KR20100090652A - Resin composition - Google Patents

Abstract

PURPOSE: A resin composition is provided to secure the lamination property of the composition, and to improve the adhesion property with an insulating layer and a conductive layer. CONSTITUTION: A resin composition for a multi-layer printed circuit board contains a cyanate ester resin, an epoxy resin, a thermoplastic resin, talcum, and silica. The thermoplastic resin is a polymer resin selected from the group consisting of a phenoxy resin, a polyimide resin, a polyamideimide resin, a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene ether resin, a polycarbonate resin, a polyetheretherketone resin, a polyester resin, a polyacetal resin, and a polybutyral resin.

Description

Resin composition

This invention relates to the resin composition suitable for formation of insulating layers, such as a multilayer printed wiring board.

In recent years, miniaturization and high performance of electronic devices have progressed, and in order to improve the mounting density of an electronic component of a multilayer printed wiring board, refinement | miniaturization of conductor wiring is advanced. As a resin composition used for the insulating layer of a multilayer printed wiring board, it is known that the resin composition containing an epoxy resin and the cyanate ester resin which functions as its hardening | curing agent can form the insulating layer excellent in dielectric properties, for example. In addition, in a multilayer printed wiring board having a high density of wirings, problems such as occurrence of cracking due to a difference in the thermal expansion coefficient of the conductor layer and the insulating layer tend to occur, and therefore, it is required to reduce the thermal expansion rate of the insulating layer low. Addition of the inorganic filler to the resin composition is widely used as a means for lowering the coefficient of thermal expansion, and as an inorganic filler, silica, which is particularly strong in physical strength, high in hardness, and excellent in hot water resistance, is generally widely used. For example, Patent Documents 1 and 2 disclose resin compositions containing epoxy resins, cyanate ester resins, silicas, and the like.

[Prior Art Literature]

[Patent Documents]

[Patent Document 1] International Publication 2003/099952 Pamphlet

[Patent Document 2] International Publication 2008/044766 pamphlet

On the other hand, when the present inventors carry out the environmental test under high temperature, high humidity with respect to the insulating layer formed by laminating | stacking the resin composition containing an epoxy resin, a cyanate ester resin, and a silica to a circuit board, and hardening the said resin composition, a conductor layer is carried out. The knowledge that the peeling strength between a material and an insulating layer falls remarkably was acquired.

An object of the present invention is to provide a resin composition suitable for forming an insulating layer of a printed wiring board, by which a circuit board can be manufactured using the resin composition so that the adhesion between the conductor layer and the insulating layer can be more stably maintained. It is done.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that when talc was mix | blended with the resin composition containing an epoxy resin and a cyanate ester resin, adhesiveness of the conductor layer and an insulating layer after an accelerated environmental test can be stably maintained. On the other hand, when the compounding quantity of talc was made large in order to maintain sufficient adhesiveness and to reduce the thermal expansion rate of an insulating layer, it turned out that the melt viscosity of a resin composition becomes high too much and is not suitable for a laminate. MEANS TO SOLVE THE PROBLEM As a result of further investigation, in the resin composition containing an epoxy resin, a cyanate ester resin, and a thermoplastic resin, adhesiveness with a conductor layer, a low thermal expansion coefficient, and a laminate are used by using a talc and a silica together as an inorganic filler in a fixed ratio. It was found that a good insulating layer having balanced properties was formed and completed the present invention.

That is, this invention includes the following content.

[1] A resin composition for a printed wiring board containing (A) cyanate ester resin, (B) epoxy resin, (C) thermoplastic resin, (D) talc and (E) silica, wherein the nonvolatile content in the resin composition is 100 mass. When it is set as%, the sum total of content of (1) component (D) talc and a component (E) silica is 35-60 mass%, and (2) resin composition whose content of component (D) talc is 5-20 mass%. .

[2] A resin composition for a printed wiring board containing (A) cyanate ester resin, (B) epoxy resin, (C) thermoplastic resin, (D) talc and (E) silica, wherein the nonvolatile content in the resin composition is 100 mass. When it is set as%, the sum total of content of (1) component (D) talc and component (E) silica is 45-60 mass%, and (2) resin composition whose content of component (D) talc is 5-20 mass%. .

[3] The resin composition according to the item [1] or [2], wherein the average particle diameter of the component (D) talc is 1.3 µm or less.

[4] The item (1) or [2], wherein the component (C) thermoplastic resin is a phenoxy resin, a polyimide resin, a polyamideimide resin, a polyetherimide resin, a polysulfone resin, a polyether sulfone resin, The resin composition which is at least 1 sort (s) of resin chosen from polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, polyacetal resin, and polybutyral resin.

[5] The resin composition according to the item [1] or [2], wherein the component (C) thermoplastic resin is a phenoxy resin.

[6] The resin composition according to any one of the above items [1] to [3], wherein the component (D) talc and the component (E) silica are surface treated in advance.

[7] The resin composition according to any one of the above items [1] to [6], wherein the thermal expansion rate is 44 ppm or less, and the adhesion retention rate before and after the environmental test is 40% or more.

[8] The resin composition according to any one of the above items [1] to [7], which is for interlayer insulation of a multilayer printed wiring board.

[9] An adhesive film, wherein the resin composition according to any one of [1] to [8] is layered on a support film.

[10] A prepreg in which the resin composition according to any one of the above items [1] to [8] is impregnated into a sheet-like reinforcing base material made of fibers.

[11] A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to any one of the above items [1] to [8], and a conductor layer formed on the insulating layer.

According to the present invention, a resin composition suitable for forming an insulating layer of a circuit board such as a multilayer printed wiring board, which has excellent lamination properties and is cured to form an insulating layer, the conductor layer and the insulating layer even after an environmental test under high temperature and high humidity. The resin composition which has sufficient adhesiveness and is excellent also in low thermal expansion coefficient is provided.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on the suitable embodiment.

[Talc, Silica]

The talc used in the present invention is not particularly limited, various talc may be used, and calcined talc may be used. 5 micrometers is preferable, 4 micrometers is more preferable, 3 micrometers is still more preferable, 2.5 micrometers is still more preferable, 1.8 micrometers is especially the upper limit of the average particle diameter of a talc from a viewpoint of microwiring and insulation reliability. It is preferable and 1.3 micrometer is especially preferable. On the other hand, 0.1 micrometer is preferable, 0.2 micrometer is more preferable, 0.3 micrometer is still more preferable from a viewpoint that the lower limit of the average particle diameter of talc prevents resin becoming too high and it becomes difficult to embed resin between fine wiring. 0.4 micrometer is further more preferable, and 0.5 micrometer is especially preferable.

