TW201501923A - Laminate, laminated sheet, printed circuit board, and production method for laminate and laminated sheet - Google Patents

Abstract

The purpose of the present invention is to provide a laminate and a laminated sheet having ample heat resistance and adhesion between a glass substrate layer and a resin composition layer, and a production method for the same. A further purpose is to provide a printed circuit board employing the laminate or laminated sheet.The laminate has one or more resin composition layers and one or more glass substrate layers, the resin composition layer containing a polyamide-imide resin and an epoxy resin. Also provided are a laminated sheet obtained through curing of the resin composition layer of this laminate, and a printed circuit board employing the laminate or laminated sheet.

Description

Laminated body, laminated board, printed wiring board, and method for manufacturing laminated body and laminated board

The present invention relates to a laminate, a laminate, a laminate, a method for producing a laminate, and a printed wiring board, which is suitable for use in a semiconductor package and a printed wiring board.

The board is required to reduce the line spacing to achieve high density lines. As a method of arranging a semiconductor for a high-density line, a flip-chip bonding method has been widely used in place of the conventional wire bonding method.

The flip chip connection method is a method of connecting a wiring board and a semiconductor using a solder ball without using a metal wire. In this method, solder balls are disposed between a wiring board and a semiconductor which are disposed to face each other, and the whole is heated to reflow (melt-bond) the solder, whereby the wiring board and the semiconductor are connected and assembled.

In this method, when the solder is reflowed, heat of approximately 300 ° C is applied to the wiring board or the like. Therefore, a circuit board or the like needs to have high heat resistance.

On the other hand, there is an increasing demand for thinner and lighter electronic devices, and thinner and higher density of semiconductor packages and printed wiring boards. Continuous development. In order to stably mount electronic components that are thinner and higher in density in accordance with the semiconductor package and the printed wiring board, it is important to suppress warpage generated during the mounting. One of the main causes of warpage of the semiconductor package during the mounting is that the laminated board used in the semiconductor package has a difference in thermal expansion coefficient between the germanium wafer mounted on the surface of the laminated board. Therefore, the thermal expansion coefficient of the laminate for a semiconductor package is made close to the thermal expansion coefficient of the tantalum wafer, that is, the thermal expansion coefficient of the laminate for a semiconductor package is reduced, and an attempt is made to use a glass film as a thermal expansion with a tantalum wafer. A layer having a coefficient of thermal expansion that substantially matches the coefficient, and laminating the resin and the glass film by pressurization, thereby reducing thermal shock stress (Patent Document 1); however, the resin used has a low adhesion to the glass substrate, and at a high temperature The stress generated by the difference in thermal expansion coefficient causes peeling between the resin layer and the glass substrate layer, so the reflow heat resistance is not sufficient.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent No. 4675554

As described above, the glass substrate and the conventional resin composition layer lack adhesiveness, and peeling occurs during solder reflow, and the heat resistance during the assembly is insufficient.

According to the above, an object of the present invention is to provide a laminated body and a laminated board, and a method of manufacturing the laminated body and the laminated board, wherein the laminated body In the laminate, the adhesion between the glass substrate layer and the resin composition layer and the heat resistance are good. Further, it is an object of the invention to provide a printed wiring board which is formed using the laminated body or laminated board.

In order to solve the above problems, the inventors of the present invention have found that the problem can be solved by including a polyamidoximine 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 polyimide film and an epoxy resin.

[2] The laminate according to [1], wherein the polyamidoximine resin is 50 to 85% by mass based on the total of the resin components.

[3] The laminate according to [1], wherein the epoxy resin has two or more epoxy groups in one molecule.

[4] The laminate according to any one of [1] to [3] wherein a resin having three or more functional groups reactive with an epoxy resin in one molecule is contained.

[5] The laminate according to the above [4], wherein the epoxy resin contains 10 to 30% by mass of the entire resin component, and the resin having three or more epoxy group-reactive functional groups in the above molecule It contains 5% or more of all resin components.

[6] The layered body according to the above [4], wherein, in a range not exceeding the solid content of the epoxy resin, three or more functional groups reactive with an epoxy group are contained in the one molecule. Base resin.

The layered product according to any one of the above-mentioned general formulas (1) to (3) At least one of a carboxylic acid derivative is reacted with at least one of the aromatic diisocyanates represented by the formula (4) to obtain: (wherein R ₁ represents a group as described below, (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, or a carbonyl group)); (wherein R ₂ represents a group as described below, (wherein R ₃ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 1 to 100)); (wherein R ₄ represents a group as described below, (wherein R ₅ and R ₆ each independently represent a divalent organic group, and 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, and n is 1 to 50; Integer)); OCN-R ₁₁ -NCO.. (4) (wherein R ₁₁ represents a group as described below, ).

[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 thickness of the glass substrate layer is 30 to 200 μm.

[10] The laminated body according to any one of [1] to [9] wherein the total thickness of the resin composition layer and the glass substrate layer is 40 to 300 μm.

[11] A laminate comprising one or more layers of a resin cured layer and one or more layers of a glass substrate, wherein the laminate is a laminate according to any one of [1] to [10] Obtained by hardening treatment.

[12] A printed wiring board formed by providing a wiring on at least one surface of a laminated board according to [11].

[13] The printed wiring board according to [12], wherein the printed wiring board comprises a plurality of laminated boards, and at least one of the laminated boards is the aforementioned laminated board according to [11].

[14] A method for producing a laminate, which comprises applying a resin composition comprising a polyimide film and an epoxy resin onto a surface of a glass substrate to form a resin Composition layer.

[15] The method for producing a laminate according to [14], wherein the resin composition layer is formed and then subjected to a drying treatment.

[16] A method for producing a laminate, which comprises first forming a film composed of a resin composition containing a polyimide film and an epoxy resin, and laminating the film on a glass using a vacuum laminator or a roll laminator. After the substrate, the film is subjected to a hardening treatment.

[17] The method for producing a laminated board according to [16], wherein the pressing treatment is performed after the film is laminated and before the hardening treatment is performed.

According to the present invention, there is provided a laminated body and a laminated board, and a method for producing the laminated body and the laminated board, wherein the resin composition layer and the glass substrate layer have good adhesion and heat resistance in the laminated body and the laminated board. Further, a printed wiring board which is formed using the laminated body or the laminated board can be provided.

