JPWO2014157468A1 - LAMINATE, LAMINATE, PRINTED WIRING BOARD, LAMINATE, AND METHOD FOR PRODUCING LAMINATE - Google Patents

Abstract

It aims at providing the laminated body and laminated board with which adhesiveness of a glass substrate layer and a resin composition layer and heat resistance are enough, and these manufacturing methods. Moreover, it aims at providing the printed wiring board using the said laminated body or laminated board. A laminate including one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer includes a polyamideimide resin and an epoxy resin. Moreover, the laminated board formed by hardening | curing the resin composition layer of this laminated body, and the printed wiring board using these laminated bodies or laminated boards are provided.

Description

  The present invention relates to a laminate suitable for a semiconductor package or a printed wiring board, a laminated board, a manufacturing method thereof and a printed wiring board.

The wiring board is required to have high-density wiring with a narrowed wiring pitch. As a semiconductor mounting method corresponding to high-density wiring, a flip chip connection method is widely used instead of the conventional wire bonding method.
The flip chip connection method is a method in which a wiring board and a semiconductor are connected by solder balls instead of wires. Solder balls are arranged between the wiring board and the semiconductor that face each other, and the whole is heated to reflow (melt connection) the solder, and the wiring board and the semiconductor are connected and mounted.
In this method, heat close to 300 ° C. is applied to the wiring board or the like during solder reflow. For this reason, high heat resistance is required.

  On the other hand, demands for thinner and lighter electronic devices are increasing, and semiconductor packages and printed wiring boards are becoming thinner and higher in density. In order to stably mount electronic components corresponding to these reductions in thickness and density, it is important to suppress warpage that occurs during mounting. One of the main causes of warpage occurring in the semiconductor package during mounting is a difference in thermal expansion coefficient between the laminated plate used in the semiconductor package and the silicon chip mounted on the surface of the laminated plate. For this reason, efforts are being made to make the thermal expansion coefficient close to the thermal expansion coefficient of the silicon chip, that is, to reduce the thermal expansion coefficient, in the laminated sheet for semiconductor packages, and the thermal expansion coefficient almost matches the thermal expansion coefficient of the silicon chip. Attempts have been made to reduce heat shock stress by pressing and laminating a resin and a glass film as a layer to have (Patent Document 1), but the adhesion between the resin to be used and the glass substrate is low. When the temperature is low and high, the reflow heat resistance is insufficient because the resin layer and the glass substrate layer peel from the stress due to the difference in thermal expansion coefficient.

Japanese Patent No. 4657554

As described above, the glass substrate and the conventional resin composition layer have poor adhesion, and peeled off during solder reflow, resulting in insufficient heat resistance during mounting.
In view of the above, an object of the present invention is to provide a laminate and a laminate having good adhesion and heat resistance between the glass substrate layer and the resin composition layer, and methods for producing them. Moreover, it aims at providing the printed wiring board using the said laminated body or laminated board.

（式中、Ｒ₁は

（ただし、Ｘ₁は単結合、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、カルボニル基である）を示す。）

（式中、Ｒ₂は

（ただし、Ｒ₃は炭素数１〜５の脂肪族炭化水素基を示し、ｎは１〜１００の整数）を示す。）

（式中、Ｒ₄は

（ただし、Ｒ₅及びＲ₆は各々独立に２価の有機基を示し、Ｒ₇〜Ｒ₁₀は各々独立に炭素数１〜２０のアルキル基、又は炭素数６〜１８のアリール基を示し、ｎは１〜５０の整数である）を示す。）

（式中、Ｒ₁₁は

を示す。）
［８］ 前記エポキシ樹脂が、脂環式の骨格を有するエポキシ樹脂である［１］〜［７］のいずれか一に記載の積層体。
［９］ 前記ガラス基板層の厚さが３０〜２００μｍである［１］〜［８］のいずれかに記載の積層体。
［１０］ 前記樹脂組成物層及び前記ガラス基板層を合わせた厚さが４０〜３００μｍである［１］〜［９］のいずれかに記載の積層体。
［１１］ １層以上の樹脂硬化物層及び１層以上のガラス基板層を含む積層板であって、［１］〜［１０］のいずれかに記載の積層体を硬化処理して得られる積層板。
［１２］ ［１１］に記載の積層板の少なくとも一方の面に配線が設けられてなるプリント配線板。
［１３］ 複数の積層板を含み、少なくとも１個の積層板が［１１］に記載の前記積層板である［１２］に記載のプリント配線板。
［１４］ ポリアミドイミド樹脂とエポキシ樹脂とを含む樹脂組成物をガラス基板の表面に塗布して樹脂組成物層を形成する積層体の製造方法。
［１５］ 前記樹脂組成物層を形成した後に乾燥処理を施す［１４］に記載の積層体の製造方法。
［１６］ ポリアミドイミド樹脂とエポキシ樹脂とを含む樹脂組成物からなるフィルムを作製し、真空ラミネーター又はロールラミネーターを用いてガラス基板上に前記フィルムを積層した後に、前記フィルムに硬化処理を施す積層板の製造方法。
［１７］ 前記フィルムを積層した後で前記硬化処理を施す前に、プレス処理を施す［１６］に記載の積層板の製造方法。As a result of investigations to solve the above problems, the present inventors have found that the problems can be solved by including a polyamideimide resin and an epoxy resin in the resin composition forming the resin composition layer. That is, the present invention is as follows.
[1] A laminate comprising one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer comprises a polyamideimide resin and an epoxy resin.
[2] The laminate according to [1], wherein the polyamideimide resin is 50 to 85% by mass in all resin components.
[3] The laminate according to [1] or [2], wherein the epoxy resin has two or more epoxy groups in one molecule.
[4] The laminate according to any one of [1] to [3], including a resin having three or more functional groups that react with an epoxy resin in one molecule.
[5] The resin having 10 to 30% by mass of the epoxy resin in all resin components and 3 or more functional groups that react with the epoxy group in one molecule is contained in 5% or more of all resin components. Laminated body.
[6] The laminate according to [4] or [5], wherein a resin having three or more functional groups that react with the epoxy group in a molecule is included within a range not exceeding the solid content of the epoxy resin.
[7] The polyamide-imide resin reacts at least one dicarboxylic acid derivative represented by the following general formulas (1) to (3) with at least one aromatic diisocyanate represented by the general formula (4). The laminated body in any one of [1]-[6] obtained by making it carry out.