As commercially available talc, D-600 (average particle diameter: 0.6 µm), D-800 (average particle diameter: 0.8 µm), D-1000 (average particle diameter: 1.0 µm) manufactured by Nippon Tark Co., Ltd., SG-95S (Average particle diameter 1.2 µm), SG-95 (average particle diameter 2.5 µm), P-8 (average particle diameter 3.3 µm), P-6 (average particle diameter 4.0 µm), P-4 (average particle diameter 4.5 µm) ), P-3 (average particle diameter 5.0 µm), P-2 (average particle diameter 7.0 µm), L-1 (average particle diameter 5.0 µm), K-1 (average particle diameter 8.0 µm), LG (average particle diameter 5.0 micrometers in diameter), etc. are mentioned. The average particle diameter of the talc can be measured by a laser diffraction scattering method based on the Mie scattering theory. Specifically, the laser diffraction particle size distribution measuring device can measure the particle size distribution of the inorganic filler on the basis of volume and make the median diameter the average particle diameter. The measurement sample can use preferably the thing which disperse | distributed talc in the water by the ultrasonic wave. As the laser diffraction particle size distribution measuring apparatus, LA-500 manufactured by Horiba Sesaku Sho, etc. may be used.

Although it does not specifically limit as a compounding quantity of talc, The upper limit of the compounding quantity of talc is 20 mass% from a viewpoint of preventing the lamination property to a circuit board from deteriorating, when the non volatile matter in a resin composition is 100 mass%. 19 mass% is more preferable, 18 mass% is more preferable, 17 mass% is further more preferable, 16 mass% is especially preferable, and 15 mass% is especially preferable. On the other hand, when the non-volatile content in the resin composition is 100% by mass, the lower limit of the blending amount of talc is preferably 5% by mass, from the viewpoint of preventing the adhesion strength between the conductor layer and the insulating layer from deteriorating, and 6 Mass% is more preferable, 7 mass% is more preferable, 8 mass% is further more preferable, 9 mass% is especially preferable, and 10 mass% is especially preferable.

Although the total compounding quantity of talc and silica is not specifically limited, The upper limit of the total compounding quantity of talc and silica is the point which prevents the lamination property to a circuit board from deteriorating, when the non volatile matter in a resin composition is 100 mass%. , 70 mass% is preferable, 65 mass% is more preferable, 62 mass% is more preferable, 60 mass% is further more preferable, 58 mass% is especially preferable, 56 mass% is especially preferable. On the other hand, when the non-volatile content in the resin composition is 100 mass%, the lower limit of the total amount of talc and silica is preferably 35% by weight, more preferably 40% by weight from the viewpoint of lowering the thermal expansion coefficient of the insulating layer. , 42 mass% is more preferable, 45 mass% is further more preferable, 47 mass% is especially preferable, and 49 mass% is especially preferable.

The silica to be blended with the resin composition of the present invention is not particularly limited, and various silicas such as amorphous silica, fused silica, crystalline silica, and synthetic silica are used, and spherical fused silica is particularly preferable. Although the average particle diameter of silica is not specifically limited, From an viewpoint of fine wiring formation, an average particle diameter of 5 micrometers or less is preferable, and it is especially preferable that it is 0.1-1.0 micrometer. When the average particle diameter is too small, the viscosity of the resin becomes too high, making it difficult for the resin to flow between fine wirings, and when it exceeds 5.0 µm, the insulation reliability between fine wirings and conductor layers tends to be lowered.

It is preferable that the talc and silica used for this invention surface-treat with a surface treating agent, and the moisture resistance and dispersibility were improved. Examples of the surface treatment agent include an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, and a titanate coupling agent. As an aminosilane-type coupling agent, aminopropyl trimethoxysilane, aminopropyl triethoxysilane, fluoride propyl triethoxysilane, N-phenylaminopropyl trimethoxysilane, N-2- (aminoethyl) aminopropyl tri Methoxysilanes are preferred. As an epoxy silane coupling agent, glycidoxy propyl trimethoxysilane, glycidoxy propyl triethoxy silane, glycidoxy propyl methyl diethoxy silane, glycidyl butyl trimethoxy silane, (3, 4- epoxy cyclo Hexyl) ethyltrimethoxysilane is preferred. As a mercaptosilane type coupling agent, mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane are preferable. As the silane coupling agent, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methoxypropyltrimethoxysilane, imidazolesilane and triazine silane are preferable. As the organosilazane compound, hexamethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane are preferable. As a titanate coupling agent, butyl titanate dimer, titanium octylene glycolate, diisopropoxy citabis bis (triethanol aluminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (Dioctylpyrophosphate) ethylene titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxy titanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) Titanate, Tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl Phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumylphenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostaroyl diac Titanate, Isopropyldimethacrylisostearoyl titanate, Isopropyl tri (dioctylphosphate) titanate, Isopropyl tridodecylbenzenesulfonyl titanate, Isopropyl tris (dioctyl pyrophosphate) titanate And isopropyl tri (N-amide ethyl aminoethyl) titanate is preferable.

[Cyanate Ester Resin]

The cyanate ester resin used in the present invention is not particularly limited, and examples thereof include novolak type (phenol novolak type and alkylphenol novolak type) cyanate ester resins and bisphenol type (bisphenol A type, Bisphenol F type, bisphenol S type, etc.) cyanate ester resins, and some triazine-ized prepolymers thereof. These may be used independently and may be used in combination of 2 or more type. Although the weight average molecular weight of cyanate ester resin is not specifically limited, Preferably it is 500-4,500, More preferably, it is 600-3,000.

As a specific example of cyanate ester resin, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis (2,6, for example) -Dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4 -Cyanatephenyl) methane, bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4- Bifunctional cyanate resins such as cyanatephenyl) thioether, bis (4-cyanatephenyl) ether, etc. polyfunctional cyanate resins derived from phenol novolak, cresol novolak, dicyclopentadiene structure-containing phenol resin and the like; Prepolymer etc. which these cyanate resin was partially triazineized are mentioned.