Hereinafter, the laminated body, the laminated board, the laminated body, the manufacturing method of the laminated board, and the printed wiring board of this invention are demonstrated in detail.

In the present specification, the term "layered body" means a thermosetting resin (polyfunctional epoxy resin) as a constituent component in the resin composition. It is an unhardened or semi-hardened material; the term "laminated board" means a material which is a constituent component, that is, a thermosetting resin is cured, or a thermosetting resin is cured by 90% or more. Further, the degree of hardening of the thermosetting resin can be measured by a reaction rate which is measured by a differential scanning calorimeter.

[layered body]

The laminate of the present invention has one or more resin composition layers and one or more glass substrate layers, and the resin composition layer contains a polyimide film and an epoxy resin.

Here, the resin composition layer of the present invention is present on the support in an uncured or semi-hardened state (B-Stage state) before being a layer of a wiring board for a wiring board or a part of a multilayer wiring board. Or on a glass substrate.

Further, the laminate of the present invention is obtained by heating the laminate of the present invention to thereby harden the resin composition layer to form a resin cured layer, thereby obtaining a laminate of the present invention.

Here, by using a glass substrate layer having a low thermal expansion coefficient and a high elastic modulus which is the same degree as the tantalum wafer, warpage is suppressed and cracking is less likely to occur. In particular, such a laminate has a glass substrate layer having high heat resistance, and has a remarkable low thermal expansion property in a temperature range of from 100 ° C to a glass transition temperature (Tg) of the cured resin. Further, by including the inorganic filler in the resin cured layer, the cured resin layer has low thermal expansion and high elasticity, and the laminate including the cured resin layer has lower thermal expansion and higher modulus of elasticity .

Further, an auxiliary adhesive layer may be provided between the cured resin layer of the present invention and the conductor layer to improve the adhesion between the cured resin layer and the conductor layer.

(resin composition)

Hereinafter, the resin composition used in the resin composition layer of the present invention will be described in detail.

The resin composition of the present invention comprises a polyamidoximine resin and an epoxy resin. In the resin composition, from the viewpoint of glass adhesion, the amount of the base resin for ensuring the adhesion of the glass, that is, the polyimide amine imide resin, is preferably 50 to 85 mass in all the resin components. %, more preferably 50 to 80% by mass. Further, the blending amount of the polyamidoximine resin is preferably from 50 to 75% by mass in terms of heat resistance. The blending amount of the polyamidoximine resin is preferably from 50 to 90% by mass, more preferably from 55 to 85% by mass, particularly preferably from 60 to 85% by mass, based on the total of the resin component. When the polyamidoximine resin is blended in the above range, it exhibits a glass adhesive property derived from a polyamidoximine resin, which is preferable.

The blending amount of the epoxy resin is preferably from 10 to 30% by mass, more preferably from 12 to 28% by mass, particularly preferably from 15 to 25% by mass, based on the total of the resin component. When the epoxy resin is blended in the above range, the crosslinking density is sufficient, and good heat resistance is obtained. Moreover, epoxy resins and polyamidoximine resins are more difficult to phase separate.

The polyamidoximine resin of the present invention is a polymer having a mercaptoamine group and a quinone imine group in the main chain.

The polyamidoximine resin of the present invention preferably has at least one of the dicarboxylic acid derivatives represented by the following general formulae (1) to (3) and is represented by the general formula (4). A polyamidoximine resin obtained by at least one reaction of an aromatic diisocyanate: (wherein R ₁ represents a group as described below, (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, or a carbonyl group)); (wherein R ₂ represents a group as described below, (wherein R ₃ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 1 to 100)); (wherein R ₄ represents a group as described below, (wherein R ₅ and R ₆ each independently represent a divalent organic group, and 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, and n is 1 to 50; Integer)); OCN-R ₁₁ -NCO.. (4) (wherein R ₁₁ represents a group shown below, ).

The polyamidoximine resin of the present invention can be synthesized by a method comprising the steps of: reacting a diamine with trimellitic anhydride to form a dicarboxylic acid derivative; and, deriving a dicarboxylic acid The step of reacting with a diisocyanate to form a polyamidoximine resin. The polyamidoximine resin of the present invention can be preferably obtained by the above method, but is not limited to the resin obtained by the above method, without departing from the gist of the present invention. For example, the polyamidoximine resin of the present invention may be a resin obtained by reacting trimellitic anhydride with a diamine, that is, a ruthenium chloride method.

The diamine used for the synthesis of the dicarboxylic acid derivative is preferably an alicyclic diamine, an aliphatic diamine or a decane diamine.

Examples of the alicyclic diamine include an alicyclic diamine having the following structural formula.

(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, or a carbonyl group)

Such an alicyclic diamine is preferably, for example, 4,4'-diaminodicyclohexylmethane or the like. Examples of the alicyclic diamine which is commercially available include Wondamine HM (amine equivalent of 100 or more, manufactured by Shin Nippon Chemical Co., Ltd., trade name).

As the aliphatic diamine, oxypropylene diamine is preferred. Commercially available aliphatic diamines include, for example, Jeffamine D-230 (Mitsui Fine Chemicals, Inc., amine equivalent: 115, trade name), Jeffamine D-400 (Mitsui Fine Chemical Co., Ltd.) Company, amine equivalent: 200, trade name), Jeffamine D-2000 (Mitsui Fine Chemical Co., Ltd., amine equivalent: 1000, trade name), Jeffamine D-4000 (Mitsui Fine Chemical Co., Ltd., amine equivalent: 2000, commodity Name) and so on.

The oxime diamine is a diamine having a siloxane skeleton, and examples thereof include a diamine having the following structural formula.

(wherein R ₅ and R ₆ each independently represent a divalent organic group, and 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, and n is 1 to 50. Integer)

A commercially available product can be used as the oxirane diamine. For example, "KF-8010" (amine equivalent 430), "X-22-161A" (amine equivalent 800), and "X-22-161B" can be used. (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 Dow Corning Toray Co., Ltd.), and the like. These oxirane diamines may be used singly or in combination of two or more.

