TWI412560B - And a resin composition for interlayer insulation of a multilayer printed wiring board - Google Patents

Abstract

Disclosed is a resin composition suitable for interlayer insulation of a flexible multilayer printed wiring board. Specifically disclosed is a resin composition for interlayer insulation of a multilayer printed wiring board, which contains the following components (A), (B) and (C). (A) a polyimide resin having a polybutadiene structure, a urethane structure and an imide structure in a molecule, while having a phenol structure at an end of the molecule (B) an epoxy resin (C) an inorganic filler having a specific surface area of 18-50 m2/g

Description

Resin composition for interlayer insulation of multilayer printed wiring board

The present invention relates to a preferred resin composition for interlayer insulation of a multilayer printed wiring board, particularly for interlayer insulation of a flexible multilayer printed wiring board. Further, the present invention relates to an adhesive film for forming an interlayer insulating layer of a multilayer printed wiring board prepared by the resin composition, and a multilayer printed wiring board in which an interlayer insulating layer is formed of the resin composition.

Since the flexible multilayer printed wiring board can be flexibly assembled even in a narrow space, it is indispensable for media equipment that is becoming smaller and thinner. As a material for interlayer insulation of a flexible multilayer printed wiring board, for example, Patent Document 1 discloses a resin composition composed of a polybutadiene structure having a polybutadiene structure and an epoxy resin, and discloses that The interlayer insulating layer obtained by the resin composition has excellent flexibility, mechanical strength, dielectric properties, and the like.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-037083

An object of the present invention is to provide a resin composition suitable for interlayer insulation of a flexible multilayer printed wiring board.

The polyimine contained in the resin composition of Patent Document 1 has an acid anhydride group or a carboxyl group at the terminal, and since these groups are easily hydrolyzed by an epoxy group to form an ester bond, it is considered to be used for precision electronic parts. In the case of insulation reliability and the like, the presence of such groups in the resin composition must be reduced or even excluded. In view of the above, the inventors of the present invention have used a polyimine resin having a phenol structure at the terminal end and a resin composition for the purpose of reducing or even eliminating a carboxyl group in a polyimide having a polybutadiene structure. As a result of the evaluation, it was found that an interlayer insulating layer excellent in flexibility, mechanical strength, dielectric properties, and the like was obtained. On the other hand, in order to use a resin composition as an interlayer insulating layer, a method of incorporating an inorganic filler typified by ruthenium oxide is known for the purpose of suppressing thermal expansion coefficient and adhesion, and the like. On the other hand, in the composition containing the phenol terminal polyimine and the epoxy resin, the inorganic filler is likely to settle, and it is difficult to obtain a uniform resin composition, which is a problem. The inventors of the present invention have found that the inorganic filler can be easily dispersed to obtain a uniform resin composition by using a range in which the specific surface area of the inorganic filler generally used is much smaller.

The present inventors completed the present invention based on the above findings. In other words, the present invention includes the following: [1] A resin composition for interlayer insulation of a multilayer printed wiring board comprising the following components (A), (B) and (C): (A) having a polybutene in a molecule a diene structure, a urethane structure, a quinone imine structure, a quinone imine resin having a phenol structure at a molecular terminal, (B) an epoxy resin, and (C) a specific surface area of 18 to 50 m ² /g. Inorganic filler.

[2] A resin composition for interlayer insulation of a multilayer printed wiring board comprising the following components (A), (B) and (C): (A) having two or more alcoholic hydroxyl groups in one molecule via [a] The polybutadiene polyol compound and the [b] diisocyanate compound are reacted to form a diisocyanate prepolymer, and [c] tetrabasic dianhydride and [d] 1 molecule have two or more phenols. A polyhydroxyimine resin having a phenol structure at a molecular terminal prepared by reacting a polyfunctional phenol compound of a hydroxyl group; (B) an epoxy resin; and (C) an inorganic filler having a specific surface area of 18 to 50 m ² /g.

[3] The resin composition according to the above [1] or [2], wherein the inorganic filler of the component (C) has a specific surface area of 18 to 40 m ² /g.

[4] The resin composition according to the above [1] or [2], wherein the inorganic filler of the component (C) has a specific surface area of 18 to 35 m ² /g.

[5] The resin composition according to the above [1] or [2], wherein the inorganic filler of the component (C) has a specific surface area of 20 to 30 m ² /g.

[6] The resin composition according to the above [1] or [2] wherein the inorganic filler is cerium oxide.

[7] The resin composition according to the above [1] or [2] wherein the phenol compound is a novolac resin.

[8] The resin composition according to the above [1] or [2] wherein the polybutadiene polyol compound is a hydrogenated polybutadiene polyol compound.

[9] The resin composition according to the above [2], which is contained in the polyamidene resin of the component (A), and has two or more alcoholic hydroxyl groups in the molecule of the reaction component [a]. The hydroxyl group of the olefin polyol and the functional group equivalent ratio of the isocyanate group of the reaction component [b] diisocyanate compound are reacted at a ratio of 1:1.5 to 1:2.5.

[10] The resin composition of the above [1] or [2], further comprising a polyfunctional phenol compound having a component [D] having two or more phenolic hydroxyl groups in one molecule.

[11] The resin composition according to the above [10], which is 100% by weight based on the total of the polyamidene resin of the component (A), the epoxy resin of the component (B), and the polyfunctional phenol compound of the component (D). It contains 40 to 85% by weight of the component (A), 15 to 40% by weight of the component (B), and 0 to 20% by weight of the component (D).

[12] An adhesive film for forming an interlayer insulating layer of a multilayer printed wiring board, characterized in that the resin composition of the above [1] or [2] is formed on a support.

[13] A multilayer printed wiring board which is formed by forming the interlayer insulating layer from the resin composition of the above [1] or [2].

According to the present invention, it is possible to provide a resin composition for interlayer insulation which is excellent for flexibility, mechanical strength, dielectric properties, and the like, which is suitable for a flexible multilayer printed wiring board.

(The best form for implementing the invention)

The polyimine resin of the component (A) in the present invention has a polybutadiene structure, a urethane structure, a quinone imine structure in a molecule, and has a phenol structure at a molecular terminal. The polyimine resin having a phenol structure at the molecular end can be obtained by the following methods using the reaction components [a] to [d]. In other words, a polybutadiene polyol compound having two or more alcoholic hydroxyl groups in [a] molecule and [b] a diisocyanate compound are reacted to form a diisocyanate prepolymer, and then [c] The tetrabasic acid dianhydride and the polyfunctional phenol compound having two or more phenolic hydroxyl groups in one molecule of [d] are reacted.

