JP2006124670A - Prepreg and metal foil-clad laminate and printed circuit board using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a prepreg having sufficiently excellent circuit filling property and heat resistance and giving a printed circuit board which can be bent and highly densely stored in a chasis of an electronic equipment. <P>SOLUTION: The prepreg comprises a fibrous base material and resin composition impregnated in the above material. The resin composition contains a polyamideimide resin and a naphthalene diglycidyl compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

  A laminated board for a printed wiring board is obtained by stacking a predetermined number of prepregs having an electrically insulating resin composition as a matrix resin, and integrating them by heating and pressing. When the printed wiring board is formed by a subtractive method, a metal-clad laminate is used. This metal-clad laminate is manufactured by stacking a metal foil such as a copper foil on the surface (one side or both sides) of the prepreg and heating and pressing. As the electrically insulating resin, a thermosetting resin such as a phenol resin, an epoxy resin, a polyimide resin, a bismaleimide-triazine resin or the like is generally used. In addition, a thermoplastic resin such as a fluororesin or a polyphenylene ether resin may be used as the electrically insulating resin.

  On the other hand, with the widespread use of information terminal devices such as personal computers and mobile phones, printed circuit boards mounted on them are becoming smaller and higher in mounting density. In order to satisfy such a requirement, a multilayer printed circuit board obtained through a process of further sequentially stacking a prepreg and a metal foil on a circuit of an inner layer substrate having circuits on both sides is used. In addition, since the circuit formed on the inner layer substrate is also densified, it is necessary to have a high circuit filling property that allows the prepreg to fill the surface recesses of the inner layer substrate without any gaps. Further, 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. When a bare chip such as a BGA is directly mounted on a substrate, the connection between the chip and the substrate is generally performed by wire bonding using thermosonic bonding. At this time, since the substrate on which the bare chip is mounted is exposed to a high temperature of 150 ° C. or higher, the electrically insulating resin needs to have a certain degree of heat resistance.

  In addition, lead-free solder has been developed from the viewpoint of environmental problems, and the melting temperature of solder has been increased accordingly, so that higher heat resistance is required for substrates. At the same time, halogen-free requirements for substrate materials are increasing, making it difficult to use brominated flame retardants. In addition, there is a case where the capability of replacing a chip once mounted, so-called repairability, is also required. When exchanging the chip, first, the chip is removed from the substrate by applying the same level of heat as the chip is mounted, and then the chip is remounted by applying heat again. Accordingly, a substrate that requires repairability is also required to have thermal cycle thermal shock resistance at a high temperature. In the conventional insulating resin system, since the thermal shock resistance is low, peeling may occur between the fiber base material and the resin when the chip is replaced or after the chip is replaced.

  A prepreg impregnated with a resin composition containing polyamideimide as an essential component on a fiber base material has been proposed in order to improve thermal wire impact resistance, reflow resistance, and crack resistance, and to improve fine wiring formation (for example, Patent Documents). 1).

In recent years, with the demand for further downsizing and higher performance of electronic devices, printed circuit boards on which components are mounted are required to be housed in a limited space. In response to such demands, a method is adopted in which 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. Further, 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

  However, conventionally, a printed circuit board that is excellent in heat resistance and at the same time has a high circuit filling property and can be filled in a limited space at a high density, and a prepreg and a metal foil-clad laminate that can provide such a printed circuit board Has not yet been proposed.

  The present invention solves the above-mentioned problems of the prior art, is sufficiently excellent in circuit filling properties and heat resistance, can be bent when used as a printed circuit board, and can be stored in a high density in the casing of an electronic device, In addition, the present invention provides a prepreg and a metal foil-clad laminate that provide the printed circuit board.

  The present invention relates to the following.

  (1) A prepreg comprising a fiber substrate and a resin composition impregnated therein, wherein the resin composition contains a polyamideimide resin and a naphthalenediglycidyl compound.

  As a factor that the prepreg of the present invention can solve the above problems, when the resin composition is heated and cured, it is considered that the heat resistance is drastically improved by the interaction between the imide skeleton of the polyamideimide resin and the naphthalene glycidyl ether compound. . Moreover, since the amide skeleton of the polyamide-imide resin has flexibility and the naphthalene glycidyl ether compound does not reduce the flexibility, it is presumed that the flexibility is maintained in a high state. Furthermore, it is considered that the elasticity of the cured body of the resin composition becomes sufficient by arranging a planar naphthalene glycidyl ether compound between the molecules of the polyamideimide resin. However, the factors are not limited to these.

  Moreover, the prepreg of the present invention exhibits excellent moldability and high thermal shock resistance. The polyamide-imide resin shows high heat resistance compared to other thermoplastic resins but is inferior in moldability. When the prepreg of the present invention containing a naphthalene glycidyl ether compound is subjected to heat and pressure treatment, it is simply polyamide. The heat resistance is further increased and the moldability is improved as compared with the case of containing an imide resin. As a factor showing such excellent moldability, it is considered that the resin composition contained in the prepreg of the present invention has a higher degree of decrease in melt viscosity than that of the conventional one during heat treatment. Moreover, as a factor which shows high thermal shock resistance, it is estimated that the cured | curing material obtained by heat-processing the prepreg of this invention becomes small compared with the conventional molecular weight between the crosslinking points. However, the factors are not limited to these.

（式（１）中、Ｒ_１、Ｒ_２は２価のアルキル基、Ｒ_３、Ｒ_４、Ｒ_７、Ｒ_８は１価のアルキル基又は置換基を有する１価のアルキル基、Ｒ_５、Ｒ_６は１価の芳香族基又は置換基を有する１価の芳香族基を示し、ｍ、ｎはそれぞれ０から４０の整数で、１≦ｎ＋ｍ≦５０を満足する。）
で表される構造を有するポリアミドイミド樹脂を含むものである、項（１）に記載のプリプレグ。本発明のプリプレグは、このようなポリアミドイミド樹脂を含むことにより、繊維基材や金属箔との接着性が更に高くなり、また耐熱性が一層向上し、さらには、より柔軟になって容易に折り曲げ可能となる。 (2) The polyamideimide resin has the following general formula (1):

(In the formula (1), R ₁ and R ₂ are divalent alkyl groups, R ₃ , R ₄ , R ₇ and R ₈ are monovalent alkyl groups or monovalent alkyl groups having a substituent, R ₅ , R ₆ represents a monovalent aromatic group or a monovalent aromatic group having a substituent, and m and n are each an integer of 0 to 40 and satisfy 1 ≦ n + m ≦ 50.
The prepreg according to item (1), comprising a polyamideimide resin having a structure represented by: By including such a polyamide-imide resin, the prepreg of the present invention is further improved in adhesion to a fiber base material and metal foil, further improved in heat resistance, and more flexible and easily. Can be bent.