As a commercially available cyanate ester resin, a part of phenol novolak-type polyfunctional cyanate ester resin of following formula (1) (Lonza Japan Co., Ltd. product, PT30, cyanate equivalent 124), and a part of bisphenol A dicyanate of following formula (2) Or a prepolymer (trione-ized by Ronza Japan Co., Ltd., BA230, cyanate equivalent weight 232) which triazine-ized and trimerized, and the dicyclopentadiene structure containing cyanate ester resin (Lonza Japan Co., Ltd. make, DT-4000) Etc. can be mentioned.

In Chemical Formula 1,

n is any number as an average value.

Although content of cyanate ester resin in a resin composition is not specifically limited, The upper limit of content of cyanate ester resin is a non-volatile content 100 in a resin composition from a viewpoint of preventing the adhesive strength of a conductor layer and an insulating layer from falling. 50 mass% is preferable with respect to mass%, 40 mass% is more preferable, and 30 mass% is further more preferable. On the other hand, the lower limit of content of cyanate ester resin is 5 mass with respect to 100 mass% of non volatile matters in a resin composition from a viewpoint of preventing the heat resistance of a resin composition from falling and preventing the thermal expansion coefficient of an insulating layer from increasing. % Is preferable, 10 mass% is more preferable, and 15 mass% is more preferable.

[Epoxy resin]

The epoxy resin used in this invention is not specifically limited, For example, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, phenol novolak-type epoxy resin, alkylphenol novolak-type Epoxy resins, biphenyl type epoxy resins, aralkyl type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, aromatic aldehydes having phenols and phenolic hydroxyl groups; Epoxides of the condensates, biphenyl aralkyl type epoxy resins, fluorene type epoxy resins, xanthene type epoxy resins, triglycidyl isocyanurates, and the like. These epoxy resins may be used independently, respectively and may be used in combination of 2 or more type. Examples of commercially available epoxy resins include "jER828EL" (liquid bisphenol A type epoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., "HP4032" and "HP4032D" manufactured by Dainippon Ink & Chemicals Co., Ltd. Naphthalene type bifunctional epoxy resin), "HP4700" by Dainippon Ink & Chemicals Co., Ltd. (naphthalene type tetrafunctional epoxy resin), "ESN-475V" and "ESN-185V" by Totokasei Co., Ltd. ( Naphthol type epoxy resin), "PB-3600" (the epoxy resin which has butadiene structure) by Daicel Chemical Industries, Ltd., "NC3000H", "NC3000L", "NC3100" and "NC3100" by Nihon Kayaku Co., Ltd. NC3000 "(biphenyl type epoxy resin)," YX4000 "(biphenyl type epoxy resin) by Japan Epoxy Resin Co., Ltd., GK3207 (biphenyl type epoxy resin) by Totokasei Co., Ltd., ash Manufactured by whether or epoxy resins, and the like "YX8800" (hereinafter anthracene skeleton type epoxy resin) of the preparation.

Although content of the epoxy resin in a resin composition is not specifically limited, Preferably it is 5-60 mass%, More preferably, it is 10-50 mass%, More preferably, with respect to 100 mass% of non volatile matters in a resin composition. Is 15-40 mass%. When there is too little content of an epoxy resin, there exists a tendency for roughening unevenness to arise easily at the time of the roughening process of the hardened composition surface mentioned later. When there is too much content of an epoxy resin, since content of cyanate ester resin will decrease relatively, there exists a tendency for the thermal expansion rate of an insulating layer to increase.

The ratio of cyanate equivalent of cyanate ester resin and epoxy equivalent of epoxy resin becomes like this. Preferably it is 1: 0.4-1: 2, More preferably, it is 1: 0.5-1: 1.5. If the equivalence ratio is out of the above range, in the wet roughening step described later, there is a tendency that compatibility between the adhesion strength of the conductor layer and the insulating layer formed by lowering roughness of the insulating layer surface and plating is difficult.

[Thermoplastic resin]

Examples of the thermoplastic resin used in the present invention include phenoxy resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, and polyether ether ketones. Resin, polyester resin, polyvinyl acetal resin, polyvinyl butyral resin and the like. These thermoplastic resins may be used independently, respectively and may be used in combination of 2 or more type.

As a thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable from a viewpoint of preventing the lamination property to a circuit board from deteriorating. As polyvinyl acetal resin, polyvinyl butyral resin is especially preferable. As a specific example of polyvinyl acetal resin, Denkabutyral 4000-2, 5000-A, 6000-C and 6000-EP by Seiki Sugigaku Kogyo Co., Ltd. Esrek BH series by Sekisui Kagaku Kogyo Co., Ltd. make , BX series, KS series, BL series and BM series. As a specific example of a phenoxy resin, FX280 and FX293 by Totokasei Co., Ltd., YX8100, YX6954, YL6974, YL7482, YL7553, YL6794, YL7213, YL7290, etc. by Japan Epoxy Resin Co., Ltd. are mentioned. It is especially preferable that polyvinyl acetal resin is 80 degreeC or more in glass transition temperature. "Glass transition temperature" here is determined according to the method of JISK7197. In addition, when a glass transition temperature is higher than a decomposition temperature and a glass transition temperature is not observed actually, a decomposition temperature can be regarded as a glass transition temperature in this invention. In addition, a decomposition temperature is defined as the temperature at which a mass reduction rate when it measures by the method of JISK7120 becomes 5%.

The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000, more preferably in the range of 10,000 to 150,000, still more preferably in the range of 15,000 to 100,000, still more preferably in the range of 20,000 to 80,000. Do. When smaller than this range, there exists a tendency for the effect of film forming ability and mechanical strength improvement not to fully be exhibited, and when larger than this range, compatibility with cyanate ester resin and an epoxy resin will fall, and the roughness after roughening of the surface of an insulating layer will be reduced. Tends to be increased.

In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). As for the weight average molecular weight by GPC method, Shodex K-800P / K by Showa Denko Co., Ltd. was made as the column of LC-9A / RID-6A by Shimadzu Corporation, Ltd. as a measuring device specifically ,. -804L / K-804L can be measured at the column temperature of 40 degreeC using chloroform etc. as a mobile phase, and can be computed using the analytical curve of standard polystyrene.

