NMP solution of polyamideimide resin (resin solid content 31.4%) of Synthesis Example 2 and 12.0 g of NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.), YP-50ME35 (manufactured by Tohto Kasei Co., Ltd.) 34.3 g of a product name, methyl ethyl ketone solution having a solid content of 35% by mass) and 0.06 g of 1-cyanoethyl-2-ethyl-4-methylimidazole are mixed and stirred for about 1 hour until the resin becomes uniform. Got.

Example 4
NMP solution of polyamide imide resin of Synthesis Example 3 (resin solid content 30.0%) 93.3 g, NC-3000H (Nippon Kayaku Co., Ltd. trade name) 12.0 g, YP-50ME35 (Toto Kasei Co., Ltd.) 34.3 g of a product name, methyl ethyl ketone solution having a solid content of 35% by mass) and 0.06 g of 1-cyanoethyl-2-ethyl-4-methylimidazole are mixed and stirred for about 1 hour until the resin becomes uniform. Got.

(Example 5)
90.0 g of NMP solution (resin solid content 31.1%) of the polyamide imide resin of Synthesis Example 4, 12.0 g of NC-3000H (Nippon Kayaku Co., Ltd. trade name), YP-50ME35 (manufactured by Toto Kasei Co., Ltd.) 34.3 g of a product name, methyl ethyl ketone solution having a solid content of 35% by mass) and 0.06 g of 1-cyanoethyl-2-ethyl-4-methylimidazole are mixed and stirred for about 1 hour until the resin becomes uniform. Got.

(Example 6)
KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content: 32.0%), and NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 4 as an epoxy resin 0.0 g, EPPN-502H (Nippon Kayaku Co., Ltd. product name) 4.0 g, HP-4032D (Dainippon Ink Co., Ltd. product name) 4.0 g, phenoxy resin as YP-50ME35 (Toto Kasei Co., Ltd. product) Name, methyl ethyl ketone solution having a solid content of 35% by mass) 22.9 g, OP930 (trade name, manufactured by Clariant Co., Ltd.) 4.0 g as a flame retardant, 4.0 g, HP-360 (trade name, manufactured by Showa Denko Co., Ltd.), curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (0.06 g) was mixed and stirred for about 1 hour until the resin became homogeneous. To obtain a fat varnish.

(Example 7)
KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content: 32.0%), and NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 12 as an epoxy resin 0.0 g, YP-50ME35 (trade name, manufactured by Toto Kasei Co., Ltd., methyl ethyl ketone solution having a solid content of 35% by mass) as a phenoxy resin, 20.0 g, OP930 (trade name, manufactured by Clariant Co., Ltd.) as a flame retardant, HP-360 (Product name manufactured by Showa Denko KK) 4.0 g, 0.06 g of 1-cyanoethyl-2-ethyl-4-methylimidazole as a curing accelerator was mixed, and stirred for about 1 hour until the resin became uniform. Got.

(Example 8)
KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content: 32.0%), and HP-4032D (trade name, manufactured by Dainippon Ink Co., Ltd.) 12 as an epoxy resin. 0.0 g, YP-50ME35 (trade name, manufactured by Toto Kasei Co., Ltd., methyl ethyl ketone solution having a solid content of 35% by mass) as a phenoxy resin, 20.0 g, OP930 (trade name, manufactured by Clariant Co., Ltd.) as a flame retardant, HP-360 (Product name manufactured by Showa Denko KK) 4.0 g, 0.06 g of 1-cyanoethyl-2-ethyl-4-methylimidazole as a curing accelerator was mixed, and stirred for about 1 hour until the resin became uniform. Got.

Example 9
KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content: 32.0%), and NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 6 as an epoxy resin 0.0 g, EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 6.0 g, HP-4032D (trade name, manufactured by Dainippon Ink Co., Ltd.) 6.0 g, YP-50ME35 (product manufactured by Toto Kasei Co., Ltd.) as a phenoxy resin Name, methyl ethyl ketone solution having a solid content of 35% by mass) 17.1 g, OP930 (trade name, manufactured by Clariant Corporation) as a flame retardant, 6.0 g, HP-360 (trade name, manufactured by Showa Denko Corporation), curing accelerator As a mixture, 0.09 g of 1-cyanoethyl-2-ethyl-4-methylimidazole was mixed and stirred for about 1 hour until the resin became homogeneous. To obtain a resin varnish.