These diamines may be used alone or in combination of two or more. In the synthesis of the dicarboxylic acid derivative, 5 to 100% by mass of the diamine used in the synthesis of the dicarboxylic acid derivative is preferably synthesized by using the above diamine. When a dicarboxylic acid derivative synthesized in this manner is used, the obtained polyamidoximine resin satisfies several characteristics. Among them, if a nonoxyldiamine is used, the obtained polyamidoximine resin exhibits good heat resistance and a low modulus of elasticity, and thus is more preferable.

Further, an aromatic diamine may be used in addition to the above diamines, as needed. Examples of the aromatic diamine include p-, m-, o-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, and diamine. Diaminodurene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, benzidine, 4,4'-diaminotriphenyl, 4,4'''-diamine linkage Tetraphenyl, 4,4'-diaminodiphenylmethane, 1,2-bis(anilino)ethane, 4,4'-diaminodiphenyl ether, diaminodiphenyl hydrazine, 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-4,4'-diaminodiphenylmethane, diaminotoluene, two Aminotrifluorotoluene, 1,4-bis(p-aminophenoxy)benzene, 4,4'-bis(p-aminophenoxy)biphenyl, 2,2'-bis[4-(p-amine) Phenoxy group) phenyl] propane, diamino hydrazine, 4,4'-bis(3-aminophenoxyphenyl)diphenyl hydrazine, 1,3-bis(anilino)hexafluoropropane, 1,4-bis(anilino)octafluorobutane, 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-double [4-(4-Aminophenoxy)-3,5-di-trifluoromethylphenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl hydrazine, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl Anthracene, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, and the like. The aromatic diamine may be used in an amount of from 0 to 95% by mass based on the diamine used in the synthesis of the dicarboxylic acid derivative.

The dicarboxylic acid derivative can be synthesized by using the above-mentioned oxirane diamine, alicyclic diamine, aliphatic diamine, and optionally diamine of an aromatic diamine, and trimellitic anhydride. . The molar ratio of the diamine to the trimellitic anhydride is preferably about 1:2. For example, the dicarboxylic acid derivative can be synthesized by using N-methyl-2-pyrrolidone (N). -methyl-2-pyrrolidone, NMP) and other solvents, the diamines are reacted with trimellitic anhydride at 50-90 ° C, and then the ring-opening reaction of the quinone ring is carried out at 120-180 ° C to synthesize dicarboxylic acid Acid derivative biological. Then, using the dicarboxylic acid derivative and reacting with a diisocyanate, a polyamidoximine resin can be synthesized. Further, in the case of synthesizing the dicarboxylic acid derivative, the nonanediamine diamine, the alicyclic diamine, and the aliphatic diamine may be used alone or in combination of two or more kinds. When the three types are used in combination, the blending amount of the oxirane diamine, the alicyclic diamine, and the aliphatic diamine is preferably 30% in terms of adhesion and compatibility with the epoxy resin. 70% of the moles, 5 to 60% of the moles, and 10 to 40% of the moles.

The diisocyanate used in the reaction is, for example, an aromatic diisocyanate represented by the formula (4), which is obtained by a reaction of an aromatic diamine with phosgene or the like. Examples of the aromatic diisocyanate include toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, and phenyl-1,3-diisocyanate.

Among the above aromatic diisocyanates, in terms of heat resistance, for example, 1,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, bis(methylphenyl)methane is preferable. Diisocyanate, naphthalene diisocyanate.

The polymerization of polyamidoximine is usually carried out in the following solvents: N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF) , N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO), dimethyl sulfate, cyclobutyl hydrazine, γ-butyrolactone, cresol , phenol, halogenated phenol, cyclohexane, dioxane, and the like. Reaction temperature, preferably 200 ° C the following. Further, in terms of controlling the molecular weight, the molar ratio of the diisocyanate to the dicarboxylic acid derivative is preferably about 1:2.

The epoxy resin used in the resin composition of the present invention is preferably an epoxy resin having two or more epoxy groups in one molecule. Further, in terms of solubility of the epoxy resin in the polyamidoximine resin, an epoxy resin having 2 to 5 epoxy groups in one molecule is preferred. Particularly preferred is an epoxy resin having a structure similar to that of a diamine used in a polyamide amine imide resin, for example, when a polyamidoximine resin is obtained using oxypropylene diamine, good dissolution is obtained. In terms of properties, the epoxy resin is preferably an aliphatic epoxy resin, and more preferably an alicyclic epoxy resin in view of heat resistance of the resin composition. Examples of such an aliphatic epoxy resin include a dicyclopentadiene phenol type epoxy resin HP7200 (manufactured by Dainippon Ink & Chemicals, Inc., trade name).

If an epoxy resin which is incompatible with the polyamide amide resin (for example, a biphenyl aldehyde varnish type epoxy resin NC3000 (manufactured by Nippon Kayaku Co., Ltd.), trade name) is used. ), the epoxy resin is phase-separated from the polyamidoximine resin, and the soluble component is easily infiltrated into the less alkali-resistant polyamide amine imide resin. On the other hand, when an epoxy resin having compatibility is used, the epoxy resin is uniformly dispersed in the polyamide amidoximine resin, thereby inhibiting the entry of the soluble component. Therefore, chemical resistance is improved.

The resin composition of the present invention preferably contains a resin having three or more reactive groups with an epoxy group in terms of chemical resistance. Functional resin. Examples of the resin having three or more functional groups reactive with an epoxy group in one molecule include a polyfunctional epoxy compound having three or more epoxy groups, a polyfunctional phenol compound, and a polyfunctional amine. Amine ester resin and the like.

Examples of the polyfunctional epoxy compound having three or more epoxy groups include polyphenols such as bisphenol A, novolac type phenol resins, and o-cresol novolac type phenol resins, or 1,4-butane. a polyglycidyl ether obtained by reacting a polyol such as an alcohol with epichlorohydrin; a polyglycidyl ester obtained by reacting a polybasic acid such as phthalic acid or hexahydrophthalic acid with epichlorohydrin; having an amine group and an anthracene An N-glycidyl derivative of an amine- or heterocyclic nitrogen-containing base compound; an alicyclic epoxy resin or the like.