で表される構造を有するポリアミドイミド樹脂を含むものである、項（１）又は（２）に記載のプリプレグ。本発明のプリプレグは、このようなポリアミドイミド樹脂を含むことにより、吸湿時の耐熱性に一層優れたものとなる。 (3) The polyamideimide resin has the following general formula (2):

The prepreg according to Item (1) or (2), comprising a polyamideimide resin having a structure represented by: By including such a polyamideimide resin, the prepreg of the present invention is further excellent in heat resistance during moisture absorption.

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

(4) A diamine having a polyamideimide resin represented by the following general formula (3a), a diamine having two or more aromatic rings represented by the following general formula (1a) or the following general formula (1b), and a siloxane diamine In any one of Items (1) to (3), comprising a polyamideimide resin obtained by reacting a diisocyanate compound with a mixture containing diimidedicarboxylic acid obtained by reacting the mixture with trimellitic anhydride. The prepreg as described. By including such a polyamide-imide resin, the prepreg of the present invention is further improved in adhesion to a fiber base material and metal foil, further improved in heat resistance, and more flexible and easily. Can be bent.

(In the formulas (1a) and (1b), X 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, and an ether group. , A carbonyl group, a single bond, or a divalent group represented by the following general formula (2a) or the following general formula (2b), Y represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms. A halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group or a carbonyl group, and R ¹ , R ² and R ³ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group. However, Z shows a C1-C3 bivalent aliphatic hydrocarbon group, a C1-C3 bivalent halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, or a single bond. .)

  (5) The prepreg according to any one of Items (1) to (4), wherein the fiber base material is a glass cloth having a thickness of 5 to 100 μm. Such a prepreg can be easily and arbitrarily bent. Further, such a prepreg can further reduce a dimensional change caused by a temperature change or moisture absorption when a printed circuit board is formed using the prepreg.

  (6) A substrate obtained by curing a resin composition by heating a predetermined number of the prepregs according to any one of (1) to (5), and provided on one or both sides of the substrate. A metal foil-clad laminate comprising:

  (7) A printed circuit board obtained by forming a circuit on the metal foil-clad laminate according to item (6).

  According to the present invention, a printed circuit board that is sufficiently excellent in circuit filling property and heat resistance, can be bent when formed into a printed circuit board, and can be stored in a high density in a casing of an electronic device, and a prepreg that provides the printed circuit board In addition, a metal foil-clad laminate can be provided. Moreover, the metal foil tension laminated board and printed circuit board obtained by the prepreg in this invention can be bent arbitrarily, and are excellent also in a moldability, dimensional stability, and a thermal shock resistance.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  The prepreg of the present invention includes a fiber base material and a resin composition impregnated therein, and the resin composition includes a polyamideimide resin and a naphthalenediglycidyl compound. The naphthalene diglycidyl compound mainly reduces the melt viscosity of the resin composition when impregnated into the fiber base material, and improves the heat resistance of the cured resin composition.

  When heat or the like is applied to a resin composition containing a polyamideimide resin and a naphthalene diglycidyl compound, the amide group of the polyamideimide resin and the glycidyl group of the naphthalene glycidyl compound mainly react to form a cured product.

  The naphthalene diglycidyl compound used in the present invention is not particularly limited as long as it is a diglycidyl ether of naphthalene which may have a substituent. As the naphthalene diglycidyl compound, naphthalene diglycidyl ether, naphthalene diglycidyl ether having an appropriate substituent on the naphthalene ring, and a novolac type formed by connecting naphthalene rings of a plurality of naphthalene diglycidyl compounds with a methanediyl group Oligomers can also be used, and those subjected to molecular distillation to lower the viscosity can also be used. Examples of the naphthalenediglycidyl compound include 2,6-naphthalenediglycidyl ether, 1,4-naphthalenediglycidyl ether, 1,5-naphthalenediglycidyl ether, 1,8-naphthalenediglycidyl ether, 1,5 dimethyl- Examples include 2,6-naphthalenediglycidyl ether. Commercially available products include HP-4032, HP-4032D (trade name, manufactured by Dainippon Ink Co., Ltd.), ESN-165, ESN-195, ESN-355, ESN-375 (trade name, manufactured by Nippon Steel Chemical Co., Ltd.). ) Etc. can be used. These are used singly or in combination of two or more.

  When a fiber base material is impregnated with a resin composition containing these naphthalene diglycidyl compounds and a polyamideimide resin, the naphthalene diglycidyl compound can reduce the melt viscosity of the resin and has excellent moldability. A prepreg can be obtained. The resin composition used in the present invention may appropriately contain a resin or a compound other than the naphthalene diglycidyl compound and the polyamideimide resin, and may contain a thermosetting resin such as an epoxy resin. The amount of naphthalene diglycidyl compound to be blended in the resin composition is within a range where the total amount of glycidyl groups of the naphthalene diglycidyl compound is equal to or less than that of the amide group of the polyamideimide resin, that is, 1 mol of the amide group. The glycidyl group is preferably used in an amount of 1 mol or less, and is 1 to 95 mol% in terms of the total amount of glycidyl groups with respect to the total amount of amide groups, that is, 1 to 95 mol parts in total amount of glycidyl groups with respect to 100 mol parts of amide groups. More preferably, the total amount of glycidyl groups with respect to the total amount of amide groups is 20 to 80 mol%, that is, the total amount of glycidyl groups with respect to 100 mol parts of the total amount of amide groups is still more preferable. When the resin composition contains an epoxy resin, the amount of naphthalene diglycidyl compound to be blended in the resin composition is the total amount of the naphthalene diglycidyl compound and the glycidyl group of the epoxy resin with respect to the amide group of the polyamideimide resin. Is in the range of less than this mole, that is, the total amount of glycidyl groups of the naphthalene diglycidyl compound and the epoxy resin is preferably not more than 1 mol with respect to 1 mol of amide groups. The total amount is more preferably 1 to 95 mol%, further preferably 20 to 80 mol%. When the amount exceeds this mole, the number of amide groups that react with the glycidyl group decreases, the curability of the thermosetting resin decreases, and the heat resistance decreases due to the presence of the unreacted naphthalene diglycidyl compound. If it is less than 1 mol%, the effect of decreasing the melt viscosity becomes insufficient.

