KR20100039245A - Epoxy resin composition - Google Patents

Abstract

PURPOSE: An epoxy resin composition is provided to show high adhesive power to roughened surface even though roughness of the roughened surface is relatively low, and to implement an insulating layer with low linear expansion. CONSTITUTION: An epoxy resin composition comprises (A) an epoxy resin, (B) an active ester compound and (C) an alicyclic structure-containing phenoxy resin. The alicyclic structure of the phenoxy resin is a terpene structure and/or trimethylcyclohexane resin. The average molecular weight of the phenoxy resin is 10000-50000. When a non-volatile component of an epoxy resin composition is based on 100 weight%, the content of the component (A) is 10-50 weight% and the content of the component(C) 1-20 weight%.

Description

Epoxy resin composition {EPOXY RESIN COMPOSITION}

The present invention relates to an epoxy resin composition suitable for forming an insulating layer of a multilayer printed wiring board.

In recent years, miniaturization and high performance of electronic devices have progressed, and in a multilayer printed wiring board, a buildup layer has been multilayered, and wiring refinement | miniaturization and high density were calculated | required.

Various measures have been taken against this. For example, Patent Document 1 discloses an epoxy resin composition comprising an epoxy resin, a specific phenol curing agent, a phenoxy resin, and rubber particles, and Patent Document 2 discloses an epoxy resin, a specific phenol curing agent, and a polyvinyl acetal resin. An epoxy resin composition is disclosed. Although the insulation layer formed by these compositions was able to achieve both the roughness and the peel strength of the conductor layer formed by plating, the concept of the low linear expansion rate was not disclosed or directed at all.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2007-254709

[Patent Document 2] Japanese Unexamined Patent Publication No. 2007-254710

The problem of the present invention is that although the roughness of the roughened surface obtained by roughening the surface of the cured product of the epoxy resin composition is relatively small, the roughened surface exhibits high adhesion to the plating conductor, It is an object of the present invention to provide an epoxy resin composition capable of achieving expansion ratio.

MEANS TO SOLVE THE PROBLEM This inventor came to complete this invention in the specific epoxy resin composition which mix | blended an epoxy resin, an active ester compound, and an alicyclic structure containing phenoxy resin as a result of repeated study in order to solve the said subject.

That is, this invention includes the following content.

[1] An epoxy resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an alicyclic structure-containing phenoxy resin.

[2] The epoxy resin composition according to the above [1], wherein the alicyclic structure of the (C) phenoxy resin is a terpene structure and / or a trimethylcyclohexane structure.

[3] The epoxy resin composition according to the above [1] or [2], wherein the weight average molecular weight of the phenoxy resin is 10000 to 50000.

[4] When the nonvolatile component of the epoxy resin composition is 100% by weight, the content of the component (A) is 10 to 50% by weight and the content of the component (C) is 1 to 20% by weight, and is present in the epoxy resin composition. The epoxy resin composition as described in any one of said [1]-[3] characterized by the ratio of the reactor of an epoxy group to an epoxy hardening | curing agent being 1: 0.4-1: 1.1.

[5] The epoxy resin composition according to any one of the above [1] to [4], further comprising (D) an inorganic filler.

[6] The epoxy resin composition according to the above [5], wherein the content of the inorganic filler is 10 to 70% by weight when the nonvolatile component of the epoxy resin composition is 100% by weight.

[7] The epoxy resin composition according to any one of the above [1] to [6], further comprising (E) a curing accelerator.

[8] The epoxy according to the above [7], wherein the content of the (E) curing accelerator is 0.1 to 5% by weight when the total amount of the epoxy resin and the phenolic curing agent contained in the epoxy resin composition is 100% by weight. Resin composition.

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

[10] A prepreg, wherein the epoxy resin composition according to any one of the above [1] to [8] is impregnated in a sheet-like fiber base material composed of fibers.

[11] A multilayer printed wiring board, wherein an insulating layer is formed of a cured product of the epoxy resin composition according to any one of the above [1] to [8].

[12] A method for producing a multilayer printed wiring board, comprising the steps of forming an insulating layer on an inner circuit board and a step of forming a conductor layer on the insulating layer, wherein the insulating layer is any one of the above [1] to [8]. It is formed by thermosetting the epoxy resin composition of Claim 1, and the said conductor layer is formed by plating on the roughening surface which roughened the said insulating layer surface, The manufacturing method of the multilayer printed wiring board characterized by the above-mentioned.

[13] A method for producing a multilayer printed wiring board comprising a step of forming an insulating layer on an inner layer circuit board and a step of forming a conductor layer on the insulating layer, wherein the insulating layer is an inner layer circuit comprising the adhesive film described in the above [9]. It laminates on a board | substrate, peels or does not peel a support film, heat-cures an epoxy resin composition, and forms a peeling of a support film, when a support film exists after hardening, and the said conductor layer forms the surface of the said insulating layer. It is formed by plating to the roughening process roughening process, The manufacturing method of the multilayer printed wiring board characterized by the above-mentioned.

[14] A method for producing a multilayer printed wiring board comprising a step of forming an insulating layer on an inner layer circuit board and a step of forming a conductor layer on the insulating layer, wherein the insulating layer is a prepreg according to the above [10]. Laminating on a board | substrate, it is formed by thermosetting an epoxy resin composition, and the said conductor layer is formed by plating on the roughening surface which roughened the said insulating layer surface, The manufacturing method of the multilayer printed wiring board characterized by the above-mentioned.

[15] The production method according to any one of [12] to [14], wherein the roughening treatment is performed using an alkaline permanganic acid solution.

Although the roughness of the roughening surface which roughened the hardened | cured material surface was comparatively small by the specific epoxy resin composition which mix | blended an epoxy resin, an active ester compound, and an alicyclic structure containing phenoxy resin, the said roughening surface is a plating conductor. It showed high adhesion with respect to it, and it became possible to achieve the low wire expansion rate of an insulating layer.

This invention is a specific epoxy resin composition which mix | blended an epoxy resin, an active ester compound, and an alicyclic structure containing phenoxy resin.

[Epoxy Resin of Component (A)]

The epoxy resin of the component (A) in this invention is not specifically limited, For example, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, phenol novolak-type epoxy resin, tert- butyl- catechol type epoxy resin , Naphthalene type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane A dimethanol type epoxy resin, a trimetholol type epoxy resin, a halogenated epoxy resin, etc. are mentioned. The epoxy resin of this invention may use 1 type (s) or 2 or more types.

The epoxy resin which has two or more epoxy groups in 1 molecule is contained. When the non-volatile component of the epoxy resin composition is 100% by weight, at least 50% by weight or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Moreover, it has 2 or more epoxy groups in 1 molecule, epoxy resin which is a liquid aromatic epoxy resin at temperature 20 degreeC, and has 3 or more epoxy groups in 1 molecule, and contains solid aromatic aromatic epoxy resin at temperature 20 degreeC. The form is preferred. In addition, the aromatic epoxy resin in this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator. In addition, epoxy equivalent (g / eq) is molecular weight per epoxy group. When the epoxy resin composition is used in the form of an adhesive film by using a liquid epoxy resin and a solid epoxy resin as the epoxy resin, sufficient flexibility can be exhibited, and an epoxy resin composition can be formed with excellent handleability. The breaking strength of the cured product of the film is improved, and the durability of the multilayer printed wiring board is improved.