The polybutadiene polyol compound having two or more alcoholic hydroxyl groups in one molecule of [a] is preferably a number average molecular weight of from 300 to 5,000. When the number average molecular weight is 300 or less, the modified polyimine resin tends to have poor flexibility. In the case of 5,000 or more, the compatibility of the modified polyimine resin with the thermosetting resin tends to be inferior, and the heat resistance and chemical resistance tend to be poor.

Further, in the present invention, the number average molecular weight is a value measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). According to the number average molecular weight of the GPC method, Shodex GPC System 21 manufactured by Showa Denko Co., Ltd. is used as the measuring device, and Shodex LF-804/KF-803/KF-made by Showa Denko Co., Ltd. 804, the mobile phase is measured by NMP at a column temperature of 40 ° C, and can be obtained by using a standard polystyrene calibration line. Make For the polybutadiene polyol, a hydrogenated polybutadiene polyol which is hydrogenated by using an unsaturated bond in a molecule may be used singly or in combination. Further, as the polybutadiene polyol, a polybutadiene polyol having a hydroxyl group at a molecular terminal is preferred. Further, the alcoholic hydroxyl group means a hydroxyl group in which a hydrogen atom of an aliphatic hydrocarbon structure is substituted with a hydroxyl group. Specific examples of the polybutadiene polyol include G-1000, G-2000, G-3000, GI-1000, and GI-2000 (the above is manufactured by Japan Soda Co., Ltd.), R-45EPI. (Ishigaku Petrochemical Co., Ltd.) and so on.

[b] The diisocyanate compound is a compound having two isocyanate groups in the molecule, and examples thereof include toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene diisocyanate, and xylene. Isocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and the like.

[c] The tetrabasic acid dianhydride is a compound having two acid anhydride groups in the molecule, and examples thereof include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and naphthalene tetra Carboxylic dianhydride, 5-(2,5-dioxotetrahydrofuran)-3-methylcyclohexene-1,2-dicarboxylic anhydride, 3,3'-4,4'-diphenyltetracarboxylic acid Anhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furan)naphtho[1,2-c]furan-1,3-dione Wait.

[d] Examples of the polyfunctional phenol compound having two or more phenolic hydroxyl groups in one molecule include bisphenol A, bisphenol F, bisphenol S, diphenol, novolak resin, and alkyl novolac resin. , bisphenol A type varnish resin, novolac resin containing dicyclopentadiene structure, containing three A novolak resin having a structure, a novolac resin containing a biphenyl skeleton, a novolac resin containing a phenyl group, a phenolic modified phenol resin, a polyvinylphenol, and the like. In particular, an alkyl novolac resin is preferred. Further, the phenolic hydroxyl group means a hydroxyl group in which a hydrogen atom of an aromatic ring structure is substituted with a hydroxyl group.

In order to efficiently obtain the polyimine resin of the present invention, it is preferred to follow the order described below. First, the polybutadiene polyol of the reaction component [a] and the diisocyanate compound of the reaction component [b] are substituted with the functional group equivalent of the isocyanate group of the diisocyanate compound of the hydroxyl group of the polybutadiene polyol. The ratio of 1 is reacted. The reaction ratio of the polybutadiene polyol to the diisocyanate compound is preferably from 1:1.5 to 1:2.5 with respect to the functional group equivalent of the isocyanate group of the diisocyanate of the hydroxyl group of the polybutadiene.

In the case where the reaction component [a] is a polybutadiene polyol having a hydroxyl group at the molecular terminal, the polybutadiene polyol can be represented by the following formula (a').

(R1 represents a divalent organic group having a polybutadiene structure)

The diisocyanate compound of the reaction component [b] can be represented by the following formula (b).

OCN-R2-NCO (b)

(R2 represents a divalent organic group)

The tetrabasic acid dianhydride of the reaction component [c] can be represented by the following formula (c).

(R3 represents a tetravalent organic group)

The diisocyanate prepolymer obtained by reacting the above polybutadiene polyol having a hydroxyl group at the terminal of the molecule with a diisocyanate compound can be represented by the following formula (a'-b).

(R1 and R2 are synonymous with the above, and n represents an integer of 1 or more and 100 or less (1≦n≦100). Preferably, n represents an integer of 1 or more and 10 or less (1≦n≦10).

Next, the diisocyanate prepolymer obtained in the above reaction is allowed to react with the tetrabasic acid dianhydride of the reaction component [c] and the polyfunctional phenol compound of the reaction component [d]. The reaction ratio is not particularly limited, and it is preferred that the isocyanate group is not left as much as possible in the composition. In order to prevent the isocyanate group from remaining in the composition as much as possible, it is preferred to confirm the disappearance of the isocyanate group by FT-IR in the reaction. The reaction sequence includes a method in which a tetrabasic acid dianhydride is first reacted, and then a polyfunctional phenol compound is reacted; and a method in which a tetrabasic acid dianhydride and a polyfunctional phenol compound are simultaneously added and reacted is mentioned. In the case of simultaneous addition, it is believed that the anhydride group preferentially reacts with the isocyanate group to form a polyimine. Then, the residual isocyanate group reacts with the polyfunctional phenol compound, The terminal is introduced into a phenol structure.

The functional group equivalent of the hydroxyl group of the polybutadiene polyol of the reaction component [a] is W, and the functional group equivalent of the isocyanate group of the diisocyanate compound of the reaction component [b] is X, and the reaction component [c] is four. The functional group equivalent of the acid dianhydride is Y, and the functional group equivalent of the polyfunctional phenol compound of the reaction component [d] is Z, and the reaction components [c] and [d] are used to satisfy Y<X-W<Y+Z. The ratio of the relationship is good.

In the case where the reaction component [a] is used in a polybutadiene polyol having a hydroxyl group at the terminal of the molecule, the polyimine of the component (A) in the present invention has the following formulas (1-a) and (1-b). ) The construction.

Specific reaction conditions, for example, the reaction of the polybutadiene polyol of the reaction component [a] with the diisocyanate compound of the reaction component [b] can be carried out in an organic solvent at a reaction temperature of 80 ° C or lower, and the reaction time is usually 2 It is carried out under conditions of 8 hours. Moreover, it may be carried out in the presence of a catalyst if necessary. Next, tetrabasic acid dianhydride and a polyfunctional phenol compound are added to the reaction solution, and the reaction is carried out at a reaction temperature of 120 to 160 ° C for a reaction time of 5 to 24 hours. The reaction is usually carried out in the presence of a catalyst. Also, you can add it It is carried out with an organic solvent.