Examples of the polyfunctional phenol compound include hydroquinone, resorcin, bisphenol A, and halides thereof, and condensates with formaldehyde, that is, novolac type phenol resins, resol phenols. Resin, etc.

The compounding amount of the resin having three or more functional groups reactive with an epoxy group is preferably from 5 to 30% by mass, more preferably from 7 to 25% by mass, particularly preferably from 8 to 20% by mass based on the entire resin component. %. When the resin having three or more functional groups reactive with an epoxy group is blended in the above range, it has both chemical resistance and adhesion.

The resin composition of the present invention may further contain a curing agent for an epoxy resin and a curing accelerator. The curing agent for the epoxy resin and the curing accelerator are not limited as long as they can react with the epoxy resin or promote hardening, for example, Amines, imidazoles, acid anhydrides and the like can be used. As the amine, for example, dicyandiamide, diaminodiphenylmethane, guanidine or the like can be used, and as the acid anhydride, for example, phthalic anhydride or diphenyl ketone tetracarboxylic dianhydride can be used. Methyl norbornene (methyl himic acid) or the like. As the hardening accelerator, for example, an alkyl-substituted imidazole, benzimidazole or the like of an imidazole can be used.

The resin composition of the present invention may also contain an inorganic filler. By blending the inorganic filler with the resin composition, the cured resin layer can be made to have low thermal expansion and high elasticity. Examples of the inorganic filler include cerium oxide, aluminum oxide, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and borosilicate glass. Among them, in terms of low thermal expansion, it is preferably cerium oxide, and more preferably spherical amorphous cerium oxide, and the spherical amorphous cerium oxide has a very small thermal expansion coefficient of about 0.6 ppm/K. And the fluidity is less reduced when a large amount is filled in the resin.

Further, the resin composition of the present invention may further contain the following additives: a decane coupling agent, an electrolytic corrosion resistance improving agent, a flame retardant, a rust preventive agent, and the like.

The polyamidoximine resin and the epoxy resin and the like are mixed as described above to obtain a resin composition, and the resin composition is laminated on a glass substrate to form a resin composition layer, whereby a laminate can be produced. The method will be described later.

(glass substrate layer)

The glass substrate constituting the glass substrate layer is preferably a thin glass having a thickness of 30 to 200 μm from the viewpoint of the purpose of thinning the laminated body and workability. The film is preferably 50 to 150 μm in thickness in consideration of ease of handling and the like. Further, from the viewpoint of thinning the laminated body, the thickness is preferably from 30 to 90 μm. Further, as the raw material of the glass substrate, glass such as alkaline bismuth carbonate glass, alkali-free glass, or quartz glass can be used, and from the viewpoint of low thermal expansion property and workability, borosilicate glass is preferable.

Further, the total thickness of the resin composition layer and the glass substrate layer is preferably 40 to 300 μm, more preferably 100 to 250 μm. By making the total thickness of the resin composition layer and the glass substrate layer 40 to 300 μm, it is possible to reduce the thickness of products such as printed wiring boards.

Further, the closer the thermal expansion coefficient of the glass substrate layer is to the thermal expansion coefficient (about 3 ppm/° C.) of the tantalum wafer, the more the warpage of the laminated body or the laminated sheet obtained from the laminated body can be suppressed, which is preferable. The coefficient of thermal expansion of the glass substrate layer is preferably 8 ppm/° C. or lower, more preferably 6 ppm/° C. or lower, and still more preferably 4 ppm/° C. or lower.

The glass substrate layer preferably has a dynamic storage elastic modulus at 40 ° C, preferably 20 GPa or more, more preferably 25 GPa or more, and still more preferably 30 GPa or more. When the dynamic storage modulus of the glass substrate layer at 40 ° C is 20 GPa or more, warpage of the laminate or the laminate obtained from the laminate is suppressed, and good results are obtained.

As a method of measuring the storage elastic modulus of the laminate at 40 ° C, for example, the following method can be mentioned. First, a test piece of 5 mm × 30 mm was cut out from the laminate. In the case of using a copper clad laminate, the copper clad laminate is impregnated After removing the copper foil in the copper etching solution, the test piece was cut. Using a wide-area viscoelasticity measuring device (DVE-V4, manufactured by Rheology Co., Ltd.), the cut test piece can be measured at 40 ° C under the conditions of a span of 20 mm, a frequency of 10 Hz, and a vibration displacement of 1 to 3 μm (vibration reduction). The lower tensile storage elastic modulus.

(Support body film and protective film)

The laminate of the present invention may have a support film or a protective film on the surface. As the support film to be used, a polyethylene terephthalate film, a polyethylene naphthalate film, a polyphenylene sulfide film, a Teflon (registered trademark) film, and a polycondensation are preferable. A ruthenium imide film, a copper foil which has not been roughened, or a low-roughened copper foil having a surface roughness (Ra) of 0.4 μm or less, and an aluminum foil. Further, as the support film, a support film having a surface-released treatment may be used to easily peel off from the resin.

The protective film may be, for example, a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate, a polycarbonate, a fluorine-based film, or a release paper. Further, the thickness of the protective film is preferably from 20 to 100 μm, and the protective film may be subjected to a mat treatment, a corona treatment, or a mold release treatment. The support film and the protective film will be described in detail in the description of the method for producing the laminated body to be described later.

[Manufacturing method of laminated body]

In the method for producing a laminate according to the present invention, the laminate of the present invention can be produced by coating a resin composition on a glass substrate or laminating a film made of a resin composition on a glass substrate. Among them, in terms of ease of production, it is preferably a method of lamination.

Hereinafter, each manufacturing method will be described in detail.

[Manufacturing method of laminated body by coating]

The coating method by coating is a method in which the resin composition is applied onto the surface of a glass substrate to form a resin composition layer to produce a laminate. For example, the above resin composition is dissolved in an organic solvent to prepare a varnish. The varnish is applied onto a glass substrate, and the organic solvent is dried by heating or hot air blowing to form a resin composition layer. The resin composition layer can be further semi-hardened. Thus, a laminate in which the resin composition layer is in an unhardened or semi-hardened state (B-stage state) can be produced.

