JP2005325162A - Prepreg, metal foil-clad laminated plate and printed circuit board obtained using these - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printed circuit board which is excellent in dimensional stability and heat resistance and can be folded to be highly densely contained in a housing of an electronic apparatus, and a prepreg and a metal foil-clad laminated plate for obtaining the printed circuit board. <P>SOLUTION: The prepreg is obtained by impregnating a fibrous base material with a resin composition comprising a compound having a structure represented by general formula (1) (wherein R<SB>1</SB>is an optionally substituted divalent aliphatic group consisting of C, O and H; and R<SB>2</SB>, R<SB>3</SB>, R<SB>4</SB>and R<SB>5</SB>are each a carbon atom as a part of a cyclic structure or a linear structure constituting the resin). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a prepreg, a metal foil-clad laminate using the prepreg, and a printed circuit board.

  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 the printed circuit is formed by a subtractive method, a metal foil-clad laminate is used. This metal foil-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.

  On the other hand, with the spread of information terminal devices such as personal computers and mobile phones, printed circuit 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.

  In addition, lead-free solder has progressed from the viewpoint of environmental issues, and the melting temperature of solder has increased. As a result, higher heat resistance is required for the substrate, and the demand for halogen-free materials has increased, making it difficult to use bromine. The use of flame retardants has become difficult. In addition, 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 is then chip mounted again. In addition, heat treatment will be added. Along with this, a substrate requiring repairability is also required to have a cyclic thermal shock resistance at a high temperature, and in a conventional insulating resin system, peeling may occur between the fiber base material and the resin.

A prepreg in which a fiber base material is impregnated with a resin composition containing polyamideimide as an essential component has been proposed in order to have excellent thermal shock resistance, reflow resistance, and crack resistance and to improve fine wiring formation (for example, Patent Document 1). See). 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.
JP 2003-55486 A

  The present invention eliminates the above-mentioned problems of the prior art, impregnates a thin fiber base material with a highly flexible resin excellent in adhesion to metal foil and fiber base material and excellent in heat resistance. Provided are a printed circuit board that is excellent in stability and heat resistance, can be bent when used as a printed circuit board, and can be stored in a high density in a casing of an electronic device, and a prepreg and a metal foil-clad laminate that provide the printed circuit board. Is.

The present invention relates to the following.
(1) A prepreg obtained by impregnating a fiber base material with a resin composition containing a compound having the structure of the general formula (1).

（Ｒ_１は置換基を有していてもよいＣ、Ｏ、Ｈからなる２価の脂肪族基、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５はそれぞれ、樹脂を構成する環状構造もしくは鎖状構造の一部の炭素原子を示す。）
（２）一般式（１）の構造を有する化合物が、ポリアミドイミド樹脂である項（１）に記載のプリプレグ。
（３）樹脂組成物が熱硬化性樹脂を含む樹脂組成物である項（１）又は（２）に記載のプリプレグ。
（４）繊維基材が厚さ５〜１００μｍのガラスクロスである項（１）乃至（３）いずれかに記載のプリプレグ。
（５）一般式（１）の構造を有する化合物が、一般式（２）で表されるジアミン、（１ａ）または（１ｂ）で表される芳香族環を２個以上有するジアミン及びシロキサンジアミンの混合物と無水トリメリット酸を反応させて得られるジイミドジカルボン酸を含む混合物とジイソシアネート化合物を反応させて得られるポリアミドイミド樹脂である項（１）乃至（４）いずれかに記載のプリプレグ。

(R ₁ is an optionally substituted divalent aliphatic group composed of C, O, and H, and R ₂ , R ₃ , R ₄ , and R ₅ are each a cyclic structure or a chain that constitutes the resin. (Indicates some carbon atoms in the structure.)
(2) The prepreg according to item (1), wherein the compound having the structure of the general formula (1) is a polyamideimide resin.
(3) The prepreg according to item (1) or (2), wherein the resin composition is a resin composition containing a thermosetting resin.
(4) The prepreg according to any one of Items (1) to (3), wherein the fiber base material is a glass cloth having a thickness of 5 to 100 μm.
(5) The compound having the structure of the general formula (1) is a diamine represented by the general formula (2), a diamine having two or more aromatic rings represented by (1a) or (1b), and a siloxane diamine. The prepreg according to any one of Items (1) to (4), which is a polyamideimide resin obtained by reacting a mixture containing diimidedicarboxylic acid obtained by reacting the mixture with trimellitic anhydride and a diisocyanate compound.