The polyamideimide resin used in the present invention preferably includes those having the structure of the general formula (1) or the general formula (2). In the general formula (1), R ₁ and R ₂ are preferably a divalent alkyl group having 1 to 10 carbon atoms. R ₃ , R ₄ , R ₇ and R ₈ are preferably a monovalent alkyl group having 1 to 3 carbon atoms or a monovalent alkyl group having a substituent. The monovalent aromatic group having R ₅ or R ₆ or the monovalent aromatic group having a substituent is preferably a phenyl group. These polyamideimide resins having the structure of the general formula (1) or the general formula (2) preferably have a diamine or an aromatic ring represented by the general formula (3a) in the presence of an aprotic solvent. It is preferably obtained by further reacting a diisocyanate with a mixture containing diimide dicarboxylic acid obtained by reacting a mixture of two or more diamines and siloxane diamines with trimellitic anhydride. These are used singly or in combination of two or more.

  Furthermore, the polyamide-imide resin is a mixture of a mole a of the diamine represented by the general formula (3a) and a total mole b of a diamine having two or more other aromatic rings (aromatic diamine) and a siloxane diamine. The ratio is preferably a / b = 0.1 / 99.9 to 99.9 / 0.1 (molar ratio), more preferably a / b = 10/90 to 50/50, It is even more preferable that b = 20/80 to 40/60. By setting a / b within this numerical range, a substrate superior in moisture absorption heat resistance can be obtained.

  Examples of the diamine represented by the general formula (3a) include commercially available wandamine (trade name, manufactured by Shin Nippon Chemical Co., Ltd.). As the aromatic diamine (a diamine having two or more aromatic rings), those represented by the general formula (1a) or (1b) are preferable. More specifically, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone, diaminodiphenylsulfone (DDS), 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, '-Bis (trifluoromethyl) biphenyl-4,4'-diamine, 2,6,2', 6'-tetramethyl-biphenyl-4,4'-diamine, 5,5'-dimethyl-2,2 ' -Sulfonyl-biphenyl-4,4'-diamine, 3,3'-dihydroxybiphenyl-4,4'-diamine, (4,4'-diamino) diphenyl ether, (4,4'-diamino) diphenylsulfone, (4 , 4′-diamino) benzophenone, (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether, etc. it can. These are used singly or in combination of two or more.

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

  As siloxane diamine, reactive silicon oil KF-8010 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 430), and siloxane diamine represented by the above general formula (3), X-22-161AS (amine) Equivalent 450), X-22-161A (amine equivalent 840), X-22-161B (amine equivalent 1500) (above, trade name manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-853 (amine equivalent 650), BY16-853B (Amine equivalent 2200) (above, trade name of Toray Dow Corning Silicone Co., Ltd.) and the like. As the siloxane diamine represented by the general formula (6), 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 illustrated. The above siloxane diamines are used alone or in combination of two or more.

（式（７）中、Ｘはメチレン基（メタンジイル基）、スルホニル基、エーテル基、カルボニル基又は単結合を示し、Ｒ^１及びＲ^２はそれぞれ水素原子、アルキル基、フェニル基又は置換フェニル基を示し、ｐは１〜５０の整数を示す。） In the synthesis of the polyamideimide resin used in the present invention, in addition to the diamine, a compound represented by the following general formula (7) can be used in combination as the aliphatic diamine.

(In formula (7), X represents a methylene group (methanediyl group), a sulfonyl group, an ether group, a carbonyl group or a single bond, and R ¹ and R ² represent a hydrogen atom, an alkyl group, a phenyl group or a substituted phenyl group, respectively. P represents an integer of 1 to 50.)

Specific examples of R ¹ and R ² are preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group or a substituted phenyl group, that is, a phenyl group having a substituent, and may be bonded to the phenyl group. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms and a halogen atom. In the aliphatic diamine, X in the general formula (7) is preferably an ether group from the viewpoint of achieving both low elastic modulus and high Tg. Examples of commercially available products of such aliphatic diamines include Jeffamine D-400 (amine equivalent 400), Jeffamine D-2000 (amine equivalent 1000), and the like (trade names manufactured by Sun Techno Chemical Co., Ltd.).

As the diisocyanate used for producing the polyamideimide resin of the present invention, aliphatic diisocyanate or aromatic diisocyanate can be used, and a compound represented by the following general formula (8) can be preferably used.

In General Formula (8), D is a divalent organic group having at least one aromatic ring or a divalent aliphatic hydrocarbon group, and —C ₆ H ₄ —CH ₂ —C ₆ H ₄ — It is preferably at least one group selected from the group consisting of a group represented by: 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 (8), an aliphatic diisocyanate or an aromatic diisocyanate can be used, but it is preferable to use an aromatic diisocyanate, and it is particularly preferable to use both in combination.

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

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

  When the aromatic diisocyanate and the aliphatic diisocyanate are used in combination, the aliphatic diisocyanate may be added in an amount of 5 to 10 mol% with respect to the aromatic diisocyanate, that is, about 5 to 10 mol parts with respect to 100 mol parts of the aromatic diisocyanate. preferable. Such combined use can further improve the heat resistance of the resulting polyamideimide resin.

  In synthesizing the polyamideimide resin, the amino group of the diamine reacts with the carboxyl group or anhydride carboxyl group of trimellitic anhydride, but it is preferable to react with the carboxyl group of anhydride. Such a reaction can be carried out in an aprotic polar solvent at 70 to 100 ° C.

  Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, cyclohexanone, and the like. However, it is preferable to use NMP.

  Such an aprotic polar solvent is preferably added in an amount such that the solid content is 10 to 70% by weight, more preferably 20 to 60% by weight, based on the total weight of the solution. When the solid content in the solution is less than 10% by weight, there is a tendency to be industrially disadvantageous because the amount of the solvent used is large, and when it exceeds 70% by weight, the solubility of trimellitic anhydride is lowered and sufficient. It may be difficult to perform a simple reaction.

  After said reaction, diimide dicarboxylic acid can be obtained by adding the aromatic hydrocarbon which can azeotrope with water, and making it react further at 150-200 degreeC, and producing dehydration ring closure reaction. Examples of aromatic hydrocarbons that can be azeotroped with water include toluene, benzene, xylene, and ethylbenzene, and it is preferable to use toluene. The aromatic hydrocarbon is preferably added in an amount of 10 to 50% by weight based on the weight of the aprotic polar solvent. When the amount of aromatic hydrocarbon added is less than 10% by weight based on the weight of the aprotic polar solvent, the water removal effect tends to be insufficient, and the amount of imide group-containing dicarboxylic acid produced is also reduced. Tend to. Moreover, when it exceeds 50 weight%, reaction temperature falls and there exists a tendency for the production amount of imide group containing dicarboxylic acid to reduce.