Moreover, when using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, the compounding ratio (liquid phase: solid) has the preferable range of 1: 0.1-1: 2 by weight ratio. If the proportion of the liquid epoxy resin is too large in excess of such a range, the adhesiveness of the epoxy resin composition becomes high, and when used in the form of an adhesive film, there is a tendency that degassing during vacuum lamination decreases and voids tend to occur. . Moreover, there exists a tendency for the peelability of a protective film and a support film to fall at the time of vacuum lamination, and the heat resistance after hardening falls. Moreover, there exists a tendency which is difficult to obtain sufficient breaking strength in the hardened | cured material of an epoxy resin composition. On the other hand, when the ratio of the solid epoxy resin is too large in excess of such a range, when used in the form of an adhesive film, sufficient flexibility cannot be obtained, handleability is lowered, and sufficient fluidity at the time of lamination is difficult. There is a tendency.

In the epoxy resin composition of the present invention, when the nonvolatile component of the epoxy resin composition is 100% by weight, the content of the epoxy resin is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, 20-35 weight% is more preferable. When content of an epoxy resin (A) deviates from this range, there exists a tendency for sclerosis | hardenability of a resin composition to fall.

[Active ester compound of component (B)]

The active ester compound (B) in the present invention is not particularly limited as long as it functions as a curing agent for an epoxy resin and has an active ester. The compound which has 2 or more active ester groups in 1 molecule is preferable, The aromatic compound which has 2 or more active ester groups in 1 molecule obtained from the compound which has a polyhydric carboxylic acid, and the aromatic compound which has a phenolic hydroxyl group is more preferable, At least 2 It is an aromatic compound obtained from the compound which has the above-mentioned carboxylic acid in one molecule, and the aromatic compound which has a phenolic hydroxyl group, and the aromatic compound which has two or more ester groups in the molecule | numerator of the said aromatic compound is more preferable. In addition, a linear or multibranched polymer may be contained. Moreover, if the compound which has at least 2 or more carboxylic acids in 1 molecule is a compound containing an aliphatic chain, compatibility with an epoxy resin (A) can be improved, and if it is a compound which has an aromatic ring, heat resistance can be made high. In particular, from the viewpoint of heat resistance and the like, an active ester compound obtained from a carboxylic acid compound, a phenol compound or a naphthol compound is preferable. Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferable. Specific examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid. Specific examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydr Hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac and the like. Among them, from the viewpoint of heat resistance and solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, 1,5-dihydroxynaphthalene, and 1,6-dihydroxynaphthalene , 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, phenol novolak are preferred. , Catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, flo Loglucin, benzenetriol, dicyclopentadienyldiphenol, phenol novolac are more preferred, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, Dihydroxybenzophenone, t Rehydroxy benzophenone, tetrahydroxy benzophenone, dicyclopentadienyl diphenol, and phenol novolak are more preferable, and dihydroxy benzophenone, trihydroxy benzophenone, tetrahydroxy benzophenone, and dicyclopentadienyl di Phenol and phenol novolak are further more preferable, dicyclopentadienyl diphenol and phenol novolak are especially preferable, and dicyclopentadienyl diphenol is especially preferable. Specific examples of the thiol compound include benzenedithiol and triadinedithiol. An active ester compound may use 2 or more types together. As an active ester compound, you may use the active ester compound disclosed by Unexamined-Japanese-Patent No. 2004-427761, and can also use a commercially available thing. Commercially available active ester compounds are preferably those containing a dicyclopentadienyldiphenol structure, an acetylide of phenol novolac, and a benzoylide of phenol novolac, and among these, a dicyclopentadienyldiphenol structure is included. More preferably. By including a dicyclopentadienyldiphenol structure, EXB-9451, EXB-9460 (manufactured by DIC Corporation), DC808 as an acetylate of phenol novolac, and YLH1026 as a benzoylate of phenol novolac (Jafen Epoxy Resin Co., Ltd.) Production).

You may use 1 type, or 2 or more types of active ester compound of this invention.

There is no restriction | limiting in particular in the manufacturing method of an active ester compound, Although it can manufacture by a well-known method, specifically, it can obtain by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. .

In the present invention, an epoxy curing agent other than the active ester may be used in combination with the active ester compound for the purpose of improving the glass potential temperature and the like. As epoxy curing agents other than active ester, TD2090, TD2131, LA7052, LA7054, LA3018, LA1356 (made by DIC Corporation), MEH-7600, MEH-7851, MEH-8000H (made by Meiwa Kasei Co., Ltd.), NHN, Phenolic curing agents such as CBN, GPH-65, GPH-103 (manufactured by Nihon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Totogsei Co., Ltd.), Fa , Anhydrides such as benzoxazine compounds such as Pd (manufactured by Shikoku Chemical Co., Ltd.) and HFB2006M (manufactured by Showa Gohun City Co., Ltd.), methylhexahydrophthalic anhydride, methylnajic acid anhydride and methyl hydride hydride anhydride Etc. can be mentioned. Especially the phenolic hardening | curing agent which is a compound which has a phenolic hydroxyl group is preferable. When using an active ester compound and another hardening | curing agent together, when all the epoxy hardening | curing agents (including an active ester compound) in an epoxy resin composition are 100 weight%, it is preferable that the weight% of an active ester compound is 10 to 100%, More preferably, it is 20 to 100%. Moreover, when all the epoxy hardening | curing agents (including an active ester compound) in an epoxy resin composition are made into 100 weight%, it is preferable that the weight% of a phenolic hardening | curing agent is 0 to 30%, and it is more preferable that it is 0 to 20%.

By using together an active ester compound and a phenol compound (phenolic hardening | curing agent), it is possible to balance the arithmetic mean roughness of a surface of an insulating layer, and a linear expansion rate. Under the present circumstances, when there are many ratios of a phenolic compound, the arithmetic mean roughness of the surface of an insulating layer will tend to increase, and when the ratio of a phenolic compound is small, it will become a tendency which a linear expansion rate will increase.

In the present invention, the amount of the epoxy curing agent containing the component (B) active ester compound in the epoxy resin composition is a ratio of the total number of epoxy groups present in the epoxy resin composition and the total number of reactors of the epoxy curing agent is 1: 0.4 to 1: It is preferable to set it as the quantity used as 1.1. The total number of epoxy groups present in the epoxy resin composition is the value obtained by dividing the solid content weight of each epoxy resin by the epoxy equivalent and adding up the total amount for all epoxy resins. The epoxy curing agent reactor (active ester group, active hydroxyl group, etc.) The total number is the value obtained by dividing the weight of the solid content of each curing agent by the reactor equivalents, for all curing agents. When content of a hardening | curing agent is out of such a preferable range, there exists a tendency for the heat resistance of the hardened | cured material obtained by hardening | curing an epoxy resin composition to become inadequate.