（Ｒ_１は置換基を有していてもよいＣ、Ｏ、Ｈからなる２価の脂肪族基を示す）

(R ₁ represents a divalent aliphatic group consisting of C, O and H which may have a substituent)

（式中、Ｘは炭素数１〜３の脂肪族炭化水素基、炭素数１〜３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（２ａ）又は（２ｂ）で表される２価の基、Ｙは炭素数１〜３の脂肪族炭化水素基、炭素数１〜３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、カルボニル基を示し、Ｒ¹、Ｒ²、Ｒ³はそれぞれ独立もしくは同一で水素原子、水酸基、メトキシ基、メチル基、ハロゲン化メチル基を示す。

(Wherein X is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, a carbonyl group, a single bond, or the following general formula (2a) Or a divalent group represented by (2b), Y is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, or a carbonyl group. R ¹ , R ² and R ³ are independent or the same and each represents a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group.

但し、Ｚは、炭素数１〜３の脂肪族炭化水素基、炭素数１〜３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である。）
（６）熱硬化性樹脂が、２個以上のグリシジル基を持つエポキシ樹脂であり、かつ樹脂組成物が前記エポキシ樹脂の硬化促進剤または硬化剤を含有する樹脂組成物である項（３）乃至（５）のいずれかに記載のプリプレグ。
（７）項（１）乃至（６）いずれかに記載のプリプレグを所定枚数重ね、その片側または両側に金属箔を配置し、加熱加圧してなる金属箔張積層板。
（８）項（７）に記載の金属箔張積層板を回路加工して得られる印刷回路板。

However, Z is a C1-C3 aliphatic hydrocarbon group, a C1-C3 halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, or a single bond. )
(6) Items (3) to (3), wherein the thermosetting resin is an epoxy resin having two or more glycidyl groups, and the resin composition is a resin composition containing a curing accelerator or a curing agent for the epoxy resin. The prepreg according to any one of (5).
(7) A metal foil-clad laminate obtained by stacking a predetermined number of the prepregs according to any one of items (1) to (6), placing a metal foil on one side or both sides, and heating and pressing.
(8) A printed circuit board obtained by circuit-processing the metal foil-clad laminate according to item (7).

  The metal foil-clad laminate and printed circuit board obtained by the prepreg in the present invention can be arbitrarily bent and are excellent in dimensional stability, heat resistance and PCT resistance.

  The prepreg of the present invention is a prepreg formed by impregnating a fiber base material with a resin composition containing a compound having the structure of the general formula (1). Examples of the compound having the structure of the general formula (1) include polyamideimide resin, polyimide resin, bismaleimide resin, bismaleimide-triazine resin, and the like, but polyamideimide resin is preferable. In particular, a mixture containing diimide dicarboxylic acid obtained by reacting a diamine represented by the general formula (2), a diamine having two or more aromatic rings (aromatic diamine) and a siloxane diamine with trimellitic anhydride; Polyamideimide resins obtained by reacting aromatic diisocyanates are more preferred.

  The synthesis of the polyamideimide resin having the structure of the general formula (1) is the sum of the diamine a represented by the general formula (2) and a diamine having two or more aromatic rings (aromatic diamine) and siloxane diamine. The mixing ratio with mol b is preferably a / b = 0.1 / 99.9 to 99.9 / 0.1 (molar ratio), and a / b = 5/95 to 40/60. More preferably, a / b = 10/90 to 30/70 is even more preferable.

