KR20110124198A - Resin composition - Google Patents

Abstract

[assignment]
In a resin composition suitable for forming an insulating layer of a circuit board, it is to provide a resin composition capable of forming a conductor layer having a high peel strength even when the roughness of the surface of the insulating layer obtained by curing the resin composition is low.
[Workaround]
Resin composition containing (A) polyfunctional epoxy resin, (B) phenolic hardening | curing agent and / or active ester-type hardening | curing agent, (C) thermoplastic resin, (D) inorganic filler, and (E) specific hardening accelerator.

Description

Resin composition

The present invention provides an insulating layer formed of a resin composition suitable for forming an insulating layer of a circuit board such as a multilayer printed wiring board, an insulating resin sheet such as an adhesive film or a prepreg obtained from the resin composition, and a cured product of the resin composition. It relates to a circuit board.

With the recent miniaturization and high performance of electronic devices, fine wiring of circuit boards has been further demanded. When the conductor layer is formed by plating after the surface of the insulating layer is roughened, the peel strength is increased when the roughness is increased, but fine wiring is disadvantageous. Therefore, it is expected to satisfy the opposite performance of making the light intensity as low as possible and making the peel strength of a conductor layer high simultaneously.

For example, when the epoxy resin composition which mix | blended an epoxy resin, a specific phenolic hardening | curing agent, and polyvinyl acetal was used for the insulating layer of a multilayer printed wiring board, even if the roughening surface obtained has a comparatively small roughness, a plating conductor is obtained. The thing which can adhere by high adhesive force with (patent document 1) is disclosed.

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2007-254710

The present invention is a resin composition suitable for forming an insulating layer of a circuit board, and an object of the present invention is to provide a resin composition capable of forming a conductor layer having a high peel strength even when the roughness of the surface of the insulating layer obtained by curing the resin composition is low. do.

In view of the above problems, the present inventors have focused on the influence of the curing accelerator in the resin composition. And the present inventors used the resin composition containing a polyfunctional epoxy resin, a thermoplastic resin, and an inorganic filler WHEREIN: In the insulating layer which hardened and formed the said resin composition by using the specific hardening | curing agent and the specific phosphorus hardening agent in combination, Even with this low roughness, it discovered that the formed conductor layer had high peel strength, and completed this invention. That is, this invention includes the following content.

[1] (A) polyfunctional epoxy resin, (B) phenolic curing agent and / or active ester curing agent, (C) thermoplastic resin, (D) inorganic filler, (E) tetrabutylphosphonium decanoate, (4- A resin composition containing at least one quaternary phosphonium-based curing accelerator selected from methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate.

[2] The component (A) according to item [1], wherein the ratio of the mass of the component (E) to the total mass of the nonvolatile components of the component (A) and the component (B) is from 100: 0.05 to 100: 2. Resin composition containing E).

[3] The component (B) according to the item [1] or [2], wherein the ratio of the epoxy group present in the resin composition and the reactor of the curing agent of the component (B) is from 1: 0.3 to 1: 1 in molar ratio. Comprising a resin composition.

[4] The resin composition according to any one of the above items [1] to [3], wherein the content of the component (C) is 1 to 20% by mass when the nonvolatile content of the resin composition is 100% by mass.

[5] The resin composition according to any one of the above items [1] to [4], wherein the content of the component (D) is 10 to 70% by mass when the nonvolatile content of the resin composition is 100% by mass.

[6] The resin composition according to any one of the above items [1] to [5], wherein the peel strength is 0.4 kgf / cm to 2 kgf / cm and the surface roughness is 30 nm to 400 nm.

[7] An adhesive film, wherein the resin composition according to any one of [1] to [6] is layered on a support.

[8] A prepreg in which the resin composition according to any one of [1] to [6] is impregnated in the sheet-like fiber base material.

[9] A circuit board on which an insulating layer is formed of the cured product of the resin composition according to any one of [1] to [6].

The resin composition of the present invention is suitable for forming an insulating layer of a circuit board, and the insulating layer obtained by curing the resin composition can form a conductor layer having a high peel strength even if the surface roughness is low, thereby making the fine wiring of the circuit board. To be advantageous.