[Alicyclic structure-containing phenoxy resin of component (C)]

In this invention, if an alicyclic structure containing phenoxy resin is a phenoxy resin which has an alicyclic structure, there will be no restriction | limiting in particular. Here, "an alicyclic structure" means "except an aromatic compound among organic compounds having a structure in which carbon atoms are cyclically bonded", and containing one double bond in a ring with a saturated hydrocarbon (cycloalkane) and an unsaturated hydrocarbon ( Cycloalken). "

Examples of the phenoxy resin having an alicyclic structure include one having a cyclohexane structure, one having a trimethylcyclohexane structure, and one having a terpene structure. Especially, it is preferable to have a trimethylcyclohexane structure, to have a terpene structure, and to have a terpene structure from a viewpoint that the effect of this invention can be further achieved.

For example, the phenoxy resin disclosed in Unexamined-Japanese-Patent No. 2006-176658 is mentioned as a phenoxy resin which has a trimethylcyclohexane structure.

As the phenoxy resin having a terpene structure, in the phenoxy resin disclosed in Japanese Patent Laid-Open No. 2006-176658, it is a bis (4-hydroxyphenyl) -3,3,5-trimethyl as a bivalent phenol compound as a raw material. And phenoxy resins synthesized using terpenediphenol instead of cyclohexane.

The phenoxy resin which has an alicyclic structure of this invention may use 1 type (s) or 2 or more types.

The upper limit of the weight average molecular weight of the alicyclic structure-containing phenoxy resin is preferably 100000, more preferably 60000, further preferably 50000, further 45000 from the viewpoint of preventing an increase in roughness and an increase in thermal expansion rate. Preferred, 40000 is particularly preferred, and 35000 is particularly preferred. On the other hand, the lower limit of the weight average molecular weight of the phenoxy resin is preferably 2000 from the viewpoint of sufficiently obtaining peel strength with the conductor layer, more preferably 10000, still more preferably 12000, still more preferably 15000, and more than 17000. This is particularly preferred, and 20000 is particularly preferred. A number average molecular weight is the value measured by the gel permeation chromatography (GPC) method (polystyrene conversion). The number average molecular weight by GPC method specifically, LC-9A / RID-6A made by Shimadzu Corporation as a measuring apparatus, Shodex K-800P / K-804L / by Showa Denko Co., Ltd. as a column. K-804L can be measured at the column temperature of 40 degreeC using the solution which melt | dissolved 0.4 mass% of lithium bromide in N-methylpyrrolidone as a mobile phase, and can compute it using the analytical curve of a standard polystyrene.

Although the manufacturing method of these phenoxy resin does not have a restriction | limiting in particular, It can manufacture by the following method. Using a bisphenol compound having a trimethylcyclohexane structure or a bisphenol compound having a terpene structure and a bifunctional epoxy resin, the equivalent ratio of the epoxy group and the phenolic hydroxyl group is about 1: 0.9 to 1: 1.1 according to the known method of phenoxy resin. It can manufacture easily by making it react in the range which becomes this.

Moreover, you may mix and use phenoxy resins other than an alicyclic structure containing phenoxy resin in the range in which the effect of this invention is exhibited. As other phenoxy resins, JAPEN EPOXY RESIN Co., Ltd. product 1256, 4250, YX8100, YX6954, YL7553, YL7482, etc. are mentioned.

In the epoxy resin composition of the present invention, when the nonvolatile component of the epoxy resin composition is 100% by weight, the content of the phenoxy resin is preferably 1 to 20% by weight, more preferably 5 to 10% by weight. If it is less than 1% by weight, sufficient flexibility cannot be obtained, and handleability decreases, or the peel strength of the conductor layer formed by plating tends not to be sufficiently obtained. If it exceeds 20% by weight, sufficient fluidity during lamination is obtained. It may not be possible or the roughness tends to be too large.

[Inorganic Fillings]

The epoxy resin composition of the present invention may further contain an inorganic filler for the purpose of lowering the linear expansion rate. As the inorganic filler, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate And magnesium titanate, bead titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among these, silica such as amorphous silica, fused silica, crystalline silica and synthetic silica is particularly suitable. You may use 1 type, or 2 or more types of inorganic fillers.

As silica, a circular thing is preferable. It is preferable that the average particle diameter of an inorganic filler is 1 micrometer or less, 0.8 micrometer or less is more preferable, 0.7 micrometer or less is especially preferable. When average particle diameter exceeds 1 micrometer, there exists a tendency for the peeling strength of the conductor layer formed by plating to fall. Moreover, when the average particle diameter of an inorganic filler becomes small too much, when the epoxy resin composition is used as the resin varnish, since the viscosity of a varnish rises and handleability tends to fall, it is preferable that average particle diameter is 0.05 micrometer or more. Moreover, in order to improve moisture resistance, it is preferable that an inorganic filler is surface-treated with surface treating agents, such as an epoxy silane coupling agent, an aminosilane coupling agent, and a titanate coupling agent.

The average particle diameter of the said inorganic filler can be measured by the 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 a volume basis and measure the median diameter as the average particle diameter. The measurement sample can use preferably what disperse | distributed the inorganic filler in water according to the ultrasonic wave. As a laser diffraction particle size distribution measuring apparatus, LA-500 manufactured by Horiba Seisakusho, etc. can be used.

When content of the said inorganic filler is mix | blended, when the non volatile component of an epoxy resin composition is 100 weight%, it changes also with the characteristic calculated | required by a resin composition, It is preferable that it is 10-70 weight%, It is 15-60 weight % Is more preferred. When content of an inorganic filler is too small, there exists a tendency for the linear expansion rate of hardened | cured material to become high, and when content is too large, film formation becomes difficult or the hardened | cured material tends to recede when preparing an adhesive film.

[Hardening accelerator]

The epoxy resin composition of this invention may contain a hardening accelerator for the purpose of adjusting hardening time and hardening temperature. As a hardening accelerator, organic phosphine compounds, such as TPP, TPP-K, TPP-S, TPTP-S (Hokko Chemical Co., Ltd. brand name), curazole 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z, for example. Imidazole compounds, such as -CNS, C11Z-A, 2MZ-OK, 2MA-OK, and 2PHZ (trademark of Shikoku Chemical Co., Ltd.), Novacure (Asahi Chemical Co., Ltd. brand name), Fujikyua (Fuji Chemical) Amine adduct compounds such as Segoyo Co., Ltd.), 1,8-diazabicyclo [5,4,0] undecene-7,4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris Amine compounds, such as (dimethylaminomethyl) phenol, are mentioned. You may use 1 type, or 2 or more types of hardening accelerators. In the epoxy resin composition of the present invention, the content of the curing accelerator is preferably 0.1 to 5% by weight when the total amount of the epoxy resin and the phenolic curing agent contained in the epoxy resin composition is 100% by weight (nonvolatile component).