  Examples of the diamine (aliphatic diamine) represented by the general formula (2) include linear aliphatic diamines such as hexamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine, and octadecamethylene diamine, and terminal aminated polypropylene. And glycols. Moreover, it is preferable that the diamine (aliphatic diamine) shown by General formula (2) contains an ether group from the viewpoint of coexistence of a low elasticity modulus and high Tg, and terminal aminated polypropylene glycol is preferable. Examples of the terminal aminated polypropylene glycol include Jeffamine D-230, D-400, D-2000, and D-4000 having different molecular weights (trade names of Sun Techno Chemical Co., Ltd.).

  Examples of the aromatic diamine include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone, and bis [4- (4-amino). Phenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4-amino) Phenoxy) 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 (trifluoro) Til) 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) diphenyl sulfone, (4,4'-diamino) benzophenone, (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether and the like can be exemplified.

  Examples of the siloxane diamine used in the present invention include the following general formulas (3) to (6).

  In addition, as siloxane diamine represented by the said General formula (3), X-22-161AS (amine equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1500), (The above is a trade name manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-853 (amine equivalent 650), BY16-853B (amine equivalent 2200), (above, product name manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like. Examples of the siloxane diamine represented by the general formula (6) include X-22-9409 (amine equivalent 700), X-22-1660B-3 (amine equivalent 2200) (above, trade name manufactured by Shin-Etsu Chemical Co., Ltd.). Etc. can be exemplified.

  As the diisocyanate used in the method for producing a polyamideimide resin, which is a compound having the structure of the general formula (1) of the present invention, a compound represented by the following general formula (7) can be used.

In the formula, D is a divalent organic group having at least one aromatic ring or a divalent aliphatic hydrocarbon group, and is a group represented by —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 represented by the general formula (7), an aliphatic diisocyanate or an aromatic diisocyanate can be used, but an aromatic diisocyanate is preferably used, and both can be used in combination.

  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 resulting polyamideimide can be improved.

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

  When using an aromatic diisocyanate and an aliphatic diisocyanate in combination, it is preferable to add the aliphatic diisocyanate in an amount of about 5 to 10 mol% with respect to the aromatic diisocyanate. Can be made.

  Examples of the thermosetting resin used in the present invention include an epoxy resin, a polyimide resin, an unsaturated polyester resin, a polyurethane resin, a bismaleimide resin, a triazine-bismaleimide resin, and a phenol resin, and the structure of the general formula (1). It is preferable to use 1 to 200 parts by weight of a thermosetting resin with respect to 100 parts by weight of the polyamide-imide resin which is a compound having the above. In the present invention, using an epoxy resin as a thermosetting resin can be cured at a temperature of 180 ° C. or less, and reacts with an amide group of a polyamide-imide resin to improve thermal, mechanical, and electrical characteristics. Therefore, an epoxy resin having two or more glycidyl groups and a curing agent thereof, an epoxy resin having two or more glycidyl groups and its curing accelerator, or an epoxy resin having two or more glycidyl groups and a curing agent, curing acceleration It is more preferable to use an agent. Further, the more glycidyl groups, the better. The blending amount varies depending on the number of glycidyl groups, and the blending amount may be smaller as the glycidyl group is larger.

  In the present invention, it is preferable to use 1 to 200 parts by weight of a thermosetting resin with respect to 100 parts by weight of the polyamideimide resin having the structure of the general formula (1). However, if it is less than 1 part by weight, the solvent resistance is inferior. Exceeding parts by weight is not preferable because Tg is lowered by the unreacted thermosetting resin, heat resistance becomes insufficient, and flexibility is lowered. Therefore, 3-100 weight part of thermosetting resins are more preferable with respect to 100 weight part of polyamideimide resin, and 10-60 weight part is especially more preferable.

  Epoxy resins include polyglycidyl ethers and phthalic acids obtained by reacting polychlorophenols such as bisphenol A, novolac phenol resins, orthocresol novolac phenol resins or polyhydric alcohols such as 1,4-butanediol with epichlorohydrin. And polyglycidyl ester obtained by reacting a polybasic acid such as hexahydrophthalic acid with epichlorohydrin, an N-glycidyl derivative of a compound having an amine, an amide or a heterocyclic nitrogen base, an alicyclic epoxy resin, and the like.