(Example 10)
KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content: 32.0%), and NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 4 as an epoxy resin 0.0 g, EPPN-502H (Nippon Kayaku Co., Ltd. product name) 4.0 g, HP-4032D (Dainippon Ink Co., Ltd. product name) 4.0 g, phenoxy resin as YP-50ME35 (Toto Kasei Co., Ltd. product) Name, methyl ethyl ketone solution having a solid content of 35% by mass) 34.3 g, OP930 (trade name, manufactured by Clariant Co., Ltd.) 4.0 g as a flame retardant, 4.0 g, HP-360 (trade name, manufactured by Showa Denko Co., Ltd.), curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (0.06 g) was mixed and stirred for about 1 hour until the resin became homogeneous. To obtain a fat varnish.

(Example 11)
KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content: 32.0%), and NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 4 as an epoxy resin 0.0 g, EPPN-502H (Nippon Kayaku Co., Ltd. product name) 4.0 g, HP-4032D (Dainippon Ink Co., Ltd. product name) 4.0 g, phenoxy resin as YP-50ME35 (Toto Kasei Co., Ltd. product) Name, methyl ethyl ketone solution having a solid content of 35% by mass) 45.7 g, OP930 (trade name, manufactured by Clariant Corporation) as a flame retardant, 4.0 g, HP-360 (trade name, manufactured by Showa Denko Corporation), curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole (0.06 g) was mixed and stirred for about 1 hour until the resin became homogeneous. To obtain a fat varnish.

(Comparative Example 1)
KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content: 32.0%), and NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 6 as an epoxy resin 0.0 g, EPPN-502H (Nippon Kayaku Co., Ltd. trade name) 6.0 g, HP-4032D (Dainippon Ink Co., Ltd. trade name) 6.0 g, flame retardant OP930 (Clariant Co., Ltd. trade name) 6 0.0 g, HP-360 (trade name, manufactured by Showa Denko KK) 6.0 g, 0.09 g of 1-cyanoethyl-2-ethyl-4-methylimidazole as a curing accelerator is mixed, and about 1 until the resin becomes uniform. The resin varnish was obtained by stirring for a period of time.

(Comparative Example 2)
KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content 32.0%), and NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 8 as an epoxy resin 0.0 g, EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 8.0 g, HP-4032D (trade name, manufactured by Dainippon Ink Co., Ltd.) 8.0 g, KA-1165 (manufactured by Dainippon Ink Co., Ltd.) as a phenol resin Product name, hydroxyl group equivalent 120) 16.0 g, OP930 as a flame retardant (product name manufactured by Clariant Co., Ltd.) 8.0 g, HP-360 (product name manufactured by Showa Denko KK) 8.0 g, 1-cyanoethyl as a curing accelerator 2-ethyl-4-methylimidazole (0.12 g) was mixed and stirred for about 1 hour until the resin became uniform to obtain a resin varnish.

(Comparative Example 3)
KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content: 32.0%), 87.5 g, NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.), 4.0 g, EPPN-502H (Nippon Kayaku Co., Ltd. trade name) 4.0 g, HP-4032D (Dainippon Ink Co., Ltd. trade name) 4.0 g, YP-50ME35 (Toto Kasei Co., Ltd. trade name, solid content 35 mass) % Methyl ethyl ketone solution) 4.6 g, OP930 (trade name, manufactured by Clariant Co., Ltd.) 4.0 g, HP-360 (product name, Showa Denko Co., Ltd.) 4.0 g, 1-cyanoethyl-2-ethyl- as a curing accelerator 0.06 g of 4-methylimidazole was mixed and stirred for about 1 hour until the resin became uniform to obtain a resin varnish.