Although content of the thermoplastic resin in a resin composition is not specifically limited, It is 1-20 mass% with respect to 100 mass% of non volatile matters in a resin composition, More preferably, it is 2-15 mass%, More preferably, Is 3-10 mass%. When the content of the thermoplastic resin is too small, the film forming ability and the effect of improving mechanical strength are not tended to be exhibited, and the effect of adhesion retention after environmental testing is not tended to be exhibited. The roughness of the layer surface tends to be increased.

When the resin composition of this invention contains (A) component, (B) component, (C) component, (D) component, and (E) component, is excellent in lamination property, and hardens and forms the insulating layer, Even after the environmental test under high temperature, high humidity, the adhesiveness of a conductor layer and an insulating layer is enough, and the resin composition excellent also in low thermal expansion coefficient can be provided.

The thermal expansion rate of the hardened | cured material of the resin composition of this invention can be grasped | ascertained by the measuring method as described in <measurement and evaluation of a coefficient of thermal expansion (coefficient of thermal expansion) mentioned later.

The thermal expansion coefficient of the cured product of the resin composition of the present invention is preferably 44 ppm or less, more preferably 42 ppm or less, still more preferably 40 ppm or less, still more preferably 38 ppm or less, particularly preferably 36 ppm or less, and 34 ppm or less. Particularly preferred. The lower limit of the thermal expansion coefficient is also preferably as low as possible, preferably 30 ppm, more preferably 25 ppm, further preferably 20 ppm, even more preferably 10 ppm, and particularly preferably 4 ppm.

The adhesion retention rate before and after the environmental test of the insulation layer and conductor layer formed from the resin composition of this invention can be grasped | ascertained by the measuring method as described in <measurement and evaluation of the adhesion strength (fill strength) of a conductor layer mentioned later.

40% or more is preferable, 45% or more is more preferable, 50% or more is more preferable, and 55% or more of the adhesion retention factor before and after the environmental test of the insulating layer and conductor layer which are formed from the resin composition of this invention is more preferable. It is still more preferable, 60% or more is particularly preferable, 65% or more is particularly preferable, and 70% or more is particularly preferable. The higher limit of the adhesion retention ratio is also as high as possible, preferably 80%, more preferably 82%, still more preferably 84%, still more preferably 90%, and particularly preferably 90%. 100% is particularly preferred.

[Organic Metal Compounds]

An organometallic compound can be further added to the resin composition of the present invention from the viewpoint of curing acceleration. As an organometallic compound, Organic copper compounds, such as copper (II) acetylacetonate; Organic zinc compounds such as zinc (II) acetylacetonate and zinc naphthenate (II); Organic cobalt compounds such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; Organic nickel compounds such as nickel (II) acetylacetonate; Organic iron compounds, such as iron (III) acetylacetonate, etc. are mentioned. The addition amount of the organometallic compound is preferably 25 to 500 ppm, more preferably 40 to 200 ppm, as the metal content of the organometallic compound, relative to 100% by mass of the nonvolatile matter in the resin composition. If it is less than 25 ppm, roughness will be low and formation of a conductor layer of high peeling strength will become difficult, and when it exceeds 500 ppm, it will become a tendency to generate | occur | produce a problem in the storage stability and insulation of a resin composition.

[Rubber particles]

From the viewpoint of improving the adhesiveness, rubber particles can be further added to the resin composition of the present invention. The rubber particles that can be used in the present invention are, for example, insoluble in organic solvents used when preparing varnishes of the resin composition, and incompatible with cyanate ester resins, epoxy resins, and the like, which are essential components. Therefore, the said rubber particle exists in a dispersion state in the varnish of the resin composition of this invention. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level that does not dissolve in an organic solvent or a resin to form a particulate.

Preferred examples of the rubber particles that can be used in the present invention include core-shell rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrenebutadiene rubber particles, acrylic rubber particles and the like.

The core-shell rubber particles are rubber particles having a core layer and a shell layer. For example, the shell layer of the outer layer is made of a glassy polymer, and the inner layer core layer is made of a rubber polymer, or the shell layer of the outer layer is The three layer structure etc. which consist of a glassy polymer, an intermediate | middle layer consist of a rubbery polymer, and a core layer consist of a glassy polymer are mentioned. A glassy polymer layer is comprised, for example from the polymer of methyl methacrylate, etc., and a rubbery polymer layer is comprised from a butylacrylate polymer (butyl rubber) etc., for example. Specific examples of the core-shell rubber particles include Staphyloid AC3832 and AC3816N (trade name, manufactured by Gansukasei Co., Ltd.) and Metablen KW-4426 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.).

As an example of crosslinked acrylonitrile butadiene rubber (NBR) particle | grains, XER-91 (an average particle diameter of 0.5 micrometer, the JSR Corporation make), etc. are mentioned.

As an example of crosslinked styrene-butadiene rubber (SBR) particle | grains, XSK-500 (an average particle diameter of 0.5 micrometer, the JSR Corporation make), etc. are mentioned.

As a specific example of acrylic rubber particle, metablene W300A (average particle diameter 0.1 micrometer), W450A (average particle diameter 0.2 micrometer) (made by Mitsubishi Rayon Corporation) etc. are mentioned.

The average particle diameter of the rubber particle to mix | blend becomes like this. Preferably it is the range of 0.005-1 micrometer, More preferably, it is the range of 0.2-0.6 micrometer. The average particle diameter of the rubber particle used by this invention can be measured using a dynamic light scattering method. For example, the rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and a particle size distribution of the rubber particles is prepared based on mass by using a thick particle diameter analyzer (FPAR-1000; manufactured by Otsuka Denshi Co., Ltd.). In addition, it can measure by making the median diameter into an average particle diameter.

Content of rubber particle | grains becomes like this. Preferably it is 1-10 mass% with respect to 100 mass% of non volatile matters in a resin composition, More preferably, it is 2-5 mass%.

[Flame retardant]

The resin composition of this invention may contain a flame retardant in the range which does not impair the effect of this invention. As a flame retardant, an organophosphorus flame retardant, an organic nitrogen containing phosphorus compound, a nitrogen compound, a silicone flame retardant, a metal hydroxide, etc. are mentioned, for example.