In this reaction, carbon dioxide is generated by the reaction of an isocyanate group with an acid anhydride group to form a quinone bond, so that the weight of the carbon dioxide can be determined by measuring the weight loss before and after the reaction, and the formation of the carbon dioxide can be calculated. The number of moles of the amine group.

After the reaction is completed, the reaction solution may be filtered to remove insolubles as needed. Thus, a varnished polyimide resin can be obtained. The amount of the solvent in the varnish can be appropriately adjusted by adjusting the amount of the solvent at the time of the reaction or adding a solvent or the like after the reaction. The polyimine resin of the present invention can be usually used to prepare a composition in the above varnish state. In the case of isolation, for example, the obtained varnish is successively added in methanol of a poor solvent to precipitate a polyimine to obtain a solid.

Examples of the solvent used in each of the above reactions include N,N'-dimethylformamide, N,N'-diethylformamide, and N,N'-dimethylacetamide. , N, N'-diethylacetamide, dimethyl hydrazine, diethyl hydrazine, N-methyl-2-pyrrolidone, tetramethyl urea, γ-butyrolactone, cyclohexanone, diethylene glycol A polar solvent such as methyl ether, triethylene glycol dimethyl ether, carbitol acetate, propylene glycol monomethyl ether acetate, or propylene glycol monoethyl ether acetate. These solvents may be used in combination of two or more kinds. Further, a nonpolar solvent such as an aromatic hydrocarbon may be appropriately mixed as needed.

Examples of the catalyst used in each of the above reactions include tetramethylbutanediamine, benzyldimethylamine, triethanolamine, triethylamine, and N,N'-dimethylpiperidine. a tertiary amine such as α-methylbenzyldimethylamine, N-ethylmorphine or triethylenediamine, or dibutyltin laurate or dimethyl An organic metal catalyst such as tin dichloride, cobalt naphthalate or zinc naphthalate. These catalysts may also be used in combination of two or more kinds. As the catalyst, triethylenediamine is particularly preferred.

Examples of the epoxy resin in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac resin, bisphenol S type epoxy resin, alkyl novolac resin, and biphenol. Type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, epoxide with condensate of phenol and phenolic hydroxyl group aromatic aldehyde, glycidyl isocyanurate, An epoxy resin having two or more functional groups in one molecule, such as an alicyclic epoxy resin. These epoxy resins may be used in combination of two or more kinds. Further, it is preferred to use a bisphenol A type epoxy resin.

In the composition of the present invention, an epoxy resin hardener may be formulated as needed. Examples of the epoxy resin curing agent include an amine curing agent, a guanidine curing agent, an imidazole curing agent, a phenol curing agent, an acid anhydride curing agent, or an epoxy addition product thereof. Microencapsulators, etc. In particular, a phenol-based curing agent is preferable in consideration of viscosity stability when the resin composition is used as a varnish. The epoxy resin hardener may be used in combination of two or more kinds.

Specific examples of the epoxy resin curing agent include dicyandiamide as an amine curing agent, imidazolium as an imidazole curing agent, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. 2,4-Diamino-6-[2'-methylimidazolium-(1')]-ethyl-s-three An isomeric cyanuric acid addition product, as a phenolic hardener, contains three A novolak resin (for example, Phenolite 7050 series: manufactured by Dainippon Ink Chemical Co., Ltd.).

As the composition of the polyimine resin of the present invention, for the component (A) It is preferable to use a polyfunctional phenol compound having two or more phenolic hydroxyl groups in the molecule of the component (D) in combination with the control of the crosslinking density of the epoxy resin of the component (B) and the epoxy resin of the component (B). . By using the component (D) in combination, the crosslinking density of the component (A) and the component (B) can be increased, whereby thermal expansion or the like at a temperature higher than the glass transition temperature can be lowered. In order to increase the crosslinking density and lower the thermal expansion, the ratio of the component (A) to the component (B) to the component (D) in the resin composition is preferably 100% by weight based on the total amount (A) It is 40 to 85% by weight, the component (B) is 15 to 40% by weight, and the component (D) is 0 to 20% by weight. The total of the phenolic hydroxyl group (x) in the component (A) and the phenolic hydroxyl group (z) in the component (D), and the molar ratio of the epoxy group (y) in the component (B) to (x + z) /(y) is preferably 0.7 to 1.3.

Examples of the polyfunctional phenol compound having two or more phenolic hydroxyl groups in one molecule of the component (D) include the same as the above-mentioned reaction component [d].

The thermosetting polyimine resin composition of the present invention may be used in combination with a curing accelerator as needed. For example, melamine, dicyandiamide, guanamine and its derivatives, amines, phenols having one hydroxyl group, organic phosphines, phosphonium salts, 4-grade ammonium salts, polybasic acid anhydrides, and light A cationic catalyst, a cyanate compound, an isocyanate compound, a blocked isocyanate compound, or the like.

The resin composition of the present invention may contain an inorganic filler having a specific surface area of 18 to 50 m ² /g. Examples of the inorganic filler include cerium oxide, aluminum oxide, and the like. Especially cerium oxide is preferred. The inorganic filler may be used in combination of two or more kinds. The amount of the inorganic filler to be added is not particularly limited, and it is preferably added in the range of 10 to 50% by mass in the resin composition. If it is less than 10% by mass, it is difficult to obtain effects such as a coefficient of thermal expansion and an improvement in tack. When it exceeds 50% by mass, not only the laser workability is deteriorated, but also the elastic modulus of the cured product is high, and there is a tendency to become a hard and brittle material.

Further, the specific surface area of the inorganic filler can be used in the range of 18 to 50 m ² /g. If it is outside this range, the filler tends to settle, making it difficult to maintain the varnish for a long period of time. The lower limit of the range of the specific surface area is more preferably 20 m ² /g or more. The upper limit of the range of the specific surface area is preferably 40 m ² /g, more preferably 35 m ² /g, and particularly preferably 30 m ² /g or less. For example, the specific surface area is preferably in the range of 18 to 40 m ² /g, more preferably in the range of 18 to 35 m ² /g, and particularly preferably in the range of 20 to 30 m ² /g.