(Where R ₁ is

(Wherein, X ₁ is a single bond, 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),. )

(Where R ₂ is

(Wherein, R ₃ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, n represents an integer of 1 to 100) shows a. )

(Where R ₄ is

(However, R ₅ and R ₆ each independently represent a divalent organic group, R _{7 to} R ₁₀ each independently represent an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms, n is an integer of 1-50. )

(Where R ₁₁ is

Indicates. )
[8] The laminate according to any one of [1] to [7], wherein the epoxy resin is an epoxy resin having an alicyclic skeleton.
[9] The laminate according to any one of [1] to [8], wherein the glass substrate layer has a thickness of 30 to 200 μm.
[10] The laminate according to any one of [1] to [9], wherein the combined thickness of the resin composition layer and the glass substrate layer is 40 to 300 μm.
[11] A laminate including one or more resin cured product layers and one or more glass substrate layers, the laminate obtained by curing the laminate according to any one of [1] to [10] Board.
[12] A printed wiring board in which wiring is provided on at least one surface of the laminated board according to [11].
[13] The printed wiring board according to [12], including a plurality of laminated boards, wherein at least one laminated board is the laminated board according to [11].
[14] A method for producing a laminate, in which a resin composition layer comprising a polyamideimide resin and an epoxy resin is applied to the surface of a glass substrate to form a resin composition layer.
[15] The method for producing a laminate according to [14], wherein a drying process is performed after the resin composition layer is formed.
[16] A laminate comprising a film made of a resin composition containing a polyamideimide resin and an epoxy resin, and the film is laminated on a glass substrate using a vacuum laminator or a roll laminator, and then the film is subjected to a curing treatment. Manufacturing method.
[17] The method for manufacturing a laminated board according to [16], in which a press treatment is performed after the film is laminated and before the curing treatment.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesive body of a resin composition layer and a glass substrate layer, the laminated body and laminated board with favorable heat resistance, and these manufacturing methods can be provided. Moreover, the printed wiring board using the said laminated body or laminated board can be provided.

Hereinafter, the laminate, the laminate, the production method thereof, and the printed wiring board of the present invention will be described in detail.
In the present specification, the “laminate” means that a thermosetting resin (polyfunctional epoxy resin) which is a constituent component in the resin composition is uncured or semi-cured, The term “plate” means that the thermosetting resin as a constituent component thereof is cured, or 90% or more of the thermosetting resin is cured. The degree of cure of the thermosetting resin can be measured by the reaction rate measured from a differential scanning calorimeter.

[Laminate]
The laminate of the present invention is a laminate having one or more resin composition layers and one or more glass substrate layers, and the resin composition layer contains a polyamideimide resin and an epoxy resin.
Here, the resin composition layer according to the present invention is in an uncured or semi-cured state (B) on a support or a glass substrate before being made a part of a layer of a laminated board for a wiring board or a multilayer wiring board. It exists in the stage state).
Moreover, the laminated board of this invention is obtained by hardening the resin composition layer by heating the laminated body of this invention, and setting it as a resin cured material layer.
Here, by using a glass substrate layer having a low thermal expansion coefficient and a high elastic modulus as much as those of a silicon chip, warpage is suppressed and cracking is difficult to occur. In particular, such a laminate has a glass substrate layer with high heat resistance, and thus has a low thermal expansion in a temperature range from 100 ° C. to less than Tg of the cured resin. Further, by including an inorganic filler in the cured resin layer, the cured resin layer becomes low thermal expansion and high elasticity, and the laminate including the cured resin layer has lower thermal expansion and high elasticity. It will be rate.
Moreover, in order to improve adhesiveness with a conductor layer, you may provide an adhesion auxiliary layer between the resin cured material layer of this invention, and a conductor layer.

(Resin composition)
The resin composition used for the resin composition layer of the present invention will be described in detail below.
The resin composition according to the present invention includes a polyamideimide resin and an epoxy resin. In the resin composition, the compounding amount of the polyamide-imide resin, which is a base resin for ensuring glass adhesion, is preferably 50 to 85% by mass in the total resin component from the viewpoint of glass adhesion, and 50 to 80 It is preferable that it is mass%. Furthermore, it is preferable that it is 50-75 mass% from a heat resistant viewpoint. The blending amount of the polyamideimide resin is preferably 50 to 90% by mass, more preferably 55 to 85% by mass, and particularly preferably 60 to 85% by mass in all resin components. When the polyamideimide resin is blended in the above range, glass adhesion derived from the polyamideimide resin is expressed, which is preferable.
It is preferable that the compounding quantity of an epoxy resin is 10-30 mass% in all the resin components, It is more preferable that it is 12-28 mass%, It is especially preferable that it is 15-25 mass%. When the epoxy resin is blended in the above range, the crosslinking density is sufficient and good heat resistance is obtained. Moreover, phase separation with the polyamide-imide resin hardly occurs.

（式中、Ｒ₁は

（ただし、Ｘ₁は単結合、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、又はカルボニル基である）を示す。）

（式中、Ｒ₂は

（ただし、Ｒ₃は炭素数１〜５の脂肪族炭化水素基を示し、ｎは１〜１００の整数）を示す。）

（式中、Ｒ₄は

（ただし、Ｒ₅及びＲ₆は各々独立に２価の有機基を示し、Ｒ₇〜Ｒ₁₀は各々独立に炭素数１〜２０のアルキル基、又は炭素数６〜１８のアリール基を示し、ｎは１〜５０の整数である）を示す。）

（式中、Ｒ₁₁は

を示す。）The polyamideimide resin of the present invention is a polymer having an amide group and an imide group in the main chain.
As the polyamideimide resin of the present invention, at least one dicarboxylic acid derivative represented by the following general formulas (1) to (3) is reacted with at least one aromatic diisocyanate represented by the general formula (4). What is obtained is preferable.

(Where R ₁ is

(Wherein, X ₁ is a single bond, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, a halogenated aliphatic hydrocarbon group having 1 to 3 carbon atoms, a sulfonyl group, a is an ether group, or a carbonyl group),. )

(Where R ₂ is

(Wherein, R ₃ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, n represents an integer of 1 to 100) shows a. )

(Where R ₄ is

(However, R ₅ and R ₆ each independently represent a divalent organic group, R _{7 to} R ₁₀ each independently represent an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms, n is an integer of 1-50. )

(Where R ₁₁ is

Indicates. )

  The polyamideimide resin of the present invention is synthesized by a method comprising a step of producing a dicarboxylic acid derivative by reaction of diamine and trimellitic anhydride and a step of producing a polyamideimide resin by reacting the dicarboxylic acid derivative and diisocyanate. can do. The polyamideimide resin of the present invention can be suitably obtained by the above method, but is not limited to the one obtained by the above method unless departing from the gist of the present invention. For example, the polyamideimide resin according to the present invention may be obtained by an acid chloride method in which trimellitic anhydride is reacted with diamine.