[Rubber particles]

The epoxy resin composition of this invention may contain a solid rubber particle for the purpose of a stress relaxation effect, etc. which raises the mechanical strength of hardened | cured material. The rubber particles in the present invention are not dissolved in an organic solvent when preparing an epoxy resin composition, are not compatible with components in a resin composition such as an epoxy resin, and are dispersed in a varnish of an epoxy resin composition. It exists as. 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. As a rubber particle, a core-shell rubber particle, a crosslinked acrylonitrile butadiene rubber particle, a crosslinked styrene butadiene rubber particle, an acrylic rubber particle, etc. are mentioned, for example. The core-shell rubber particles are rubber particles in which the particles have a core layer and a shell layer. For example, the shell layer of the outer layer is made of a glass polymer, the inner layer of the core layer is made of a rubber polymer, or the shell layer of the outer layer is glass. The three-layer structure etc. which a type polymer, an intermediate | middle layer consist of a rubber type polymer, and a core layer consist of a glass type polymer are mentioned. The glass layer is made of, for example, a polymer of methyl methacrylate, or the like, and the rubber polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber) or the like. Specific examples of the core-shell rubber particles include starpiroid AC3832, AC3816N, (Kantzugasei Co., Ltd. brand name), and metablene W-5500 (Mitsubishi Rayon Co., Ltd. brand name). As an example of an acrylonitrile butadiene rubber (NBR) particle | grain, XER-91 (average particle diameter 0.5 micrometer, JSR Corporation make), etc. are mentioned. Specific examples of the styrene butadiene rubber (SBR) particles include XSK-500 (average particle size of 0.5 µm, manufactured by JSR Corporation), and the like. Specific examples of the acrylic rubber particles include metablenne W300A (average particle diameter of 0.1 µm) and W450A (average particle diameter of 0.5 µm (manufactured by Mitsubishi Rayon Co., Ltd.).

The range of 0.005-1 micrometer is preferable, and, as for the average particle diameter of the rubber particle to mix | blend, the range of 0.2-0.6 micrometer is more preferable. The average particle diameter of the rubber particle in this invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and FPRA-1000 (manufactured by Otsuka Denshi Co., Ltd.) is used to prepare the particle size distribution of the rubber particles based on weight, and the median. It can be measured by making diameter into an average particle diameter.

When the non-volatile component of the epoxy resin composition in the case of blending the rubber particles is 100% by weight, the content in the epoxy resin composition is preferably 0.5 to 10% by weight, more preferably 1 to 4% by weight.

[Other thermosetting resins]

The epoxy resin composition of this invention can mix | blend thermosetting resins, such as a cyanate resin, a maleimide compound, a bisaryl nadiiimide compound, a vinyl benzyl resin, and a vinyl benzyl ether resin, as needed in the range which does not impair the effect of this invention. have. As cyanate resin, BADCY, LECY, BA230S70, PT15, PT30, PT60 (made by Ronder), BEI1000, BMI2000, BMI3000, BMI4000, BMI5100 (made by Yamato Kasei Kogyo Co., Ltd.), BMI, BMI-70 as maleimide resin , BMI-80 (Keiagasei Co., Ltd.), ANILIX-MI (Mitsugagaku Fine Co., Ltd.), bisaryl nadiiimide compound, BANI-M, BANI-X (Maruzen Seki Yugaku Kogyo Co., Ltd.) Ltd.) V5000 (made by Showa Gohun City Co., Ltd.) and V1000X and V1100X (made by Showa Gohun City Co., Ltd.) are mentioned as vinyl benzyl resin. You may use 1 type (s) or 2 or more types of other thermosetting resins.

[Flame retardant]

The epoxy 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 organic phosphorus 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 Co., Ltd. and HFB-2006M manufactured by Showa Kohunshi Co., Ltd., and Ajinomoto Fine Leopard 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP made by Techno Co., Ltd., PPQ, client of Hokogagaku Kogyo Co., Ltd. make Phosphate ester compounds, such as OP930 by the Co., Ltd., PX200 by Daihachi Chemical Co., Ltd., phosphorus containing epoxy resins, such as FX289 and FX310 by Toto Kasei Co., Ltd., ERF001 by Totogsei Co., Ltd., etc. Phosphorus containing phenoxy resin, etc. are mentioned. Examples of the organic nitrogen-containing phosphorus compound include phosphate compounds such as SP670 and SP703 manufactured by Shikoku Chemical Co., Ltd., and phosphazene compounds such as SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and the like. Examples of the metal hydroxides include magnesium hydroxides such as UD65, UD650, and UD653 manufactured by Ube Materials, Inc., B-30, B-325, B-315, B-308, and B-303, manufactured by Tomoe Kogyo Co., Ltd. Aluminum hydroxide, such as UFH-20, etc. are mentioned. A flame retardant may use 1 type, or 2 or more types.

[Resin additive]

The epoxy resin composition of this invention may arbitrarily contain various resin additives other than the above-mentioned in the range in which the effect of this invention is exhibited. Examples of the resin additives include organic fillers such as silicon powder, nylon powder, and fluorine powder, thickeners such as olben and benton, silicone, fluorine and polymer antifoaming agents or leveling agents, imidazole series, thiazole series, triazole series, and silane coupler. Adhesive agents such as ringing agents, coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black, and the like. You may use 1 type, or 2 or more types of resin additives.

Although the use of the resin composition of this invention is not specifically limited, Resin, such as an adhesive film, insulating resin sheets, such as a prepreg, a circuit board, a soldering resist, an underfill material, a die-bonding material, a semiconductor sealing material, a hole filling resin, a component supplement resin, etc. It can be used for a wide range of applications where a composition is required.

[Adhesive Film]

The resin composition of this invention can be apply | coated on a support film, and a resin composition layer can be formed and it can be set as the adhesive film for multilayer printed wiring boards. Although the resin composition of this invention can be apply | coated to a circuit board and can form an insulating layer, industrially, it can generally be used for formation of an insulating layer in the form of an adhesive film.

The adhesive film of this invention prepares the resin varnish which melt | dissolved the resin composition in the organic solvent, the method known to a person skilled in the art, for example, uses a support film as a support body, apply | coats this resin varnish, and heats or hot air sprays, etc. It can manufacture by drying an organic solvent and forming a resin composition layer.

As the organic solvent, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetate esters such as carbitol acetate, cellosolve, butyl Carbitols such as carbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetoamide, and N-methylpyrrolidone. You may use an organic solvent in combination of 2 or more type.

Although drying conditions are not specifically limited, It drys so that the content rate of the organic solvent with respect to a resin composition layer may be 10 weight% or less, Preferably it is 5 weight% or less. Drying conditions can appropriately set suitable drying conditions by simple experiments. Although it changes also with the amount of the organic solvent in a varnish, for example, the varnish containing 30 to 60 weight% of the organic solvent can be dried at 50-150 degreeC for 3 to 10 minutes.

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 is normally in the range of 5-80 micrometers, it is preferable that the thickness of a resin composition layer has a thickness of 10-100 micrometers. The resin composition layer may be protected by the protective film mentioned later. By protecting with a protective film, adhesion and scratches such as dust on the surface of the resin composition layer can be prevented.

As the support film and the protective film in the present invention, polyolefin, such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyester such as polyethylene naphthalate, and polycarbonate And metal foils such as polyimide, release paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mat treatment and the corona treatment.