The analysis of the specific surface area can be carried out by the so-called "BET method" in which the specific surface area of the sample is adsorbed at a temperature of liquid nitrogen by a known molecule on the surface of the powder particle. Out. The most frequently used by the user is the BET method of physical adsorption by low temperature and low humidity of an inert gas.

In the resin composition of the present invention, various resin additives and resin components other than the components (A) and (B) may be blended in a range in which the effects of the present invention can be exhibited. Examples of the resin additive include a tackifier such as urethane or bentonite, a silicone system, a fluorine-based or alkali-based antifoaming agent, a smoothing agent, an imidazole-based compound, a thiazole system, and a triazole. a surface treatment agent such as a adhesion imparting agent or a decane coupling agent, a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black, a phosphorus-containing compound, a bromine-containing compound, or a hydroxide An oxidation inhibitor such as a flame retardant such as aluminum or magnesium hydroxide, a phosphate oxidation inhibitor, or a phenol oxidation inhibitor.

The resin composition of the present invention is particularly suitably used for interlayer insulation as a multilayer printed wiring board. Particularly preferred form that can be used is an RCC-type adhesive film in which an adhesive film composed of a resin composition layer (A layer) and a support film (B layer) and a resin composition layer (A layer) are formed on a copper foil. The form.

Then, the film can be produced by a method known to a person skilled in the art. For example, the thermosetting resin composition of the present invention is dissolved in an organic solvent to prepare a varnish, and the varnish is applied onto a support film and a copper foil by heating or The organic solvent is dried by blowing hot air or the like to form a thermosetting resin composition layer.

The support film (layer B) is a support for the production of the adhesive film, and it is necessary to peel or remove the multilayer printed wiring board at the end. Examples of the support film include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter also referred to as "PET"), and polyethylene naphthalate. Polycarbonate, metal foil such as release paper or copper foil, and the like. A heat resistant resin such as polyimine, polyamine, polyamidimide or a liquid crystal polymer can also be used. Further, in the case where the copper foil is used as the support film, it can be removed by etching using an etching solution such as ferric chloride or copper chloride. The support film may also be subjected to a mat treatment or a corona treatment, and when the peelability is considered, it is more preferable to perform a mold release treatment. The thickness of the support film is not particularly limited, and it is usually 10 to 150 μm, preferably 25 to 50 μm.

In the case of the RCC type, the copper foil is used as a part of the conductor layer of the multilayer printed wiring board. Usually, an electrolytic copper foil, a rolled copper foil, or an ultra-thin copper foil can also be used. The ultra-thin copper foil may also be accompanied by a carrier copper foil. Thick copper foil The degree is not particularly limited, and it is preferable to form a wiring having a fine pitch to use an extremely thin copper foil.

Examples of the organic solvent used to prepare the varnish include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, fibrin acetate, propylene glycol monomethyl ether acetate, and card. Acetate such as alcoholic acid acetate, cellulase, carbitol, etc., aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamidine Amine, N-methylpyrrolidone, and the like. The organic solvent may be used in combination of two or more kinds.

The drying conditions are not particularly limited, and it is important to maintain the adhesion, and it is important to harden the thermosetting resin composition as much as possible during drying. In addition, when a large amount of the organic solvent remains in the adhesive film, the bulging occurs after the curing. Therefore, the content of the organic solvent in the thermosetting resin composition is usually desirably dried to 5% by mass or less, and 3% by mass. The following is better. The specific drying conditions vary depending on the amount of the organic solvent in the thermosetting resin composition and the varnish. For example, in a varnish containing 30 to 60% by mass of an organic solvent, it is usually dried at 80 to 120 ° C for 3 to 13 minutes. about. The industry can set appropriate and optimal drying conditions by simple experimentation.

The thickness of the resin composition layer (layer A) can be usually set in the range of 5 to 500 μm. The preferred range of the thickness of the layer A varies depending on the application of the film, and in the case of manufacturing a multilayer printed wiring board by a build-up process, the thickness of the conductor layer forming the line is usually 5 to 70 μm. Therefore, the thickness of the layer A corresponding to the interlayer insulating layer is preferably in the range of 10 to 100 μm.

Layer A can also be protected with a protective film. By protecting with a protective film, it is possible to prevent dust and the like on the surface of the resin composition layer from adhering and scratching. Protective film can Stripped at the time of lamination. As the protective film, the same material as the support film can be used. The thickness of the protective film is not particularly limited, and is preferably in the range of 1 to 40 μm.

The adhesive film of the present invention can be preferably laminated to a circuit substrate by a vacuum laminator. The inner layer circuit board used herein mainly includes an inner layer circuit board such as a polyester substrate, a polyimide substrate, a polyimide film, or a liquid crystal polymer substrate. Further, the adhesive film of the present invention can also be used for the purpose of further multilayering the multilayer printed wiring board. Further, the surface of the wiring is preliminarily treated by a surface treatment agent such as hydrogen peroxide/sulfuric acid or MEC Etch Bond (manufactured by MEC Co., Ltd.), and the insulating layer is densely bonded to the wiring substrate. The consideration of sex is better.

For example, a Vacuum Applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum press laminator manufactured by a famous machine manufacturer, and a Hitachi Techno Engineering Co., Ltd. Roller Dry Coater, vacuum laminator manufactured by Hitachi AIC Inc., etc.

In the case of laminating, in the case where the film is provided with a protective film, after the protective film is removed, the film is pressed against the wiring substrate while being pressed and heated. The lamination condition is to preheat the adhesive film and the circuit substrate as needed, and the pressing temperature is preferably 70 to 140 ° C, and the pressing pressure is preferably 1 to 11 kgf / cm ² , and the air pressure is 20 mmHg or less. It is preferred to carry out lamination under reduced pressure. Further, the laminating method may be a batch type or a continuous type using a roll.

In the case of the adhesive film composed of the resin composition layer (layer A) and the support film (layer B), the following procedure is employed. Film lamination After the substrate, it was cooled to near room temperature to peel off the support film. Then, the thermosetting resin composition laminated on the wiring substrate is heat-hardened. The conditions for heat hardening are usually selected from the range of 150 to 220 ° C for 20 minutes to 180 minutes, and more preferably for the range of 160 to 200 ° C for 30 minutes to 120 minutes. Further, in the case where the support film has a release layer or a release layer such as silicone, the support film can be peeled off after heat curing of the thermosetting resin composition or after heat curing and opening.