(式中、Ｘ₁は単結合、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、又はカルボニル基である。)
このような脂環式ジアミンとしては、例えば、４，４′−ジアミノジシクロヘキシルメタン等が好ましい。商業的に入手可能な脂環式ジアミンとしては、ワンダミンＨＭ（アミン当量１００以上、新日本理化株式会社製、商品名）等が挙げられる。As the diamine used for the synthesis of the dicarboxylic acid derivative, alicyclic diamine, aliphatic diamine, and siloxane diamine are preferable.
Examples of the alicyclic diamine include alicyclic diamines having the following structural formula.

(In the formula, X ₁ is a single bond, 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.)
As such alicyclic diamine, for example, 4,4′-diaminodicyclohexylmethane is preferable. Examples of commercially available alicyclic diamines include Wandamine HM (amine equivalent of 100 or more, trade name, manufactured by Shin Nippon Rika Co., Ltd.).

  As the aliphatic diamine, oxypropylene diamine is preferable. As what is marketed, for example, Jeffamine D-230 (Mitsui Chemical Fine Co., Ltd., amine equivalent: 115, trade name), Jeffamine D-400 (Mitsui Chemical Fine Co., Ltd., amine equivalent: 200, trade name) ), Jeffermin D-2000 (Mitsui Chemical Fine Co., Ltd., amine equivalent: 1000, trade name), Jeffamine D-4000 (Mitsui Chemical Fine Co., Ltd., amine equivalent: 2000, trade name) and the like.

（ただし、Ｒ₅及びＲ₆は各々独立に２価の有機基を示し、Ｒ₇〜Ｒ₁₀は各々独立に炭素数１〜２０のアルキル基、又は炭素数６〜１８のアリール基を示し、ｎは１〜５０の整数である）Siloxane diamine is a diamine having a siloxane skeleton, and examples thereof include those having the following structural formula.

(However, R ₅ and R ₆ each independently represent a divalent organic group, R _{7 to} R ₁₀ each independently represent an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms, n is an integer of 1 to 50)

  As such siloxane diamine, a commercially available product can be used. For example, “KF-8010” (amine equivalent 430), “X-22-161A” (amine equivalent 800), “X-22-161B” ( Amine equivalent 1500), “KF-8012” (amine equivalent 2200), “KF-8008” (amine equivalent 5700), “X-22-9409” (amine equivalent 700), “X-22-1660B-3” ( Amine equivalent 2200) (above, manufactured by Shin-Etsu Chemical Co., Ltd.), “BY-16-853U” (amine equivalent 460), “BY-16-853” (amine equivalent 650), “BY-16-853B” (amine) Equivalent 2200) (above, manufactured by Toray Dow Corning Co., Ltd.). These can be used alone or in admixture of two or more.

  These diamines can be used alone or in combination of two or more. In the synthesis of the dicarboxylic acid derivative, the diamine is preferably synthesized using 5 to 100% by mass of the diamine used for the synthesis of the dicarboxylic acid derivative. When the dicarboxylic acid derivative synthesized in this way is used, the resulting polyamideimide resin tends to satisfy a plurality of characteristics. Among these, the use of siloxane diamine is more preferable because the obtained polyamideimide resin tends to exhibit good heat resistance and low elastic modulus.

  Moreover, in addition to said diamine, aromatic diamine can also be used as needed. Examples of the aromatic diamine include p-, m-, o-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, diaminodiurene 1,5-diaminonaphthalene, 2, 6-diaminonaphthalene, benzidine, 4,4′-diaminoterphenyl, 4,4 ′ ″-diaminoquaterphenyl, 4,4′-diaminodiphenylmethane, 1,2-bis (anilino) ethane, 4,4 '-Diaminodiphenyl ether, diaminodiphenyl sulfone, 2,2-bis (p-aminophenyl) propane, 2,2-bis (p-aminophenyl) hexafluoropropane, 2,6-diaminonaphthalene, 3,3 -Dimethylbenzidine, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4, '-Diaminodiphenylmethane, diaminotoluene, diaminobenzotrifluoride, 1,4-bis (p-aminophenoxy) benzene, 4,4'-bis (p-aminophenoxy) biphenyl, 2,2'-bis [4- ( p-aminophenoxy) phenyl] propane, diaminoanthraquinone, 4,4′-bis (3-aminophenoxyphenyl) diphenylsulfone, 1,3-bis (anilino) hexafluoropropane, 1,4-bis (anilino) octafluoro Butane, 1,5-bis (anilino) decafluoropentane, 1,7-bis (anilino) decafluorobutane, 2,2-bis [4- (p-aminophenoxy) phenyl] hexafluoropropane, 2,2- Bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [ 4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4 -Aminophenoxy) -3,5-ditrifluoromethylphenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoro) Methylphenoxy) biphenyl, 4,4′-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4 ′ -Bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-3-tri Fluoromethylphenoxy) phenyl] hexafluoropropane and the like. The aromatic diamine can be used as necessary in the range of 0 to 95% by mass of the diamine used for the synthesis of the dicarboxylic acid derivative.

A dicarboxylic acid derivative can be synthesized using the above siloxane diamine, alicyclic diamine, aliphatic diamine, and aromatic diamine diamines used as necessary, and trimellitic anhydride. The molar ratio of diamines to trimellitic anhydride is preferably about 1: 2, and for example, the reaction is performed at 50 to 90 ° C. using a solvent such as N-methyl-2-pyrrolidone (NMP), and then 120 to A dicarboxylic acid derivative can be synthesized by performing an imide ring closing reaction at 180 ° C. Next, this dicarboxylic acid derivative can be used to react with diisocyanate to synthesize a polyamideimide resin.
In synthesizing the dicarboxylic acid derivative, siloxane diamine, alicyclic diamine, and aliphatic diamine can be used alone or in combination of two or more. When three types are used in combination, the blending amounts of siloxane diamine, alicyclic diamine, and aliphatic diamine are in the range of about 30 to 70 mol%, 5 to 60 mol%, and 10 to 40 mol%, respectively. From the viewpoint of compatibility between the adhesiveness and the epoxy resin.

Examples of the diisocyanate used in the reaction include aromatic diisocyanates represented by the general formula (4) obtained by a reaction of an aromatic diamine and phosgene. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, and phenylene-1,3-diisocyanate.
Among such aromatic diisocyanates, for example, 1,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, bis (methylphenyl) methane diisocyanate, and naphthalene diisocyanate are preferable in terms of heat resistance.