Examples of the organophosphorus flame retardant include phosphorus-containing benzoxazine compounds such as HCA, HCA-HQ and HCA-NQ manufactured by Sanko Corp., HFB-2006M manufactured by Showa Kohunshi Co., Ltd., and Ajinomoto Fine Techno Co., Ltd. Leopards 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140 and TIBP, PPQ, Clariton Corporation, Hokkaido, Ltd. Phosphoric acid ester compounds, such as OP930 by Kaisha, PX200 by Daihachi Chemical Co., Ltd., phosphorus containing epoxy resins, such as FX289 and FX310 by Totokasei Co., Ltd., ERF001 by Totokasei Co., Ltd. Phenoxy resin etc. are mentioned.

Examples of the organic nitrogen-containing phosphorus compound include phosphate ester mid compounds such as SP670 and SP703 manufactured by Shikoku Chemical Co., Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Seisakusho Co., Ltd. The phosphazene compound etc. are mentioned.

Examples of the metal hydroxides include magnesium hydroxides such as UD65, UD650, and UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308, B-308, manufactured by Tomoe Kogyo Co., Ltd., and the like. Aluminum hydroxide, such as UFH-20, etc. are mentioned.

[Other Ingredients]

Another component can be mix | blended with the resin composition of this invention as needed in the range which does not impair the effect of this invention. As another component, For example, organic fillers, such as a silicone powder, nylon powder, a fluorine powder; Thickeners such as orbene and benton; Antifoaming agents or leveling agents based on silicon, fluorine and polymers; Adhesion imparting agents such as imidazole series, thiazole series, triazole series, and silane coupling agents; Curing accelerators such as imidazole series and amine series; And coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, and carbon black.

The preparation method of the resin composition of this invention is not specifically limited, For example, a cyanate ester resin, an epoxy resin, a thermoplastic resin, talc, a silica which is an essential component, a hardening accelerator, a hardening catalyst, a rubber particle, The method of mixing other components using a rotary mixer etc. are mentioned.

Although the use of the resin composition of this invention is not specifically limited, Insulation resin sheets, such as an adhesive film and a prepreg, a circuit board, a soldering resist, an under-fill material, a die bonding material, a semiconductor sealing material, a hole filling resin, and a part embedding resin Etc., it can use widely for the use which requires a resin composition. Among these, it can use suitably in order to form an insulation layer in manufacture of a multilayer printed wiring board. Although the resin composition of this invention can also be hardened | cured after apply | coating to a circuit board in a varnish state, and can form an insulating layer, industrially, it is generally used in the form of sheet-like laminated materials, such as an adhesive film and a prepreg. desirable. As for the softening point of a resin composition, 40-150 degreeC is preferable from a lamination property of a sheet-like laminated material.

[Adhesive Film]

The adhesive film of this invention prepares the resin varnish which melt | dissolved the resin composition in the organic solvent by the method known to those skilled in the art, for example, apply | coats the resin varnish to the support film which is a support body using a die coater, etc. Furthermore, it can manufacture by drying an organic solvent by heating, or blowing with hot air, and forming a resin composition layer.

As said organic solvent, For example, ketones, such as acetone, methyl ethyl ketone, cyclohexanone; Acetate esters, such as ethyl acetate, butyl acetate, a cellosolve acetate, a propylene glycol monomethyl ether acetate, and carbitol acetate; Cellosolves; Carbitols such as butyl carbitol; Aromatic hydrocarbons such as toluene and xylene; Dimethyl formamide, dimethyl acetamide, N-methylpyrrolidone, etc. are mentioned. You may use the organic solvent in combination of 2 or more type.

Although the conditions which dry-dry an organic solvent are not specifically limited, It is preferable to dry so that content of the organic solvent in a resin composition layer may be 10 mass% or less, More preferably, it is 5 mass% or less. Although the amount of the organic solvent in the varnish and the boiling point of the organic solvent vary, for example, the content of the organic solvent is 10 by drying the varnish containing 30 to 60 mass% of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes. The resin composition layer which is the mass% or less is formed. Those skilled in the art can appropriately set suitable drying conditions by simple experiments.

The thickness of the resin composition layer formed in an adhesive film is made into the thickness of a conductor layer normally. Since the thickness of the conductor layer which a circuit board has normally is in the range of 5-70 micrometers, it is preferable that a resin composition layer has a thickness of 10-100 micrometers.

The support film in this invention is polyolefin, such as polyethylene, a polypropylene, and polyvinyl chloride; Polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate; Polycarbonate; The film which consists of polyimide etc., metal foil, such as a release paper, copper foil, aluminum foil, etc. are mentioned. In addition, in addition to a mat process and a corona treatment, the mold release process may be sufficient for the support film and the protective film mentioned later.

Although the thickness of a support film is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

The protective film based on a support film can be further laminated | stacked on the surface in which the support film of a resin composition layer is not in close contact. Although the thickness of a protective film is not specifically limited, 1-40 micrometers is preferable. By laminating | stacking a protective film, adhesion | attachment and a scratch of dust etc. to the surface of a resin composition layer can be prevented. An adhesive film can also be wound and stored in roll shape.

[Multilayer printed wiring board using adhesive film]

Next, an example of the method of manufacturing a multilayer printed wiring board using the adhesive film manufactured as mentioned above is demonstrated.

First, an adhesive film is laminated on one side or both sides of a circuit board using a vacuum laminator. As a board | substrate used for a circuit board, a glass epoxy board | substrate, a metal board | substrate, a polyester board | substrate, a polyimide board | substrate, a BT resin board | substrate, a thermosetting polyphenylene ether board | substrate, etc. are mentioned, for example. In addition, a circuit board means here that the conductor layer (circuit) pattern-processed was formed in one side or both surfaces of the above board | substrates. In the multilayer printed wiring board formed by alternately laminating the conductor layer and the insulating layer, it is also possible to form a conductor layer (circuit) on which one side or both sides of the outermost layer of the multilayer printed wiring board is patterned. Included. Moreover, the roughening process may be previously performed by the blackening process, copper micro etching, etc. on the conductor layer surface.

In the said laminate, when an adhesive film has a protective film, after removing the said protective film, an adhesive film and a circuit board are preheated as needed, and it crimp | bonds to a circuit board, pressing and heating an adhesive film. In the adhesive film of this invention, the method of laminating to a circuit board under reduced pressure by the vacuum lamination method is used suitably. The conditions of the laminate are not particularly limited, but for example, the crimping temperature (laminate temperature) is preferably 70 to 140 ° C, and the crimping pressure is preferably 1 to 11 kgf / cm 2 (9.8 × 10 ⁴ to 107.9 × 10). ⁴ N / m 2), and is laminated under a reduced pressure of 20 mmHg (26.7 hPa) or less. In addition, the laminating method may be a batch type or a continuous type in a roll.

Vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo Morton Co., Ltd., a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, and Hitachi AIC Co., Ltd. The vacuum laminator made by Shikisha-shi etc. is mentioned.

In addition, the lamination | stacking process which heats and pressurizes under reduced pressure can also be performed using a general vacuum hot press machine. For example, it can carry out by pressing metal plates, such as a heated SUS board, from the support body layer side.

Press conditions make the pressure reduction degree below 1x10 <^-2> MPa normally, Preferably it is 1x10 <^-3> MPa or less. Although heating and pressurization may be performed in one step, it is preferable to divide and perform conditions in two or more steps from a viewpoint of controlling that a resin leaks out. For example, the press of the 1st stage is a range whose temperature is 70-150 degreeC, the pressure is 1-15 kgf / cm <2>, and the press of the 2nd stage has a temperature of 150-200 degreeC and a pressure of 1-40 kgf / cm <2>. It is preferable to carry out in the range. The time of each step is preferably carried out in 30 to 120 minutes. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Sesaku Sho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

After laminating an adhesive film to a circuit board, after cooling to around room temperature, when peeling a support film, an insulating layer can be formed in a circuit board by peeling and thermosetting. Although the conditions of thermosetting may be selected suitably according to the kind, content, etc. of the resin component in a resin composition, Preferably it is 20 to 180 minutes at 150-220 degreeC, More preferably, it is 30 to 120 minutes at 160-200 degreeC. Is selected from the range.

When a support film is not peeled off before hardening, it peels after forming an insulating layer. Subsequently, as necessary, holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. The punching can be carried out by a known method such as a drill, a laser, a plasma, or the like, or a combination of these methods as necessary, but the punching by a laser such as a carbon dioxide laser or a YAG laser can be performed. This is the most common way.

Subsequently, a conductor layer is formed on an insulating layer by dry plating or wet plating. As dry plating, well-known methods, such as vapor deposition, sputtering, and ion plating, can be used. In addition, in the case of wet plating, the surface of the hardened resin composition layer (insulation layer) is previously subjected to wet roughening. The wet roughening treatment is a treatment which forms a protruding anchor by roughening with an oxidizing agent such as permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid. Especially as an oxidizing agent, aqueous sodium hydroxide solution (alkaline permanganate aqueous solution), such as potassium permanganate and sodium permanganate, is used preferably. Following the roughening treatment, the conductor layer is formed by a combination of electroless plating and electrolytic plating. In addition, a plating resist having an inverse pattern can be formed with the conductor layer, and the conductor layer can be formed only by electroless plating. As a method of pattern formation after that, the subtractive method, the semiadditive method, etc. which are known to a person skilled in the art can be used, for example.

The surface of the conductor layer thus produced is roughened. The roughness of the conductor layer surface has the effect of improving the adhesiveness with the resin in contact with the conductor layer. In order to match a conductor layer, it is preferable to use organic acid type microetching agents CZ-8100, CZ-8101, CZ-5480, etc. Moreover, since adhesiveness improves compared with the conventional resin composition irrespective of the grade of the roughening of the conductor layer surface by using the resin composition for printed wiring boards of this invention, it is a low thermal expansion rate, lamination property, and adhesiveness with the conductor layer after environmental tests. An insulating layer having a balanced performance such as strength is formed.

[Prepreg]

The prepreg of this invention can be manufactured by impregnating the resin composition of this invention with the sheet-like reinforcement base material which consists of fibers by a hot melt method or the solvent method, and heating and semi-hardening. That is, it can be set as the prepreg which becomes the state in which the resin composition of this invention is impregnated into the sheet-like reinforcement base material which consists of fibers. As a sheet-like reinforcement base material which consists of a fiber, what consists of fibers commonly used as prepreg fiber, such as glass cross and aramid fiber, can be used, for example.

The hot-melt method does not dissolve the resin in an organic solvent and coats it on a coated paper having good peelability with the resin, and then laminates it on a sheet-like reinforcing base material or does not dissolve the resin in an organic solvent and forms the sheet by a die coater. It is a method of manufacturing a prepreg by apply | coating directly to a phase reinforcement base material. In the solvent method, the resin is dissolved in an organic solvent in the same manner as in the adhesive film to prepare a resin varnish, the sheet-like reinforcement base material is immersed in the varnish, the resin varnish is impregnated into the sheet-like reinforcement base material, and then dried. It is a way.

[Multilayer Printed Wiring Board Using Prepreg]

Next, an example of the method of manufacturing a multilayer printed wiring board using the prepreg manufactured as mentioned above is demonstrated. One or more plural prepregs of the present invention are stacked on a circuit board and sandwiched on a metal plate via a release film, and press laminated under pressure and heating conditions. The pressurization and heating conditions are preferably 5 to 40 kgf / cm 2 (49 × 10 ⁴ to 392 × 10 ⁴ N / m 2), and the temperature is 20 to 100 minutes at 120 to 200 ° C. In the same manner as in the adhesive film, the prepreg may be laminated on a circuit board by a vacuum lamination method, and then heat cured. Thereafter, in the same manner as described above, the cured prepreg surface is roughened as described above, and then a conductor layer is formed by plating to manufacture a multilayer printed wiring board.