  Also, during the dehydration and ring closure reaction, aromatic hydrocarbons may be distilled simultaneously with water, so that the amount of aromatic hydrocarbons may be less than the above preferred range. It is preferable to keep the amount of aromatic hydrocarbons at a constant ratio, for example, by separating the aromatic hydrocarbons distilled into the vessel and then returning them to the reaction solution. In addition, after completion | finish of a spin-drying | dehydration ring-closing reaction, it is preferable to maintain the temperature at about 150-200 degreeC, and to remove the aromatic hydrocarbon which can azeotrope with water.

  The reaction between diimide dicarboxylic acid and diisocyanate is a reaction that occurs mainly between the carboxyl group of diimide dicarboxylic acid and the isocyanate group of diisocyanate. Such a reaction can be performed at a reaction temperature of 130 to 200 ° C. by adding diisocyanate to a solution containing diimide dicarboxylic acid obtained by the above reaction.

  The reaction between diimidedicarboxylic acid and diisocyanate is preferably performed at 70 to 180 ° C., more preferably 120 to 150 ° C. in the presence of a basic catalyst. When such a reaction is performed in the presence of a basic catalyst, the reaction can be performed at a lower temperature than when the reaction is performed in the absence of a basic catalyst. It is possible to obtain a high molecular weight polyamideimide resin.

  Examples of such basic catalysts include trialkylamines such as trimethylamine, triethylamine, tripropylamine, tri (2-ethylhexyl) amine, and trioctylamine. Among them, triethylamine is basic suitable for promoting the reaction. In addition, it is particularly preferable because removal after the reaction is easy.

  The weight average molecular weight of the polyamideimide resin obtained as described above is preferably 20000 to 300000, more preferably 30000 to 200000, and particularly preferably 40000 to 150,000. In addition, the weight average molecular weight here is measured by gel permeation chromatography and converted by a calibration curve prepared using standard polystyrene.

  As described above, in the resin composition used in the present invention, it is preferable to use a thermosetting resin in combination with a naphthalenediglycidyl compound or a polyamideimide resin. Examples of the thermosetting resin include epoxy resins, polyimide resins, unsaturated polyester resins, polyurethane resins, bismaleimide resins, triazine-bismaleimide resins, phenol resins, and the like. It is preferable to use 1 to 200 parts by weight of thermosetting resin with respect to 100 parts by weight of polyamideimide resin. When the thermosetting resin is less than 1 part by weight relative to 100 parts by weight of the polyamideimide resin, the solvent resistance is poor. On the other hand, if it exceeds 200 parts by weight, the Tg of the resin composition is lowered due to the influence of the unreacted thermosetting resin, the heat resistance becomes insufficient, and the flexibility is lowered, which is not preferable. 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. In this invention, the thermosetting resin which has the organic group which can react with the amide group in a polyamide-imide resin in a molecule | numerator is preferable, and the epoxy resin which has a glycidyl group is more preferable.

  Examples of the epoxy resin include polyglycidyl ethers and phthalates obtained by reacting a polyhydric phenol such as bisphenol A, a novolac type phenol resin or an orthocresol novolac type phenol resin or a polyhydric alcohol such as 1,4-butanediol with epichlorohydrin. N-glycidyl derivatives, alicyclic epoxy resins, salicylaldehydes of compounds having polyglycidyl esters, amines, amides or heterocyclic nitrogen bases obtained by reacting polybasic acids such as acid or hexahydrophthalic acid with epichlorohydrin Type epoxy resin.

  In the present invention, a naphthalene diglycidyl compound and another epoxy resin are used in combination, the glycidyl group of those substances reacts with the amide group of the polyamideimide resin, and the thermal, mechanical and electrical properties are improved. It is preferable because of improvement. Also, an epoxy resin having two or more glycidyl groups and its curing agent, an epoxy resin having two or more glycidyl groups and its curing accelerator, or an epoxy resin having two or more glycidyl groups, its curing agent, and its More preferably, a curing accelerator is used. Moreover, the more the number of glycidyl groups per molecule of the naphthalene diglycidyl compound and other epoxy resins, the better. Depending on the number of glycidyl groups per molecule, the blending amounts of the naphthalene diglycidyl compound and other epoxy resins differ, and the blending amount may be smaller as the number of glycidyl groups per molecule is larger.

  The curing agent and curing accelerator of the epoxy resin are not limited as long as they react with the epoxy resin or accelerate the curing. For example, amines, imidazoles, polyfunctional phenols, acid anhydrides, etc. Can be mentioned. As the amines, dicyandiamide, diaminodiphenylmethane, guanylurea and the like can be used. As the polyfunctional phenols, hydroquinone, resorcinol, bisphenol A and their halogen compounds, novolak type phenol resins and resol type phenol resins which are condensates of phenol and formaldehyde can be used. As the acid anhydrides, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid and the like can be used. For imidazoles, alkyl group-substituted imidazoles, benzimidazoles, and the like can be used as curing accelerators. These are used singly or in combination of two or more.

  When these curing agents or curing accelerators are used, the required amount is preferably an amount of amines such that the equivalent of the active hydrogen of the amine is substantially equal to the epoxy equivalent of the epoxy resin. In the case of imidazoles which are curing accelerators, it is preferably not 0.001 to 10 parts by weight based on 100 parts by weight of the epoxy resin, based on experience, without simply having an equivalent ratio with active hydrogen. In the case of polyfunctional phenols and acid anhydrides, the phenolic hydroxyl group or carboxyl group is preferably 0.6 to 1.2 equivalents per 1 equivalent of epoxy group in the epoxy resin. If the amount of these curing agents or curing accelerators is small, uncured epoxy resin remains, and Tg (glass transition temperature) becomes low. If too large, unreacted curing agents and curing accelerators remain, and insulating properties are maintained. Decreases. The epoxy group of the epoxy resin can also react with the amide group of the polyamideimide resin. Therefore, the blending amount of the curing agent or curing accelerator of the epoxy resin is preferably adjusted in consideration of that point.