[Manufacturing method of laminated body by lamination]

The laminate can be produced by laminating an adhesive film formed using the resin composition of the present invention and a glass substrate. This adhesive film will be described later. Further, lamination can be carried out using a commercially available vacuum laminator or roll laminator.

Further, as the epoxy resin in the resin composition, it is preferred to use an epoxy resin which can be melted at a temperature equal to or lower than the temperature at the time of lamination. For example, in the case of laminating using a vacuum laminator or a roll laminator, it is usually carried out at a temperature of 140 ° C or less. Therefore, the epoxy resin in the above resin composition is preferably 140 ° C or less. Epoxy resin that melts at temperature.

First, the above-mentioned adhesive film will be described, and next, a lamination method using the adhesive film will be described.

(adhesive film)

When a laminate is produced by a vacuum laminator or a roll laminator, it is preferred to form the resin composition as an adhesive film.

As the adhesive film used in the present invention, an adhesive film having the following laminated structure is preferably used.

(1) Supporting film/resin composition layer

In addition, the adhesive film having the laminated structure of the above-mentioned (1) and the laminated structure of the protective film may be preferably used.

(2) Supporting 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 without the support film. Protective film prevents foreign matter from adhering or damaging.

Further, the portions of the adhesive film after removing the support film and the protective film are sometimes referred to as an adhesive film body.

The adhesive film having the laminated structure of the above (1) and (2) can be produced by a method known to those skilled in the art.

As an example of the production of the adhesive film of the above (1), the resin composition can be dissolved in an organic solvent to prepare a varnish. Then, the varnish is applied as a support by using a support film, and the organic solvent is dried by heating or hot air blowing to form a resin composition layer.

As an example of the production of the adhesive film of the above (2), the resin composition can be dissolved in an organic solvent to prepare a varnish. Then, the varnish is applied to the support Any one of the body film and the protective film, and the other of the support film and the protective film is disposed on the varnish, and the organic solvent of the varnish is dried by heating or hot air blowing, thereby forming a resin Composition layer.

As the brushing device of the resin composition layer, a brushing device known to those skilled in the art, for example, a comma coater, a bar coater, can be used. Bar coater, kiss coater, roll coater, gravure coater, die coater, etc., preferably made according to a bar coater, a kiss coater, a roll coater, a die coater, etc. The film thickness is suitable for selecting a painting device.

Further, in the above adhesive film, the resin composition layer may be semi-hardened.

The support film is a support for producing an adhesive film. When a multilayer printed wiring board is produced, the support film is usually peeled off or removed at the end.

Next, an example of a lamination method using the above adhesive film will be described.

When the adhesive film has a protective film, the protective film is removed, and then the adhesive film is pressure-bonded to the glass substrate while being pressed and heated toward the adhesive film. The lamination conditions are as follows: The adhesive film and the glass substrate are preheated as needed, and laminated at a pressure bonding temperature (lamination temperature) of preferably 60 to 140 ° C and a pressure contact pressure of preferably 1 to 11 kgf/cm ² . Further, when a vacuum laminator is used, it is preferable to laminate under a reduced pressure condition of an air pressure of 20 mmHg (26.7 hPa) or less. Further, the lamination method may be a batch type or a continuous type using a roll.

As described above, after the adhesive film is laminated on the glass substrate, it is cooled to near room temperature. The support film is peeled off as needed.

[Manufacturing method of laminated board]

Next, a specific example of a method of manufacturing a laminated board will be described.

(Production example by heat-hardening a laminate)

The laminate obtained by the above-described method for producing a laminate obtained by coating is subjected to heat curing (hardening treatment), whereby a laminated sheet can be produced.

In addition, the laminate obtained by lamination may be subjected to a peeling of the support film as needed, and then the resin composition layer may be heat-cured to form a resin cured layer to produce a laminate.

The conditions for heat curing can be selected from 150 ° C to 220 ° C for 20 minutes to 80 minutes, more preferably from 160 ° C to 200 ° C for 30 minutes to 120 minutes. When a support film which has been subjected to mold release treatment is used, the support film may be peeled off after heat curing.

According to this method, since it is not necessary to pressurize the laminated sheet, it is possible to suppress cracking during production.

The thickness of the cured resin layer is preferably 5 to 200 μm. When the thickness is 5 μm or more, cracking of the laminated board can be suppressed. When the thickness is 200 μm or less, the thickness of the glass substrate is relatively increased, and the low thermal expansion coefficient and the high elastic modulus of the laminated plate can be achieved. From this point of view, the thickness of the cured resin layer is more preferably from 10 to 150 μm, still more preferably from 10 to 100 μm.

However, depending on the thickness of the glass substrate layer, the number of layers, and the number of the cured resin layers, the appropriate range of the thickness of the cured resin layer is different, and therefore, it is not limited to the above range.

The resin cured layer has a storage elastic modulus at 40 ° C, preferably 1 to 80 GPa. When the storage elastic modulus is 1 GPa or more, the glass substrate can be protected and the crack of the laminated board can be suppressed. When the storage elastic modulus is 80 GPa or less, the stress caused by the difference in thermal expansion coefficient between the glass substrate and the cured resin layer can be suppressed, and warpage and cracking of the laminated plate can be suppressed. From this point of view, the storage elastic modulus of the resin cured layer is more preferably from 3 to 70 GPa, and still more preferably from 5 to 60 GPa.

Further, a metal foil such as copper or aluminum may be provided on one or both sides of the laminate. The metal foil is not particularly limited as long as it is a metal foil used in the use of an electrical insulating material.

(manufacturing example by suppression method)

Further, the laminated board of the present invention can be produced by a pressing method.

For example, the laminated body obtained by laminating the above may be heated and pressed by a pressing method to be hardened, thereby producing a laminated board.

In addition, the adhesive film or the adhesive film body formed by removing the support film and the protective film from the adhesive film may be superposed on the glass substrate, and heated and pressed by a pressing method to be cured, thereby producing a laminate. board.