  The polymerization reaction of polyamideimide is usually N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), dimethyl sulfate. , Sulfolane, γ-butyrolactone, cresol, phenol, halogenated phenol, cyclohexane, dioxane and the like. The reaction temperature is preferably 200 ° C. or lower. The molar ratio of diisocyanate and dicarboxylic acid derivative is preferably about 1: 2 from the viewpoint of molecular weight control.

  The epoxy resin used in the resin composition of the present invention preferably has two or more epoxy groups in one molecule. From the viewpoint of solubility of the epoxy resin in the polyamide-imide resin, those having 2 to 5 epoxy groups in one molecule are preferable. Epoxy resins having a structure close to the skeleton structure of the diamine used in the polyamideimide resin are particularly preferable. For example, in the case of a polyamideimide resin using oxypropylenediamine, an aliphatic epoxy resin is preferable because good solubility is obtained. Considering the heat resistance of the resin composition, an alicyclic epoxy resin is more preferable. Examples of such aliphatic epoxy resins include dicyclopentadiene phenol type epoxy resin HP7200 (manufactured by DIC Corporation, trade name).

  When an epoxy resin that is incompatible with the polyamideimide resin (for example, biphenyl novolac type epoxy resin NC3000 (trade name, manufactured by Nippon Kayaku Co., Ltd.)) is used, it is phase-separated from the polyamideimide resin and dissolved in the polyamideimide resin that is weak in alkali resistance Sexual components can easily penetrate. On the other hand, by using a compatible epoxy resin, the epoxy resin is finely dispersed in the polyamide-imide resin, thereby inhibiting the entry of the soluble component. Therefore, chemical resistance is improved.

It is preferable that the resin composition of this invention contains resin which has 3 or more of functional groups which react with an epoxy group in the molecule | numerator from a chemical-resistant point. Examples of the resin having three or more functional groups that react with an epoxy group in one molecule include polyfunctional epoxy compounds having three or more epoxy groups, polyfunctional phenol compounds, polyfunctional amines, and urethane resins. It is done.
Examples of the polyfunctional epoxy compound having three or more epoxy groups include polyphenols such as bisphenol A, novolac type phenol resins, orthocresol novolac type phenol resins, polyhydric alcohols such as 1,4-butanediol, and epichlorohydrin. N-glycidyl of a compound having a polyglycidyl ester, amine, amide or heterocyclic nitrogen base obtained by reacting a polybasic acid such as polyglycidyl ether, phthalic acid or hexahydrophthalic acid obtained by reacting with epichlorohydrin Examples thereof include derivatives and alicyclic epoxy resins.
Examples of the polyfunctional phenol compound include hydroquinone, resorcinol, bisphenol A and their halogen compounds, and also novolak-type phenol resins and resol-type phenol resins that are condensates with formaldehyde.
The amount of the resin having three or more functional groups that react with the epoxy group is preferably 5 to 30% by mass, more preferably 7 to 25% by mass, and 8 to 20% by mass in the total resin components. It is particularly preferred that When a resin having three or more functional groups that react with an epoxy group is blended within the above range, chemical resistance and adhesiveness tend to be compatible.

  The resin composition of the present invention may contain an epoxy resin curing agent and a curing accelerator. The epoxy resin curing agent and curing accelerator are not particularly limited as long as they react with the epoxy resin or accelerate curing, and for example, amines, imidazoles, acid anhydrides, and the like can be used. Examples of amines that can be used include dicyandiamide, diaminodiphenylmethane, and guanylurea. Examples of acid anhydrides that can be used include phthalic anhydride, benzophenone tetracarboxylic dianhydride, and methyl hymic acid. As the curing accelerator, for example, alkyl group-substituted imidazole, benzimidazole and the like can be used as imidazoles.

The resin composition of the present invention may contain an inorganic filler. By mix | blending an inorganic filler with a resin composition, a resin cured material layer can be made low thermal expansion and high elasticity. Examples of the inorganic filler include silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. Among these, from the viewpoint of low thermal expansion, silica is preferable, and furthermore, the coefficient of thermal expansion is as small as about 0.6 ppm / K, and spherical amorphous silica with little decrease in fluidity when highly filled in a resin is used. More preferred.
Moreover, the resin composition of this invention may also contain additives, such as a silane coupling agent, an electric corrosion resistance improvement agent, a flame retardant, and a rust preventive agent.

  A polyamide imide resin and an epoxy resin as described above are mixed to obtain a resin composition, and this resin composition is laminated on a glass substrate to form a resin composition layer to produce a laminate. However, the manufacturing method will be described later.

(Glass substrate layer)
As the glass substrate constituting the glass substrate layer, a thin glass film having a thickness of 30 to 200 μm is preferable from the viewpoint of thinning the laminate and workability, and considering ease of handling and the like. The thickness is more preferably 50 to 150 μm. Furthermore, from the viewpoint of reducing the thickness of the laminate, the thickness is preferably 30 to 90 μm. Further, as a material for the glass substrate, glass such as alkali silicate glass, non-alkali glass, and quartz glass can be used, but borosilicate glass is preferable from the viewpoint of low thermal expansion and workability.
In addition, it is preferable that it is 40-300 micrometers, and, as for the thickness which match | combined the resin composition layer and the glass substrate layer, it is more preferable that it is 100-250 micrometers. When the thickness is 40 to 300 μm, a product such as a printed wiring board can be thinned.

Further, the thermal expansion coefficient of the glass substrate layer may suppress the warpage of the laminated body or a laminated board obtained from the laminated body as the thermal expansion coefficient of the silicon chip (approximately 3 ppm / ° C.) is closer, but preferably 8 ppm. / ° C. or less, more preferably 6 ppm / ° C. or less, and further preferably 4 ppm / ° C. or less.
The larger the dynamic storage elastic modulus of this glass substrate layer at 40 ° C., the better. However, it is preferably 20 GPa or more, more preferably 25 GPa or more, and further preferably 30 GPa or more. When the dynamic storage elastic modulus at 40 ° C. of the glass substrate layer is 20 GPa or more, it is possible to obtain a result that warpage of the laminate or a laminate obtained from the laminate may be suppressed.
Examples of a method for measuring the storage elastic modulus of the laminate at 40 ° C. include the following methods. First, a 5 mm × 30 mm test piece is cut out from the laminate. When using a copper clad laminated board, after removing copper foil by immersing in a copper etching liquid, a test piece is cut out. Using a wide-area viscoelasticity measurement device (DVE-V4, manufactured by Rheology), the tensile strength at 40 ° C. of the cut specimen was 20 mm between spans, 10 Hz in frequency, and 1 to 3 μm in vibration displacement (stop excitation). Storage modulus can be measured.