Although the thickness of a support film is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers can be used more preferably. Moreover, the thickness of a protective film is not specifically limited, either, 1-40 micrometers is preferable, and 10-30 micrometers can be used more preferably. Moreover, as mentioned later, the support film used as a support body in the manufacturing process of an adhesive film can also be used as a protective film which protects the surface of a resin composition layer.

The support film in this invention peels after laminating to a circuit board or forming an insulating layer by heat-hardening. By peeling a support film after heat-hardening an adhesive film, adhesion | attachment of dust etc. in a hardening process can be prevented, and the surface smoothness of the insulating layer after hardening can be improved. When peeling after hardening, it is preferable that a release process is given to a support film beforehand. Moreover, it is preferable to form the resin composition layer formed on a support film so that the area of a layer may become smaller than the area of a support film. Moreover, an adhesive film can be wound up in roll shape, and can be preserve | saved and stored.

[Prepreg]

The resin composition of the present invention is not particularly limited as a sheet-type reinforcing base material which can be formed into a prepreg by impregnating the sheet-like reinforcing base material (fiber-embedded) with a hot melt method or a solvent method, and heating and semi-curing the material. It may be used. Specifically, what consists of fibers for prepregs, such as glass cross and aramid fiber, can be used.

In the hot-melt method, the resin composition of the present invention is not dissolved in an organic solvent, but is coated on a coated paper having good peelability with the resin, and is then laminated on a sheet-like reinforcing base material, or the resin is not dissolved in an organic solvent. It is a method of manufacturing a prepreg by apply | coating directly to a sheet-like reinforcement base material by a coater. The solvent method is a method of dissolving the resin in an organic solvent in the same manner as in the adhesive film to prepare a resin varnish, immersing the sheet-like reinforcing base material in the varnish, impregnating the resin varnish into the sheet-like reinforcing base material, and then drying.

[Multilayer Printed Wiring Board]

By using the adhesive film and prepreg of this invention, a multilayer printed wiring board can be manufactured further.

The method of manufacturing the multilayer printed wiring board of this invention using the adhesive film of this invention is demonstrated. When the resin composition layer is protected by the protective film, after peeling them, it laminates on one side or both surfaces of a circuit board so that a resin composition layer may directly contact a circuit board. In the adhesive film of this invention, the method of laminating to a circuit board under pressure by a vacuum lamination method is used suitably. The method of lamination may be batch or continuous in a roll. In addition, before performing lamination, you may heat (preheat) an adhesive film and a circuit board as needed.

The conditions of the laminate are preferably the crimping temperature (laminate temperature) is 70 to 140 ℃, the crimping pressure is preferably 1 to 11kgf / ㎠ (9.8 × 10 ⁴ to 107.9 × 10 ⁴ N / m ² ), the air pressure It is preferable to laminate under a pressure of 20 mmHg (26.7 hPa) or less.

Vacuum lamination can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, Nichigo Morton Co., Ltd. product change up redirector, the Meiki Seisakusho Co., Ltd. vacuum press type laminator, the Hitachi Industries Co., Ltd. roll type dry coater, Hitachi AIC Inc. A manufacturing vacuum laminator etc. are mentioned.

The inner layer circuit board in the present invention mainly includes a conductor layer patterned on one or both surfaces of a substrate such as a glass epoxy, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate ( Circuit) is formed. Moreover, when manufacturing a multilayer printed wiring board in which a conductor layer and an insulating layer are alternately layered, and the single side or both sides become the patterned conductor layer (circuit), the intermediate | middle manufacture to which an insulating layer and a conductor layer should be further formed also It is contained in the inner layer circuit board in the present invention. In the inner circuit board, it is preferable that the surface of the conductor circuit layer is subjected to a roughening treatment in advance by blackening treatment or the like from the viewpoint of the adhesion of the insulating layer to the inner circuit board.

Thus, after laminating an adhesive film to a circuit board, when peeling a support film, an insulating layer can be formed in a circuit board by peeling and thermosetting. The conditions of heat curing are selected in the range of 20 minutes to 180 minutes at 150 ° C to 220 ° C, and more preferably 30 to 120 minutes at 160 ° C to 200 ° C.

After forming an insulating layer, when a support film is not peeled before hardening, it peels here. Next, through holes are formed in the insulating layer formed on the circuit board to form via holes and through holes. Immediately after the hole, for example, by a known method such as a drill, a laser, a plasma, or a combination of these methods as necessary, perforation by a laser such as a carbon dioxide laser or a YAG laser is the most common method. to be.

Then, a roughening process is performed to the insulating layer surface. It is preferable to perform the roughening process in this invention by the wet roughening method using 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. Preferably, it is preferable to use an alkaline and manganese acid solution (for example, potassium permanganate and sodium permanganate aqueous solution of sodium permanganate), which is an oxidizing agent, which is generally used for roughening the insulating layer in the manufacture of the multilayer printed wiring board by the built-up method. Do.

The roughness of the roughened surface obtained by roughening the surface of the insulating layer is preferably 0.5 µm or less in Ra value after forming fine wirings. In addition, Ra value is a kind of numerical value which means surface roughness, and is called arithmetic mean roughness, and the arithmetic mean is measured by measuring the absolute value of the height which changes in a measurement area from the surface which is an average line specifically ,. For example, using WYKO NT3300 by a non-coins tool company, it can request | require by the numerical value obtained by making a measurement range 121 micrometer x 92 micrometers with a VSI contact mode and a 50x lens.

Next, a conductor layer is formed on the surface of the resin composition layer in which the anchor which protrudes by the roughening process is combined with electroless plating and electrolytic plating. Moreover, a conductor layer can form the plating resist of a reverse pattern, and can form a conductor layer only by electroless plating. After the conductor layer is formed, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes. It is preferable that the peeling strength of a conductor layer is 0.6 kgf / cm or more.

Moreover, as a method of patterning a conductor layer and forming a circuit, the subtractive method, the semiadditive method, etc. well-known to a person skilled in the art can be used, for example.

The prepreg of this invention can be manufactured by impregnating the resin composition of this invention by the hot-melt method or the solvent method to the sheet-like fiber base which consists of fibers, and semi-hardening by heating. In other words, it can be set as the prepreg in which the resin composition of this invention is impregnated to the sheet-like fiber base which consists of fibers.

As a sheet-like fiber base which consists of fibers, what is commercially available as a fiber for prepregs, such as glass cross and aramid fiber, can be used, for example.

In the hot-melt method, a resin is not dissolved in an organic solvent, and the resin is first coated on a resin and a coated paper having good peelability, which is then laminated on a sheet-like fibrous substrate or directly coated by a die coater to produce a prepreg. to be. The solvent method is a method of immersing a sheet-like fibrous base in a resin varnish in which resin is dissolved in an organic solvent like an adhesive film, impregnating the resin varnish into a sheet-fiber base, and then drying.