Further, the resin composition may be brushed and dried to form a B-stage state, and the resin composition in the B-stage state may be superposed on a glass substrate, and heated and pressed by a pressing method to be cured. Laminated board. In this case, it is preferred to carry out heating in a range of from 120 to 300 ° C, more preferably at a temperature of from 150 ° C to 250 ° C. If it is 120 ° C or more, the resin cured product The adhesion between the layer and the glass substrate tends to be good, and when it is 300 ° C or lower, thermal decomposition of the polyamide amide resin is suppressed, which is preferable. Further, it is preferred to pressurize at 1 to 5 MPa, and more preferably at 2 to 5 MPa.

[Multilayer laminate and its manufacturing method]

The multi-layer laminate of the present invention comprises a plurality of laminates, and at least one laminate is the aforementioned laminate of the present invention.

The method for producing the multilayered laminate is not particularly limited.

For example, a plurality of the laminated sheets formed by removing the support film and the protective film from the adhesive film may be laminated and multilayered.

Further, a plurality of laminated sheets can be produced by laminating a plurality of sheets (for example, 2 to 20 sheets) and laminating them. Specifically, it can be molded under the following conditions: a multi-stage laminator, a multi-stage vacuum laminator, a continuous molding machine, an autoclave molding machine, etc., at a temperature of about 100 to 250 ° C and a pressure of 2 to 100 MPa. The molding is carried out in the range of about 0.1 to 5 hours in the left and right and the heating time.

[Printed circuit board and its manufacturing method]

The printed wiring board of the present invention is formed by providing a wiring on at least one surface of the laminated board of the present invention. Further, the printed wiring board of the present invention is sometimes composed of a plurality of laminated boards (multilayer printed wiring boards), and at this time, at least one of the laminated boards is a laminated board of the present invention.

Next, a method of manufacturing the printed wiring board will be described.

(formation of via holes, etc.)

On the above laminated board, a hole, a via hole or a through hole is formed by a method such as a drill, a laser, a plasma, or a combination thereof. As the laser, a carbon dioxide laser or a yttrium-aluminum-garnet laser (YAG laser), an ultraviolet laser (UV laser), an excimer laser, or the like is generally used. After forming a via hole or the like, an oxidizing agent may also be used for desmear treatment. As the oxidizing agent, it is more suitable as permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid; more suitable is potassium permanganate or sodium permanganate. Aqueous sodium hydroxide solution (alkaline permanganic acid aqueous solution).

(formation of line pattern)

As a method of forming the subsequent pattern, for example, a known method of a subtractive process, a semi-additive process, or the like can be employed.

In the case where the circuit is processed by the plating method on the resin cured layer of the laminated board or the multilayered laminated board of the present invention, first, the roughening treatment is performed. As the roughening liquid at this time, 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 fluoroboric acid roughening liquid can be used. The roughening treatment can be carried out, for example, by first adding an aqueous solution of diethylene glycol monobutyl ether and NaOH as a swelling liquid to a temperature of 70 ° C, and immersing the laminate or the multilayer laminate for 5 minutes. Next, an aqueous solution of KMnO ₄ and NaOH was used as a roughening liquid, and the mixture was heated to 80 ° C and immersed for 10 minutes. Then, it is neutralized by a immersion treatment in a neutralizing liquid, for example, a hydrochloric acid aqueous solution of stannous chloride (SnCl ₂ ) at room temperature for 5 minutes.

After the roughening treatment, a plating catalyst application treatment is performed to adhere the palladium. The plating catalyst application treatment is carried out by immersing in a palladium chloride-based plating catalyst liquid. Then, it was immersed in an electroless plating solution, and subjected to electroless plating treatment to deposit an electroless plating layer (conductor layer) having a thickness of 0.3 to 1.5 μm.

Then, after the plating resist is formed, a plating process is performed to form a circuit of a desired thickness at a desired portion. The electroless plating solution used in the electroless plating treatment may be a known electroless plating solution, and is not particularly limited. The plating resist can also be a known plating resist, and is not particularly limited. Further, the plating treatment can be carried out by a known method, and is not particularly limited. These platings are preferably copper plated. Further, an electroless plating layer of an unnecessary portion is removed by etching, whereby an outer layer circuit can be formed.

[Multilayer printed wiring board and method of manufacturing the same]

As one form of the printed wiring board, a plurality of laminated boards in which the wiring pattern is formed as described above may be laminated as a multilayer printed wiring board.

When the multilayer printed wiring board is manufactured, a plurality of the laminated sheets forming the wiring pattern are laminated via the adhesive film main body to form a multilayer. 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 sheet and multi-layer laminated board with metal foil, and manufacturing method of the same]

The laminated board of the present invention and the multi-layered laminated board using the laminated board of the present invention may be a laminated metal sheet and a multilayer laminated board having a metal foil such as copper or aluminum on one or both sides.

The method for producing the metal foil-clad laminate is not particularly limited. For example, a metal foil-attached laminate can be produced by using a metal foil as a support film as described above. Alternatively, it may be produced by laminating or brushing the laminated body obtained by laminating or brushing, using one sheet or a plurality of sheets (for example, 2 to 20 sheets), and arranging the metal foil on one or both sides thereof. Lamination molding is carried out to thereby produce a laminate with a metal foil.

The molding conditions can be suitably carried out by using a laminate or a multilayer laminate for an electrically insulating material, for example, molding can be carried out using a multi-stage laminator, a multi-stage vacuum laminator, a continuous molding machine, and an autoclave. The molding machine or the like is formed at a temperature of about 100 to 250 ° C, a pressure of about 2 to 100 MPa, and a heating time of about 0.1 to 5 hours.

Next, the present invention will be specifically described by way of examples, but the scope of the invention is not limited to the examples.

[Examples] (Synthesis of polyamidoximine resin)

To a 500 ml separable flask equipped with a thermocouple, a stirrer, and a nitrogen gas inlet, a nitrogen gas of about 250 ml/min was introduced while adding X-22-161A (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) 32.0 g, 4,4'-Diaminodicyclohexylmethane (Wondamine HM (WHM), New Japan Chemical Co., Ltd., trade name) 0.935g, Jeffamine D2000 (Mitsui Fine Chemical Co., Ltd.) 40.0g, trimellitic anhydride (hereinafter referred to as TMA) 17.9g and N-methyl-2-pyrrolidone 250g And stir to dissolve. 100 g of toluene was added to the solution, and dehydration reflux was carried out at a temperature of 150 ° C or higher for 6 hours to carry out a ring closure reaction of the imide ring, and then toluene was distilled off, and after cooling, 4,4'-diphenylmethane diisocyanate was added ( MDI) 13.4 g was reacted at 150 ° C for 2 hours to synthesize a polyamidoximine resin. Thereafter, 1.6 g of TMA was added, and the mixture was stirred at 80 ° C for 1 hour to synthesize a polyamidoximine resin solution.

