JP5444825B2 - Insulating resin composition, prepreg, metal foil-clad laminate, printed wiring board, and multilayer wiring board - Google Patents

Description

  The present invention relates to an insulating resin composition, a prepreg, a metal foil-clad laminate, a printed wiring board, and a multilayer wiring board.

  In the production of a printed wiring board, when a printed circuit is formed by a subtractive method, a metal foil-clad laminate (metal-clad laminate) is used. In general, this metal foil-clad laminate is obtained by stacking a predetermined number of prepregs having a resin composition (insulating resin) having electrical insulation as a matrix, and stacking a metal foil such as a copper foil on the surface thereof and applying heat and pressure. Manufactured. As the insulating resin, for example, a thermosetting resin such as a phenol resin, an epoxy resin, a polyimide resin, a bismaleimide-triazine resin or the like is widely used, but a thermoplastic resin such as a fluororesin or a polyphenylene ether resin is used. Sometimes used.

  A prepreg using an insulating resin mainly composed of a phenol resin or an epoxy resin is widely used as a material for a metal foil-clad laminate because the material may be inexpensive. In particular, the prepreg using an insulating resin mainly composed of an epoxy resin has improved resin components, such as high heat resistance, halogen-free flame retardant, low dielectric constant, low dielectric loss, etc. Is progressing.

  Since these conventional insulating resins are composed of a resin having a relatively low molecular weight, conventionally, when processing such as cutting is performed on a prepreg in a B-stage state, dust such as a powdery substance derived from the resin is generated. It tends to occur. Therefore, when manufacturing a metal foil-clad laminate or the like using the prepreg after processing, it is necessary to pay attention so that the metal foil such as a copper foil laminated by the dust is not contaminated.

  By the way, a printed wiring board obtained using such a metal foil-clad laminate is mounted on various electronic devices. In recent years, with the widespread use of information terminal devices such as personal computers and mobile phones, printed wiring boards mounted on them have been reduced in size and density. And the mounting form of the chip component (chip) on the printed wiring board is changing from the pin insertion type to the surface mounting type, and further to the area array type represented by BGA (ball grid array) using a plastic substrate. .

  For example, when 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. In this case, the substrate on which the bare chip is mounted is exposed to a high temperature of 150 ° C. or higher. Therefore, a certain degree of heat resistance is required for the insulating resin used for the prepreg that is a constituent material of the substrate.

  However, when a prepreg using a conventional insulating resin is used, particularly when a multilayer wiring board is manufactured, heat between solder reflows causes a gap between the core substrate and the multilayered layer resin, or between the inner layer circuit and the multilayered layer. There was a tendency for peeling to occur easily with the resin.

  Therefore, in order to satisfy the above requirements, polyamide imide resin is an essential component in the fiber base material as a prepreg that is excellent in heat resistance, reflow resistance and adhesion to metal foil, and can also improve fine wiring formability. A prepreg formed by impregnating a resin composition is disclosed (see Patent Document 1).

  Recently, along with further downsizing and higher performance of electronic devices and the like, it has become necessary to store a printed wiring board on which chip parts and the like are mounted in a limited space. As the technique, a method is known in which a plurality of printed wiring boards are arranged in multiple stages and these are connected by a wire harness or a flexible wiring board. Also known is a method of forming a rigid-flex substrate having a rigid portion and a flexible portion by multilayering a flexible substrate based on a prepreg and bending the flexible portion (see Patent Document 2).

JP 2003-55486 A JP 2006-237555 A

  However, when the printed wiring board is to be stored at a high density in the limited space as described above, the dust derived from the insulating resin generated during the processing of the prepreg is generated from the printed wiring board (for example, from the metal foil). The adverse effect on the circuit, etc.) tends to increase. Therefore, it is being demanded that the generation of such dust is extremely small for the prepreg. Further, as described above, since the printed wiring board may be folded for storage, it is required to have high flexibility and good bendability.

  The present invention has been made in view of such circumstances, and is excellent in properties such as heat resistance, reflow resistance and adhesion to a metal foil in a cured state, and also has very little dust generation and is a thin sheet. It is an object of the present invention to provide an insulating resin composition suitable for metal foil-clad laminates and printed wiring boards, which has the characteristics of exhibiting good flexibility and excellent bendability when cured. Another object of the present invention is to provide a prepreg using such an insulating resin composition, a metal foil-clad laminate obtained by using this prepreg, a printed wiring board, and a multilayer wiring board.

  In order to achieve the above object, the present invention provides an insulating resin composition containing (A) a polyamideimide resin, (B) an epoxy resin, and (C) a phenoxy resin.

  The insulating resin composition of the present invention includes a combination of an epoxy resin and a phenoxy resin in addition to a polyamideimide resin. Conventionally, phenoxy resins are difficult to mix homogeneously because of their low compatibility with polyamideimide resins, and it has been difficult to obtain a good coating film in combination with polyamideimide resins. In contrast, the insulating resin composition of the present invention can be a homogeneous resin composition by mixing a phenoxy resin with a polyamide-imide resin in the presence of an epoxy resin. Furthermore, when the insulating resin composition of the present invention is used as a prepreg or a metal foil-clad laminate by such blending, not only excellent heat resistance, reflow resistance and adhesion to the metal foil can be obtained. In addition to flexibility and good bendability, dust generation can be greatly suppressed.

  In the insulating resin composition of the present invention, the content ratio of (C) phenoxy resin is the solid content of (A) polyamideimide resin, (B) epoxy resin and (C) phenoxy resin (amount excluding the solvent in the components) ) Is preferably 5 to 30% by mass with respect to the total mass. Thereby, the above-described characteristics can be obtained more satisfactorily.

  Moreover, as (C) phenoxy resin, the bisphenol A type phenoxy resin or the copolymerization type phenoxy resin of bisphenol A and bisphenol F is preferable.

Furthermore, as the (A) polyamideimide resin, a structure represented by the following general formula (1), a structure represented by the following general formula (2), a structure represented by the following general formula (3a), and the following general formula Those containing at least one structure selected from the group consisting of the structure represented by (3b) and the structure represented by the following general formula (4) are preferred.

[In Formula (1), R ¹¹ and R ¹² are each independently a divalent aliphatic hydrocarbon group, and R ¹³ , R ¹⁴ , R ¹⁷ and R ¹⁸ are each independently having a substituent. Good monovalent aliphatic hydrocarbon groups, R ¹⁵ and R ¹⁶ each independently represent a monovalent aromatic hydrocarbon group which may have a substituent, and m and n are each independently 0 to 0 40 is an integer satisfying 1 ≦ m + n ≦ 50. ]


[In Formula (3a) and Formula (3b), X ³¹ is a C 1-3 divalent aliphatic hydrocarbon group, a C 1-3 divalent halogenated aliphatic hydrocarbon group, or a sulfonyl group. , an ether group, a carbonyl group, a single bond, a divalent group represented by the following general formula a divalent radical or the following general formula represented by ^{(31a) (31b), X} 32 is 1 to carbon atoms 3 is a divalent aliphatic hydrocarbon group, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group or a carbonyl group, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group.

In the formula (31a), 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. Indicates a group or a single bond. ]

[In formula (4), X ⁴¹ represents a methylene group, a sulfonyl group, an ether group, a carbonyl group or a single bond, and R ⁴¹ and R ⁴² each independently have a hydrogen atom, an alkyl group or a substituent. And p is an integer of 1 to 50. ]

  The present invention also provides a prepreg having a fiber base material and an insulating resin impregnated in the fiber base material, wherein the insulating resin comprises (A) a polyamideimide resin, (B) an epoxy resin, and (C ) A prepreg formed by using an insulating resin composition containing a phenoxy resin is provided.