  Moreover, it is preferable that the resin composition of this invention contains an addition type flame retardant for the purpose of an improvement of a flame retardance. The additive-type flame retardant that can be used in the present invention is preferably a filler containing phosphorus. As the phosphorus-containing filler, OP930 (trade name, manufactured by Clariant, phosphorus content 23.5% by weight), HCA-HQ ( Sanko Co., Ltd. trade name, phosphorus content 9.6% by weight), melamine polyphosphate PMP-100 (phosphorus content 13.8% by weight), PMP-200 (phosphorus content 9.3% by weight), PMP- 300 (phosphorus content: 9.8% by weight) (trade name, manufactured by Nissan Chemical Co., Ltd.) and the like.

  FIG. 1 is a perspective view showing an embodiment of a prepreg according to the present invention. A prepreg 100 shown in FIG. 1 is a sheet-like prepreg composed of a fiber base material and a resin composition impregnated therein. The resin composition in the prepreg 100 is the above-described resin composition.

  The prepreg of the present invention is preferably prepared by impregnating a fiber base material with a varnish of a resin composition obtained by mixing, dissolving or dispersing a resin composition for prepreg in an organic solvent, and drying. 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. As described above, the resin composition for obtaining the prepreg is preferably a resin composition containing a polyamideimide resin, a naphthalenediglycidyl compound, and an epoxy resin. Thereby, the volatilization rate of the organic solvent of the varnish of the resin composition is fast, and it is possible to reduce the residual organic solvent content to 5% by weight or less even at a low temperature of 150 ° C. or less that does not promote the curing reaction of the thermosetting resin. It is possible to obtain a prepreg which has good adhesion to a fiber base and a metal foil such as a copper foil and is excellent in moldability. In addition, when the residual organic solvent content is small, when laminating with a metal foil such as copper foil, the occurrence of swelling due to volatilization of the organic solvent is suppressed, and the resulting metal foil-clad laminate is further excellent in soldering heat resistance. It can be.

  The prepreg of the present invention is preferably produced by impregnating a varnish of a resin composition into a fiber substrate and drying (removing the solvent from the varnish) in a range of 80 ° C. to 180 ° C. The fiber base material used in the prepreg of the present invention is not particularly limited as long as it is generally used when producing a metal foil-clad laminate or a multilayer printed circuit board, but usually a woven fabric, a nonwoven fabric, etc. A fiber substrate is used. The material of the fibers constituting the fiber substrate includes glass, alumina, asbestos, boron, silica alumina glass, silica glass, tyranno, silicon carbide, silicon nitride, zirconia, and other inorganic fibers, aramid, polyether ether ketone, poly Examples thereof include organic fibers such as ether imide, polyether sulfone, carbon and cellulose, and mixed papers thereof. Among these, a glass fiber woven fabric (glass cloth) is particularly preferably used. Moreover, it is preferable that the thickness of a fiber base material is 5-100 micrometers. As the fiber substrate used for the prepreg, a glass cloth of 5 to 100 μm is particularly preferably used. When a glass cloth having a thickness of 5 to 100 μm is used, a printed circuit board that can be arbitrarily bent can be obtained very easily when combined with the above-described resin composition. It is possible to reduce the dimensional change caused by.

  The conditions for producing 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. There are no restrictions on the production method, drying conditions, etc., the temperature during drying is 80 ° C. to 180 ° C., the time is not particularly limited in consideration of the gelation time of the varnish, and is preferably a time that does not cause the varnish to gel. . The amount of varnish impregnated in the resin composition is preferably such that the resin solid content in the varnish is 30 to 80% by weight with respect to the total amount of the resin solid content and the fiber substrate in the varnish.

  An insulating plate using the prepreg of the present invention is produced as follows. First, one or a plurality of prepregs of the present invention are laminated to obtain a laminate. Next, the laminate is heated and pressure-molded at a temperature usually in the range of 150 to 280 ° C., preferably in the range of 180 ° C. to 250 ° C., usually at a pressure in the range of 0.5 to 20 MPa, preferably 1 to 8 MPa. Thus, an insulating plate is produced.

  FIG. 2 is a partial cross-sectional view showing an embodiment of a metal foil-clad laminate according to the present invention. The metal foil-clad laminate 200 includes a sheet-like substrate 30 obtained by heating and pressing a laminate in which a plurality of prepregs 100 are laminated, and two metal foils 10 provided in close contact with both surfaces of the substrate 30. It consists of.

  The substrate 30 is made of a laminate in which a plurality of fiber reinforced resin layers 3 derived from a plurality of prepregs 100 are laminated. In order to increase the flexibility of the metal foil-clad laminate and the printed circuit board, the thickness of the substrate 30 is preferably 10 to 500 μm. In each fiber reinforced resin layer 3, the fiber base material is impregnated with resin as a matrix. In this resin, a crosslinked structure is formed by a crosslinking reaction between a polyamideimide resin and a naphthalenediglycidyl compound.

  The metal foil-clad laminate can be obtained by stacking metal foil on both sides of a laminate in which a predetermined number (preferably 10 or less) of prepregs 100 are laminated, and heating and pressing the laminate. At this time, the heating temperature and pressure are not particularly limited, but the heating temperature is usually 150 to 280 ° C. (preferably 180 to 250 ° C.), and the pressure is usually 0.5 to 20 MPa (preferably 1 to 8 MPa). It is.

  As the metal foil 10, a copper foil or an aluminum foil is generally used, but a copper foil is preferable. The metal foil 10 having a thickness of 5 to 200 μm, which is used for a normal metal foil-clad laminate, can be used. In order to increase the flexibility of the printed circuit board, the thickness is 5 to 18 μm. It is more 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.

  The embodiment of the metal foil-clad laminate is not limited to the above aspect. For example, using one prepreg 100, the substrate may be composed of one fiber reinforced resin layer, or a metal foil may be provided on only one side of the substrate. Further, the printed circuit board according to the present invention can be obtained by patterning the metal foil of the metal foil-clad laminate by etching or the like.

  FIG. 3 is a schematic cross-sectional view showing an embodiment of a printed circuit board according to the present invention. The printed circuit board 300 shown in FIG. 3 is a multilayer printed circuit board, and includes an inner layer circuit board 315 formed by arranging inner layer circuits 313a and 313b on both sides of an insulating substrate 310 in which a through hole 311 is filled with a conductor 312. Insulating substrates 320a, b provided on both sides of the inner circuit board 315, with through holes 321a, b filled with conductors 322a, b, respectively, and circuits 323a formed outside the insulating substrates 320a, 320b , B.

  The printed circuit board 300 is formed as follows, for example. First, the prepreg 100 according to the present invention is laminated on both sides of the inner layer circuit board 315 and cured by heating and pressurization to form the insulating substrates 320a and 320b. Next, through holes 321a and b are provided in the insulating substrates 320a and 320b, and conductors 322a and b are filled therein. Then, patterned circuits 323a and 323b are formed outside the insulating substrates 320a and 320b to complete the printed circuit board 300.