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

Example

Example 1

30 mass parts of prepolymers of bisphenol A dicyanate (Lonza Japan Co., Ltd. product "BA230S75", cyanate equivalent-approximately 232, methyl ethyl ketone (it abbreviates as MEK) solution of 75 mass% of non volatile matters hereafter), phenol no 10 mass parts and MEK 10 mass parts of volak-type polyfunctional cyanate ester resin ("PT30" by Ronza Japan Co., Ltd., cyanate equivalent weight) are stirred and mixed with 10 mass parts of MEK, and Totokasei Co., Ltd. is a naphthol type epoxy resin. 40 mass parts of "ESN-475V" of manufacture (it is represented by following formula 3. MEK solution of 65 mass% of non volatile matters of epoxy equivalent about 340), and liquid bisphenol A type epoxy resin ("jER828EL" made by Japan Epoxy Resin Co., Ltd.) 8 parts by mass of epoxy equivalent approximately 185), phenoxy resin solution ("YX6954" manufactured by Japan Epoxy Resin Co., Ltd.), MEK and cyclohexanone having a weight average molecular weight of 40000 and a nonvolatile content of 30% by mass Mixed solution) 20 parts by mass of cobalt (II) acetylacetonate (Co (acac) _2, Tokyo Kasei Kaisha manufacture, Ltd.) 4 parts by weight of N, N- dimethylformamide (DMF) solution of 1% by mass of talc ( The surface treatment of Nihontar Co., Ltd. product "D-800" with aminosilane, 6 mass parts of average particle diameters of 0.8 micrometer, and spherical silica ("SO-C2" made by Adomatex Corporation) are aminosilane. After surface-treating and 42 mass parts of average particle diameters (0.5 micrometer) were mixed, 20 mass parts of MEKs were added, it was disperse | distributed uniformly by the high speed rotary mixer, and the thermosetting resin composition varnish was produced.

Next, such a resin composition varnish is uniformly coated on a polyethylene terephthalate film (thickness 38 mu m, hereinafter referred to as PET film) with a die coater so that the thickness of the resin composition layer after drying is 40 mu m, and 80 to 120 ° C. It dried at (average 100 degreeC) for 6 minutes (amount of residual solvent in resin composition layer: about 1.5 mass%). Next, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film to the surface of a resin composition layer. The roll-like adhesive film was slit to a width of 507 mm to obtain a sheet-shaped adhesive film of 507 x 336 mm size.

In Chemical Formula 3,

n is an average of 1 to 6,

X is a glycidyl group or a C1-C8 hydrocarbon group, and the ratio of a hydrocarbon group / glycidyl group is 0.05-2.0.

Example 2

An adhesive film was obtained in the same manner as in Example 1 except that 10 parts by mass of D800 of Example 1 and 38 parts by mass of SO-C2 were used.

Example 3

An adhesive film was obtained in the same manner as in Example 1 except that 12 parts by mass of D800 of Example 1 and 36 parts by mass of SO-C2 were used.

Example 4

An adhesive film was obtained in the same manner as in Example 1, except that 16 parts by mass of D800 of Example 1 and 32 parts by mass of SO-C2 were used.

Example 5

An adhesive film was obtained in the same manner as in Example 1 except that 18 parts by mass of D800 of Example 1 and 30 parts by mass of SO-C2 were used.

Example 6

An adhesive film was obtained in the same manner as in Example 1 except that 22 parts by mass of D800 of Example 1 and 26 parts by mass of SO-C2 were used.

Example 7

An adhesive film was obtained in the same manner as in Example 1 except that 24 parts by mass of D800 of Example 1 and 24 parts by mass of SO-C2 were used.

Example 8

An adhesive film was obtained in the same manner as in Example 1 except that 11 parts by mass of D800 of Example 1 and 28 parts by mass of SO-C2 were used.

Example 9

An adhesive film was obtained in the same manner as in Example 1 except that 15 parts by mass of D800 of Example 1 and 57 parts by mass of SO-C2 were used.

Example 10

An adhesive film was obtained in the same manner as in Example 1, except that 18 parts by mass of D800 of Example 1 and 90 parts by mass of SO-C2 were used.

Example 11

An adhesive film was obtained in the same manner as in Example 1 except that 8 parts by mass of D800 of Example 1 and 66 parts by mass of SO-C2 were used.

Example 12

An adhesive film was obtained in the same manner as in Example 1 except that 22 parts by mass of D800 of Example 1 and 50 parts by mass of SO-C2 were used.

Example 13

Adhesive film in the same manner as in Example 1, except that 15 parts by mass of SG-95 (surface-treated with aminosilane, 2.5 µm in average particle diameter) and 57 parts by mass of SO-C2 were used instead of D800 of Example 1. Obtained.

Comparative Example 1

An adhesive film was obtained in the same manner as in Example 1 except that SO-C2 was set to 48 parts by mass without using D800 of Example 1.

Comparative Example 2

An adhesive film was obtained in the same manner as in Example 1 except that 4 parts by mass of D800 of Example 1 and 45 parts by mass of SO-C2 were used.

Comparative Example 3

An adhesive film was obtained in the same manner as in Example 1 except that 30 parts by mass of D800 of Example 1 and 18 parts by mass of SO-C2 were used.

Comparative Example 4

An adhesive film was obtained in the same manner as in Example 1 except that 48 parts by mass of D800 of Example 1 and SO-C2 were not used.

Comparative Example 5

An adhesive film was obtained in the same manner as in Example 1 except that 10 parts by mass of D800 of Example 1 and 21 parts of SO-C2 were used.

Comparative Example 6

An adhesive film was obtained in the same manner as in Example 1 except that 21 parts by mass of D800 of Example 1 and 115 parts by mass of SO-C2 were used.

Comparative Example 7

An adhesive film was obtained in the same manner as in Example 1 except that 13 parts by mass of D800 of Example 1 and 54 parts by mass of SO-C2 were not used and YX6954 was not blended.

<Preparation of adhesive strength measurement sample>

(1) base treatment of laminate

In order to evaluate the adhesion strength between the conductor layer and the insulating layer, both sides of the double-sided copper clad laminate (18 μm thick copper foil, 0.3 mm thick substrate, R5715ES manufactured by Matsushita Denko Co., Ltd.) on which an inner layer circuit was formed were manufactured by Mac. It was immersed in Mac etch bond CZ-8100 of, and the roughening process (Ra value = 1 micrometer) was performed to the circuit surface.

(2) Lamination of Adhesive Film

The adhesive films produced in Examples 1 to 10 and Comparative Examples 1 to 6 were laminated on both sides of the laminate using a batch vacuum pressurizer laminator MVLP-500 (trade name manufactured by MEI KK). Lamination was performed by depressurizing for 30 second and making atmospheric pressure 13 hPa or less, and then pressurizing at 100 degreeC at 0.74 Mpa for 30 second.

(3) base treatment of copper foil

Glossy surface of 3EC-III (electric copper foil, 35 µm) manufactured by Mitsui Kinzoku Kozan Co., Ltd. was immersed in Mac Etch Bond CZ-8100 manufactured by Mac Corporation and roughened on the surface of copper foil (Ra value = 1 μm).