After the insulating layer formed of the cured product of the resin composition is formed, the circuit substrate may be drilled, laser, plasma, or a combination thereof to form a via hole, if necessary, to form a via hole. Or through hole. In particular, opening by means of a laser such as a carbon dioxide laser or a YAG laser is often employed.

Next, the surface treatment of the insulating layer is performed. The surface treatment may be carried out by a method used in a desumia process or in the form of a decontamination step. As the drug used in the decontamination step, it is usually an oxidizing agent. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. The oxidizing agent widely used for the roughening of the insulating layer in the multilayer printed wiring board by the build-up process is preferred. It is preferred to carry out the treatment with an alkaline permanganic acid solution (for example, potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide). Treatment with a swelling agent can also be carried out prior to treatment with an oxidizing agent. Further, after the treatment with an oxidizing agent, the neutralization treatment by a reducing agent is usually carried out.

The above-mentioned decontamination step also has the function of increasing the formation by plating. The peeling strength of the conductor layer is such that the surface of the insulator layer is roughened to provide irregularities.

After the surface treatment, a conductor layer is formed on the surface of the insulator layer by plating. Conductor layer formation can be performed by a combination of electroless plating and electroplating. Further, a plating resist layer having a pattern opposite to the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. After the conductor layer is formed, the peeling strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C for 20 to 90 minutes.

As a method of forming a line of a conductor layer to form a line, a subtractive method, a semi-additive method, or the like which is well known to those skilled in the art can be used. In the case of the subtraction method, the thickness of the non-electric copper plating layer is 0.1 to 3 μm, preferably 0.3 to 2 μm. After forming a plating layer (panel plating layer) of 3 to 35 μm (preferably having a thickness of 5 to 20 μm), an etching photoresist layer is formed by using iron chloride, copper chloride or the like. After the etching solution is etched to form a conductor pattern, the etching photoresist layer is peeled off, whereby a wiring substrate can be obtained. Further, in the case of the semi-additive method, after forming a non-electric copper plating layer having a thickness of 0.1 to 3 μm (preferably 0.3 to 2 μm) of the non-electroless copper plating layer, a patterned photoresist layer is formed, and then After the copper plating, it is peeled off, whereby a wiring substrate can be obtained.

In the case of forming an RCC-type adhesive film of a resin composition layer (layer A) on a copper foil, the following procedure is employed. The adhesive film was laminated on the wiring substrate, and the thermosetting resin composition was heat-hardened as described above. Then, opening was performed as described above, and the surface treatment of the via holes was performed by soft etching. Then, electroless plating is performed, and the circuit substrate can be obtained by subtraction or the like as described above. As the copper foil to be used, 12 or 18 μm is usually used. Examples of the electrolytic copper foil include "DFF" manufactured by Mitsui Mining & Mining Co., Ltd., "NS-VLP", and "JTC" manufactured by Nippon Mining & Metals Co., Ltd. In addition, it is possible to use a very thin copper foil in accordance with the requirements of a fine line, and examples thereof include "Micro Thin Ex" manufactured by Mitsui Mining & Mining Co., Ltd., and "YSMAP" manufactured by Japan Electrolysis Co., Ltd.

In the following, the present invention is specifically described by way of examples, but the present embodiment is not intended to limit the invention.

[Manufacturing Example 1]

<Production of Polyimine Resin (Polyimide Resin Varnish A)>

In a beaker equipped with a stirring device, a thermometer and a condenser, 203.07 g of γ-butyrolactone as a solvent, 30.60 g of Solveso 150 as a solvent, and 88.8 g (0.4 mol) of isophorone diisocyanate and hydrogenated polybutyrene were added. Diene diol (hydroxyl value 48.5 KOH-mg/g, molecular weight 2313) 231.3 g (0.1 mol), and polybutadiene diol (hydroxyl value 52.6 KOH-mg/g, molecular weight 2133) 213.3 g (0.1 Mo Ear), reacted at 70 ° C for 4 hours. Then, a nonyl novolac resin (hydroxyl equivalent of 229.4 g/eq, an average of 4.27 functional groups, an average molecular weight of 979.5 g/mole) of 195.9 g (0.2 mol) and ethylene glycol bistriphenyl hexahydride 41.0 g (0.1) was added. Mohr), the temperature was raised to 150 ° C over 2 hours, and allowed to react for 12 hours.

After the reaction, it became a transparent brown liquid, and obtained a nonvolatile content of 60% and a viscosity of 15 Pa. s (25 ° C) polyimine resin solution. The solution of the obtained polyimine resin was applied to a KBr plate, and the infrared absorption spectrum of the sample obtained by volatilizing the solvent was measured. The characteristic absorption of the isocyanate group was completely disappeared at 2270 cm ^-1 , and it was confirmed that it was 725 cm ^{-1 .} Absorption with an imine ring of 1780 cm ^-1 and 1720 cm ^-1 . Further, the absorption of the urethane bond was confirmed at 1540 cm ^-1 . Further, the amount of carbon dioxide generated as the hydrazine imidization progressed was found to be 8.8 g (0.2 mol) by the change in the weight change added to the beaker. The anhydride of the ethylene glycol bistriphenyl hexahydride anhydride had an equivalent weight of 0.2 mol, and the amount of carbon dioxide produced was also 0.2 mol. It was concluded that the acid anhydride was all used for the formation of quinone imine, and no carboxylic acid anhydride was present.

From this, it can be concluded that 0.2 moles in the isocyanate group is converted into a quinone bond, and the remaining isocyanate groups are combined with the hydroxyl group of the hydrogenated polybutadiene diol and polybutadiene diol and the nonyl phenol varnish. The phenolic hydroxyl groups in the resin together form a urethane bond, and the phenolic hydroxyl group of the nonyl novolak resin is imparted to the resin, and a part of the phenolic hydroxyl group can be modified to be modified with the urethane. Polyurethane phthalimide resin.

[Manufacturing Example 2]

<Production of Polyimine Resin (Polyimide Resin Varnish B)>

In a beaker equipped with a stirring device, a thermometer and a condenser, 292.09 g of ethylene glycol ester as a solvent, 292.09 g of Solveso 150, and 88.8 g (0.4 mol) of isophorone diisocyanate and polybutane were added. The olefinic diol (hydroxyl value 52.6 KOH-mg/g, molecular weight 2133) 426.6 g (0.2 mol) was reacted at 70 ° C for 4 hours. Then, a nonyl novolac resin (hydroxyl equivalent 229.4 g/eq, an average of 4.27 functional groups, an average molecular weight of 979.5 g/mole) of 195.9 g (0.2 mol) and ethylene glycol bistriphenyl was added. 41.0 g (0.1 mol) of hexaformic anhydride was heated to 150 ° C over 2 hours to allow a reaction for 12 hours.