  Alternatively, the prepreg 100 according to the present invention is laminated on both sides of the inner layer circuit board 315, through holes 321a and b are provided, and conductors 322a and b are filled therein. Further, a metal foil is laminated on the outside of the prepreg 100 and heated and pressurized, and then the metal foil is patterned by etching or the like to form circuits 323a and b, thereby completing the printed circuit board 300. In this case, since the prepreg 100 of the present invention is excellent in dimensional stability, a change in the hole diameter of the through holes 321a and 321b is suppressed even by heating and pressurizing treatment, and the through holes 321a and b and the conductors 322a and 322b It is difficult for voids to occur between them.

  The prepreg of the present invention can be laminated in close contact with the surfaces of the insulating substrates 320a and 320b on which the inner layer circuits 313a and 313b are not provided by improving the fluidity of the polyamideimide resin. For the same reason, the outer surfaces of the insulating substrates 320a and 320b obtained by curing the prepreg of the present invention are smooth surfaces with unevenness suppressed.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

Examples are described below, but the present invention is not limited to these examples.

(Synthesis Example 1)
19.8 g of DDS (diaminodiphenyl sulfone) 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 (0.08 mol), reactive silicone oil KF-8010 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 430) 17.2 g (0.02 mol) as siloxane diamine, and Jeffamine D2000 (Sun Techno Chemical Co., Ltd.) as aliphatic diamine Product name, amine equivalent 1000) 80.0 g (0.04 mol), 12.5 g (0.06 mol) of Wandamine (trade name, manufactured by Shin Nippon Rika Co., Ltd.) as a diamine represented by the general formula (3a), TMA ( Trimellitic anhydride) 80.7 g (0.42 mol), and aprotic polar solution They were charged NMP (N-methyl-2-pyrrolidone) 514 g as, and stirred at 80 ° C. 30 min. Then, 150 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature was raised and refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated in the moisture determination receiver about 7.2 ml or more, and that no water is being distilled, and while removing the distillate collected in the moisture determination receiver, The temperature was raised to 190 ° 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 (resin solid content 32% by weight) was obtained.

(Synthesis Example 2)
DDS (diaminodiphenyl sulfone) 14.9 g 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 (0.06 mol), reactive silicon oil KF-8010 (trade name, amine equivalent 430, manufactured by Shin-Etsu Chemical Co., Ltd.) as siloxane diamine, 17.2 g (0.02 mol) as aliphatic diamine, Jeffamine D2000 (Sun Techno Chemical Co., Ltd.) Product name, amine equivalent 1000) 80.0 g (0.04 mol), Wandamine (trade name, manufactured by Shin Nippon Rika Co., Ltd.) 16.7 g (0.08 mol) as a diamine represented by the general formula (3a), TMA ( Trimellitic anhydride) 80.7 g (0.42 mol), and aprotic polar solution They were charged NMP (N-methyl-2-pyrrolidone) 508 g as, and stirred at 80 ° C. 30 min. Then, 150 ml of toluene was added as an aromatic hydrocarbon azeotropic with water, and then the temperature was raised and refluxed at about 160 ° C. for 2 hours. Confirm that water has accumulated in the moisture determination receiver about 7.2 ml or more, and that no water is being distilled, and while removing the distillate collected in the moisture determination receiver, The temperature was raised to 190 ° 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 (resin solid content: 34% by weight) was obtained.

Example 1
212.5 g of NMP solution of polyamideimide resin of Synthesis Example 1 (resin solid content 32 wt%), 12.5 g of HP4032D (trade name, manufactured by Dainippon Ink Co., Ltd.) as a naphthalene diglycidyl compound (resin solid content of 80 wt%) Methyl ethyl ketone solution), 40.0 g of EPPN-502H as epoxy resin (methyl ethyl ketone solution with a resin solid content of 50% by weight) (trade name, manufactured by Nippon Kayaku Co., Ltd.), 2E4MZ-CN (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator ) 1.5 g (5% by weight methyl ethyl ketone solution), 20.0 g of phosphorus filler OP930 (trade name, manufactured by Clariant Co., Ltd.) as a flame retardant, and stirred for about 1 hour until the resin composition is uniform, Add methyl ethyl ketone to adjust the viscosity of the varnish of the resin composition to 1000 cP 24 hours, allowed to stand at room temperature (25 ° C.) for, and a resin composition varnish.

(Example 2)
The NMP solution of the polyamideimide resin of Synthesis Example 2 (205.9 g (resin solid content: 34% by weight)) and HP4032D (trade name, manufactured by Dainippon Ink Co., Ltd.) 25.0 g (resin solid content: 80% by weight) as the naphthalene diglycidyl compound. Methyl ethyl ketone solution), 20.0 g of EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin (methyl ethyl ketone solution having a resin solid content of 50% by weight), and 2E4MZ-CN (product of Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator Name) After blending 1.5 g (5 wt% methyl ethyl ketone solution) and 20.0 g of a phosphorus filler OP930 (trade name, manufactured by Clariant Co., Ltd.) as a flame retardant, stirring for about 1 hour until the resin composition is uniform The viscosity of the varnish of the resin composition is adjusted to 1100 cP by adding methyl ethyl ketone, 24 hours for, it was room temperature (25 ° C.) in to stand resin composition varnish.

(Example 3)
212.5 g of NMP solution of polyamideimide resin of Synthesis Example 1 (resin solid content 32 wt%), 12.5 g of HP4032D (trade name, manufactured by Dainippon Ink Co., Ltd.) as a naphthalene diglycidyl compound (resin solid content of 80 wt%) Methyl ethyl ketone solution), N-770 (trade name, manufactured by Dainippon Ink Co., Ltd.) as an epoxy resin, 33.3 g (methyl ethyl ketone solution having a resin solid content of 60% by weight), and 2E4MZ-CN (product of Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator Name) After blending 1.5 g (5 wt% methyl ethyl ketone solution) and 20.0 g of a phosphorus filler OP930 (trade name, manufactured by Clariant Co., Ltd.) as a flame retardant, stirring for about 1 hour until the resin composition is uniform The viscosity of the varnish of the resin composition was adjusted to 1000 cP by adding methyl ethyl ketone, 24 hours because, was room temperature (25 ° C.) in to stand resin composition varnish.