  Since the prepreg of the present invention includes an insulating resin using the insulating resin composition of the present invention, when the insulating layer is formed by curing, for example, not only heat resistance and reflow resistance can be obtained. In addition to having flexibility and excellent bendability, generation of dust can be greatly suppressed. Further, for example, when a metal foil-clad laminate is used, the adhesiveness to the metal foil is excellent.

  In the prepreg of the present invention, the fiber base material preferably has a thickness of 5 to 50 μm. Although the prepreg having such a thin fiber base material is suitable for downsizing of a printed wiring board, there has been a tendency that the above-described characteristics required for a prepreg have not been sufficiently obtained. On the other hand, since the present invention uses the above-described insulating resin composition, sufficient characteristics can be obtained even with such a thin substrate.

  The present invention also provides a metal foil-clad laminate obtained using the prepreg of the present invention. That is, the metal foil-clad laminate of the present invention comprises an insulating layer made of a cured product of the prepreg of the present invention and a metal foil provided on at least one surface of the insulating layer. Such a metal foil-clad laminate has an insulating layer obtained by using the prepreg of the present invention, so it has excellent heat resistance, reflow resistance and adhesion to the metal foil, has flexibility and is bent. Therefore, it is possible to manufacture a multilayer wiring board that can be stored at high density.

  The present invention further provides a printed wiring board obtained by processing the metal foil in the metal foil-clad laminate of the present invention to form a wiring. Also provided is a multilayer wiring board comprising at least such a printed wiring board, an adhesive layer formed on the wiring of the printed wiring board, and a wiring different from the wiring formed on the adhesive layer. Since these printed wiring boards and multilayer wiring boards have a layer (insulating layer) made of a cured product of prepreg formed using the insulating resin composition of the present invention, excellent heat resistance and reflow resistance are provided. In addition, it has adhesiveness to the metal foil and further generates very little dust.

  According to the present invention, a prepreg having excellent properties such as heat resistance, reflow resistance, and adhesion to a metal foil, flexibility, good bendability, and extremely low dust generation properties. It becomes possible to provide an insulating resin composition that can be formed. Also provided are a prepreg having the above characteristics obtained by using this insulating resin composition, and a metal foil-clad laminate, printed wiring board, and multilayer wiring board having the above characteristics and capable of being stored at high density. It becomes possible to do.

1 is a perspective view schematically showing a prepreg according to a preferred embodiment of the present invention. It is a figure which shows typically the cross-sectional structure of the metal foil tension laminated board which concerns on suitable embodiment.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary.

[Insulating resin composition]
The insulating resin composition of the present invention contains (A) a polyamideimide resin, (B) an epoxy resin, and (C) a phenoxy resin. By having such a composition, while having excellent heat resistance and reflow resistance when made into a prepreg, it has flexibility and bendability and can further suppress the generation of dust. . Moreover, when it is set as a metal foil tension laminated board, the adhesiveness with the outstanding metal foil is acquired. In such an insulating resin composition, the content ratio of the (C) phenoxy resin is based on the total of the solids (amount excluding the solvent in the component) of the component (A), the component (B) and the component (C). If it is 5 to 30% by mass, the above properties are particularly excellent, which is preferable.

(Polyamideimide resin)
(A) Polyamidoimide resin is a high molecular compound which has an amide group and an imide group in a repeating unit. As the polyamide-imide resin, those obtained by a production method in which diimide dicarboxylic acid obtained by reacting diamine and trimellitic anhydride and diisocyanate are reacted are preferable.

The polyamideimide resin contains at least one structure selected from the group consisting of structures represented by the following general formulas (1), (2), (3a), (3b) and (4) in the structure. And preferred.

[In Formula (1), R ¹¹ and R ¹² are each independently a divalent aliphatic hydrocarbon group, and R ¹³ , R ¹⁴ , R ¹⁷ and R ¹⁸ are each independently having a substituent. Good monovalent aliphatic hydrocarbon groups, R ¹⁵ and R ¹⁶ each independently represent a monovalent aromatic hydrocarbon group which may have a substituent, and m and n are each independently 0 to 0 40 is an integer satisfying 1 ≦ m + n ≦ 50. ]


[In Formula (3a) and Formula (3b), X ³¹ is a C 1-3 divalent aliphatic hydrocarbon group, a C 1-3 divalent halogenated aliphatic hydrocarbon group, or a sulfonyl group. , an ether group, a carbonyl group, a single bond, a divalent group represented by the following general formula a divalent radical or the following general formula represented by ^{(31a) (31b), X} 32 is 1 to carbon atoms 3 is a divalent aliphatic hydrocarbon group, a divalent halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group or a carbonyl group, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group.

In the formula (31a), 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. Indicates a group or a single bond. ]

[In formula (4), X ⁴¹ represents a methylene group, a sulfonyl group, an ether group, a carbonyl group or a single bond, and R ⁴¹ and R ⁴² each independently have a hydrogen atom, an alkyl group or a substituent. And p is an integer of 1 to 50. ]

  These structures are preferably introduced by using those containing these structures as diamines in the production method described above.

That is, first, the structure represented by the general formula (1) is obtained by using a diamine represented by the following general formula (5). In addition, all the codes | symbols in a formula are synonymous with the said General formula (1).

  The diamine represented by the general formula (5) is a siloxane diamine. As the siloxane diamine represented by the general formula (5), 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 silicone oil KF8010 (amine equivalent 430) (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-853 (amine equivalent) 650), BY16-853B (amine equivalent 2200), (above, Toray Dow Corning Silicone Co., Ltd., trade name) and the like.

The structure represented by the general formula (2) is obtained by using a diamine represented by the following general formula (6). The diamine represented by the following general formula (6) is available as Wandamine (trade name, manufactured by Shin Nippon Chemical Co., Ltd.).

The structures represented by the general formulas (3a) and (3b) are obtained by diamines represented by the following general formulas (7a) and (7b), respectively. In addition, all the codes | symbols in a formula are synonymous with the said general formula (3a) and (3b).

  The diamine represented by the general formulas (7a) and (7b) is an aromatic diamine. Examples of such aromatic diamines 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 (to Fluoromethyl) 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) diphenyl sulfone, (4,4'-diamino) benzophenone, Examples include (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, and the like.

The structure represented by the general formula (4) is obtained by a diamine represented by the following general formula (8).

The diamine represented by the general formula (8) is an aliphatic diamine. The symbols in general formula (8) have the same meaning as in general formula (4). R ⁴¹ and R ⁴² are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a substituted phenyl group. Examples of the substituent substituted on the phenyl group in the substituted phenyl group include an alkyl group having 1 to 3 carbon atoms and a halogen atom.

In the diamine represented by the general formula (8), the group represented by X ⁴¹ is preferably an ether group from the viewpoint of achieving both a low elastic modulus and a high Tg. Examples of such aliphatic diamines include Jeffamine D-400 (amine equivalent 200), Jeffamine D-2000 (amine equivalent 1000) (above, Mitsui Chemicals Fine, trade name), and the like.

  The polyamideimide resin is represented by at least the general formula (3a) or (3b) among the structures represented by the general formulas (1), (2), (3a), (3b), and (4). It is preferable to have a structure, and it is more preferable to have a combination of these and the structure represented by the general formula (1) or (4), and in addition, the structure is represented by the general formula (2). More preferably, it has a structure. In the polyamide-imide resin, the structure represented by the general formula (3a) or (3b) is preferably contained in an amount of 2 to 25% by mass, and the structure represented by the general formula (1) or (4) is 20 It is preferable to be contained in an amount of ˜55 mass%, and the structure represented by the general formula (2) is preferably contained in an amount of 0 to 5 mass%.