(Support film and protective film)
The laminate of the present invention may have a support film or a protective film on its surface. As a support film to be used, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyphenylene sulfide film, a Teflon (registered trademark) film, a polyimide film, a non-roughened copper foil or a surface roughness (Ra) is 0.4 μm or less. Low roughened copper foil, aluminum foil, and the like are preferable. Moreover, you may use for these support body films the surface by which the mold release process was carried out in order to make peeling with resin easy.
Examples of the protective film include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polycarbonates, fluorine-based films, and release papers as in the case of the support substrate. In addition, as for the thickness of the said protective film, it is more preferable that it is 20-100 micrometers, and a mud process, a corona treatment, and a mold release process may be performed to a protective film. About these support body films and protective films, it demonstrates in detail in description of the manufacturing method of the below-mentioned laminated body.

[Manufacturing method of laminate]
The manufacturing method of the laminated body of this invention can be manufactured by the application | coating to the glass substrate of a resin composition, the lamination to the glass substrate of the film which consists of a resin composition, etc. Among these, the method using lamination is preferable from the viewpoint of easy production.
Each manufacturing method will be described in detail below.

[Method for producing laminate by coating]
The production method by coating is a method for producing a laminate by coating the above-described resin composition on the surface of a glass substrate to form a resin composition layer. For example, the above resin composition is dissolved in an organic solvent to prepare a varnish. The resin composition layer can be formed by applying the varnish to a glass substrate and drying the organic solvent by heating or blowing hot air. This resin composition layer may be further semi-cured. In this way, it is possible to produce a laminate in which the resin composition layer is in an uncured or semi-cured state (B stage state).

[Manufacturing method of laminate by lamination]
Said laminated body can be manufactured by laminating | stacking the adhesive film and glass substrate using the resin composition which concerns on this invention. This adhesive film will be described later. Lamination can be performed using a commercially available vacuum laminator or roll laminator.
In addition, as an epoxy resin in said resin composition, what melt | dissolves below the temperature at the time of lamination is used suitably. For example, when laminating using a vacuum laminator or a roll laminator, since it is generally performed at 140 ° C. or lower, the epoxy resin in the above resin composition is preferably melted at 140 ° C. or lower.

First, the adhesive film will be described, and then a laminating method using the adhesive film will be described.
(Adhesive film)
When manufacturing a laminated body using a vacuum laminator or a roll laminator, it is preferable that said resin composition is an adhesive film.

As an adhesive film used for this invention, what has the following laminated structure is used suitably.
(1) Support Film / Resin Composition Layer In the laminated structure of (1), those having the following laminated structure in which a protective film is further laminated are also preferably used.
(2) Support Film / Resin Composition Layer / Protective Film The protective film is provided on the surface of the resin composition layer of the present invention provided on the support film where the support film is not provided. The protective film can prevent adhesion of foreign substances and scratches.
In addition, what remove | excluded the support body film and the protective film from these adhesive films may be called an adhesive film main body.
The adhesive film having the laminated structure of (1) and (2) can be produced according to a method known to those skilled in the art.
As an example for producing the above adhesive film (1), the above resin composition is dissolved in an organic solvent to prepare a varnish. Next, the resin composition layer may be formed by applying the varnish using the support film as a support and drying the organic solvent by heating, hot air blowing, or the like.
As an example for producing the adhesive film (2), the above resin composition is dissolved in an organic solvent to prepare a varnish. Next, this varnish is applied to either the support film or the protective film, the other of the support film and the protective film is placed on the varnish, and the organic solvent of the varnish is removed by heating, hot air blowing, or the like. What is necessary is just to form a resin composition layer by making it dry.

As a coating device for these resin composition layers, for example, a coating device known to those skilled in the art, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, a die coater, etc., can be used. It is preferable to select as appropriate.
In the above adhesive film, the resin composition layer may be semi-cured.
The above support film serves as a support when producing an adhesive film, and is usually finally peeled off or removed when producing a multilayer printed wiring board.

Next, an example of a laminating method using the above adhesive film will be described.
When the adhesive film has a protective film, after removing the protective film, the adhesive film is pressure-bonded to the glass substrate while being pressurized and heated. As for the lamination conditions, the adhesive film and the glass substrate are preheated as necessary, and the pressure bonding temperature (laminating temperature) is preferably 60 ° C. to 140 ° C. and the pressure bonding pressure is preferably 1 to 11 kgf / cm ² . Moreover, when using a vacuum laminator, it is preferable to laminate under a reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The laminating method may be a batch method or a continuous method using a roll.
As described above, after the adhesive film is laminated on the glass substrate, it is cooled to around room temperature. The support film is peeled off as necessary.

[Manufacturing method of laminate]
Next, a specific example of a method for manufacturing a laminated board will be described.
(Production example by heat curing of laminate)
A laminate can be produced by heat-curing (curing treatment) the laminate obtained by the above-described method for producing a laminate by coating.
Moreover, also in the laminated body obtained by the above-mentioned lamination, after peeling a support body film as needed, a laminated board is manufactured by heat-hardening a resin composition layer and setting it as a resin cured material layer. be able to.
The conditions for heat curing are selected in the range of 20 to 80 minutes at 150 to 220 ° C, more preferably 30 to 120 minutes at 160 to 200 ° C. When a support film subjected to a release treatment is used, the support film may be peeled off after being cured by heating.
According to this method, since it is not necessary to pressurize at the time of manufacture of a laminated board, it is controlled that a crack arises at the time of manufacture.
The thickness of the cured resin layer is preferably 5 to 200 μm. If the thickness is 5 μm or more, cracking of the laminate is suppressed. When the thickness is 200 μm or less, the thickness of the glass substrate is relatively increased, so that the thermal expansion coefficient and the high elastic modulus of the laminated plate can be reduced. From this viewpoint, the thickness of the cured resin layer is more preferably 10 to 150 μm, and further preferably 10 to 100 μm.
However, since the appropriate range of the thickness of the cured resin layer varies depending on the thickness of the glass substrate layer, the number of layers, and the number of cured resin layers, the range is not limited to the above range.