The present invention comprises (A) a polyfunctional epoxy resin, (B) a phenolic curing agent and / or an active ester curing agent, (C) a thermoplastic resin, (D) an inorganic filler, and (E) a specific curing accelerator. Resin composition.

[(A) Polyfunctional Epoxy Resin]

The component (A) polyfunctional epoxy resin in the present invention is not particularly limited as long as it has the effects of the present invention. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, tertiary -Butyl-catechol type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro Ring-containing epoxy resins, cyclohexanedimethanol type epoxy resins, trimethylol type epoxy resins, halogenated epoxy resins, and the like.

Although an epoxy resin may use 2 or more types together, it is preferable to contain the epoxy resin which has two or more epoxy groups in 1 molecule. When the nonvolatile component in the resin composition is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Moreover, the form which has two or more epoxy groups in 1 molecule, is an 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 a solid aromatic epoxy resin at temperature 20 degreeC desirable. In addition, the aromatic epoxy resin in this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator.

Moreover, when using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, the compounding ratio (liquid: solid) has the preferable mass ratio of the range of 1: 0.1-1: 2. When the ratio of liquid epoxy resin is too large beyond such a range, the adhesiveness of a resin composition will become high, and when using in the form of an adhesive film, there exists a tendency for the deaeration property at the time of vacuum lamination to fall and a void tends to generate | occur | produce. Moreover, there exists a tendency for the peelability of a protective film and a support film to fall, and the heat resistance after hardening falls at the time of vacuum lamination. Moreover, there exists a tendency for sufficient breaking strength to be hard to be obtained in the hardened | cured material of a resin composition. On the other hand, if there is too much ratio of solid epoxy resin beyond such a range, when using it in the form of an adhesive film, sufficient flexibility will not be obtained and sufficient fluidity at the time of lamination will become difficult to be obtained when handleability falls, etc. Tends to

In the resin composition of this invention, when the non volatile component in a resin composition is 100 mass%, it is preferable that content of an epoxy resin is 10-50 mass%, More preferably, it is 20-45 mass%, Especially preferable Preferably it is 25-42 mass%. When content of an epoxy resin (A) is out of this range, there exists a tendency for sclerosis | hardenability of a resin composition to fall.

[(B) Phenolic Curing Agent and / or Active Ester Curing Agent]

Although the phenol type hardening | curing agent and / or active ester type hardening | curing agent of component (B) in this invention have the effect of this invention, it does not specifically limit, It may respectively be used independently and may be used in mixture. Especially from a viewpoint of the mechanical characteristic of hardened | cured material, a phenolic hardening | curing agent is preferable.

A phenolic hardening | curing agent is a compound containing a phenol skeleton or a naphthol skeleton, and says what has a hardening effect of an epoxy resin. As a phenol type hardening | curing agent, the phenol type hardening | curing agent which has a novolak structure from the viewpoint of heat resistance and water resistance, and the naphthol type hardening | curing agent which has novolak structure is preferable. As a commercial item, MEH-7700, MEH-7810, MEH-7851 (made by Meiwa Kasei Co., Ltd.), NHN, CBN, GPH (made by Nihon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (made by Totogsei Co., Ltd.), LA7052, LA7054 (made by Dainippon Ink & Chemicals Co., Ltd.), etc. are mentioned. An active ester type hardening | curing agent has an ester group with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine ester, and ester of a heterocyclic hydroxy compound, and says that it has a hardening effect of an epoxy resin. Examples of the active ester curing agent include EXB-9460 (manufactured by Dainippon Ink & Chemicals Co., Ltd.), DC808, and YLH1030 (manufactured by Japan Epoxy Resin Co., Ltd.).