(Comparative Example 1)
218.8 g of NMP solution of polyamideimide resin of Synthesis Example 1 (resin solid content 32% by weight) and 16.7 g of DER331L (trade name, manufactured by Dainippon Ink Co., Ltd.) as an epoxy resin (methyl ethyl ketone solution having a resin solid content of 60% by weight) ), EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.) 33.3 g (methyl ethyl ketone solution having a resin solid content of 60% by weight), 2E4MZ-CN (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 1.5 g as a curing accelerator (5% by weight methyl ethyl ketone solution), 20.0 g of a phosphorus filler OP930 (trade name, manufactured by Clariant Co., Ltd.) as a flame retardant, and after stirring for about 1 hour until the resin composition becomes uniform, methyl ethyl ketone was added. The viscosity of the varnish of the resin composition is adjusted to 1000 cP, and for defoaming for 24 hours at room temperature (25 ° C.) And location, and a resin composition varnish containing no naphthalene diglycidyl compound.

(Comparative Example 2)
210.0 g of NMP solution of polyamideimide resin of Synthesis Example 1 (resin solid content 32% by weight) and 50.0 g of DER331L (trade name, manufactured by Dainippon Ink Co., Ltd.) as an epoxy resin (methyl ethyl ketone solution having a resin solid content of 60% by weight) ), 2E4MZ-CN (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 1.5 g (5% by weight methyl ethyl ketone solution) as a curing accelerator, and phosphorus-based filler OP930 (trade name, manufactured by Clariant Co., Ltd.) 20.0 g as a flame retardant. After mixing and stirring for about 1 hour until the resin composition becomes uniform, methyl ethyl ketone is added to adjust the viscosity of the varnish of the resin composition to 1000 cP, and it is left at room temperature (25 ° C.) for 24 hours for defoaming. Thus, a resin composition varnish containing no naphthalene diglycidyl compound was obtained.

(Preparation of prepreg and double-sided copper foil-clad laminate)
The resin composition varnishes produced in Examples 1 to 3 and Comparative Examples 1 and 2 were impregnated into a glass cloth having a thickness of 28 μm (trade name: 1037 manufactured by Asahi Sebel Co., Ltd.), then heated at 150 ° C. for 15 minutes and dried. A prepreg having a resin solid content of 70% by weight was obtained. A 12 μm thick electrolytic copper foil (trade name: F2-WS-12, manufactured by Furukawa Electric Co., Ltd.) is stacked on both sides of one prepared prepreg so that the adhesive surface is aligned with the prepreg, 230 ° C., 90 minutes, 4.0 MPa A double-sided copper foil-clad laminate with an insulating layer thickness of 50 μm was produced under the above pressing conditions.

(Evaluation of impact resistance)
Four rows of daisy chain patterns having 250 connection holes with a diameter of 0.25 mm were prepared on the double-sided copper foil-clad laminates of Examples 1 to 3 and Comparative Examples 1 and 2 by ordinary drilling, plating, and photolithography processes. Each start point and end point were connected with a lead wire by solder, each printed circuit board having a conductive pattern of 1000 holes in a row was produced, and the initial resistance of the conductive pattern was measured. Thereafter, each printed circuit board was mounted on a predetermined housing, dropped a predetermined number of times from a height of 1.5 m, and the presence or absence of disconnection and the resistance value after dropping were measured. After dropping 1000 times, the resistance change rate is within 10%, and the case where it exceeds 10% is evaluated as x. The results are shown in Table 1.

(Measurement of peel strength of copper foil)
The metal foil adhesive strength (copper foil peeling strength) of the double-sided copper foil-clad laminates of Examples 1 to 3 and the double-sided copper foil-clad laminates of Comparative Examples 1 and 2 was measured by a peeling test in the 90 ° C. direction. The maximum load at that time was defined as the peel strength of the copper foil. The results are shown in Table 1.

(Evaluation of solder heat resistance)
The double-sided copper foil-clad laminates of Examples 1 to 3 and the double-sided copper foil-clad laminates of Comparative Examples 1 and 2 were immersed in solder baths at 260 ° C., 288 ° C. and 300 ° C. to evaluate solder heat resistance. Table 1 shows the time until an abnormality such as blistering or peeling was observed after immersion in the solder bath.

(Evaluation of bendability)
Evaluation of bendability was performed as follows. First, the laminated board which removed the copper foil of the double-sided copper foil tension laminated board of Examples 1-3 and Comparative Examples 1 and 2 by the whole surface etching was cut | disconnected to width 10mm x length 100mm, and the sample was produced. Next, a rectangular aluminum plate having a thickness of 5 mm was placed on the main surface of the sample so that the length direction was orthogonal. Then, while pressing the aluminum plate from above, the state of the sample after bending the laminated plate upward by 90 degrees at the side end portion was observed. In the evaluation, the case where there was no abnormality in the folded part of the laminated board was evaluated as “◯”, the case where it was whitened by a partial crack, “Δ”, and the case where it was whitened due to an overall crack as “X”. The results are shown in Table 1.

(Measurement of flow amount)
The prepregs of Examples 1 to 3 and Comparative Examples 1 to 2 were punched into a circular shape with a diameter of 10 mm, sandwiched between two polyimide films (trade names manufactured by Upilex 50S Ube Industries Co., Ltd.), each of which was released from the mold, Pressing was performed at 230 ° C., 6 MPa, and 5 minutes. One half of the difference between the average of the three diameters after pressing and the initial diameter of 10 mm was measured and evaluated as the amount of deformation (flow amount) due to exudation. The results are shown in Table 1.

(Evaluation of circuit fillability)
The prepregs of Examples 1 to 3 and Comparative Examples 1 to 2 are formed on an inner circuit board on which a comb-shaped pattern having a line / space width of 50 μm / 50 μm, 75 μm / 75 μm, 100 μm / 100 μm, 150 μm / 150 μm, 200 μm / 200 μm is formed. One sheet was laminated. Furthermore, an electrolytic copper foil having a thickness of 12 μm (trade name F2-WS-12, manufactured by Furukawa Electric Co., Ltd.) is stacked so that the adhesive surface is combined with the prepreg, and the test is performed at 230 ° C., 90 minutes, 4.0 MPa pressing conditions. A multilayer board was produced. The copper foil was removed by etching, and the filling property of the cured body of the prepreg on the concave portion of the comb-shaped pattern of the inner layer circuit board was observed with a microscope. The case where no void was observed was marked with ◯, and the case where a void was recognized was marked with x. The results are shown in Table 1.