  The curing agent and curing accelerator of the epoxy resin are not limited as long as they react with the epoxy resin or accelerate curing. For example, amines, imidazoles, polyfunctional phenols, acid anhydrides, etc. Can be used. As amines, dicyandiamide, diaminodiphenylmethane, guanylurea, etc. can be used. As polyfunctional phenols, hydroquinone, resorcinol, bisphenol A and their halogen compounds, and novolak-type phenol resins that are condensates with formaldehyde, resole 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.

  In the case of amines, the necessary amounts of these curing agents or curing accelerators are preferably such that the equivalent of the active hydrogen of the amine is approximately equal to the epoxy equivalent of the epoxy resin. In the case of imidazole, which is a curing accelerator, it is not simply an equivalent ratio with active hydrogen, but is empirically required to be 0.001 to 10 parts by weight per 100 parts by weight of the epoxy resin. In the case of polyfunctional phenols and acid anhydrides, 0.6 to 1.2 equivalents of phenolic hydroxyl groups and carboxyl groups are required for 1 equivalent of epoxy resin. If the amount of these curing agents or accelerators is small, uncured epoxy resin remains, and Tg (glass transition temperature) is low. If too large, unreacted curing agent and curing accelerator remain, and insulating properties are maintained. Decreases. The epoxy equivalent of the epoxy resin is preferably taken into account because it can also react with the amide group of the polyamideimide resin.

  In the present invention, a prepreg can be prepared by impregnating and drying a varnish obtained by mixing, dissolving and dispersing a resin composition for prepreg in an organic solvent. Such an organic solvent is not limited as long as solubility is obtained, and examples thereof include dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, γ-butyrolactone, sulfolane, and cyclohexanone. It is done.

  The resin composition for obtaining the prepreg is preferably a resin composition containing 100 parts by weight of a polyamideimide resin having a structure of the general formula (1) and 1 to 200 parts by weight of a thermosetting resin, whereby a varnish solvent The volatilization rate of the resin is high, and the residual solvent content can be reduced to 5% by weight or less even at a low temperature of 150 ° C. or less, which does not promote the curing reaction of the thermosetting resin, and has good adhesion to the fiber substrate and copper foil. A metal foil-clad laminate can be obtained.

  In the present invention, a fiber base material is impregnated with a varnish of a resin composition and dried to produce a prepreg. Although it will not restrict | limit especially if it is used when manufacturing a metal foil clad laminated board and a multilayer printed circuit board as a fiber base material, Usually fiber base materials, such as a woven fabric and a nonwoven fabric, are used. Examples of the fiber base material include glass, alumina, asbestos, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, and other inorganic fibers, aramid, polyetheretherketone, polyetherimide, polyether There are organic fibers such as sulfone, carbon, cellulose and the like and mixed papers thereof, and glass fiber woven fabrics are particularly preferably used. As a fiber base material used for a prepreg, it is preferable that thickness is 5-100 micrometers, and 5-50 micrometers is more preferable. A glass cloth having a thickness of 5 to 100 μm is particularly preferably used. By using a glass cloth having a thickness of 5 to 100 μm, it is possible to obtain a printed circuit board that can be bent arbitrarily, and it is possible to reduce dimensional changes associated with temperature, moisture absorption, and the like in the manufacturing process.

  The production conditions of the prepreg are not particularly limited, but it is preferable that the solvent used for the varnish of the resin composition is volatilized by 80% by weight or more. For this reason, there are no restrictions on the production method, drying conditions, etc., the temperature during drying is 80 ° C. to 180 ° C., and the time is not particularly limited in consideration of the gelling time of the varnish. The solid content of the varnish resin is preferably 30 to 80% by weight based on the total amount of the solid content and the fiber base material.

  The manufacturing method of an insulating board, a laminated board, or a metal foil tension laminated board is as follows. In the present invention, a metal foil is laminated on one or both sides of the prepreg or a laminate obtained by laminating a plurality of the prepregs, if necessary, and usually at a temperature in the range of 150 to 280 ° C, preferably 180 ° C to 250 ° C, usually 0. An insulating plate, a laminate or a metal foil-clad laminate can be produced by heat and pressure molding at a pressure in the range of 5 to 20 MPa, preferably 1 to 8 MPa. By using a metal foil as a metal foil-clad laminate, circuit processing can be applied to this to obtain a printed circuit board.