(A) Polyamideimide resin can be obtained by reacting diimide dicarboxylic acid obtained by reacting diamine as described above (a mixture of diamines when plural kinds are used) and trimellitic anhydride and diisocyanate. . Suitable diisocyanate includes a compound represented by the following general formula (9).

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

  Examples of the diisocyanate represented by the general formula (9) include both an aromatic diisocyanate in which D is a divalent organic group having an aromatic ring and an aliphatic diisocyanate in which D is a divalent aliphatic hydrocarbon group. Although applicable, it is preferable to use at least an aromatic diisocyanate.

  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. Among these, it is preferable to use MDI. By using MDI as the aromatic diisocyanate, the flexibility of the resulting polyamideimide can be improved, and as a result, the flexibility of the prepreg also tends to be improved. Specific examples include 4,4'-diphenylmethane diisocyanate (trade name, manufactured by Nippon Polyurethane Co., Ltd.).

  On the other hand, examples of the aliphatic diisocyanate include hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and isophorone diisocyanate. As the diisocyanate, aromatic diisocyanate and aliphatic diisocyanate may be used in combination. When using together, the heat resistance of the polyamideimide obtained by adding about 5-10 mol% of aliphatic diisocyanate with respect to aromatic diisocyanate can further be improved, and it is preferable.

(Epoxy resin)
(B) Various epoxy resins can be applied as the epoxy resin, and among them, an epoxy resin having two or more glycidyl groups is preferable. Examples of such epoxy resins include polyphenols obtained by reacting polychlorophenols such as bisphenol A, novolak-type phenol resins, ortho-cresol novolak-type phenol resins or polyhydric alcohols such as 1,4-butanediol with epichlorohydrin. N-glycidyl derivatives of compounds having polyglycidyl esters, amines, amides or heterocyclic nitrogen bases obtained by reacting polybasic acids such as glycidyl ether, phthalic acid and hexahydrophthalic acid with epichlorohydrin, or alicyclic rings An epoxy resin etc. are mentioned.

  Specific examples of the epoxy resin include YD128, YD8125, YD907, YDCN-704, YDCN-700-10 (trade name, manufactured by Tohto Kasei Co., Ltd.), Ep815, Ep828 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.), DER337 (made by Dow Chemical Japan Co., Ltd., trade name), EPICLON153, N-673-80M, N-680-75M, N-690-75M, HP-4032D (made by DIC Corporation, trade name), EX-212L, EX-214L (trade name, manufactured by Nagase ChemteX Corporation), Celoxide 2021P (trade name, manufactured by Daicel Chemical Industries, Ltd.), EPPN-502H, NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.), and the like. It is done.

  From the viewpoint of obtaining good thermal, mechanical, and electrical characteristics, the epoxy resin is more preferable to contain a combination of a curing agent and a curing accelerator in the above epoxy resin having two or more glycidyl groups. It is.

  The curing agent for the epoxy resin can be used without limitation as long as it reacts with the epoxy resin. For example, amines, imidazoles, polyfunctional phenols, acid anhydrides and the like can be mentioned. Examples of amines include dicyandiamide, diaminodiphenylmethane, guanylurea, polyamide, and polyamideimide. Examples of polyfunctional phenols include hydroquinone, resorcinol, bisphenol A and their halogen compounds, and novolak-type phenol resins and resol-type phenol resins that are condensates with formaldehyde. Examples of acid anhydrides include phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, and the like. Examples of imidazoles include alkyl group-substituted imidazoles and benzimidazoles. These can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the curing agent include KS9900B (trade name, manufactured by Hitachi Chemical Co., Ltd.), CSD-40 (trade name, manufactured by Hitachi Chemical Coated Sand Co., Ltd.), and FG-2000 (trade name, manufactured by Teijin Chemicals Ltd.). Etc.

  When the curing agent is an amine, the compounding amount of the curing agent is preferably an amount such that the active hydrogen equivalent of the amine and the epoxy equivalent of the epoxy resin are substantially equal. When the curing agent is imidazole, it is not simply an equivalent ratio with active hydrogen, but is empirically preferably about 0.001 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. In the case of polyfunctional phenols and acid anhydrides, such an amount that their phenolic hydroxyl groups and carboxyl groups are 0.6 to 1.2 equivalents relative to 1 equivalent of epoxy resin is preferable. If there is little compounding quantity of a hardening | curing agent, uncured epoxy resin will remain and Tg (glass transition temperature) tends to become low. On the other hand, when it is too much, unreacted curing agent remains, and the insulation tends to be lowered. In addition, about polyamide and polyamideimide, it can also mix | blend as a main component of the insulating resin composition of this invention not only as a hardening | curing agent. In this case, these can be blended in an amount of preferably 0.01 to 500 parts by weight, more preferably 0.1 to 400 parts by weight with respect to 100 parts by weight of the epoxy resin. Degradation is unlikely to occur.

  Moreover, the hardening accelerator of an epoxy resin can be used without a restriction | limiting, if it reacts with an epoxy resin. For example, amines, imidazoles, polyfunctional phenols, and acid anhydrides can be used. Examples of amines include diaminodiphenylmethane and guanylurea. Examples of polyfunctional phenols include hydroquinone, resorcinol, bisphenol A and their halogen compounds, and novolak-type phenol resins and resol-type phenol resins that are condensates with formaldehyde. Examples of acid anhydrides include phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid, and the like. Examples of imidazoles include alkyl group-substituted imidazoles and benzimidazoles. These can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the curing accelerator include 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN), 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-1-methylimidazole, and the like. Can be mentioned.

  When the curing accelerator is an amine, the blending amount of the curing accelerator is preferably an amount such that the active hydrogen equivalent of the amine and the epoxy equivalent of the epoxy resin are substantially equal. When the curing accelerator is imidazole, it is not simply an equivalent ratio with active hydrogen, and is preferably empirically 0.001 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. In the case of polyfunctional phenols and acid anhydrides, such an amount that their phenolic hydroxyl groups and carboxyl groups are 0.6 to 1.2 equivalents relative to 1 equivalent of epoxy resin is preferable.

  When the blending amount of the curing accelerator is too smaller than the above-mentioned preferable amount, an uncured epoxy resin remains, and Tg (glass transition temperature) after curing tends to be low. On the other hand, when it is too much, unreacted curing accelerator remains, and the insulation after curing tends to decrease.

(Phenoxy resin)
As the (C) phenoxy resin, known phenoxy resins can be applied without limitation, and examples thereof include polyhydroxy polyethers synthesized by reacting bisphenols with epichlorohydrin, and are represented by the following general formula (10a). A bisphenol A type having a copolymer type structure of bisphenol A and bisphenol F represented by the following general formula (10b) is preferable.

[Wherein q, r and s are each independently a positive integer. ]

  From the viewpoint of obtaining excellent properties such as film formation by an insulating resin composition containing these phenoxy resins and flexibility and toughness of cured products, phenoxy resins have an average molecular weight (gel permeation chromatography ( The weight average molecular weight determined in terms of standard polystyrene by GPC) is preferably 20000 or more, and more preferably 30000 or more. However, if the molecular weight is too large, the heat resistance is lowered due to separation from the polyamide-imide resin, and therefore the upper limit of the average molecular weight of the phenoxy resin is preferably about 80000. In addition, when calculating | requiring the average molecular weight of phenoxy resin by GPC, tetrahydrofuran (THF) is used, for example as an eluent of GPC, and TSKgel G4000H and TSKgel G3000H (both are the Tosoh Corporation make, brand name) are used as a column. It can be obtained using what is connected.