After the reaction, it became a transparent brown liquid, and obtained a non-volatile content of 56% and a viscosity of 12 Pa. s (25 ° C) polyimine resin solution. The solution of the obtained polyimine resin was applied to a KBr plate, and the infrared absorption spectrum of the sample obtained by volatilizing the solvent was measured. The characteristic absorption of the isocyanate group was completely disappeared at 2270 cm ^-1 , and it was confirmed that it was 725 cm ^{-1 .} Absorption with an imine ring of 1780 cm ^-1 and 1720 cm ^-1 . Further, the absorption of the urethane bond was confirmed at 1540 cm ^-1 . Further, the amount of carbon dioxide generated as the hydrazine imidization progressed was found to be 8.8 g (0.2 mol) by the change in the weight change added to the beaker. The anhydride of the ethylene glycol bistriphenyl hexahydride anhydride had an equivalent weight of 0.2 mol, and the amount of carbon dioxide produced was also 0.2 mol. It was concluded that the acid anhydride was all used for the formation of quinone imine, and no carboxylic acid anhydride was present. From this, it can be concluded that 0.2 moles in the isocyanate group is converted into a quinone bond, and the remaining isocyanate groups are combined with the hydroxyl group of the hydrogenated polybutadiene diol and polybutadiene diol and the nonyl phenol varnish. The phenolic hydroxyl groups in the resin together form a urethane bond, and the phenolic hydroxyl group of the nonyl novolak resin is imparted to the resin, and a part of the phenolic hydroxyl group can be modified to be modified with the urethane. Polyurethane phthalimide resin.

<Reference Example 1>

40 parts of the polyamidene resin composition varnish A obtained as the component (A), and ethylene glycol monoethyl ether acetate of the bisphenol A varnish type epoxy resin as the component (B) (hereinafter referred to as 10.9 parts of a varnish (50% solid content, epoxy equivalent 210, "157S70" manufactured by Nippon Epoxy Co., Ltd.) mixed with EDGAc) and Ipuzol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.). 0.5 parts of an imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.), 6 parts of spherical cerium oxide (specific surface area: 80 m ² /g), and 10 parts of toluene and 5.5 parts of γ-butyrolactone were prepared into a varnish. The resin composition.

<Reference Example 2>

40 parts of the polyamidene resin composition varnish A obtained as the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) (solid content 50%) , epoxy equivalent 210, "157S70" manufactured by Nippon Epoxy Co., Ltd.), 10.9 parts, imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.), 0.5 part, spherical cerium oxide (specific surface area: 6.2 m ^{2 )} /g) 6 parts, and 10 parts of toluene, prepared into a varnish-like resin composition.

<Reference Example 3>

40 parts of the polyimine resin composition varnish B obtained in Production Example 2 of the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) (solid content 50%) , an epoxy equivalent of 210, "157S70" made by Nippon Epoxy Co., Ltd.), 10.9 parts, an imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.), 0.5 part, spherical ceria (specific surface area: 80 m ² / g) 6 parts, and 10 parts of toluene and 5.5 parts of γ-butyrolactone to prepare a resin composition in the form of a varnish.

<Reference Example 4>

40 parts of the polyimine resin composition varnish B obtained in Production Example 2 of the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) (solid content 50%) , epoxy equivalent 210, "157S70" manufactured by Nippon Epoxy Co., Ltd.), 10.9 parts, imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.), 0.5 part, spherical cerium oxide (specific surface area: 6.2 m ^{2 )} /g) 6 parts, and 10 parts of toluene, prepared into a varnish-like resin composition.

[Example 1]

40 parts of the polyamidene resin composition varnish A obtained as the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) (solid content 50%) , an epoxy equivalent of 210, "157S70" manufactured by Nippon Epoxy Co., Ltd.), 10.9 parts, an imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.), 0.5 parts, spherical cerium oxide (specific surface area: 30 m ² / g) 6 parts, and 10 parts of toluene and 2 parts of γ-butyrolactone, and prepared into a varnish-like resin composition.

[Example 2]

40 parts of the polyimine resin composition varnish B obtained in Production Example 2 of the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) (solid content 50%) , an epoxy equivalent of 210, "157S70" manufactured by Nippon Epoxy Co., Ltd.), 10.9 parts, an imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.), 0.5 parts, spherical cerium oxide (specific surface area: 30 m ² / g) 6 parts, and 10 parts of toluene and 2 parts of γ-butyrolactone, and prepared into a varnish-like resin composition.

[Example 3]

40 parts of the polyamidene resin composition varnish A obtained as the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) (solid content 50%) , epoxy equivalent 210, "157S70" manufactured by Nippon Epoxy Co., Ltd.), 10.9 parts, imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.), 0.5 parts, spherical cerium oxide (specific surface area: 20 m ² / g) 6 parts, and 10 parts of toluene and 4 parts of γ-butyrolactone, and prepared into a varnish-like resin composition.

[Example 4]

40 parts of the polyimine resin composition varnish B obtained in Production Example 2 of the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) (solid content 50%) , epoxy equivalent 210, "157S70" manufactured by Nippon Epoxy Co., Ltd.), 10.9 parts, imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.), 0.5 parts, spherical cerium oxide (specific surface area: 20 m ² / g) 6 parts, and 10 parts of toluene and 4 parts of γ-butyrolactone, and prepared into a varnish-like resin composition.

[Example 5]

40 parts of the polyamidene resin composition varnish A obtained as the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) (solid content 50%) , epoxy equivalent 210, "157S70" manufactured by Nippon Epoxy Co., Ltd.), 10.9 parts, imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.), 0.5 parts, spherical alumina (specific surface area: 22 m ² /g) 6 parts and 10 parts of toluene were prepared into a varnish-like resin composition.

[Example 6]

40 parts of the polyimine resin composition varnish B obtained in Production Example 2 of the component (A), EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) (solid content 50%) , epoxy equivalent 210, "157S70" manufactured by Nippon Epoxy Co., Ltd.), 10.9 parts, imidazole derivative ("P200H50" manufactured by Nippon Epoxy Co., Ltd.), 0.5 parts, spherical alumina (specific surface area: 22 m ² /g) 6 parts and 10 parts of toluene were prepared into a varnish-like resin composition.