  As the metal foil used in the present invention, a copper foil or an aluminum foil is generally used. A metal foil of 5 to 200 μm which is usually used for a laminate can be used, but a copper foil is preferable. 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 be used.

Examples are described below, but the present invention is not limited to these examples.
(Synthesis Example 1)
BAPP (2,2-bis [4-) is a diamine having two or more aromatic rings in a 1-liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer. (4-aminophenoxy) phenyl] propane) 61.58 g (0.15 mol), Jeffamine D2000 (trade name, amine equivalent 1000, manufactured by Sun Techno Chemical Co.) as a diamine represented by the general formula (2) 100.0 g (0 0.05 mol) and TMA (trimellitic anhydride) 80.68 g (0.42 mol) as an aprotic polar solvent were charged with 562 g of NMP (N-methyl-2-pyrrolidone) and stirred at 80 ° C. for 30 minutes. Then, 150 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, the solution was returned to room temperature (25 ° C.), 60.1 g (0.24 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin having the structure of the general formula (1) was obtained.

(Synthesis Example 2)
BAPP (2,2-bis [4-) is a diamine having two or more aromatic rings in a 1-liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer. 49.26 g (0.12 mol) of (4-aminophenoxy) phenyl] propane), 32.0 g (0 of Jeffamine D400 (trade name, amine equivalent 200 manufactured by Sun Techno Chemical Co., Ltd.) as the diamine represented by the general formula (2) 0.08 mol) and TMA (trimellitic anhydride) 80.68 g (0.42 mol) as an aprotic polar solvent were charged with 472 g of NMP (N-methyl-2-pyrrolidone) and stirred at 80 ° C. for 30 minutes. Then, 150 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, the solution was returned to room temperature (25 ° C.), 60.1 g (0.24 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin having the structure of the general formula (1) was obtained.

(Synthesis Example 3)
29.76 g of DDS (diaminodiphenylsulfone) as a diamine having two or more aromatic rings in a 1 liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer and a stirrer 0.12 mol), reactive silicone oil KF-8010 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 450) as siloxane diamine, 36.0 g (0.04 mol), Jeffer as diamine represented by general formula (2) NMP (N-methyl) using 80.0 g (0.04 mol) of Min D2000 (trade name, amine equivalent 1000, manufactured by Sun Techno Chemical Co., Ltd.) and 80.7 g (0.42 mol) of TMA (trimellitic anhydride) as an aprotic polar solvent -2-pyrrolidone) 609 g was charged and stirred at 80 ° C. for 30 minutes. Then, 150 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, the solution was returned to room temperature (25 ° C.), 60.1 g (0.24 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin having the structure of the general formula (1) was obtained.

(Synthesis Example 4)
BAPP (2,2-bis [4-) is a diamine having two or more aromatic rings in a 1-liter separable flask equipped with a 25 ml water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer. (4-Aminophenoxy) phenyl] propane) 49.26 g (0.12 mol), reactive silicone oil KF-8010 (trade name, amine equivalent 450, manufactured by Shin-Etsu Chemical Co., Ltd.) as a siloxane diamine 27.0 g (0.03 mol) ), As a diamine represented by the general formula (2), Jeffamine D2000 (trade name, amine equivalent 1000, manufactured by Sun Techno Chemical Co., Ltd.) 100.0 g (0.05 mol), TMA (trimellitic anhydride) 80.68 g (0. 42 mol) is used as an aprotic polar solvent and 740 g of NMP (N-methyl-2-pyrrolidone) is prepared. Look, and the mixture was stirred at 80 ℃ 30 minutes. Then, 150 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and the temperature was raised and refluxed at about 160 ° C. for 2 hours. While confirming that approximately 7.2 ml or more of water has accumulated in the moisture determination receiver and that no distillation of water has been observed, while removing the distillate accumulated in the moisture determination receiver, The temperature was raised to 0 ° C. to remove toluene. Thereafter, the solution was returned to room temperature (25 ° C.), 60.07 g (0.24 mol) of MDI (4,4′-diphenylmethane diisocyanate) was added as an aromatic diisocyanate, and reacted at 190 ° C. for 2 hours. After completion of the reaction, an NMP solution of polyamideimide resin having the structure of the general formula (1) was obtained.