(varnish A)

To a solution of a polyamidoxime imide resin having a solid content of 70 g, 20 g of a dicyclopentadiene phenol type epoxy resin HP7200 (manufactured by DIC Corporation, trade name) was added, and three or more reactive groups were reacted with an epoxy group. Resin-based resin EPPN-502H (manufactured by Nippon Kayaku Co., Ltd., trade name, polyfunctional epoxy resin) 10 g, hardening accelerator 2E4MZ-CN (manufactured by Shikoku Chemical Co., Ltd., trade name) 0.15 g, used The varnish A was prepared by diluting NMP to a solid concentration of 30%.

(varnish B~ varnish C)

In the same manner as the varnish A, the varnish B to the varnish C was prepared in the amount shown in Table 1.

(varnish D)

A varnish D was prepared in the same manner as the varnish A except that the epoxy resin HP7200 was used instead of the epoxy resin HP3000 (manufactured by Nippon Kayaku Co., Ltd., trade name).

In the above formulation, HP7200 is an epoxy resin having two or more epoxy groups in one molecule and compatible with a polyamidoximine resin; and NC3000 has two or more epoxy groups in one molecule. And an epoxy resin which is incompatible with the polyamidoximine resin; EPPN-502H is a resin having three or more functional groups reactive with an epoxy group in one molecule.

(Manufacture of adhesive film)

Resin varnish A to resin varnish D was applied to a polyethylene film (PET) film having a thickness of 38 μm and subjected to release treatment using a bar coater to a thickness of 5 μm. -38X, a release-treated surface of a product manufactured by Lintec Corporation (trade name), and dried at 140 ° C for 15 minutes to form a resin composition layer, thereby obtaining an adhesive film.

(Manufacture of film for auxiliary adhesive layer)

Formulated with N,N-dimethylacetamide (DMAc) 91.4 in 10.2 g of polybutadiene modified polyamine (manufactured by Nippon Kayaku Co., Ltd., trade name: BPAM-155) containing phenolic hydroxyl group. After g, a biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000H) 40.0 g, bisphenol A novolac (manufactured by Mitsubishi Chemical Corporation) was added. , trade name: YLH129) 12.6g, as a hardening accelerator 2-phenylimidazole (manufactured by Shikoku Chemicals Corporation, trade name: 2PZ) 0.4 g, fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name: R972) After 3.6 g, it was diluted with a mixed solvent of DMAc and methyl ethyl ketone (MEK/DMAc = 7/3 (mass ratio)) (solid content concentration: about 25% by mass). Thereafter, a resin varnish for an auxiliary adhesive layer was obtained using a disperser (Nanomizer, trade name, manufactured by Yoshida Kikai Co., Ltd.).

Using a bar coater, the auxiliary adhesive layer was coated with a resin varnish to a thickness of 20 μm and applied to a copper foil having a thickness of 20 μm (NC foil, Furukawa Electric Co., Ltd.). The shiny surface of the manufactured) was dried at 140 ° C for 10 minutes to prepare a resin film for an auxiliary adhesive layer.

[Manufacture of laminated board for glass adhesion evaluation (resin cured layer / glass substrate layer / resin cured layer)] (Examples 1 to 4)

An ultra-thin glass film "OA-10G" (trade name, thickness: 100 μm) manufactured by Nippon Electric Glass Co., Ltd. was used as a glass substrate. The resin composition layer of the produced adhesive film was placed on both surfaces of the glass substrate so as to contact the glass substrate, and a batch type vacuum pressure laminating machine "MVLP-500" (Ming Machine Co., Ltd.) was used. Manufactured by Meiki Co., Ltd.), which is laminated by lamination to obtain a product. Layer body. At this time, the degree of vacuum 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 gloss surface was in contact with the resin composition layer, and then hot pressed at 185 ° C, 3 MPa, and 1 hour to perform thermocompression bonding. The copper foil was etched to obtain a laminate (resin cured layer/glass substrate layer/resin cured layer) for evaluation of glass adhesion. The laminated sheets for glass adhesion evaluation using the adhesive film made from the varnish A~ varnish D correspond to Example 1 - Example 4, respectively.

(Reference example)

An ultra-thin glass film "OA-10G" (trade name, thickness: 100 μm) manufactured by Nippon Electric Glass Co., Ltd. is used as a glass substrate, and the resin film for auxiliary adhesion is placed on the glass so that the resin layer contacts the glass substrate. Hot pressing was performed on both surfaces of the substrate at 185 ° C, 3 MPa, and 1 hour, thereby performing thermocompression bonding. Then, the copper foil was etched to obtain a laminate (adhesive adhesion layer/glass substrate layer/auxiliary adhesion layer) for evaluation of glass adhesion.

Next, the adhesion sheets for glass adhesion evaluation obtained in the examples and the reference examples were measured and evaluated for adhesion to glass by the following method.

[Glass Adhesion]

Adhesion was evaluated by a cross-cut test.

Cross-cut test: Cut the checkerboard shape on the laminated board produced by using the cross-cutting guide CCJ-1 (manufactured by Cotec Co., Ltd., trade name) The slits were respectively five tangential lines in the horizontal and vertical directions, and the width between the tangential lines was 2 mm. The surface state after adhering the TQC ISO attachment tape and peeling off the adhesive tape was observed, and the number of squares which were not peeled out in the 25 squares was examined. Furthermore, the experimental method is based on the Japanese Industrial Standard (JIS) K56005-6.

The experimental results are shown in Table 2.

Next, a laminate for solder heat resistance evaluation was obtained by a series of steps using a resin film for an auxiliary adhesive layer to evaluate solder heat resistance at the time of mounting.