  Examples of such phenoxy resins include PKHH, PKHJ (manufactured by Union Carbide, trade name), YP-70, YP-50, YP-50EK35, YP-55U, ZX-1356-2 (all Chemical name, product name) and the like.

(Amount of each component in the insulating resin composition)
The preferred content of the main components in the insulating resin composition is as follows. That is, first, the content ratio of the (A) polyamideimide resin is 35 to 35% of the total mass of the solids (amount excluding the solvent in the component) of the component (A), the component (B) and the component (C). It is preferable in it being 70 mass%, and it is more preferable in it being 50-70 mass%. If the content of the polyamideimide resin is too much, moldability may be lowered. On the other hand, if it is too little, flexibility may be lowered or dust may be easily generated.

  Moreover, the content rate of (B) epoxy resin is 15-35 mass% with respect to the total mass of solid content (Amount except the solvent in a component) of (A) component, (B) component, and (C) component. It is preferable and it is more preferable in it being 15-25 mass%. If the content of the epoxy resin is too much, the flexibility may be lowered or dust may be easily generated. On the other hand, if the content is too small, the moldability and heat resistance tend to be lowered. .

  Furthermore, the content rate of (C) phenoxy resin is 5-30 mass% with respect to the total mass of (A) component, (B) component, and the solid content (Amount except the solvent in a component) of (C) component. It is preferable that When the proportion of the phenoxy resin is less than 5% by mass, the flexibility of the cured product of the insulating resin composition tends to be insufficient. On the other hand, if it exceeds 30% by mass, the flexibility of the cured product of the insulating resin composition is lowered, and the heat resistance may be insufficient. (C) The content ratio of the phenoxy resin is more preferably 5 to 25% by mass, and further preferably 15 to 25% by mass. When the ratio of the phenoxy resin is within such a range, the generation of dust tends to be effectively suppressed particularly when a prepreg is produced and processed.

  Furthermore, the content ratio of the (C) phenoxy resin in the total mass of the solid content of the component (A) and the component (C) (amount excluding the solvent in the component) is in the range of 10 to 40% by mass. preferable. If the content is less than 10% by mass, the bendability may be deteriorated. On the other hand, if it exceeds 40% by mass, heat resistance and bendability are deteriorated, and dust generation may occur easily.

(Other ingredients)
The insulating resin composition may further contain other components in addition to (A) the polyamideimide resin, (B) the epoxy resin, and (C) the phenoxy resin. As other components, it is preferable to further contain a flame retardant for the purpose of improving the flame retardancy of the cured product of the insulating resin composition, and thus the prepreg. Examples of the flame retardant include a phosphorus-containing filler, aluminum hydroxide, a reactive phosphorus-containing cyclic compound, a melamine-based flame retardant, and a molybdate compound. Specifically, OP930 (trade name, manufactured by Clariant Co., Ltd.) as the phosphorus-containing filler, HP-360 (trade name, manufactured by Showa Denko KK) as the aluminum hydroxide, and HCA-HQ (Sanko) as the reactive phosphorus-containing cyclic compound. Co., Ltd., trade name), melamine polyphosphate PMP-100, PMP-200, PMP-300 (trade name, manufactured by Nissan Chemical Co., Ltd.) as melamine flame retardant, Chemguard 911A (Sherwin Product name) manufactured by Williams Co., Ltd.

  In addition, the insulating resin composition may further contain an antioxidant, a flow regulator, a coupling agent, an inorganic filler, and the like. In addition, it is preferable that content of the other component in an insulating resin composition is the range which does not inhibit the effect of this invention, for example, is the sum total of another component, and is 100 of the component of said (A)-(C). It is suitable that it is about 1-40 mass parts with respect to mass parts.

[Prepreg]
Although the insulating resin composition has been described in detail above, a preferred embodiment of a prepreg using such an insulating resin composition will be described below.

  FIG. 1 is a perspective view schematically showing a prepreg according to a preferred embodiment of the present invention. A prepreg 100 shown in FIG. 1 is composed of a fiber base material and an insulating resin impregnated in the fiber base material, and has a sheet-like shape as a whole. In the prepreg 100, the insulating resin is preferably a state in which the above-described insulating resin composition is impregnated into a fiber base material and then dried and partially cured, that is, in a B-stage state. Adhesive function due to partial curing.

  In the prepreg 100, as a fiber base material, it can apply without a restriction | limiting especially if it is generally used when manufacturing a metal foil tension laminated board and a printed wiring board. The material of the fiber base includes glass, alumina, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, and other inorganic materials, aramid, polyetheretherketone, polyetherimide, polyethersulfone , Organic materials such as carbon and cellulose. The fiber base material may be a single one of these or a combination thereof (mixed paper type). There is no restriction | limiting in particular as a form of a fiber base material, Although a woven fabric or a nonwoven fabric may be sufficient, a woven fabric is preferable and a glass cloth (woven fabric of glass fiber) is used more preferable. Specific examples of the glass cloth include WEX-1017, WEX-1027, WEX-1037 (manufactured by Asahi Sebel Co., Ltd., trade name) and the like.

  The thickness of the fiber base is generally 5 to 100 μm, but is preferably 5 to 50 μm in the present invention. By using a fiber substrate having such a thickness, a printed wiring board that can be bent arbitrarily can be obtained very easily when combined with the above-described insulating resin composition, and the temperature in the manufacturing process can be obtained. It is possible to reduce the dimensional change accompanying moisture absorption and the like. In addition, by combining with the above-described insulating resin composition, a prepreg with less dust generation during processing can be obtained even with such a thin fiber substrate.

  The thickness of the prepreg 100 itself is generally 5 to 120 μm, but is preferably 5 to 60 μm in the present invention. This is the thickness obtained by combining the above-mentioned fiber base material and the above-mentioned insulating resin composition. With the prepreg thus obtained, a printed wiring board that can be bent arbitrarily can be obtained very easily, and the dimensional change accompanying temperature, moisture absorption, etc. in the manufacturing process can be reduced. .

  In the prepreg 100, the ratio of the insulating resin composition impregnated into the fiber base (in terms of mass, solid content (components other than the solvent)) is 30 with respect to the entire prepreg (the total of the fiber base and the resin composition). It is preferable in it being -85 mass%, and it is more preferable in it being 60-80 mass%. When the ratio of the insulating resin composition is less than 30% by mass, the amount of impregnation of the insulating resin composition into the fiber base material is not sufficient, and voids remain, and the metal foil is produced during the production of the metal foil-clad laminate. It may be difficult to stack with. On the other hand, when it exceeds 85% by mass, the prepreg having a uniform thickness cannot be obtained due to too much insulating resin composition, or when it is used as a varnish of an insulating resin composition as described later, When the metal foil-clad laminate is used, the heat resistance tends to be insufficient.

  The prepreg 100 having the above-described configuration can be manufactured, for example, by applying an insulating resin composition to a fiber base material and impregnating the fiber base material.

  The insulating resin composition may not contain a solvent, but may be in the form of a varnish in which each component is dissolved or dispersed in the solvent. In this case, the solvent is not particularly limited as long as the good solubility and dispersibility of the resin composition can be obtained. For example, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, dimethylacetamide, dimethylformamide, dimethyl Examples include sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, and cyclohexanone.