The method to manufacture the multilayer printed wiring board of this invention using the prepreg of this invention is demonstrated. One or several prepregs of the present invention are stacked on the circuit board, and a metal plate is sandwiched through a release film and press laminated under pressure and heating conditions. The pressure is preferably 5 to 40 kgf / cm 2 (49 × 10 ⁴ to 39 ² × 10 ⁴ N / m ² ), and the temperature is preferably molded at 20 to 100 minutes at 120 to 200 ° C. Moreover, after laminating to a circuit board by the vacuum lamination method similarly to an adhesive film, it can also manufacture by heat-hardening. Then, after roughening the surface of the prepreg hardened with the oxidizing agent like the above-mentioned method, a multilayer printed wiring board can be manufactured by forming a conductor layer by plating.

Example

Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this does not limit this invention in any meaning. In addition, in the following description, "part" means a "weight part."

Experimental Example 1

30 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, JP Epoxy Resin Co., Ltd. "jER828EL") and 30 parts of biphenyl type epoxy resin (Epoxy equivalent 291, Nihon Kayaku Co., Ltd. "NC3000H") It melt | dissolved by stirring, stirring 15 parts of ethyl ketones (it abbreviates as "MEK" hereafter), and 15 parts of cyclohexanone. Here, 80 parts of active ester compounds (DIC Corporation make "EXB9460-65T", active ester equivalent weight 223, toluene solution of 65% of solid content), a hardening accelerator (Kogegaku Kogyo Co., Ltd. product, "4-dimethyl Aminopyridine ”), 120 parts of spherical silica (average particle diameter: 0.5 μm, manufactured by SO-C2 Co., Ltd.) with amino silane treatment, phenoxy resin (JP-A 2006-A). As in Example 1 of 176658, bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 3,3 ', 5,5'-tetramethyl-4,4'-biphenoldiglyci A phenoxy resin synthesized from dil ether, a MEGA of 30% by weight of nonvolatile matter, a 1: 1 solution of cyclohexanone, and 40 parts by weight average molecular weight of 30000) were mixed and uniformly dispersed by a high speed rotary mixer to prepare a resin varnish. (49 parts by weight of solid content of 244 parts of silica and the ratio of the reactor of the epoxy group and the epoxy curing agent 1: 0.87).

Next, this resin varnish is applied onto a polyethylene terephthalate (thickness 38 mu m, hereinafter abbreviated as "PET") with a die coater so that the resin thickness after drying is 40 mu m, and then to 80 to 120 ° C (average 100 ° C). It dried for 6 minutes (about 2 weight% of residual solvent amount). Next, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film to the surface of a resin composition. The roll-shaped adhesive film was slit to a width of 507 mm to obtain a sheet-shaped adhesive film having a size of 507 × 336 mm.

Experimental Example 2

30 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, JP Epoxy Resin Co., Ltd. "jER828EL") and 30 parts of biphenyl type epoxy resin (Epoxy equivalent 291, Nihon Kayaku Co., Ltd. "NC3000H") It melt | dissolved by stirring, stirring 15 parts of ethyl ketones (it abbreviates as "MEK" hereafter), and 15 parts of cyclohexanone. Here, 40 parts of active ester compounds (DIC Corporation make "EXB9460-65T", active ester equivalent weight 223, toluene solution of 65% of solid content), phenolic hardening agent LA7052 (DIC Corporation make, triazine structure containing phenolo) 15 parts of volac resin, phenol hydroxyl group equivalent 120, MEK solution of 60% of solid content), 0.5 part of hardening accelerators (made by Koe Chemical Co., Ltd., "4-dimethylaminopyridine"), spherical silica (average particle diameter: 0.5 micrometer, 100 parts of amino silane treatment part "SO-C2" by Admatex Co., Ltd., bis (4-hydroxyphenyl) -3 like phenoxy resin (Example 1 of Unexamined-Japanese-Patent No. 2006-176658) Phenoxy resin synthesized from 3,5-trimethylcyclohexane and 3,3 ', 5,5'-tetramethyl-4,4'-biphenol diglycidyl ether, MEK with 30% by weight of non-volatile content and cyclo A 1: 1 solution of hexanone and 40 parts by weight average molecular weight 30000) were mixed and uniformly dispersed with a high speed rotary mixer to prepare a resin varnish. (207 parts of solid content, 48 weight% of silicas, ratio 1: 0.72 of the reactor of an epoxy group and an epoxy hardening | curing agent). Next, using this resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

Experimental Example 3

30 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, JP Epoxy Resin Co., Ltd. "jER828EL") and 30 parts of biphenyl type epoxy resin (Epoxy equivalent 291, Nihon Kayaku Co., Ltd. "NC3000H") It melt | dissolved by stirring, stirring 15 parts of ethyl ketones (it abbreviates as "MEK" hereafter), and 15 parts of cyclohexanone. Here, 40 parts of active ester compounds (DIC Corporation make "EXB9460-65T", active ester equivalent weight 223, toluene solution of 65% of solid content), phenolic hardening agent LA7052 (DIC Corporation make, triazine structure containing phenolo) 15 parts of volac resin, phenol hydroxyl group equivalent 120, MEK solution of 60% of solid content), 0.5 part of hardening accelerators (made by Koe Chemical Co., Ltd., "4-dimethylaminopyridine"), spherical silica (average particle diameter: 0.5 micrometer, 100 parts of "SO-C2" (made by admatex) with amino silane treatment, phenoxy resin (in Example 1 of JP 2006-176658, bis (4-hydroxyphenyl) -3, Instead of 3,5-trimethylcyclohexane, a mixture of phenoxy resins synthesized in the same manner using terpendiphenol, MEK of 40% by weight of non-volatile content and 1: 1 solution of cyclohexanone, and 30 parts by weight average molecular weight , Uniformly dispersed with a high-speed rotary mixer to produce a resin varnish (207 parts of solids, 48% by weight of silica, ratio 1: 0.72 of the reactor of epoxy group and epoxy curing agent). Next, using this resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

Experimental Example 4

30 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, JP Epoxy Resin Co., Ltd. "jER828EL") and 30 parts of biphenyl type epoxy resin (Epoxy equivalent 291, Nihon Kayaku Co., Ltd. "NC3000H") It melt | dissolved by stirring, stirring 15 parts of ethyl ketones (it abbreviates as "MEK" hereafter), and 15 parts of cyclohexanone. Here, 80 parts of active ester compounds (DIC Corporation make "EXB9460-65T", active ester equivalent weight 223, toluene solution of 65% of solid content), a hardening accelerator (Kogegaku Kogyo Co., Ltd. product, "4-dimethyl Aminopyridine "), 0.5 parts of spherical silica (average particle diameter: 0.5 micrometer, 130 parts of" SO-C2 "made by ADAMEX with amino silane treatment), phenoxy resin (JP-A-2006-176658) In the same manner as in Example 1, bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 3,3 ', 5,5'-tetramethyl-4,4'-biphenol diglycidyl ether 40 parts of a phenoxy resin synthesized from a 1% solution of MEK and cyclohexanone having a nonvolatile content of 30% by weight, an average molecular weight of 30000), and 8 parts of core-shell acrylic rubber particles ("W450" manufactured by Mitsubishi Rayon Co., Ltd.) The mixture was uniformly dispersed with a high speed rotary mixer to prepare a resin varnish (252 parts of solid content, 50% by weight of silica, epoxy group and epoxide). The ratio of the reactor hardener 1: 0.87). Next, using this resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