<dispersibility>

In Reference Examples 1 to 4, when the varnish was allowed to stand at room temperature for about 12 hours, the filler settled and the varnish was separated, and in Examples 1 to 6, the filler was maintained in a uniformly dispersed state.

[Example 7]

The varnish obtained in Example 1 was subjected to release treatment of polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as PET) to form a resin composition. The coating machine was applied so that the thickness of the resin after drying became 60 μm, and dried at 80 to 120 ° C (average 100 ° C) for 12 minutes to form a resin composition layer, thereby obtaining a film.

[Example 8]

With respect to the varnish obtained in Example 2, a resin composition layer was formed on PET in the same manner as in Example 7 to obtain a film.

[Example 9]

With respect to the varnish obtained in Example 3, a resin composition layer was formed on PET in the same manner as in Example 7 to obtain a film.

[Example 10]

With respect to the varnish obtained in Example 4, a resin composition layer was formed on PET in the same manner as in Example 7 to obtain a film.

[Example 11]

With respect to the varnish obtained in Example 5, a resin composition layer was formed on PET in the same manner as in Example 7 to obtain a film.

[Example 12]

With respect to the varnish obtained in Example 6, a resin composition layer was formed on PET in the same manner as in Example 7 to obtain a film.

The adhesive film obtained in Examples 7 to 12 was heated at 180 ° C. 90 minutes. The cured product properties of the respective resin compositions are shown in Table 1. Further, the tensile strength at break was measured in accordance with Japanese Industrial Standards (JIS) K7127. Further, the dielectric properties were evaluated by a cavity resonance perturbation method (E8362B manufactured by Agilent Technologies Co., Ltd.). The characteristic values are shown in Table 1.

<Comparative Example 1>

In Comparative Example 1, an interlayer insulating material made of an epoxy resin (ABF-GXcode 13 manufactured by Ajinomoto Seiki Co., Ltd.) was heat-cured at 180 ° C for 90 minutes to obtain a cured product. The characteristic values of the cured product are shown in Table 1 in the same manner as above.

[Example 13]

Closeness with copper foil (1)

The adhesive film obtained in Example 7 was placed on the S surface and the M surface of a copper foil (manufactured by Nippon Steel Co., Ltd., JTC foil) by a laminator manufactured by a famous machine manufacturer. One-side lamination was carried out under conditions of a temperature of 100 ° C, a pressure of 7 kgf/cm ² , and a gas pressure of 5 mmHg or less, and a three-layer product of copper foil/attach film/PET was prepared. Then, the release-treated PET was peeled off, and laminated to a copper clad laminate treated with MEC Etch Bond CZ8100 in the same manner. Then, it was subjected to heat hardening at 120 ° C for 30 minutes and then at 180 ° C for 90 minutes. The peel strength at the interface of the resin/copper foil was measured using the obtained substrate, and the peel strength of the S surface was 0.66 kgf/cm, and the peel strength of the M surface was 1.22 kgf/cm. Further, the peel strength measurement was carried out in accordance with JIS C6481, and the thickness of the copper foil was set to 18 μm.

[Example 14]

Close contact with copper foil (2)

Using the adhesive film obtained in Example 8, the peel strength at the interface of the resin/copper foil was measured in the same manner as in Example 13, and the peel strength of the S surface was 0.73 kgf/cm, and the peel strength of the M surface was 1.05 kgf/cm. .

[Example 15]

Closeness with copper foil (3)

Using the film obtained in Example 9, the peel strength at the interface of the resin/copper foil was measured in the same manner as in Example 13, and the peel strength of the S surface was 0.50 kgf/cm, and the peel strength of the M surface was 1.04 kgf/cm. .

[Example 16]

Closeness with copper foil (4)

The film obtained in Example 10 was used in the same manner as in Example 13. The peel strength of the interface of the resin/copper foil was measured, and the peel strength of the S surface was 0.67 kgf/cm, and the peel strength of the M surface was 0.94 kgf/cm.

[Example 17]

Close contact with copper foil (5)

Using the film obtained in Example 11, the peel strength at the interface of the resin/copper foil was measured in the same manner as in Example 13, and the peel strength of the S surface was 0.46 kgf/cm, and the peel strength of the M surface was 1.13 kgf/cm. .

[Example 18]

Closeness with copper foil (6)

Using the adhesive film obtained in Example 12, the peel strength at the interface of the resin/copper foil was measured in the same manner as in Example 13, and the peel strength of the S surface was 0.44 kgf/cm, and the peel strength of the M surface was 1.06 kgf/cm. .

<Comparative Example 2>

The peel strength at the interface of the resin/copper foil was measured in the same manner as in Example 13 using an interlayer insulating material made of epoxy resin (ABF-GXcode 13 manufactured by Ajinomoto Precision Technology Co., Ltd.), and the peel strength of the S surface was obtained. 0.29 kgf/cm, and the peeling strength of the M surface was 1.44 kgf/cm.

The results of Examples 13-18 and Comparative Example 2 are summarized in Table 2. It can be seen that in the examples, even a smooth surface like the S surface of the copper foil showed good adhesion.

[Example 19]

About plating peeling (1)

The adhesive film obtained in Example 8 was laminated on a copper clad laminate processed by MEC Etch Bond CZ8100 by a laminator manufactured by a famous machine manufacturer. The conditions of a temperature of 100 ° C, a pressure of 7 kgf / cm ² , and a gas pressure of 5 mmHg or less were laminated on both sides. Then, the release-treated PET was peeled off, and heat-hardened at 180 ° C for 30 minutes to form an insulating layer. The surface treatment process of the insulating layer which has both the decontamination step uses the following liquid solutions of Attotec (Japan) Co., Ltd.: swelling agent "Swelling Dip Securiganth" and oxidizing agent "Concentrate Compact CP" (permanganic acid alkali solution) And reducing agent "Reduction solution Securiganth P-500".

The surface treatment was carried out with a swelling agent solution at a temperature of 80 ° C for 5 minutes, then surface-treated with an oxidizing agent at a temperature of 80 ° C for 5 minutes, and finally neutralized with a reducing agent solution at 40 ° C for 5 minutes. Then, a non-electric copper plating catalyst was applied to the surface of the insulating layer, and then immersed in a non-electrolytic copper plating solution at 32 ° C for 30 minutes to form a 1.5 μm non-electric copper plating film. This was dried at 150 ° C for 30 minutes, and then acid-washed, and a phosphorus-containing copper plate was used as an anode, and copper plating was performed at a cathode current density of 2.0 A/dm ² for 12 minutes to form a copper plating film. Then, annealing treatment was further performed at 180 ° C for 30 minutes. The peel strength of the obtained conductor layer was 0.71 kgf/cm. Further, the peel strength measurement was evaluated in accordance with JIS C6481, and the thickness of the conductor plating layer was set to be about 25 μm.