  In the case of using an insulating resin composition containing a solvent in the production of the prepreg 100, it is preferable to dry the solvent by volatilizing the solvent by heating after impregnation into the fiber base material. The heating conditions for drying are preferably such that the insulating resin composition is not cured and about 80% by mass of the solvent is removed. For example, the temperature can be 80 to 180 ° C. The time is preferably set in consideration of the gelation time of the insulating resin composition. At the time of drying, the insulating resin composition may be partially cured as long as it cannot be used as a prepreg.

[Metal foil-clad laminate]
FIG. 2 is a diagram schematically showing a cross-sectional configuration of a metal foil-clad laminate according to a preferred embodiment. As shown in FIG. 2, the metal foil-clad laminate 200 is composed of a substrate 30 on which a plurality (three in this case) of prepregs 100 are laminated, and a metal foil 10 provided on both surfaces of the substrate 30. The The metal foil-clad laminate is not limited to such a form. For example, the prepreg 100 may be only one layer, and the metal foil 10 may be disposed only on one side of the substrate 30.

  The thickness of the metal foil-clad laminate is generally 10 to 800 μm, but is preferably 10 to 200 μm in the present invention. By using the metal foil-clad laminate having such a thickness, a printed wiring board that can be arbitrarily bent can be obtained.

  In the metal foil-clad laminate 200, the prepreg 100 is the same as that described above, but is in a cured state and does not develop a new adhesive force even when heated from that state (ie, C-stage). State). In addition, the hardened | cured material of the prepreg 100 is a thing of the state which the insulating resin composition contained in a prepreg hardened | cured. Moreover, as the metal foil 10, what is used as a constituent material of the circuit of a printed wiring board can be applied without a restriction | limiting in particular, For example, what has a thickness of 5-200 micrometers can be applied. For example, in addition to copper foil and aluminum foil, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as intermediate layers, and a copper layer of 0.5 to 15 μm on both sides A composite foil having a three-layer structure in which a copper layer of 10 to 300 μm is provided, or a two-layer structure composite foil in which aluminum and a copper foil are combined can be used.

  The surface of the metal foil 10 may be roughened. For example, when the surface on which the prepreg 100 is disposed is roughened, good adhesion to the substrate 30 made of a cured product of the prepreg 100 is obtained, and the reliability is high and the formation of a fine circuit is achieved. Etc. are possible. The 10-point average roughness (Rt) on the roughened surface is preferably 10 μm or less, and more preferably 5 μm or less. The ten-point average roughness (Rt) is the ten-point average roughness (Rt) defined in JIS B0601-1994. The metal foil-clad laminate 200 including the metal foil 10 having such a surface roughness can be obtained while maintaining a sufficient level of adhesion between the conductive layer made of the metal foil 10 and the insulating layer made of a cured product of the prepreg 100. The high-frequency transmission characteristics of the printed wiring board can be further improved.

  Such a metal foil-clad laminate 200 is formed by, for example, laminating a metal foil 10, a substrate 30 (a prepreg 100 or a laminate of a plurality of prepregs 100), and a metal foil 10 in this order, and preferably 150 to 280 ° C, More preferably, it can be produced by hot pressing in the laminating direction at a pressure in the temperature range of 180 to 250 ° C., and preferably in the range of 0.5 to 20 MPa, more preferably 1 to 8 MPa. This example is an example of a double-sided metal foil-clad laminate, but in the case of a single-sided metal foil-clad laminate, one metal foil 10 is not laminated. Since the metal foil-clad laminate thus obtained is formed by a prepreg using the above-described insulating resin composition, it is excellent in heat resistance, reflow resistance and adhesion to the metal foil, and generates less dust. In addition, when the thickness of the substrate is flexible enough to be bent, the bendability is also excellent.

[Printed wiring boards and multilayer wiring boards]
The prepreg 100 and the metal foil-clad laminate 200 described above can be used for manufacturing printed wiring boards and multilayer wiring boards.

  For example, the metal foil-clad laminate 200 can be formed into a printed wiring board by processing the metal foil 10 on the surface thereof to form a wiring. Wiring processing of the metal foil 10 can be performed by a known method.

  Further, for example, in the prepreg 100, the prepreg 100 and the copper foil are stacked in this order on an inner layer printed wiring board on which an inner layer circuit (inner layer circuit) is formed, preferably 150 to 280 ° C., more preferably 170. It can be used for multilayering of a printed wiring board by a method such as heating and pressurizing at a temperature range of ˜240 ° C. and preferably a pressure of 0.5 to 20 MPa, more preferably 1 to 8 MPa. The multilayer wiring board thus obtained has a structure in which an adhesive layer made of prepreg is provided on an inner layer circuit, and wiring is further provided thereon.

  Also, the printed wiring board can be multi-layered by preparing two or more printed wiring boards having an inner layer circuit and sandwiching the prepreg 100 between them to perform heat and pressure molding. When it is necessary to connect the laminated printed wiring boards, it is preferable to align each printed wiring board in accordance with the connection site. At this time, a plurality of prepregs 100 may be used between the layers.

  The plurality of printed wiring boards stacked via the prepreg 100 is, for example, preferably in the temperature range of 150 to 280 ° C., more preferably 170 to 240 ° C., and preferably 0.5 to 20 MPa, more preferably 1 to Multi-layering can be achieved by applying heat and pressure at a pressure in the range of 8 MPa. The multilayer wiring board thus obtained is excellent in heat resistance and reflow resistance, and generates less dust.

  Further, a resin film that is not a prepreg and a copper foil are stacked in this order on the printed circuit board for the inner layer on which the circuit for the inner layer (inner layer circuit) is formed, and preferably 150 to 280 ° C., more preferably 170 to 240. The printed wiring board can be multilayered by a method such as heating and pressurizing at a temperature range of ° C. and preferably a pressure in the range of 0.5 to 20 MPa, more preferably 1 to 8 MPa.

  Furthermore, the copper foil with resin obtained by applying a resin on one side of the copper foil is overlaid on the printed wiring board for the inner layer so that the copper foil surface of the copper foil with resin is on the outside, preferably 150 to 280 ° C., More preferably, the printed wiring board can be multilayered by a method such as heating and pressurizing at a temperature range of 170 to 240 ° C., preferably 0.5 to 20 MPa, more preferably 1 to 8 MPa. .

  The multilayer wiring board obtained by these is also excellent in heat resistance and reflow resistance by using a printed wiring board formed from a metal foil-clad laminate using the prepreg of the present invention as a printed wiring board for the inner layer. Is less likely to occur.

  Further, when the metal foil-clad laminate 200 has a foldable thickness, for example, the metal foil-clad laminate 200 can be bent by processing the metal foil on the surface to form a predetermined circuit. It can be set as a simple printed wiring board. Such a printed wiring board can also be used in combination with other foldable printed wiring boards. Examples of the foldable printed wiring board to be combined include flexible wiring boards such as Espanex (trade name, manufactured by Nippon Steel Chemical Co., Ltd.).

  Moreover, you may use the printed wiring board of this invention for multilayering of a printed wiring board by laminating | stacking on a general rigid board | substrate.

  As described above, the multilayer wiring board obtained by using the prepreg or metal foil-clad laminate of the present invention is excellent in heat resistance, reflow resistance and adhesion to metal foil, and generates less dust. . Furthermore, since it can be bent and used, it can be stored with high density.