[Manufacture of laminate for solder heat resistance evaluation] (Examples 1 to 4)

A very thin glass film "OA-10G" (trade name, thickness: 100 μm) manufactured by Nippon Electric Glass Co., Ltd. was used as a glass substrate. The resin composition layer of the produced adhesive film was placed on both surfaces of the glass substrate so as to contact the glass substrate, and a batch type vacuum pressure laminating machine "MVLP-500" (manufactured by Nagoya Co., Ltd.) was used. , trade name), 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 after the resin layer of the resin film for the auxiliary adhesive layer is brought into contact with the resin composition layer provided on the glass substrate, the resin film for the auxiliary adhesive layer is placed. The hot pressing was carried out under the conditions of 185 ° C, 3 MPa, and 1 hour, thereby performing thermocompression bonding. Thereafter, the copper foil was etched to obtain a laminate.

The following operations were carried out to chemically roughen the obtained laminate: an aqueous solution of 200 ml/L of diethylene glycol monobutyl ether and 5 g/L of NaOH was prepared as a swelling liquid, and the mixture was heated to 70 ° C for 5 Minute immersion treatment. Next, an aqueous solution of 60 g/L of KMnO ₄ and 40 g/L of NaOH was prepared, and the mixture was heated to 80 ° C as a roughening liquid, and immersed for 10 minutes. Then, neutralization was carried out 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 laminate which is subjected to chemical roughening, first, it is carried out for 10 minutes at room temperature in an electroless plating catalyst HS-202B (trade name, manufactured by Hitachi Chemical Co., Ltd.) containing PdCl ₂ . After immersion treatment, it was washed with water, and further immersed in a plating solution for electroless copper plating CUST-201 (manufactured by Hitachi Chemical Co., Ltd., trade name) for 15 minutes at room temperature to further perform copper sulfate plating. Thereafter, annealing was performed at 180 ° C for 60 minutes to form a conductor layer having a thickness of 25 μm, thereby obtaining a laminate for evaluation of solder heat resistance. The laminate for solder heat resistance evaluation using an adhesive film made of varnish A to varnish D corresponds to Examples 1 to 4.

(Reference example)

An ultra-thin glass film "OA-10G" (trade name, thickness: 100 μm) manufactured by Nippon Electric Glass Co., Ltd. is used as a glass substrate, and the resin film for auxiliary adhesion is placed on the glass so that the resin layer contacts the glass substrate. Hot pressing was performed on both surfaces of the substrate at 185 ° C, 3 MPa, and 1 hour, thereby performing thermocompression bonding. Then, the copper foil was etched to obtain a laminate (auxiliary adhesive layer/glass substrate layer/auxiliary adhesive layer). Then, by the same as the previous embodiment In this method, a conductor layer is formed on a laminate, and a laminate for evaluation of solder heat resistance is obtained.

The solder heat resistance of the obtained laminate for solder heat resistance evaluation was evaluated as follows.

[265°C solder heat resistance]

The laminate for solder heat resistance evaluation prepared in each example was cut into 25 mm square, floated in a solder bath adjusted to 265 ± 2 ° C, and the time (seconds) taken until expansion occurred was examined. The results are shown in Table 2.

As is apparent from Table 2, in Examples 1 to 4 of the present invention, the adhesion between the resin composition layer and the glass substrate layer was high. Further, it has been found that the laminated sheet produced by using the resin composition layer of the present invention is excellent in solder heat resistance, and thus it is possible to manufacture a wiring board which takes the environment into consideration.

According to the above results, according to the present invention, it is possible to provide a laminated board in which the resin composition layer and the glass substrate layer are excellent in adhesion and heat resistance.

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 polyimide film and an epoxy resin. The laminate according to claim 1, wherein the polyamidoximine resin is 50 to 85% by mass based on the total of the resin components. The laminate according to claim 1 or claim 2, wherein the epoxy resin has two or more epoxy groups in one molecule. The laminate according to any one of claims 1 to 3, which comprises a resin having three or more functional groups reactive with an epoxy resin in one molecule. The laminate according to claim 4, wherein the epoxy resin is contained in an amount of 10 to 30% by mass based on the entire resin component, and the resin having three or more epoxy group-reactive functional groups in the above molecule is used in all the resins. The composition contains 5% or more. The laminate according to claim 4, wherein the resin having three or more functional groups reactive with an epoxy group in the one molecule is contained in a range not exceeding the solid content of the epoxy resin. . The laminate according to any one of claims 1 to 3, wherein the polyamidoximine resin is derived from a dicarboxylic acid represented by the following formula (1) to formula (3). At least one of the substances is obtained by reacting with at least one of the aromatic diisocyanates represented by the formula (4): (wherein R ₁ represents a group as described below, (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, or a carbonyl group)); (wherein R ₂ represents a group as described below, (wherein R ₃ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 1 to 100)); (wherein R ₄ represents a group as described below, (wherein R ₅ and R ₆ each independently represent a divalent organic group, and 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, and n is 1 to 50. Integer)); OCN-R ₁₁ -NCO.. (4) (wherein R ₁₁ represents a group as described below, ). 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 the preceding claims, wherein the resin composition layer and the glass substrate layer have a total thickness of 40 to 300 μm. A laminated board comprising a resin cured layer of one or more layers and a glass substrate layer of one or more layers, wherein the laminated board is subjected to hardening treatment of the laminate according to any one of claims 1 to 10. And get. A printed wiring board formed by arranging a line on at least one side of a laminate as described in claim 11. The printed wiring board of claim 12, wherein the printed wiring board comprises a plurality of laminated boards, and at least one of the laminated boards is the aforementioned laminated board as claimed in claim 11. A method for producing a laminate in which a resin composition comprising a polyimide film and an epoxy resin is applied onto a surface of a glass substrate to form a resin composition layer. The method for producing a laminate according to claim 14, wherein the resin composition layer is formed and then subjected to a drying treatment. A method for producing a laminate, which comprises first forming a film composed of a resin composition containing a polyimide film and an epoxy resin, and laminating the film on a glass substrate using a vacuum laminator or a roll laminator Implementing the aforementioned film Hardening treatment. The method for producing a laminated board according to claim 16, wherein the pressing treatment is performed after the film is laminated and before the hardening treatment is performed.