(Comparative Example 4)
KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content: 32.0%), 87.5 g, NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.), 4.0 g, EPPN-502H (Nippon Kayaku Co., Ltd. trade name) 4.0 g, HP-4032D (Dainippon Ink Co., Ltd. trade name) 4.0 g, YP-50ME35 (Toto Kasei Co., Ltd. trade name, solid content 35 mass) % Methyl ethyl ketone solution) 57.1 g, OP930 (trade name, manufactured by Clariant Co., Ltd.) 4.0 g, HP-360 (trade name, manufactured by Showa Denko Co., Ltd.) 4.0 g, and 1-cyanoethyl-2-ethyl- as a curing accelerator 0.06 g of 4-methylimidazole was mixed and stirred for about 1 hour until the resin became uniform to obtain a resin varnish.

(Comparative Example 5)
KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an NMP solution of polyamideimide resin (resin solid content: 32.0%), 87.5 g, NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.), 4.0 g, EPPN-502H (Nippon Kayaku Co., Ltd. trade name) 4.0 g, HP-4032D (Dainippon Ink Co., Ltd. trade name) 4.0 g, YP-50ME35 (Toto Kasei Co., Ltd. trade name, solid content 35 mass) % Methyl ethyl ketone solution) 68.6 g, OP930 (trade name, manufactured by Clariant Co., Ltd.) 4.0 g, HP-360 (product name, Showa Denko Co., Ltd.) 4.0 g, 1-cyanoethyl-2-ethyl- as a curing accelerator 0.06 g of 4-methylimidazole was mixed and stirred for about 1 hour until the resin became uniform to obtain a resin varnish.

[Production of metal foil with resin]
The resin varnishes prepared in Examples 1 to 11 and Comparative Examples 1 to 5 were prepared from electrolytic copper foils having a thickness of 12 μm (trade name F3-WS-12, manufactured by Furukawa Metal Co., Ltd., surface roughness (10-point average roughness Rz). : 2.4 μm), and the resin layer thickness after drying is 50 μm, respectively, and heated at 140 ° C. for 15 minutes to provide a resin-coated copper foil having a resin layer on the copper foil ( Metal foil with resin) (F1 to F16) was obtained.

[Production of adhesive film]
The resin varnishes prepared in Examples 1 to 11 and Comparative Examples 1 to 5 were not subjected to release treatment of a release PET film having a thickness of 50 μm (trade name “Purex A63” manufactured by Teijin DuPont Films Ltd.). The adhesive film (A1 to A16) provided with a resin layer on a PET film is obtained by coating the surface so that the thickness of the resin layer after drying is 50 μm and heating at 140 ° C. for 15 minutes. It was.

(Production of double-sided copper-clad laminate)
On the resin layer side of the resin-coated copper foils (F1 to F16), an electrolytic copper foil having a thickness of 12 μm (trade name F3-WS-12, manufactured by Furukawa Metal Co., Ltd., surface roughness (ten-point average roughness Rz): 2. 4 μm) were laminated so that the roughened surface and the resin surface were combined to obtain a laminate. This laminated body was heated and pressurized under 200 ° C. for 60 minutes and 4.0 MPa pressing conditions to obtain a double-sided copper-clad laminate.

  Similarly, the PET film is peeled from the adhesive film (A1 to A16), and an electrolytic copper foil having a thickness of 12 μm (trade name F3-WS-12, manufactured by Furukawa Metal Co., Ltd., surface roughness (ten-point average roughness) on both sides. Rz): 2.4 μm) was laminated so that the roughened surface was combined with the adhesive film to obtain a laminate. This laminated body was heated and pressurized under 200 ° C. for 60 minutes and 4.0 MPa pressing conditions to obtain a double-sided copper-clad laminate.