  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)
BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane was added to 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 silicone oil KF-8010 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, amine equivalent 415) 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. When it was confirmed that water was no longer distilled in the moisture determination receiver, the temperature was raised to about 180 ° C. while removing the distillate accumulated in the moisture determination receiver to remove toluene.

  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% by mass) was obtained.

(Synthesis Example 2)
BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane was added to 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 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name, amine equivalent 415) 373.5 g (0.45 mol), Wandamine (manufactured by Shin Nippon Rika Co., Ltd., trade name) 37 .9 g (0.18 mol), TMA (trimellitic anhydride) 346.6 g (1.805 mol), and NMP (N-methyl-2-pyrrolidone) 2400 g 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. When it was confirmed that water was no longer distilled in the moisture determination receiver, the temperature was raised to about 180 ° C. while removing the distillate accumulated in the moisture determination receiver to remove toluene.

  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, followed by reaction at 150 ° C. for 3 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin solid content 31.4% by mass) was obtained.

(Synthesis Example 3)
To a 5 liter separable flask equipped with a 25 ml moisture meter with a cock connected to a reflux condenser, a thermometer and a stirrer, KF-8010 (trade name, amine equivalent 415) 365, manufactured by Shin-Etsu Chemical Co., Ltd. 0.2 g (0.440 mol), DDS (diaminodiphenyl sulfone) 65.6 g (0.264 mol), Wandamine (manufactured by Shin Nippon Rika Co., Ltd., trade name) 37.0 g (0.176 mol), TMA (trimellitic anhydride ) 338.9 g (1.764 mol) and NMP (N-methyl-2-pyrrolidone) 2400 g 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. When it was confirmed that water was no longer distilled in the moisture determination receiver, the temperature was raised to about 180 ° C. while removing the distillate accumulated in the moisture determination receiver to remove toluene.

  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, followed by reaction at 150 ° C. for 3 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin solid content: 30.0% by mass) was obtained.

(Synthesis Example 4)
To a 25-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 Chemicals Fine, 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. When it was confirmed that water was no longer distilled in the moisture determination receiver, the temperature was raised to about 180 ° C. while removing the distillate accumulated in the moisture determination receiver to remove toluene.

  Thereafter, the solution was cooled to 80 ° C. or less, 195.9 g (0.783 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and the mixture was reacted at 150 ° C. for 3 hours. After completion of the reaction, an NMP solution of polyamideimide resin (resin solid content: 31.1% by mass) was obtained.

[Adjustment of insulating resin composition (resin varnish)]
An insulating resin composition containing a combination of predetermined components was prepared by the following method.

(Preparation Example 1)
CSD-40 (manufactured by Hitachi Chemical Coated Sand Co., Ltd., trade name) which is an NMP solution of polyamideimide resin (resin solid content 30.0% by mass), epoxy resin NC-3000H (manufactured by Nippon Kayaku Co., Ltd.) (Trade name) 12.0 g, phenoxy resin YP-50EK35 (weight average molecular weight 60000-80000, bisphenol A type, manufactured by Tohto Kasei Co., Ltd., trade name, methyl ethyl ketone solution having a solid content of 35% by mass), 34.3 g, and a curing accelerator 0.06 g of 1-cyanoethyl-2-ethyl-4-methylimidazole was mixed and stirred for about 1 hour until the resin became uniform to obtain an insulating resin composition.

(Preparation Example 2)
NMP solution of polyamideimide resin of Synthesis Example 1 (resin solid content 32.9% by mass) 85.1 g, epoxy resin NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 12.0 g, phenoxy resin YP-50EK35 ( Toto Kasei Co., Ltd., trade name, methyl ethyl ketone solution having a solid content of 35% by mass) 34.3 g and a curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole 0.06 g are mixed to make the resin uniform. Was stirred for about 1 hour to obtain an insulating resin composition.

(Preparation Example 3)
89.2 g of NMP solution (resin solid content 31.4% by mass) of Synthesis Example 2 and 12.0 g of epoxy resin NC-3000H (manufactured by Nippon Kayaku Co., Ltd., trade name), phenoxy resin YP-50EK35 ( Toto Kasei Co., Ltd., trade name, methyl ethyl ketone solution having a solid content of 35% by mass) 34.3 g and a curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole 0.06 g are mixed to make the resin uniform. Was stirred for about 1 hour to obtain an insulating resin composition.

(Preparation Example 4)
NMP solution of polyamide imide resin of Synthesis Example 3 (resin solid content 30.0 mass%) 93.3 g, epoxy resin NC-3000H (Nippon Kayaku Co., Ltd., trade name) 12.0 g, phenoxy resin YP-50EK35 ( Toto Kasei Co., Ltd., trade name, methyl ethyl ketone solution having a solid content of 35% by mass) 34.3 g and a curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole 0.06 g are mixed to make the resin uniform. Was stirred for about 1 hour to obtain an insulating resin composition.

(Preparation Example 5)
90.0 g of NMP solution of polyamideimide resin of Synthesis Example 4 (resin solid content 31.1% by mass), epoxy resin NC-3000H (product name, manufactured by Nippon Kayaku Co., Ltd.) 12.0 g, phenoxy resin YP-50EK35 ( Toto Kasei Co., Ltd., trade name, methyl ethyl ketone solution having a solid content of 35% by mass) 34.3 g and a curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole 0.06 g are mixed to make the resin uniform. Was stirred for about 1 hour to obtain an insulating resin composition.

(Preparation Example 6)
KS9900B (made by Hitachi Chemical Co., Ltd., trade name) which is an NMP solution of polyamideimide resin (resin solid content 32.0% by mass), epoxy resin NC-3000H (made by Nippon Kayaku Co., Ltd., trade name) 4.0 g, epoxy resin EPPN-502H (made by Nippon Kayaku Co., Ltd., trade name) 4.0 g, epoxy resin HP-4032D (made by DIC Corporation, trade name) 4.0 g, phenoxy resin YP-50EK35 (Toto Kasei) Product name, trade name, methyl ethyl ketone solution having a solid content of 35% by weight 22.9 g, flame retardant OP930 (product name, manufactured by Clariant Co., Ltd.) 4.0 g, flame retardant HP-360 (product name, Showa Denko KK, product name) ) 4.0 g and 0.06 g of curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole are mixed to make the resin uniform. In about 1 hour under stirring to obtain an insulating resin composition.

(Preparation Example 7)
KS9900B (made by Hitachi Chemical Co., Ltd., trade name) which is an NMP solution of polyamideimide resin (resin solid content 32.0% by mass), epoxy resin NC-3000H (made by Nippon Kayaku Co., Ltd., trade name) 12.0 g, phenoxy resin YP-50EK35 (trade name, methyl ethyl ketone solution having a solid content of 35% by mass) 22.9 g, flame retardant OP930 (product name, manufactured by Clariant Co., Ltd.) 4.0 g, flame retardant HP-360 (manufactured by Showa Denko KK, trade name) 4.0 g and a curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole 0.06 g are mixed and stirred for about 1 hour until the resin becomes uniform. Thus, an insulating resin composition was obtained.

(Preparation Example 8)
KS9900B (trade name) manufactured by Hitachi Chemical Co., Ltd., which is an NMP solution of polyamideimide resin (resin solid content: 32.0 mass%), epoxy resin HP-4032D (trade name, manufactured by DIC Corporation) 12. 0 g, phenoxy resin YP-50EK35 (trade name, methyl ethyl ketone solution having a solid content of 35% by mass) 22.9 g, flame retardant OP930 (product name, manufactured by Clariant Co., Ltd.) 4.0 g, flame retardant HP- 360 (Showa Denko Co., Ltd., trade name) and 0.06 g of curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole are mixed and stirred for about 1 hour until the resin is uniform. An insulating resin composition was obtained.