(Measurement of elastic modulus of resin composition)
The resin composition varnishes obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were applied to a 12 μm thick electrolytic copper foil (Furukawa Electric Co., Ltd., trade name F2-WS-12) as a sample (coating film). The coating was applied to a thickness of about 50 to 100 μm to obtain a coating film and heated at 150 ° C. for 15 minutes. Next, another electrolytic copper foil having a thickness of 12 μm was laminated on the surface opposite to the electrolytic copper foil side of the coating film as a sample so that the surface and the adhesive surface of the copper foil overlapped, and 230 ° C. The coating film was cured while being vacuum-pressed in the laminating direction under conditions of heating at 4 MPa for 60 minutes. Thereafter, the cured resin obtained by removing the copper foil by etching was used as a test substrate. This test substrate was cut out to about 30 mm × 5 mm and measured using a dynamic viscoelasticity measuring device Regel-E-4000 manufactured by UBM under the conditions of a measurement length of 20 mm and a measurement frequency of 10 Hz. The dynamic elastic modulus at 25 ° C. of the obtained dynamic viscoelastic curve was taken as a measured value. The results are shown in Table 1.

(Measurement of Tg of resin composition)
The resin composition varnishes obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were applied to a 12 μm thick electrolytic copper foil (Furukawa Electric Co., Ltd., trade name F2-WS-12) as a sample (coating film). The coating was applied to a thickness of about 50 to 100 μm to obtain a coating film and heated at 150 ° C. for 15 minutes. Next, another electrolytic copper foil having a thickness of 12 μm was laminated on the surface opposite to the electrolytic copper foil side of the coating film as a sample so that the surface and the adhesive surface of the copper foil overlapped, and 230 ° C. The coating film was cured while being vacuum-pressed in the laminating direction under conditions of heating at 4 MPa for 60 minutes. Thereafter, the cured resin obtained by removing the copper foil by etching was used as a test substrate. This test substrate was cut out to about 30 mm × 5 mm, and measured using a dynamic viscoelasticity measuring device Regel-E-4000 manufactured by UBM, measuring length 20 mm, measuring frequency 10 Hz, heating rate 5 ° C./min, measuring range 30 to 300. Tg (glass transition point) was measured under the condition of ° C. The results are shown in Table 1.

  As a result of measuring the metal foil adhesive strength (copper foil peeling strength) of the obtained double-sided copper foil-clad laminate, F2-WS-12 and any of the prepregs of Examples 1 to 3 and Comparative Examples 1 and 2 The combination was 0.9 to 1.2 kN / m. As a result of immersing in a solder bath at 260 ° C., 288 ° C. and 300 ° C. and measuring solder heat resistance, Examples 1 to 3 and Comparative Example 1 showed abnormalities such as blistering and peeling for 5 minutes at any temperature. There wasn't. However, in Comparative Example 2, blistering that appeared to be caused by prepreg voids occurred at 288 ° C. for 60 seconds. In addition, the double-sided copper foil-clad laminate from which the copper foil was removed by etching was highly flexible and could be bent arbitrarily.

  In Examples 1 to 3 containing a naphthalenediglycidyl compound, the flow amount was 9 mm or more, but in Comparative Examples 1 and 2, they were 4.5 mm and 7.2 mm, respectively. In Examples 1 to 3 containing a naphthalene diglycidyl compound, the resin was filled in the recesses between the comb circuits without any gaps, but in Comparative Examples 1 and 2, there was a gap in the recesses between the circuits. Many were recognized.

  The impact resistance was good in each of Examples 1 to 3 and Comparative Examples 1 and 2. Moreover, since Examples 1-3 which contain a naphthalene diglycidyl compound have the large amount of flow of a resin composition compared with Comparative Examples 1-2, and Tg of a resin composition is large, a moldability and heat resistance are good. It turns out that it is excellent.

It is a fragmentary perspective view which shows one Embodiment of the prepreg by this invention. It is a fragmentary sectional view showing one embodiment of a metal foil tension laminate sheet by the present invention. 1 is a partial cross-sectional view illustrating an embodiment of a printed circuit board according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 3 ... Fiber reinforced resin layer, 10 ... Metal foil, 30 ... Board | substrate, 100 ... Prepreg, 200 ... Metal foil tension laminated board, 300 ... Printed circuit board, 313a, 313b, 323a, 323b ... Circuit, 315 ... Inner layer circuit board, 311, 321 a, 321 b... Through-hole, 412, 322 a, 322 b... Conductor, 310, 320 a, 320 b.

Claims (7)

A fiber base material, and a resin composition impregnated therein,
A prepreg in which the resin composition includes a polyamideimide resin and a naphthalenediglycidyl compound. The polyamideimide resin has the following general formula (1):

(In the formula (1), R ₁ and R ₂ are divalent alkyl groups, R ₃ , R ₄ , R ₇ and R ₈ are monovalent alkyl groups or monovalent alkyl groups having a substituent, R ₅ , R ₆ represents a monovalent aromatic group or a monovalent aromatic group having a substituent, and m and n are each an integer of 0 to 40 and satisfy 1 ≦ n + m ≦ 50.
The prepreg according to claim 1, comprising a polyamideimide resin having a structure represented by: The polyamideimide resin has the following general formula (2):

The prepreg according to claim 1, comprising a polyamideimide resin having a structure represented by: A mixture of a diamine represented by the following general formula (3a), a diamine having two or more aromatic rings represented by the following general formula (1a) or the following general formula (1b), and a siloxane diamine; The prepreg as described in any one of Claims 1-3 which contains the polyamidoimide resin obtained by making a diisocyanate compound react with the mixture containing the diimide dicarboxylic acid obtained by making it react with trimellitic anhydride.

(In the formulas (1a) and (1b), X 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, and an ether group. , A carbonyl group, a single bond, or a divalent group represented by the following general formula (2a) or the following general formula (2b), Y represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms. A halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group or a carbonyl group, and R ¹ , R ² and R ³ each independently represent a hydrogen atom, a hydroxyl group, a methoxy group, a methyl group or a halogenated methyl group. However, Z shows a C1-C3 bivalent aliphatic hydrocarbon group, a C1-C3 bivalent halogenated aliphatic hydrocarbon group, a sulfonyl group, an ether group, a carbonyl group, or a single bond. .)

  The prepreg as described in any one of Claims 1-4 whose said fiber base material is a glass cloth with a thickness of 5-100 micrometers.   A substrate obtained by curing the resin composition by heating a predetermined number of the prepregs according to any one of claims 1 to 5, a metal foil provided on one side or both sides of the substrate, A metal foil clad laminate.   A printed circuit board obtained by forming a circuit on the metal foil-clad laminate according to claim 6.

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