In the present invention, the content of the phenolic curing agent and / or the active ester curing agent in the resin composition is a ratio of the total number of epoxy groups of the epoxy resin present in the resin composition and the total number of reactors of the curing agent is 1: 0.3 to 1: 2. It is preferable to set it as the quantity used, and it is further more preferable to set it as the quantity used as 1: 0.4-1: 1.5. The total number of epoxy groups in the epoxy resin present in the resin composition is the value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent and adding up the total amount for all epoxy resins, and the reactor (active hydroxyl group, active ester group) of the curing agent. The total number of is the value which totaled the value which divided | segmented the solid content mass of each hardening | curing agent by the reactor equivalent, about all the hardening | 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 a resin composition to become inadequate.

[(C) Thermoplastic Resin]

The component (C) thermoplastic resin in the present invention is not particularly limited as long as it has the effects of the present invention. Examples thereof include phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamideimide resins, polyethersulfone resins, Polysulfone resin etc. are mentioned, A phenoxy resin and a polyvinyl acetal resin are preferable, A phenoxy resin is especially preferable. You may use 2 or more types of thermoplastic resins in mixture. It is preferable that it is the range of 1-20 mass% with respect to 100 mass% of non volatile matters in a resin composition, and, as for content of a thermoplastic resin, it is more preferable that it is the range which is 5-15 mass%. When there is too little content, the flexibility of hardened | cured material tends to fall, and when there is too much content, the viscosity of a resin composition will become high too much, lamination property will fall, and it exists in the tendency for the embedding to a wiring pattern on a circuit to become difficult. . The weight average molecular weight of the thermoplastic resin is preferably in the range of 8000 to 70000, more preferably 10000 to 60000, still more preferably 20000 to 60000. When molecular weight is too small, there exists a tendency for the peeling strength of a conductor layer to fall, and when molecular weight is too large, there exists a tendency for roughness to become large and thermal expansion coefficient to become large. A weight average molecular weight is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). The weight 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 chloroform etc. as a mobile phase, and can be computed using the analytical curve of standard polystyrene.

Examples of the phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, and acetonitrile. The thing which has 1 or more types of frame | skeleton selected from a tantan skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton is mentioned. You may use phenoxy resin in mixture of 2 or more types. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. As a commercial item, Japan Epoxy Resin Co., Ltd. make 1256, 4250 (bisphenol A frame | skeleton containing phenoxy resin), Japan Epoxy resin make YX8100 (bisphenol S frame | skeleton containing phenoxy resin), Japan Epoxy resin make YX6954 (bisphenol acetphenone) Skeleton-containing phenoxy resin), FX280, FX293 by Totogsei Co., Ltd., YL7553, YL6794, YL7213, YL7290, YL7482, etc. are mentioned.

Specific examples of the polyvinyl acetal resin include Denki Chemical Co., Ltd., Denwa Butyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Co., Ltd. Esrek BH series, BX Series, KS series, BL series, BM series, etc. are mentioned. As a specific example of a polyimide resin, the polyimide "Rika coat SN20" and "Rika coat PN20" by Shin-Nihon Rica Co., Ltd. are mentioned. In addition, linear polyimides (described in JP-A-2006-37083) and polysiloxane skeleton-containing polyimides obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic anhydride (Japanese Patent Laid-Open) Modified polyimide such as those described in Japanese Patent Application Laid-Open No. 2002-12667, Japanese Laid-Open Patent Publication No. 2000-319386, and the like. As a specific example of polyamide-imide resin, the polyamide-imide "Biromax HR11NN" and "Biromax HR16NN" by Toyo Joseki Co., Ltd. are mentioned. Moreover, modified polyamideimide, such as polysiloxane frame | skeleton containing polyamideimide "KS9100" and "KS9300" by Hitachi Chemical Co., Ltd., is mentioned. Specific examples of the polyether sulfone resin include Sumitomogagaku Co., Ltd. polyether sulfone, "PES5003P", and the like. Specific examples of the polysulfone resin include polysulfones " P1700 ", " P3500 " manufactured by Solen Advanced Polymers, Inc., and the like. You may use these various thermoplastic resins in mixture of 2 or more types.