(Comparative Example 1)

30 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, JP Epoxy Resin Co., Ltd. "jER828EL") and 30 parts of biphenyl type epoxy resin (Epoxy equivalent 291, Nihon Kayaku Co., Ltd. "NC3000H") 15 parts of ethyl ketone (hereinafter abbreviated as "MEK") and 15 parts of cyclohexanone are heated and dissolved while stirring. Here, 80 parts of active ester compounds (DIC Corporation make "EXB9460-65T", active ester equivalent weight 223, toluene solution of 65% of solid content), a hardening accelerator (Kogegaku Kogyo Co., Ltd. product, "4-dimethyl Aminopyridine ") 0.5 parts, spherical silica (average particle diameter 0.5 micrometer, 120 parts of" SO-C2 "with amino silane treatment admadex), phenoxy resin (weight average molecular weight 50000, japenepoxy resin (note ) 30 parts of manufactured "1256B40" bisphenol A structure phenoxy resin and 40% by weight of non-volatile content MEK solution) were mixed and uniformly dispersed by a high speed rotary mixer to prepare a resin varnish (244 parts of solid content, 49 parts by weight of silica, 1: 0.87 ratio of reactor to epoxy group and epoxy curing agent). Next, using this resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

(Comparative Example 2)

30 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, JP Epoxy Resin Co., Ltd. "jER828EL") and 30 parts of biphenyl type epoxy resin (Epoxy equivalent 291, Nihon Kayaku Co., Ltd. "NC3000H") It melt | dissolved by stirring, stirring 15 parts of ethyl ketones (it abbreviates as "MEK" hereafter), and 15 parts of cyclohexanone. Here, 40 parts of active ester compounds (DIC Corporation make "EXB9460-65T", active ester equivalent weight 223, toluene solution of 65% of solid content), phenolic hardening agent LA7052 (DIC Corporation make, triazine structure containing phenolo) 15 parts of volac resin, phenol hydroxyl group equivalent 120, MEK solution of 60% of solid content), 0.5 part of hardening accelerators (made by Koe Chemical Co., Ltd., "4-dimethylaminopyridine"), spherical silica (average particle diameter: 0.5 micrometer, 100 parts of "SO-C2" with Amino silane treatment made by admatex), phenoxy resin (weight average molecular weight 50000, product made by Jaffen Epoxy Resin Co., Ltd. "1256B40" (bisphenol A structure phenoxy resin, nonvolatile matter) 30 parts of 40% by weight MEK solution) were mixed and uniformly dispersed with a high speed rotary mixer to prepare a resin varnish (207 parts of solid content, 48 parts by weight of silica, and a ratio of the reactor of the epoxy group and the epoxy curing agent 1: 0.72). Next, using this resin varnish, Example 1 and In the same manner still to obtain an adhesive film.

(Comparative Example 3)

30 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, JP Epoxy Resin Co., Ltd. "jER828EL") and 30 parts of biphenyl type epoxy resin (Epoxy equivalent 291, Nihon Kayaku Co., Ltd. "NC3000H") It melt | dissolved by stirring, stirring 15 parts of ethyl ketones (it abbreviates as "MEK" hereafter), and 15 parts of cyclohexanone. Here, 40 parts of phenolic hardening | curing agents LA7052 (DIC Corporation make, a triazine structure containing phenol novolak resin, phenol hydroxyl group equivalent 120, MEK solution of 60% of solid content), hardening accelerator (Kogegaku Kogyo Co., Ltd. product) , "4-dimethylaminopyridine") 0.5 part, spherical silica (average particle diameter 0.5 micrometer, 100 parts of "SO-C2" admadex with amino silane treatment), phenoxy resin (JP-A-JP) As in Example 1 of 2006-176658, bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 3,3 ', 5,5'-tetramethyl-4,4'-biphenol A phenoxy resin synthesized from diglycidyl ether, a 1: 1 solution of 30% by weight of nonvolatile matter MEK and cyclohexanone, and 40 parts by weight average molecular weight of 30000) were mixed and uniformly dispersed by a high speed rotary mixer to obtain a resin varnish. Was prepared (196 parts of solid content, 51 weight% of silica, ratio 1: 0.75 of the reactor of an epoxy group and an epoxy hardening | curing agent). Next, using this resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

(Comparative Example 4)

30 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, JP Epoxy Resin Co., Ltd. "jER828EL") and 30 parts of biphenyl type epoxy resin (Epoxy equivalent 291, Nihon Kayaku Co., Ltd. "NC3000H") It melt | dissolved by stirring, stirring 15 parts of ethyl ketones (it abbreviates as "MEK" hereafter), and 15 parts of cyclohexanone. Here, 60 parts of 50% MEK solution of phenol type hardening | curing agent SN485 (manufactured by Totogsei Co., Ltd., naphthol aralkyl type, phenol hydroxyl group equivalent 215), a hardening accelerator (Kogegaku Kogyo Co., Ltd. product, "4- Dimethylaminopyridine ''), 120 parts of spherical silica (average particle size 0.5 占 퐉, `` SO-C2 '' manufactured by Amadex Co., Ltd. with amino silane treatment), phenoxy resin (of JP 2006-176658 As in Example 1, bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 3,3 ', 5,5'-tetramethyl-4,4'-biphenoldiglycidyl Phenoxy resin synthesized with ether, 1: 1 solution of 30% by weight of nonvolatile matter MEK and cyclohexanone, weight average molecular weight 30000), 40 parts of core-shell acrylic rubber particles (manufactured by Mitsubishi Rayon Co., Ltd., "W450") Eight parts were mixed and uniformly dispersed with a high speed rotary mixer to prepare a resin varnish (solid content 199.5, silica weight 50%, epoxy group and epoxy curing). The ratio of the reactor 1: 0.73). Next, using this resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

<Preparation of Sample for Measuring Peel Strength and Ra Value>

(1) base treatment of laminate

Both sides of the laminated sheet [18 micrometers of copper foil, 0.3 mm of substrate thickness, Matsushita Denko Co., Ltd. R5715ES] of the glass cloth base material epoxy resin double-sided copper with an inner layer circuit were immersed in Mech Corporation CZ8100, The roughening process was performed.

(2) Lamination of Adhesive Film

The adhesive film produced by the Example and the comparative example was laminated on both surfaces of the laminated board using the batch type vacuum pressurizing laminator MVLP-500 (made by Meiki Seisakusho, brand name). The laminate was pressurized for 30 seconds to bring the pressure to 13 hPa or less, and then pressurized at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) curing of the resin composition

The PET film was peeled off from the laminated adhesive film, and the resin composition was cured under curing conditions at 180 ° C. for 30 minutes.

(4) coordination treatment

The laminated board was immersed for 5 minutes at 60 degreeC in dipping glycol monobutyl ether containing diethylene glycol monobutyl ether containing swelling liquid at 60 degreeC, and it is a condensate of Art-Tech Japan Penn. Immerse in compact P (KMn O4: 60g / L, NaOH: 40g / L aqueous solution) at 80 ° C for 20 minutes, and finally, as a neutralizing solution, at Artecjapan Co., Ltd.'s Reduction Solucine Security P at 40 ° C. Immerse in minutes. The arithmetic surface roughness Ra of the insulating layer was measured about the laminated board after this roughening process.