(Comparative Example 3)

An insulating layer was formed in the same manner as in Example 19, using an interlayer insulating material made of epoxy resin (ABF-GXcode 13 manufactured by Ajinomoto Seiki Co., Ltd.). The surface treatment was carried out in the same manner using a drug solution manufactured by Attotec (Japan) Co., Ltd.

The surface treatment was carried out by a swelling agent solution at a temperature of 60 ° C for 5 minutes, and then surface treatment was carried out by an oxidizing agent at a temperature of 80 ° C for 15 minutes, and finally, a neutralization treatment was carried out by a reducing agent solution at 40 ° C for 5 minutes. Further, the peel strength of the obtained conductor layer was 0.6 kgf/cm.

[Manufacturing Example 3]

<Manufacture of linear modified polyimine resin (linear modified polyimine resin varnish C)>

In the reactor, 50 g of G-3000 (2-functional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g / eq., solid content of 100% by weight, Japan's Soda (stock) 2) g of Ipuzol 150 and 0.005 g of dibutyltin laurate were mixed to uniformly dissolve. When the temperature was uniform, the temperature was raised to 50 ° C, and then 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g/eq.) was added thereto with stirring, and the mixture was allowed to react for about 3 hours. Then, the reactant was cooled to room temperature, and then benzophenonetetracarboxylic dianhydride (anhydride equivalent = 161.1 g / eq.) 8.96 g, triethylenediamine 0.07 g, ethylene glycol acetate ( 40.4 g of Diacel Chemical Industry Co., Ltd. was heated to 130 ° C with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak of 2250 cm ^-1 by FT-IR was confirmed. The confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction was cooled to room temperature and filtered through a 100-mesh filter cloth to obtain a linear modified polyimine resin (linear modified polyimine resin varnish). C).

Linear modified polyimine resin varnish A properties: viscosity = 7.5Pa. s (25 ° C, E-type viscometer) Acid value = 16.9 mg KOH / g solid content = 50% by weight

<Reference Example 5>

35 parts of the EDGAc and Ipuzol 150 mixed varnish of the bisphenol A varnish type epoxy resin as the component (B) as the component (A) in the polyimine resin varnish C obtained in the production example 3, and 10.9 parts (solid) 50%, epoxy equivalent 210, "157S70" made by Nippon Epoxy Co., Ltd.), 4.5 parts of novolac ("T2090-60M" manufactured by Dainippon Ink Chemicals Co., Ltd.), spherical cerium oxide (specific surface area 4.1) 6 parts of m ² /g), and 10 parts of toluene and 2 parts of γ-butyrolactone were prepared into a resin composition in the form of a varnish.

<dispersibility>

In Comparative Example 4, even if the varnish was allowed to stand at room temperature for about 12 hours, the seasoning was maintained in a state of uniform dispersion.

<physical value>

In the varnish obtained in Comparative Example 4, a resin composition layer was formed on PET in the same manner as in Example 7 to obtain a film which was heat-cured at 180 ° C for 90 minutes. The characteristic values of the cured product are shown in Table 3. Further, the peeling strength at the interface of the resin/copper foil was measured in the same manner as in Example 13 using the film obtained in Comparative Example 4, and the peel strength of the S surface was 0.55 kgf/cm, and the peel strength of the M surface was 0.67 kgf. /cm.

Claims (13)

A resin composition for interlayer insulation of a multilayer printed wiring board, which comprises the following components (A), (B) and (C): (A) having a polybutadiene structure or a urethane in a molecule A polyimine resin having a phenol structure at the molecular end, (B) an epoxy resin, and (C) an inorganic filler having a specific surface area of 18 to 50 m ² /g. A resin composition for interlayer insulation of a multilayer printed wiring board, comprising the following components (A), (B), and (C): (A) having two or more alcoholicities in one molecule via [a] The hydroxyl group polybutadiene polyol compound and the [b] diisocyanate compound are reacted to form a diisocyanate prepolymer, and the [c] tetrabasic dianhydride and the [d] 1 molecule have two or more a polyphenyleneimine resin having a phenol structure at a molecular terminal prepared by reacting a polyfunctional phenol compound of a phenolic hydroxyl group; (B) an epoxy resin; (C) an inorganic filler having a specific surface area of 18 to 50 m ² /g . The resin composition according to claim 1 or 2, wherein the inorganic filler of the component (C) has a specific surface area of 18 to 40 m ² /g. The resin composition according to claim 1 or 2, wherein the inorganic filler of the component (C) has a specific surface area of 18 to 35 m ² /g. The resin composition according to claim 1 or 2, wherein the inorganic filler of the component (C) has a specific surface area of 20 to 30 m ² /g. The resin composition of claim 1 or 2, wherein the inorganic filler is cerium oxide. The resin composition according to claim 1 or 2, wherein the phenol compound is a novolak resin. The resin composition of claim 1 or 2, wherein the polybutadiene polyol compound is a hydrogenated polybutadiene polyol compound. The resin composition of the second aspect of the patent application is a polybutadiene having two or more alcoholic hydroxyl groups in the molecule of the reaction component [a] in the polyimine resin of the component (A). The hydroxyl group of the polyol and the functional group equivalent ratio of the isocyanate group of the reaction component [b] diisocyanate compound are reacted at a ratio of 1:1.5 to 1:2.5. The resin composition of claim 1 or 2 further contains a polyfunctional phenol compound having a component [D] having two or more phenolic hydroxyl groups in one molecule. The resin composition of claim 10, which is 100% by weight based on the total of the polyamidene resin of the component (A), the epoxy resin of the component (B), and the polyfunctional phenol compound of the component (D). The component (A) is contained in an amount of 40 to 85% by weight, the component (B) is 15 to 40% by weight, and the component (D) is 0 to 20% by weight. An adhesive film for forming an interlayer insulating layer of a multilayer printed wiring board, which is characterized in that the resin composition of the first or second aspect of the invention is formed on a support. A multilayer printed wiring board characterized in that an interlayer insulating layer is formed by a resin composition as claimed in claim 1 or 2.