(4) Lamination and insulation layer formation of copper foil

Peeling a PET film from the adhesive film laminated in said (2), making the process surface of the copper foil processed by (3) into the resin composition layer side, and copper foil on both surfaces of a circuit board on the conditions similar to (2). Lamination was performed on the formed resin composition layer. The sample was produced by hardening a resin composition on 190 degreeC and 90 minutes of curing conditions, and forming an insulating layer.

<Measurement and evaluation of coefficient of thermal expansion (CTE)>

In Examples and Comparative Examples, the same resin composition as in Examples and Comparative Examples was performed in the same manner except that PET ("Fluorojushi RL50KSE" manufactured by Mitsubishi Jushi Co., Ltd.) treated with a fluororesin-releasing agent (ETFE) was used for the support. An adhesive film having a layer was obtained, and the obtained adhesive film was thermally cured by heating at 190 ° C. for 90 minutes to peel off the support, thereby obtaining a cured product in the form of a sheet having a width of about 5 mm and a length of about 15 mm. The specimen was cut into pieces and subjected to thermomechanical analysis using a tensile weighting method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Co., Ltd.). The measurement was performed twice in succession under the measurement conditions of /min.The average linear thermal expansion rate (ppm) from 25 ° C to 150 ° C in the second measurement was calculated. The case where it was only "◎", the case where 35 ppm or more and less than 40 ppm was made into "(circle)", the case where 40 ppm or more and less than 45 ppm was made into "△", and the case where 45 ppm or more was evaluated by "x". 2 is described.

<Evaluation of Lamination>

The film of an Example and a comparative example was laminated on the circuit board on the lamination conditions as described in said (3), and it judged as follows by external appearance inspection. The results are shown in Tables 1 and 2.

(Circle): There is no void in the circuit part of a circuit board, and resin flows sufficiently.

X: A void generate | occur | produces in the circuit board of a circuit board, and resin flow is insufficient.

<Measurement and Evaluation of Adhesion Strength (Peel Strength) with Conductor Layer>

The sample 510 × 340 mm described in (4) above was cut into small pieces of 150 × 30 mm. A notch is placed in a small piece of copper foil at a width of 10 mm and a length of 100 mm, and one end of the copper foil is peeled off and grasped with tongs. The load at the time of peeling 35 mm was measured and it was set as the peeling strength before an environmental test.

In addition, the same sample was subjected to a highly accelerated life test device PM422 (manufactured by Kutsumoto Kasei Co., Ltd.), and then subjected to an accelerated environmental test for 100 hours at 130 ° C. and 85% RH, and then the peel strength was measured in the same manner. It was set as the post peel strength. The value of "filling strength after environmental test / peeling strength * 100 before an environmental test" was made into the adhesion retention ratio (%), and the peeling strength before and after an accelerated environmental test was compared. The case where the adhesion retention rate is 75% or more is referred to as "◎", the case where less than 75% is 50% or more as "○", the case where less than 50% is 40% or more as "△", and the case where it is less than 40% is "x". Evaluated as. The results are shown in Tables 1 and 2.

From the results of Tables 1 and 2, in Examples, all of the low thermal expansion coefficient, the lamination properties, and the adhesive strength after the environmental test were excellent, and these performances were balanced. On the other hand, since Comparative Examples 1 and 2 had little talc content, the fall of the adhesive strength after an environmental test became remarkable. Moreover, since the comparative examples 3 and 4 have too much content of talc, lamination property is deteriorating. In addition, in Comparative Example 5, since the total content of talc and silica is small, the coefficient of thermal expansion is increased. In Comparative Example 6, since the total amount of talc and silica is too large, lamination properties are deteriorated. Compared with Examples 9 and 13, in which the inorganic filler ratio and the talc ratio are the same, in Comparative Example 7, since the thermoplastic resin which is an essential component is not blended, the adhesion retention rate of the peel strength before and after the environmental test is reduced. Moreover, since a phenoxy resin is not mix | blended, viscosity becomes too low and lamination property is also worsening.

[Industry availability]

The resin composition of this invention was able to provide the adhesive film, the prepreg, and the multilayer printed wiring board which the adhesiveness of a conductor layer and an insulating layer is favorable, and there is little fall of the adhesiveness after an environmental test. In addition, electric appliances such as computers, cellular phones, digital cameras, televisions, and the like, and vehicles such as motorcycles, automobiles, trams, ships, aircrafts, etc. can be provided.

Claims (11)

As a resin composition for printed wiring boards containing (A) cyanate ester resin, (B) epoxy resin, (C) thermoplastic resin, (D) talc, and (E) silica,
When the non volatile matter in a resin composition is 100 mass%,
The resin composition whose content of (1) component (D) talc and component (E) silica is 35-60 mass%, and (2) content of component (D) talc is 5-20 mass%. As a resin composition for printed wiring boards containing (A) cyanate ester resin, (B) epoxy resin, (C) thermoplastic resin, (D) talc, and (E) silica,
When the non volatile matter in a resin composition is 100 mass%,
The resin composition whose content of (1) component (D) talc and component (E) silica is 45-60 mass%, and (2) content of component (D) talc is 5-20 mass%. The resin composition of Claim 1 or 2 whose average particle diameter of a component (D) talc is 1.3 micrometers or less. The component (C) thermoplastic resin is a phenoxy resin, a polyimide resin, a polyamideimide resin, a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, or a polyphenylene ether resin. The resin composition which is at least 1 sort (s) of polymeric resin chosen from polycarbonate resin, polyether ether ketone resin, polyester resin, polyacetal resin, and polybutyral resin. The resin composition of Claim 1 or 2 whose component (C) thermoplastic resin is a phenoxy resin. The resin composition according to any one of claims 1 to 3, wherein component (D) talc and component (E) silica are surface treated in advance. The resin composition according to any one of claims 1 to 6, wherein the thermal expansion ratio is 44 ppm or less, and the adhesion retention rate before and after the environmental test is 40% or more. The resin composition of any one of Claims 1-7 for interlayer insulation of a multilayer printed wiring board. The adhesive film in which the resin composition of any one of Claims 1-8 is layered on a support film. The prepreg in which the resin composition of any one of Claims 1-8 is impregnated in the sheet-like reinforcement base material which consists of fibers. The printed wiring board provided with the insulating layer containing the hardened | cured material of the resin composition of any one of Claims 1-8, and the conductor layer formed on the said insulating layer.