(5) Plating by semiadditive process

Isolated in order to form a circuit on the surface layer, was immersed in the laminate, in an electroless plating solution comprising a PdCl _2, was immersed in the year following the electroless copper plating solution. After heating at 150 degreeC for 30 minutes and performing an annealing process, an etching resist was formed, after the pattern formation by etching, copper sulfate electroplating was performed and the conductor layer was formed in the thickness of 30 +/- 5micrometer. Next, annealing was performed at 180 degreeC for 60 minutes. The peeling strength of the plated copper was measured for this laminate.

[Peel Strength (Peel Strength) of Plating Conductor Layer]

A cut of 10 mm in width and a length of 100 mm is placed in the conductor layer of the laminated board, and this end is peeled off and held by a handle (TS, Inc., Autocom Type Tester AC-50C-SL) and vertical at a speed of 50 mm / min at room temperature. The load when peeling 35 mm in the direction was measured.

[Surface Roughness After Harmonization]

Using a non-contact surface roughness meter (WYKO NT3300, manufactured by Noncoin Tool Corporation), the value of the arithmetic mean roughness (Ra) is determined using a VSI contact mode and a value obtained by setting the measurement range to 121 μm × 92 μm by a 50x lens. Obtained. Moreover, it measured by obtaining the average roughness of 10 points.

[Measurement of linear expansion coefficient]

The adhesive films obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were thermally cured at 190 ° C. for 90 minutes to obtain sheet-shaped cured products. The hardened | cured material was cut into the test piece of about 5 mm in width and about 15 mm in length, and the thermomechanical analysis was carried out by the tension-weighting method using the Rigaku Corporation thermomechanical analyzer (Thermo Plus TMA 8310). After attaching a test piece to the said apparatus, it measured continuously twice under the measurement conditions of a load of 1g and a temperature increase rate of 5 degree-C / min. The average linear thermal expansion rate from 25 degreeC to 150 degreeC in the 2nd measurement was computed.

The results are shown in Table 1.

As can be seen from the comparison between Example 1 and Comparative Example 1, Example 1 using an alicyclic structure-containing phenoxy resin compared to Comparative Example 1 using a phenoxy resin having a bisphenol A structure, although the surface roughness is low High peel strength and linear expansion rate also decreased. Similarly, when Examples 2 and 3 were compared with Comparative Example 2, in Comparative Example 2, although the phenoxy resin was replaced with the bisphenol A structure for Examples 2 and 3, it was found that the values of the surface roughness and the linear expansion rate were increased. Can be.

In Examples 2 and 3, an active ester compound and a phenol compound are used in combination as a curing agent. Compared with Example 1, the surface roughness tends to increase slightly, but the linear expansion ratio decreases, and both can be balanced by the combination. It can be seen that there is. Moreover, although only the phenolic compound was used as a hardening | curing agent in the comparative example 3, compared with Example 2, surface roughness resulted in the big increase.

Example 4 and Comparative Example 4 are compositions containing rubber particles, and the difference between the case where an active ester compound and a phenol compound are used as a curing agent is compared. However, Example 4 using the active ester compound has a small surface roughness and a linear expansion ratio. It became a low value.

Although the roughness of the roughening surface which roughened the hardened | cured material surface of an epoxy resin composition is small, the said epoxy roughening surface shows high adhesive force with respect to a plating conductor, and the epoxy resin composition which can achieve the insulating layer with small linear expansion rate, Adhesive films, prepregs and multilayer printed wiring boards can be provided. It is also possible to provide electric products such as computers, mobile phones, digital cameras, TVs, and the like, and vehicles such as motorcycles, automobiles, trams, ships, and aircraft.

Claims (15)

An epoxy resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an alicyclic structure-containing phenoxy resin. The method of claim 1, The epoxy resin composition of said (C) phenoxy resin is a terpene structure and / or a trimethylcyclohexane structure. The method according to claim 1 or 2, Epoxy resin composition, characterized in that the weight average molecular weight of the phenoxy resin is from 10000 to 50000. The method according to any one of claims 1 to 3, When the nonvolatile component of the epoxy resin composition is 100% by weight, the content of the component (A) is 10 to 50% by weight and the content of the component (C) is 1 to 20% by weight, and the epoxy group present in the epoxy resin composition Epoxy resin composition, characterized in that the ratio of the reactor of the epoxy curing agent is 1: 0.4 to 1: 1.1. The method according to any one of claims 1 to 4, (D) An epoxy resin composition comprising an inorganic filler. The method of claim 5, When the non-volatile component of the epoxy resin composition is 100% by weight, the content of the inorganic filler (D) is 10 to 70% by weight, characterized in that the epoxy resin composition. 7. The method according to any one of claims 1 to 6, Moreover, (E) hardening accelerator is contained, The epoxy resin composition characterized by the above-mentioned. The method of claim 7, wherein When the total amount of the epoxy resin and the phenolic curing agent contained in the epoxy resin composition is 100% by weight, the content of the (E) curing accelerator is 0.1 to 5% by weight. The epoxy resin composition as described in any one of Claims 1-8 is layered on the support film, The adhesive film characterized by the above-mentioned. The prepreg impregnated in the sheet-like fiber base material which consists of fibers in the epoxy resin composition in any one of Claims 1-8. The insulating layer is formed of the hardened | cured material of the epoxy resin composition of any one of Claims 1-8, The multilayer printed wiring board characterized by the above-mentioned. A method of manufacturing a multilayer printed wiring board comprising a step of forming an insulating layer on an inner circuit board and a step of forming a conductor layer on the insulating layer, The said insulating layer is formed by thermosetting the epoxy resin composition in any one of Claims 1-8, and the said conductor layer is formed by plating in the roughening surface which roughened the surface of the said insulating layer, It characterized by the above-mentioned. The manufacturing method of the multilayer printed wiring board characterized by the above-mentioned. A method of manufacturing a multilayer printed wiring board comprising a step of forming an insulating layer on an inner circuit board and a step of forming a conductor layer on the insulating layer, An insulating layer laminates the adhesive film of Claim 9 on an inner layer circuit board, heat-cures an epoxy resin composition, or does not peel a support film, and peels a support film, when a support film exists after hardening. And the conductor layer is formed by plating on a roughened surface obtained by roughening the surface of the insulating layer. A method of manufacturing a multilayer printed wiring board comprising a step of forming an insulating layer on an inner circuit board and a step of forming a conductor layer on the insulating layer, The insulating layer laminates the prepreg according to claim 10 on the inner layer circuit board, is formed by heat curing the epoxy resin composition, and the conductor layer is formed by plating on the roughened surface obtained by roughening the surface of the insulating layer. The manufacturing method of the multilayer printed wiring board characterized by the above-mentioned. The process according to any one of claims 12 to 14, wherein the roughening treatment is carried out using an alkaline permanganic acid solution.