The storage elastic modulus at 40 ° C. of the cured resin layer is preferably 1 to 80 GPa. A glass substrate is protected as it is 1 GPa or more, and the crack of a laminated board is suppressed. When it is 80 GPa or less, stress due to the difference in coefficient of thermal expansion between the glass substrate and the cured resin layer is suppressed, and warpage and cracking of the laminate are suppressed. From this viewpoint, the storage elastic modulus of the cured resin layer is more preferably 3 to 70 GPa, and further preferably 5 to 60 GPa.
Furthermore, you may have metal foil, such as copper and aluminum, on the single side | surface or both surfaces of a laminated board. The metal foil is not particularly limited as long as it is used for electrical insulating material applications.

(Production example by press method)
Moreover, the laminated board which concerns on this invention can be manufactured by the press method.
For example, a laminate can be produced by curing a laminate obtained by the above-described laminate by heating and pressurizing by a pressing method.
In addition, the laminated film is obtained by overlaying the above-described adhesive film or the adhesive film main body obtained by removing the support film or the protective film from the adhesive film, and the glass substrate, and curing by heating and pressurizing by a pressing method. Can also be manufactured.
Furthermore, a laminated board can also be manufactured by applying a resin composition on a glass substrate, drying it, and superposing it in a B-stage state, followed by heating and pressing by a pressing method and curing. In that case, it is preferable to heat in the range of 120-300 degreeC, and it is more preferable to heat at 150 degreeC or more and 250 degrees C or less. If it is 120 degreeC or more, there exists a tendency for the adhesiveness of a resin cured material layer and a glass substrate to become favorable, and when 300 degreeC or less, since thermal decomposition of a polyamide-imide resin is suppressed, it is preferable. Moreover, it is preferable to pressurize at 1-5 MPa, and it is more preferable to pressurize at 2-5 MPa.

[Multi-layer laminate and its manufacturing method]
The multilayer laminate of the present invention is a multilayer laminate including a plurality of laminates, and at least one laminate is the aforementioned laminate of the present invention.
There is no restriction | limiting in particular in the manufacturing method of this multilayer laminated board.
For example, a plurality of the above-described laminated plates may be laminated to form a multilayer through an adhesive film body obtained by removing the support film and the protective film from the above-described adhesive film.
Moreover, a multilayer laminated board can also be manufactured by laminating | stacking several laminated bodies (for example, 2-20 sheets) and carrying out lamination | stacking shaping | molding. Specifically, using a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc., the temperature is about 100 to 250 ° C., the pressure is about 2 to 100 MPa, and the heating time is about 0.1 to 5 hours. Can be molded.

[Printed wiring board and manufacturing method thereof]
The printed wiring board of the present invention is formed by providing wiring on at least one surface of the laminated board of the present invention. In addition, there may be a configuration (multilayer printed wiring board) including a plurality of laminated boards. In that case, at least one laminated board is the laminated board of the present invention.
Next, a method for manufacturing this printed wiring board will be described.

(Formation of via holes)
The above laminated plate is drilled by a method such as drilling, laser, plasma, or a combination thereof as necessary to form a via hole or a through hole. As the laser, a carbon dioxide laser, YAG laser, UV laser, excimer laser, or the like is generally used. After forming the via hole or the like, desmear treatment may be performed using an oxidizing agent. As the oxidizing agent, permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid are suitable, and potassium permanganate, sodium permanganate A sodium hydroxide aqueous solution (alkaline permanganic acid aqueous solution) such as the above is more preferable.

(Formation of wiring pattern)
As a subsequent pattern formation method, for example, a known subtractive method or semi-additive method can be used.
When circuit processing is performed by plating on the cured resin layer of the laminate or multilayer laminate of the present invention, first, roughening treatment is performed. As the roughening liquid in this case, an oxidizing roughening liquid such as a chromium / sulfuric acid roughening liquid, an alkaline permanganic acid roughening liquid, a sodium fluoride / chromium / sulfuric acid roughening liquid, or a borofluoric acid roughening liquid should be used. Can do. As the roughening treatment, for example, as a swelling liquid, an aqueous solution of diethylene glycol monobutyl ether and NaOH is first heated to 70 ° C., and the laminate or multilayer laminate is immersed for 5 minutes. Next, as a roughening liquid, an aqueous solution of KMnO ₄ and NaOH is heated to 80 ° C. and immersed for 10 minutes. Subsequently, it is neutralized by immersing it in a neutralizing solution, for example, a stannous chloride (SnCl ₂ ) aqueous hydrochloric acid solution at room temperature for 5 minutes.

After the roughening treatment, a plating catalyst application treatment for adhering palladium is performed. The plating catalyst application treatment is performed by immersing in a palladium chloride plating catalyst solution. Next, it is immersed in an electroless plating solution, and an electroless plating treatment for depositing an electroless plating layer (conductor layer) having a thickness of 0.3 to 1.5 μm is performed.
Next, after forming a plating resist, electroplating is performed to form a circuit with a desired thickness at a desired location. As the electroless plating solution used for the electroless plating treatment, a known electroless plating solution can be used, and there is no particular limitation. As the plating resist, a known plating resist can be used, and there is no particular limitation. Also, the electroplating treatment can be performed by a known method and is not particularly limited. These platings are preferably copper platings. Furthermore, the outer layer circuit can be formed by etching away the electroless plating layer at unnecessary portions.

[Multilayer printed wiring board and manufacturing method thereof]
As one form of the printed wiring board described above, a multilayer printed wiring board may be formed by laminating a plurality of laminated boards on which wiring patterns are formed as described above.
In order to manufacture this multilayer printed wiring board, a multilayer is formed by laminating a plurality of laminated boards on which the above-described wiring pattern is formed via the adhesive film main body described above. Thereafter, through holes or blind via holes are formed by drilling or laser processing, and interlayer wiring is formed by plating or conductive paste. In this way, a multilayer printed wiring board can be manufactured.

[Laminated plate with metal foil and multilayer laminated plate, and production methods thereof]
The laminate of the present invention and the multilayer laminate using the laminate may be a laminate with a metal foil and a multilayer laminate having a metal foil such as copper or aluminum on one side or both sides.
There is no restriction | limiting in particular in the manufacturing method of this laminated sheet with metal foil. For example, as described above, a laminate with a metal foil can be produced by using a metal foil as the support film. In addition, by laminating one or a plurality (for example, 2 to 20) of laminates obtained by the above-described lamination or coating, and laminating and forming the metal foil on one or both sides, a metal foil is obtained. A laminated board can also be manufactured.
The molding conditions can be applied to a laminated plate for an electrical insulating material or a multilayer plate, for example, using a multistage press, a multistage vacuum press, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 100 to 250 ° C., a pressure of 2 Molding can be performed in a range of about 100 MPa and a heating time of about 0.1 to 5 hours.