(Preparation Example 9)
KS9900B (trade name) manufactured by Hitachi Chemical Co., Ltd., which is an NMP solution of polyamideimide resin (resin solid content: 32.0% by mass), epoxy resin NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 6.0 g, Epoxy resin EPPN-502H (Nippon Kayaku Co., Ltd., trade name) 6.0 g, Epoxy resin HP-4032D (DIC Corporation, trade name) 6.0 g, Phenoxy resin YP-50EK35 (Tohto Kasei) Product name, trade name, methyl ethyl ketone solution with a solid content of 35% by mass) 17.1 g, flame retardant OP930 (product name, manufactured by Clariant Co., Ltd.) 6.0 g, flame retardant HP-360 (product name, Showa Denko KK, product name) ) 6.0 g and the curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole 0.09 g were mixed to make the resin uniform. Stirred for about one hour to obtain an insulating resin composition to.

(Preparation Example 10)
KS9900B (made by Hitachi Chemical Co., Ltd., trade name) which is an NMP solution of polyamideimide resin (resin solid content 32.0% by mass), epoxy resin NC-3000H (made by Nippon Kayaku Co., Ltd., trade name) 4.0 g, epoxy resin EPPN-502H (made by Nippon Kayaku Co., Ltd., trade name) 4.0 g, epoxy resin HP-4032D (made by DIC Corporation, trade name) 4.0 g, phenoxy resin YP-50EK35 (Toto Kasei) Product name, trade name, methyl ethyl ketone solution having a solid content of 35% by weight 34.3 g, flame retardant OP930 (product name, manufactured by Clariant Co., Ltd.) 4.0 g, flame retardant HP-360 (product name, Showa Denko KK, product name) ) 4.0 g and 0.06 g of curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole are mixed to make the resin uniform. In about 1 hour under stirring to obtain an insulating resin composition.

(Preparation Example 11)
KS9900B (made by Hitachi Chemical Co., Ltd., trade name) which is an NMP solution of polyamideimide resin (resin solid content 32.0% by mass), epoxy resin NC-3000H (made by Nippon Kayaku Co., Ltd., trade name) 4.0 g, epoxy resin EPPN-502H (made by Nippon Kayaku Co., Ltd., trade name) 4.0 g, epoxy resin HP-4032D (made by DIC Corporation, trade name) 4.0 g, phenoxy resin YP-50EK35 (Toto Kasei) Product name, trade name, methyl ethyl ketone solution having a solid content of 35% by mass) 45.7 g, flame retardant OP930 (product name, manufactured by Clariant Co., Ltd.) 4.0 g, flame retardant HP-360 (product name, Showa Denko KK, product name) ) 4.0 g and 0.06 g of curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole are mixed to make the resin uniform. In about 1 hour under stirring to obtain an insulating resin composition.

(Preparation Example 12)
KS9900B (made by Hitachi Chemical Co., Ltd., trade name) which is an NMP solution of polyamideimide resin (resin solid content 32.0% by mass) and epoxy resin NC-3000H (made by Nippon Kayaku Co., Ltd., trade name) 4.0 g, epoxy resin EPPN-502H (made by Nippon Kayaku Co., Ltd., trade name) 4.0 g, epoxy resin HP-4032D (made by DIC Corporation, trade name) 4.0 g, phenoxy resin YP-55U (bisphenol A) Type, weight average molecular weight 40000-45000, Toto Kasei Co., Ltd., trade name) varnish (solid content 35 mass%) 22.9 g dissolved in methyl ethyl ketone, flame retardant OP930 (Clariant Co., trade name) 4.0 g , Flame retardant HP-360 (trade name, manufactured by Showa Denko KK), and curing accelerator 1-cyanoethyl-2- Mixing the chill-4-methylimidazole 0.06 g, was obtained insulating resin composition was stirred for about 1 hour until the resin became uniform.

(Preparation Example 13)
KS9900B (made by Hitachi Chemical Co., Ltd., trade name) which is an NMP solution of polyamideimide resin (resin solid content 32.0% by mass) and epoxy resin NC-3000H (made by Nippon Kayaku Co., Ltd., trade name) 4.0 g, epoxy resin EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 4.0 g, epoxy resin HP-4032D (product name, manufactured by DIC Corporation) 4.0 g, phenoxy resin ZX-1356-2 ( 22.9 g of varnish (solid content 35% by mass) in which bisphenol A and bisphenol F are copolymerized, weight average molecular weight 60000-80000, manufactured by Tohto Kasei Co., Ltd., dissolved in methyl ethyl ketone, flame retardant OP930 (Clariant Corporation) Made, product name) 4.0 g, flame retardant HP-360 (made by Showa Denko KK, product name) 4.0 g, and Accelerator mixture of 1-cyanoethyl-2-ethyl-4-methylimidazole 0.06 g, was obtained insulating resin composition was stirred for about 1 hour until the resin became uniform.

(Preparation Example 14)
KS9900B (made by Hitachi Chemical Co., Ltd., trade name) which is an NMP solution of polyamideimide resin (resin solid content 32.0% by mass) and epoxy resin NC-3000H (made by Nippon Kayaku Co., Ltd., trade name) 5.3 g, epoxy resin EPPN-502H (product name, manufactured by Nippon Kayaku Co., Ltd.) 5.3 g, epoxy resin HP-4032D (product name, manufactured by DIC Corporation) 5.3 g, phenoxy resin ZX-1356-2 ( 22.9 g of varnish (solid content 35% by mass) dissolved in methyl ethyl ketone, product name) manufactured by Toto Kasei Co., Ltd., 4.0 g of flame retardant OP930 (product name of Clariant Co., Ltd.), flame retardant HP-360 (Showa Denko) Made by Co., Ltd., trade name) 4.0 g and curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole 0.08 g were mixed, To obtain an insulating resin composition was stirred for about 1 hour until homogeneous.

(Preparation Example 15)
KS9900B (trade name) manufactured by Hitachi Chemical Co., Ltd., which is an NMP solution of polyamideimide resin (resin solid content: 32.0% by mass) and epoxy resin NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 2.7 g, epoxy resin EPPN-502H (trade name) manufactured by Nippon Kayaku Co., Ltd., 2.7 g, epoxy resin HP-4032D (trade name, manufactured by DIC Corporation) 2.7 g, phenoxy resin ZX-1356-2 ( 22.9 g of varnish (solid content 35% by mass) dissolved in methyl ethyl ketone, product name of Toto Kasei Co., Ltd., 4.0 g of flame retardant OP930 (product name of Clariant Co., Ltd.), flame retardant HP-360 (Showa Denko) Made by Co., Ltd., trade name) 4.0 g, and curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole 0.04 g, Fat obtain an insulating resin composition was stirred for about 1 hour until homogeneous.

(Comparative Preparation Example 1)
KS9900B (trade name) manufactured by Hitachi Chemical Co., Ltd., which is an NMP solution of polyamideimide resin (resin solid content: 32.0% by mass), epoxy resin NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 6.0 g, epoxy resin EPPN-502H (made by Nippon Kayaku Co., Ltd., trade name) 6.0 g, epoxy resin HP-4032D (made by DIC Corporation, trade name) 6.0 g, flame retardant OP930 (made by Clariant Co., Ltd.) , Trade name) 6.0 g, flame retardant HP-360 (made by Showa Denko KK, trade name) 6.0 g, and curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole 0.09 g are mixed, An insulating resin composition was obtained by stirring for about 1 hour until the resin was uniform.