(Example 1)
228.6 g of NMP solution of polyamideimide resin of Synthesis Example 1 (resin solid content 35 wt%) and NC3000H (epoxy resin, Nippon Kayaku Co., Ltd. trade name) 40.0 g (resin solid content 50 wt%) as thermosetting resin % Dimethylacetamide solution) and 0.2 g of 2-ethyl-4-methylimidazole, and the mixture was stirred for about 1 hour until the resin became homogeneous, and then allowed to stand at room temperature (25 ° C.) for 24 hours for defoaming. Thus, a resin composition varnish was obtained.

(Example 2)
250.0 g of NMP solution of polyamideimide resin of Synthesis Example 2 (resin solid content 32 wt%) and NC 3000H (epoxy resin, Nippon Kayaku Co., Ltd. trade name) 40.0 g (resin solid content 50 wt%) as thermosetting resin % Dimethylacetamide solution) and 0.2 g of 2-ethyl-4-methylimidazole, and the mixture was stirred for about 1 hour until the resin became homogeneous, and then allowed to stand at room temperature (25 ° C.) for 24 hours for defoaming. Thus, a resin composition varnish was obtained.

(Example 3)
250.0 g of NMP solution of polyamideimide resin of Synthesis Example 3 (resin solid content 32 wt%) and NC 3000H (epoxy resin, Nippon Kayaku Co., Ltd. trade name) 40.0 g (resin solid content 50 wt%) as thermosetting resin % Dimethylacetamide solution) and 0.2 g of 2-ethyl-4-methylimidazole, and the mixture was stirred for about 1 hour until the resin became homogeneous, and then allowed to stand at room temperature (25 ° C.) for 24 hours for defoaming. Thus, a resin composition varnish was obtained.

Example 4
266.7 g of NMP solution of polyamideimide resin of Synthesis Example 4 (resin solid content 30 wt%) and NC3000H (epoxy resin, trade name of Nippon Kayaku Co., Ltd.) as thermosetting resin 40.0 g (resin solid content 50 wt%) % Dimethylacetamide solution) and 0.2 g of 2-ethyl-4-methylimidazole, and the mixture was stirred for about 1 hour until the resin became homogeneous, and then allowed to stand at room temperature (25 ° C.) for 24 hours for defoaming. Thus, a resin composition varnish was obtained.

(Comparative Example 1)
Instead of the polyamide-imide resin of Synthesis Example 1, 285.7 g (resin solid content 28% by weight) of KS6000 (trade name, manufactured by Hitachi Chemical Co., Ltd.) is used as the polyamide-imide resin not including the structure of the general formula (1). A resin composition varnish was prepared in the same manner as in Example 1 except that.

(Comparative Example 2)
Instead of the polyamideimide resin of Synthesis Example 1, 285.7 g (resin solid content 28% by weight) of KS6000 (trade name, manufactured by Hitachi Chemical Co., Ltd.) is used as a polyamideimide not including the structure of the general formula (1). And the resin composition varnish was produced like Example 1 except having used YDE205 (aliphatic epoxy resin, Japan Epoxy Resin Co., Ltd. brand name) instead of NC3000H as a thermosetting resin.

(Preparation of prepreg and metal foil-clad laminate)
The resin composition varnishes produced in Examples 1 to 4 and Comparative Examples 1 and 2 were impregnated into a glass cloth having a thickness of 0.028 mm (trade name 1037 manufactured by Asahi Schwer, Inc.), then heated at 150 ° C. for 15 minutes and dried. Thus, a prepreg having a resin content of 70% by weight was obtained.