  EXAMPLES Next, although an Example demonstrates this invention concretely, the scope of the present invention is not limited to these Examples.

(Synthesis of polyamide-imide resin)
X-22-161A (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 32.0 g, 4,4′− while flowing about 250 ml / min of nitrogen into a 500 ml separable flask equipped with a thermocouple, stirrer and nitrogen inlet Diaminodicyclohexylmethane (Wandamine HM (WHM), manufactured by Shin Nippon Rika Co., Ltd., trade name) 0.935 g, Jeffamine D2000 (Mitsui Chemicals Fine) 40.0 g, trimellitic anhydride (hereinafter abbreviated as TMA) 17.9 g and N-methyl-2-pyrrolidone 250 g were added and stirred to dissolve. To this solution was added 100 g of toluene, and after imide ring closure reaction by dehydration reflux for 6 hours at a temperature of 150 ° C. or higher, toluene was distilled off, and after cooling, 13.4 g of 4,4′-diphenylmethane diisocyanate (MDI) was added. In addition, it was reacted at 150 ° C. for 2 hours to synthesize a polyamideimide resin. Thereafter, 1.6 g of TMA was added and stirred at 80 ° C. for 1 hour to synthesize a polyamideimide resin solution.

(Varnish A)
20 g of dicyclopentadienephenol type epoxy resin HP7200 (trade name, manufactured by DIC Corporation) in a polyamideimide resin solution having a solid content of 70 g, resin EPPN-502H (Nippon Kayaku Co., Ltd.) having 3 or more functional groups that react with epoxy groups Product, trade name, polyfunctional epoxy resin) 10 g, curing accelerator 2E4MZ-CN (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name) 0.15 g, diluted with NMP to a solid content concentration of 30%, Varnish A was prepared.

(Varnish B to C)
Like varnish A, it was blended in the blending amounts shown in Table 1.

(Varnish D)
It was blended in the same manner as Varnish A except that biphenyl novolac type epoxy resin NC3000 (manufactured by Nippon Kayaku Co., Ltd., trade name) was used in place of epoxy resin HP7200.

  In the above blending example, HP7200 has two or more epoxy groups in one molecule and is compatible with polyamideimide resin, NC3000 has two or more epoxy groups in one molecule, and polyamideimide resin and An incompatible epoxy resin, EPPN-502H, is a resin having three or more functional groups that react with epoxy groups in one molecule.

(Manufacture of adhesive film)
Resin varnishes A to D were dried to 5 μm using a bar coater on the release treatment surface of a release-treated polyethylene terephthalate (PET) film (PET-38X, manufactured by Lintec Co., Ltd.) having a thickness of 38 μm. It was applied so that it was dried at 140 ° C. for 15 minutes to form a resin composition layer, and an adhesive film was obtained.

(Manufacture of film for adhesion auxiliary layer)
After blending 91.4 g of N, N-dimethylacetamide (DMAc) with 10.2 g of phenolic hydroxyl group-containing polybutadiene modified polyamide (Nippon Kayaku Co., Ltd., trade name: BPAM-155), biphenylaralkyl epoxy resin ( Nippon Kayaku Co., Ltd., trade name: NC-3000H) 40.0 g, bisphenol A novolak (Mitsubishi Chemical Corporation, trade name: YLH129) 12.6 g, 2-phenylimidazole (Shikoku Chemicals Co., Ltd.) as a curing accelerator 0.4 g of company-made product name: 2PZ) and 3.6 g of fumed silica (manufactured by Nippon Aerosil Co., Ltd., product name: R972) were added, followed by a mixed solvent consisting of DMAc and methyl ethyl ketone (MEK / DMAc = 7/3). (Mass ratio)) (solid content concentration of about 25% by mass). Thereafter, a resin varnish for an auxiliary adhesion layer was obtained using a disperser (Nanomizer, trade name, manufactured by Yoshida Kikai Kogyo Co., Ltd.).
The adhesive varnish resin varnish was applied to a glossy surface of a 20 μm thick copper foil (NC foil, manufactured by Furukawa Electric Co., Ltd.) using a bar coater so that it would be 5 μm after drying, and at 140 ° C. for 10 minutes. It was made to dry and the resin film for adhesion auxiliary layers was produced.

[Production of laminated sheet for glass adhesion evaluation (cured resin layer / glass substrate layer / cured resin layer)]
(Examples 1-4)
As the glass substrate, an ultrathin glass film “OA-10G” (trade name, thickness 100 μm) manufactured by Nippon Electric Glass Co., Ltd. was used. The resin composition layer of the produced adhesive film is disposed on both surfaces of the glass substrate so as to be in contact with the glass substrate, and a batch type vacuum pressure laminator “MVLP-500” (trade name, manufactured by Meiki Co., Ltd.) And laminated by lamination to obtain a laminate. The degree of vacuum at this time was 30 mmHg or less, the temperature was set to 120 ° C., and the pressure was set to 0.5 MPa.
After cooling to room temperature, the support film was peeled off, and the copper foil was placed so that the glossy surface was in contact with the resin composition layer, and then thermocompression bonded with a hot press at 185 ° C., 3 MPa for 1 hour. The copper foil was etched to obtain a laminated sheet for glass adhesion evaluation (cured resin layer / glass substrate layer / cured resin layer). What used the adhesive film created by varnish AD correspond to Examples 1-4, respectively.
(Reference example)
As the glass substrate, an ultra-thin glass film “OA-10G” (trade name, thickness 100 μm) manufactured by Nippon Electric Glass Co., Ltd. was used. It arrange | positioned so that it might contact | connect a board | substrate and thermocompression bonded with the hot press on conditions of 185 degreeC, 3 MPa, and 1 hour. Next, the copper foil was etched to obtain a laminated sheet for glass adhesion evaluation (adhesion auxiliary layer / glass substrate layer / adhesion auxiliary layer).

Next, the adhesion to glass was measured and evaluated for the glass adhesive evaluation laminates obtained in Examples and Reference Examples by the following methods.
[Glass adhesion]
Adhesion was evaluated by a cross-cut test.
Cross-cut test: After cross-cut guide CCJ-1 (product name, manufactured by Co-Tech Co., Ltd.), 5 cuts with a width of 2 mm were put into the prepared laminate, and the TQC ISO adhesion tape was peeled off. The surface state was observed, and the number of squares that did not peel off in 25 squares was examined. In addition, the experiment method was based on JISK56005-6.
The results are shown in Table 2.

  Next, in order to evaluate the solder heat resistance at the time of mounting, the laminated film for solder heat resistance evaluation was obtained by a series of processes using the resin film for adhesion auxiliary layers.