(Comparative Preparation Example 2)
KS9900B (trade name) manufactured by Hitachi Chemical Co., Ltd., which is an NMP solution of polyamideimide resin (resin solid content: 32.0% by mass), epoxy resin NC-3000H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 8.0 g, epoxy resin EPPN-502H (trade name) manufactured by Nippon Kayaku Co., Ltd., 8.0 g, epoxy resin HP-4032D (trade name, manufactured by DIC Corporation) 8.0 g, phenol resin KA-1165 (DIC stock) 16.0 g made by company, trade name, hydroxyl equivalent weight 120), flame retardant OP930 (trade name, manufactured by Clariant Co., Ltd.) 8.0 g, flame retardant HP-360 (trade name, manufactured by Showa Denko KK), 8.0 g, and Mix 0.12 g of curing accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole and stir for about 1 hour until the resin is uniform. To obtain a composition.

[Preparation of prepreg and double-sided copper foil-clad laminate]
Preparation Examples 1 to 15 and Comparative Preparation Examples using the insulating resin composition prepared in 1-2, the following Reference Examples according to the method 1, a prepreg and double-sided copper Examples 3-15 and Comparative Examples 1-2 Each of the foil-clad laminates was produced. In the case of using the insulating resin composition of Preparation Examples 1 to 15 each Reference Examples 1 and 2, and correspond to Example 3-15, using an insulating resin composition of Comparative Preparation Examples 1-2 The cases correspond to Comparative Examples 1 and 2, respectively.

(Preparation of prepreg)
The insulating resin composition was coated on a 19 μm thick glass cloth WEX-1027 (trade name, manufactured by Asahi Schavel Co., Ltd.) so that the thickness of the prepreg after drying was 50 μm, and heated at 140 ° C. for 15 minutes. As a result, various prepregs in which the glass cloth was impregnated with the insulating resin formed from the respective insulating resin compositions were obtained.

(Production of double-sided copper foil-clad laminate)
On both sides of the prepreg, 12 μm thick electrolytic copper foil (Furukawa Metal Co., Ltd., trade name: F3-WS-12, surface roughness (10-point average roughness Rt): 2.4 μm) The laminate was obtained by stacking so that the surface faced the prepreg. After this laminate was placed in the press part of the press machine and the degree of vacuum of the press part was 40 hPa, pressure heating of the laminate was started at a molding pressure of 4 MPa and a heating rate of 5 ° C./min. When it reached 200 ° C., it was maintained for 60 minutes (molding time). Thereafter, the pressure heating was stopped and air cooling was performed, and then the press part was returned to the atmospheric pressure to obtain a double-sided copper foil-clad laminate. The thickness of the obtained double-sided copper-clad laminate was 70 μm.

[Characteristic evaluation of prepreg and double-sided copper foil-clad laminate]
The following evaluations were performed on the prepregs and double-sided copper foil-clad laminates of Reference Examples 1 and 2, Examples 3 to 15 and Comparative Examples 1 and 2 obtained above. The obtained results are shown in Tables 1 and 2. In Tables 1 and 2, the composition of the insulating resin composition used for each prepreg and the content of the phenoxy resin in the insulating resin composition are shown together. Here, the content rate of phenoxy resin is the mass% of phenoxy resin with respect to the total mass of the solid content (amount remove | excluding the solvent in a component) of the polyamidoimide resin contained in an insulating resin composition, an epoxy resin, and a phenoxy resin. is there.

(1) Copper foil peeling strength (copper foil adhesive strength)
About a double-sided copper foil tension laminated board, it cut out to width 5mm x length 10cm, the peeling test of the 90 degree direction of copper foil was done, and the strength at that time was made into copper foil peeling strength (copper foil adhesive strength).

(2) Solder heat resistance The double-sided copper foil-clad laminate is floated in a solder bath heated to 288 ° C, the state of the laminate after 300 seconds is visually observed, and solder is soldered based on the degree of abnormality such as blistering. The heat resistance was evaluated. As for the result, “○” indicates that no abnormality such as blistering was observed, and the content of the abnormality was indicated when an abnormality was observed.

(3) Moisture absorption heat resistance Solder heated to 260 ° C after treating a sample from which copper on one side of a double-sided copper foil-clad laminate was removed by etching with a saturated PCT device at 121 ° C and 2 atmospheres for 2 hours A treatment of immersing in a bath for 20 seconds was performed. The state of the sample after this treatment was visually observed, and the moisture absorption heat resistance was evaluated based on the degree of abnormality such as blistering. As for the result, “○” indicates that no abnormality such as blistering was observed, and the content of the abnormality was indicated when an abnormality was observed.

(4) Bending test Copper of the double-sided copper foil-clad laminate was removed by etching, and this was used as a test substrate. The test substrate was bent 180 degrees with a pin gauge (0.10 mmφ or 0.38 mmφ) sandwiched between the bent portions of the test substrate, and the finger was moved along the bent portion while pressing firmly with the finger, and then the test substrate was returned to its original position. . The test substrate after this operation was observed, and it was confirmed whether or not cracks or breaks had occurred in the bent portion, and the bendability was evaluated. 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".

(5) Dust generation Ten prepregs were cut into 1 cm wide and 25 cm long by a cutter (manufactured by Olfa), and the presence or absence of generation of dust (dust) derived from the resin composition was confirmed. .

From Table 1 and Table 2, the prepregs of Reference Examples 1 and 2 and Examples 3 to 15 are free from dust, and the solder heat resistance and moisture absorption heat resistance of the double-sided copper foil-clad laminate laminated with copper foil are as follows. It was good. Further, no blistering or the like was observed, and the bending resistance was good. In particular, no cracks were observed even when bending with a pin gauge of 0.10 mmφ.

  On the other hand, in Comparative Examples 1 and 2 that did not contain a phenoxy resin, the solder heat resistance and moisture absorption heat resistance were good, but cracks occurred in the bent portion of the test substrate in a bending test performed with a 0.10 mmφ pin gauge.

  DESCRIPTION OF SYMBOLS 10 ... Metal foil, 30 ... Board | substrate, 100 ... Pre-preg, 200 ... Metal foil tension laminated board.

Claims (6)

(A) containing a polyamideimide resin having a structure represented by the following general formula (2), (B) an epoxy resin and (C) a phenoxy resin ,
The (C) phenoxy resin is a bisphenol A type phenoxy resin or a copolymer type phenoxy resin of bisphenol A and bisphenol F,
The content ratio of the (C) phenoxy resin is 5 to 30% by mass with respect to the total mass of the solid content of the (A) polyamideimide resin, the (B) epoxy resin, and the (C) phenoxy resin. Resin composition.
A prepreg having a fiber substrate and an insulating resin impregnated in the fiber substrate,
A prepreg in which the insulating resin is formed using the insulating resin composition according to claim 1 . The prepreg according to claim 2 , wherein the fiber base has a thickness of 5 to 50 μm. An insulating layer comprising a cured product of the prepreg according to claim 2 or 3 ,
A metal foil provided on at least one side of the insulating layer;
A metal foil clad laminate. A printed wiring board obtained by processing the metal foil in the metal foil-clad laminate according to claim 4 to form a wiring. A multilayer wiring board comprising at least a printed wiring board according to claim 5, an adhesive layer formed on the wiring of the printed wiring board, and a wiring different from the wiring formed on the adhesive layer.