[Preparation of multilayer wiring board for evaluation]
Base material for flexible printed circuit board (designated by Nippon Steel Chemical Co., Ltd., trade name: Espanex MB-12-25-12CEG) in which two copper foils with resin (F1 to F16) are subjected to a predetermined circuit (thickness 12 μm) A laminated body was obtained by superposing the resin layers of the resin-coated copper foil in contact with each other. This laminated body was heated and pressurized under the press conditions of 200 ° C., 60 minutes and 4.0 MPa to obtain a multilayer wiring board for evaluation.
Moreover, the base material for flexible printed wiring boards (Nippon Steel Chemical Co., Ltd. brand name Espanex MB-12-25) which gave the predetermined circuit (thickness 12 micrometers) to the resin layer side of two adhesive films (A1-A16) -12CEG). The PET film on the resin surface side that is not in contact with the base material for the flexible printed wiring board of the adhesive film of this laminate is peeled off, and an electrolytic copper foil having a thickness of 12 μm (trade name F3-WS-12, manufactured by Furukawa Metal Co., Ltd.). The surface roughness (ten-point average roughness Rz): 2.4 μm) was overlapped so that the roughened surface and the resin surface were combined, and heated and pressurized under a press condition of 200 ° C., 60 minutes, 4.0 MPa, A multilayer wiring board for evaluation was obtained.

[Evaluation of metal foil with resin and adhesive film]
(1) Dust generation properties The resin-coated metal foils and adhesive films obtained in Examples 1 to 11 and Comparative Examples 1 to 5 were cut into 10 pieces to a width of 1 cm and a length of 25 cm with a cutter (manufactured by Olfa) to obtain resin powder. The presence or absence of occurrence was confirmed. The results are shown in Tables 1 and 2.
In addition, the case where dust generation was not seen was shown by "OK", and the case where dust generation was seen was shown by "NG", respectively.
[Evaluation of double-sided copper-clad laminate and multilayer wiring board for evaluation]
The following evaluation was performed about the double-sided copper clad laminated board obtained in Examples 1-11 and Comparative Examples 1-5 and the multilayer wiring board for evaluation. The results are shown in Tables 1 and 2.
(2) Copper foil peeling strength (copper foil adhesive strength)
The obtained double-sided copper-clad laminate was subjected to a 90 ° peel test, and the strength at that time was defined as the copper foil peel strength (copper foil adhesive strength).
(3) Solder heat resistance The obtained multilayer wiring board was floated in a solder bath heated to 288 ° C., and the state of the laminated board after 300 seconds was visually observed. Evaluated. As for the results, “○” indicates that no abnormality such as blistering was observed, and the abnormality content was indicated if an abnormality was observed.
(4) Moisture absorption heat resistance A sample obtained by etching copper on one side of the obtained multilayer wiring board for evaluation was treated with a saturated PCT apparatus at 121 ° C. under 2 atm for 2 hours and then heated to 260 ° C. After dipping for 20 seconds, the state of the sample was visually observed, and the moisture absorption heat resistance was evaluated from abnormalities such as blistering. As for the results, “○” indicates that no abnormality such as blistering was observed, and the abnormality content was indicated if an abnormality was observed.
(5) Goby folding test (foldability with radius of curvature R = 0)
Copper of the obtained double-sided copper-clad laminate was removed by etching, and this was used as a test substrate. The test substrate was bent 180 degrees, and the finger was moved along the bent portion while being strongly pressed with a finger, and then the test substrate was returned to its original state to evaluate goblet fold resistance based on the presence or absence of cracks or breakage. In addition, the case where a crack generation and a fracture | rupture generation | occurrence | production are not seen is shown by "OK", and the case where crack generation | occurrence | production or fracture | rupture generation | occurrence | production was seen was shown by "NG".
(6) Breaking strength and breaking elongation The copper of the obtained double-sided copper-clad laminate was removed by etching, and the distance between chucks was 60 mm and the tensile speed was 50 mm / min with an autograph (Shimadzu Corporation AG-100). Tensile tests were conducted to measure the breaking strength and breaking elongation.

In Experimental Examples 1 to 11, solder heat resistance and moisture absorption heat resistance were good, no blistering or the like was observed, the folding resistance was good, and no cracks were observed even when goby folding was performed.
On the other hand, in Comparative Examples 1 to 3 in which the content of the phenoxy resin is less than 5% by mass, the solder heat resistance and the moisture absorption heat resistance were good, but cracks occurred in the test substrate in the goby folding test.
In Comparative Examples 4 and 5 having a phenoxy resin content of more than 30% by mass, blistering occurred in the test substrate in the solder heat resistance test and moisture absorption heat resistance test, and cracks occurred in the test substrate in the goby folding test.