[Manufacture of laminates for solder heat resistance evaluation]
(Examples 1-4)
As the glass substrate, an ultrathin glass film “OA-10G” (trade name, thickness 100 μm) manufactured by Nippon Electric Glass Co., Ltd. was used. On both surfaces of this glass substrate, the resin composition layer of the produced adhesive film is arranged so as to be in contact with the glass substrate, and a batch type vacuum pressure laminator “MVLP-500” (trade name, manufactured by Meiki Co., Ltd.) And laminated by lamination. The degree of vacuum at this time was 30 mmHg or less, the temperature was set to 120 ° C., and the pressure was set to 0.5 MPa. After cooling to room temperature, the support film of the adhesive film is peeled off, and the resin layer of the adhesion auxiliary layer resin film is placed in contact with the resin composition layer provided on the glass substrate, and then 185 ° C., 3 MPa, 1 hour. Thermocompression bonding was performed with a hot press under the conditions described above. Thereafter, the copper foil was etched to obtain a laminate.

In order to chemically roughen the obtained laminate, an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L, NaOH: 5 g / L was prepared as a swelling liquid, heated to 70 ° C. and immersed for 5 minutes. Next, an aqueous solution of KMnO ₄ : 60 g / L and NaOH: 40 g / L was prepared as a roughening solution, heated to 80 ° C. and immersed for 10 minutes. Subsequently, it was neutralized by immersing in an aqueous solution of a neutralizing solution (SnCl ₂ : 30 g / L, HCl: 300 ml / L) at room temperature for 5 minutes.

In order to form a conductor layer on a chemically roughed laminate, first, it is immersed for 10 minutes at room temperature in HS-202B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is an electroless plating catalyst containing PdCl _2. This was treated, washed with water, immersed in a plating solution CUST-201 (trade name, manufactured by Hitachi Chemical Co., Ltd.) for electroless copper plating for 15 minutes at room temperature, and further subjected to copper sulfate electrolytic plating. Thereafter, annealing was performed at 180 ° C. for 60 minutes to form a conductor layer having a thickness of 25 μm to obtain a laminated board for solder heat resistance evaluation. What used the adhesive film created by varnish AD correspond to Examples 1-4, respectively.
(Reference example)
As the glass substrate, an ultra-thin glass film “OA-10G” (trade name, thickness 100 μm) manufactured by Nippon Electric Glass Co., Ltd. was used. It arrange | positioned so that it might contact | connect a board | substrate and thermocompression bonded with the hot press on conditions of 185 degreeC, 3 MPa, and 1 hour. Subsequently, the copper foil was etched to obtain a laminate (adhesion auxiliary layer / glass substrate layer / adhesion auxiliary layer). Next, a conductor layer was formed on the laminate by the same method as in the above-described example, and a laminate for solder heat resistance evaluation was obtained.

About the obtained laminated board for solder heat resistance evaluation, solder heat resistance was evaluated as follows.
[265 ° C solder heat resistance]
The solder heat resistance evaluation laminate produced in each example was cut into 25 mm squares, floated in a solder bath adjusted to 265 ± 2 ° C., and the time (seconds) until blistering was examined. The results are shown in Table 2.

As is clear from Table 2, Examples 1 to 4 of the present invention have high adhesion between the resin composition layer and the glass substrate layer. Moreover, since the laminated board produced using the resin composition layer by this invention is excellent also in solder heat resistance, it turns out that a wiring board in consideration of the environment can be manufactured.
From the above results, according to the present invention, it is possible to provide a laminate having excellent adhesion and heat resistance between the resin composition layer and the glass substrate layer.

Claims (17)

  A laminate comprising one or more resin composition layers and one or more glass substrate layers, wherein the resin composition layer comprises a polyamideimide resin and an epoxy resin.   The laminated body of Claim 1 whose said polyamide-imide resin is 50-85 mass% in all the resin components.   The laminate according to claim 1 or 2, wherein the epoxy resin has two or more epoxy groups in one molecule.   The laminated body as described in any one of Claims 1-3 containing resin which has 3 or more of functional groups which react with an epoxy resin in 1 molecule.   The laminate according to claim 4, wherein the epoxy resin is contained in an amount of 10 to 30% by mass in all resin components, and a resin having 3 or more functional groups that react with the epoxy group in one molecule is contained in 5% or more of all resin components. .   The laminate according to claim 4 or 5, wherein a resin having three or more functional groups that react with the epoxy group in a molecule is contained within a range not exceeding the solid content of the epoxy resin. The polyamideimide resin is obtained by reacting at least one dicarboxylic acid derivative represented by the following general formulas (1) to (3) with at least one aromatic diisocyanate represented by the general formula (4). The laminate according to any one of claims 1 to 6.

(Where R ₁ is

(Wherein, X ₁ is a single bond, 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),. )

(Where R ₂ is

(Wherein, R ₃ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, n represents an integer of 1 to 100) shows a. )

(Where R ₄ is

(However, R ₅ and R ₆ each independently represent a divalent organic group, R _{7 to} R ₁₀ each independently represent an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms, n is an integer of 1-50. )

(Where R ₁₁ is

Indicates. )   The laminate according to any one of claims 1 to 7, wherein the epoxy resin is an epoxy resin having an alicyclic skeleton.   The laminate according to any one of claims 1 to 8, wherein the glass substrate layer has a thickness of 30 to 200 µm.   The laminate according to any one of claims 1 to 9, wherein a total thickness of the resin composition layer and the glass substrate layer is 40 to 300 µm.   It is a laminated board containing 1 or more layers of resin cured material layers and 1 or more glass substrate layers, Comprising: The laminated board obtained by hardening-processing the laminated body of any one of Claims 1-10.   The printed wiring board by which wiring is provided in the at least one surface of the laminated board of Claim 11.   The printed wiring board according to claim 12, comprising a plurality of laminated boards, wherein at least one laminated board is the laminated board according to claim 11.   The manufacturing method of the laminated body which apply | coats the resin composition containing a polyamidoimide resin and an epoxy resin to the surface of a glass substrate, and forms a resin composition layer.   The manufacturing method of the laminated body of Claim 14 which performs a drying process after forming the said resin composition layer.   A method for producing a laminate, comprising producing a film comprising a resin composition containing a polyamideimide resin and an epoxy resin, laminating the film on a glass substrate using a vacuum laminator or a roll laminator, and then subjecting the film to a curing treatment. .   The manufacturing method of the laminated board of Claim 16 which performs a press process before giving the said hardening process after laminating | stacking the said film.