  An electrolytic copper foil (trade name: F2-WS-12, manufactured by Furukawa Electric Co., Ltd.) having a thickness of 12 μm is stacked on both sides of this prepreg so that the adhesive surface is aligned with the prepreg, and 230 ° C., 90 minutes, 4.0 MPa pressing conditions A double-sided copper-clad laminate was prepared. The evaluation shown below was performed using the produced double-sided copper-clad laminate.

(Evaluation item)
(1) The copper foil peeling strength of the obtained double-sided copper-clad laminate was measured.
(2) As solder heat resistance, it was immersed in a solder bath at 260 ° C., 288 ° C. and 300 ° C., and the time until occurrence of abnormalities such as blistering and peeling was measured.
(3) The double-sided copper-clad laminate from which the copper foil was removed by etching was bent and evaluated for flexibility. ○: No break, ×: Break
(4) As moisture resistance, the copper foil on one side is removed by etching, subjected to moisture absorption treatment at 121 ° C. saturation condition for 1 hour, and then immersed in a solder bath at 260 ° C. for 20 seconds to check for abnormalities such as swelling and peeling. Observed. ○: No abnormality, ×: Abnormal. The results are shown in Table 1.

  In combination with any prepreg of Examples 1 to 4, the copper foil peel strength was 1.1 to 1.2 kN / m. Moreover, as a result of immersing in a solder bath of 260 ° C., 288 ° C., and 300 ° C. and measuring the solder heat resistance, no abnormality such as blistering or peeling was observed at any temperature for 5 minutes or more. The double-sided copper-clad laminate from which the copper foil was removed by etching was rich in flexibility in Examples 1 to 4, and could be arbitrarily bent. As the moisture resistance, no abnormality such as swelling or peeling was observed.

On the other hand, the double-sided copper clad laminate of the comparative example was insufficient in flexibility. In Comparative Example 1, the base material was broken when bent, and in Comparative Example 2, the resin and the glass cloth were cracked. In terms of moisture resistance, in Comparative Examples 1 and 2, swelling occurred between the copper foil and the base material.

Claims (8)

A prepreg obtained by impregnating a fiber base material with a resin composition containing a compound having the structure of the general formula (1).

(R ₁ is an optionally substituted divalent aliphatic group composed of C, O, and H, and R ₂ , R ₃ , R ₄ , and R ₅ are each a cyclic structure or a chain that constitutes the resin. (Indicates some carbon atoms in the structure.)   The prepreg according to claim 1, wherein the compound having the structure of the general formula (1) is a polyamideimide resin.   The prepreg according to claim 1 or 2, wherein the resin composition is a resin composition containing a thermosetting resin.   The prepreg according to any one of claims 1 to 3, wherein the fiber base material is a glass cloth having a thickness of 5 to 100 µm. The compound having the structure of the general formula (1) is a diamine represented by the general formula (2), a mixture of a diamine having two or more aromatic rings represented by (1a) or (1b) and a siloxane diamine and anhydrous The prepreg according to any one of claims 1 to 4, which is a polyamide-imide resin obtained by reacting a mixture containing diimide dicarboxylic acid obtained by reacting trimellitic acid with a diisocyanate compound.

(R ₁ represents a divalent aliphatic group consisting of C, O and H which may have a substituent)

(Wherein X is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, a carbonyl group, a single bond, or the following general formula (2a) Or a divalent group represented by (2b), Y is an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, an ether group, or a carbonyl group. R ¹ , R ² and R ³ are independent or the same and each represents a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group.

However, Z is a C1-C3 aliphatic hydrocarbon group, a C1-C3 halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, or a single bond. )   6. The thermosetting resin is an epoxy resin having two or more glycidyl groups, and the resin composition is a resin composition containing a curing accelerator or a curing agent for the epoxy resin. The prepreg described in 1.   A metal foil-clad laminate obtained by stacking a predetermined number of the prepregs according to any one of claims 1 to 6, arranging a metal foil on one side or both sides thereof, and heating and pressing. A printed circuit board obtained by forming a circuit on the metal foil-clad laminate according to claim 7.