(Dynamic viscoelasticity)
The dynamic viscoelasticity measurement results of Example 6 and Comparative Example 1 are shown in FIGS.
The dynamic viscoelasticity was measured by using a dynamic viscoelasticity measuring apparatus (trade name: Rheogel-E4000 manufactured by UBM Co., Ltd.), which is an evaluation sample obtained by removing the copper of the double-sided copper-clad laminate by etching.
In Comparative Example 1 in FIG. 2, there is one Tg in the vicinity of 200 ° C., whereas in Example 6 in FIG. 1, there are two Tg in the vicinity of 102 ° C. and in the vicinity of 200 ° C. Is a phase separation system. In the present invention, when the phenoxy resin component is 5 to 30% by mass, the polyamideimide resin / epoxy resin and the phenoxy resin are phase-separated, the breaking strength and breaking elongation of the cured product are increased, and the bending resistance is improved. I found it.

It is drawing which shows the dynamic viscoelasticity measurement result of Example 6. FIG. 6 is a drawing showing the results of dynamic viscoelasticity measurement of Comparative Example 1.

Claims (4)

An adhesive film comprising a) a polyamideimide resin, b) an epoxy resin, and c) a phenoxy resin as essential components,
The adhesive film is characterized in that the content of the c) phenoxy resin component in the adhesive film is 5 to 30% by mass. The adhesive according to claim 1, wherein the a) polyamideimide resin has at least a structure of any one of the following general formulas (1), (2), (3a), (3b), and (4). the film.

[In the formula (1), R ¹ and R ² are divalent alkyl groups, R ³ , R ⁴ , R ⁷ and R ⁸ are monovalent alkyl groups or alkyl groups having a substituent, and R ⁵ and R ⁶ are A monovalent aromatic group or an aromatic group having a substituent is shown, and m and n are each an integer of 0 to 40, and 1 ≦ n + m ≦ 50. ]

[In the formulas (3a) and (3b), X ¹ represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether. A divalent group represented by a group, a carbonyl group, a single bond or the following general formula (31a) or (31b), wherein X ² is a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms; To 3 divalent halogenated aliphatic hydrocarbon groups, sulfonyl groups, ether groups or carbonyl groups, wherein R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogen atom. Represents a methylated group. ]

[In the formula (31a), Z is a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, a carbonyl group, or Indicates a single bond. ]

[In Formula (4), X represents a methylene group, a sulfonyl group, an ether group, a carbonyl group or a single bond, R ²¹ and R ²² represent a hydrogen atom, an alkyl group, a phenyl group or a substituted phenyl group, respectively; An integer of 50 is shown. ] A metal foil with a resin in which a resin layer is provided on a metal foil,
The resin layer contains a) polyamideimide resin, b) epoxy resin, and c) phenoxy resin as essential components,
The resin-attached metal foil, wherein the content of the c) phenoxy resin component in the resin layer is 5 to 30% by mass. The resin according to claim 3, wherein the a) polyamideimide resin has at least a structure of any one of the following general formulas (1), (2), (3a), (3b), and (4): With metal foil.

[In the formula (1), R ¹ and R ² are divalent alkyl groups, R ³ , R ⁴ , R ⁷ and R ⁸ are monovalent alkyl groups or alkyl groups having a substituent, and R ⁵ and R ⁶ are A monovalent aromatic group or an aromatic group having a substituent is shown, and m and n are each an integer of 0 to 40, and 1 ≦ n + m ≦ 50. ]

[In the formulas (3a) and (3b), X ¹ is a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether. A divalent group represented by a group, a carbonyl group, a single bond or the following general formula (31a) or (31b), wherein X ² is a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms; To 3 divalent halogenated aliphatic hydrocarbon groups, sulfonyl groups, ether groups or carbonyl groups, wherein R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogen atom. Represents a methylated group. ]

[In the formula (31a), Z is a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, a carbonyl group, or Indicates a single bond. ]

[In Formula (4), X represents a methylene group, a sulfonyl group, an ether group, a carbonyl group or a single bond, R ²¹ and R ²² represent a hydrogen atom, an alkyl group, a phenyl group or a substituted phenyl group, respectively; An integer of 50 is shown. ]

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