[Inorganic Filler of (D)]

The component (D) inorganic filler in the present invention is not particularly limited as long as it has the effects of the present invention. Examples thereof include 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, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Silicas, such as crystalline silica and synthetic silica, are particularly suitable. As silica, a circular thing is preferable. You may use an inorganic filler in combination of 2 or more type.

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 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 resin composition is made into a 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. The average particle diameter of an inorganic filler can be measured by the laser diffraction scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on the basis of a volume by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as an average particle diameter. The measurement sample can use preferably what disperse | distributed the inorganic filler in water by the ultrasonic wave. As a laser diffraction particle size distribution measuring apparatus, LA-500 manufactured by Horiba Seisakusho, etc. can be used.

Inorganic fillers include aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidepropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and N-2 (amino for improving the moisture resistance, dispersibility, etc.). Aminosilane-based coupling agents such as ethyl) aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxy Epoxy silane coupling agents such as silane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercaptosilane-based coupling agents such as mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, and methyltri Silane coupling agents such as methoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methoxypropyltrimethoxysilane, imidazolesilane, and triazinesilane, hexamethylsilazane, hexaphenyl Organosilazane compounds such as disilazane, dimethylaminotrimethylsilane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, butyl titanate dimer, titanium Octylene glycolate, diisopropoxy citabis bis (triethanol aluminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, bis (di Octylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate , Tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diaryloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyltrioctanoyl titanate, isopropyl T Cumylphenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacrylic isostearoyl titanate, isopropyl tri (dioctylphosphate) titanate, One or more surface treatments, such as isopropyl tridodecylbenzenesulfonyl titanate, the isopropyl tris (dioctyl pyrophosphate) titanate, and the titanate coupling agent of isopropyl tri (N-amide ethyl amino ethyl) titanate It may be zeroed.

The average particle diameter of an inorganic filler can be measured by the laser diffraction scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on the basis of a volume by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as an average particle diameter. The measurement sample can use preferably what disperse | distributed the inorganic filler in water by the ultrasonic wave. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Corporation | KK Corporation | KK can be used.

It is preferable that it is the range of 10-70 mass% with respect to 100 mass% of non volatile matters in a resin composition, It is more preferable that it is the range of 15-65 mass%, and, as for content of an inorganic filler, it is 20-60 mass% still more. desirable. When there is too little content of an inorganic filler, there exists a tendency for a thermal expansion rate to rise, and when there is too much content, there exists a tendency for the flexibility of an insulated resin sheet to fall.

[Quality 4 Phosphorium Curing Accelerator]

The component (E) quaternary phosphonium-based curing accelerator in the present invention is not particularly limited as long as it has the effects of the present invention, but quaternary refers to a functional group selected from an alkyl group, an aralkyl group, and an aryl group. Specifically, quaternary phosphonium thiocyanate and quaternary phosphonium long chain fatty acid salt are mentioned. In particular, tetrabutyl phosphonium decanoate, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, and butyl triphenyl phosphonium thiocyanate are preferable. The lower limit of the content (mass%) of the component (E) to the total mass of the nonvolatile matter of the component (A) and the component (B) is preferably 0.05, more preferably 0.07, still more preferably 0.09, and 0.11 It is further more preferable, 0.13 is especially preferable, and 0.15 is especially preferable. 2 is preferable, as for the upper limit of content (mass%) of the component (E) with respect to the total mass of the non volatile matter of a component (A) and a component (B), 1 is more preferable, 0.8 is still more preferable, 0.7 is It is further more preferable, 0.6 is especially preferable, and 0.5 is especially preferable. When the ratio of the component (E) is less than 0.05, there is a tendency that the desired low light effect is difficult to be obtained, and when it exceeds 2, the peel strength tends to decrease.

The resin composition of this invention contains (A) component, (B) component, (C) component, (D) component, and (E) component, even if the roughness of the insulating layer surface obtained by hardening | curing the said resin composition is low, The resin composition which can form the conductor layer which has high peeling strength can be provided.

Peel strength of the cured product of the resin composition containing the component (A), the component (B), the component (C), the component (D) and the component (E) of the present invention is described below. Can be understood by the measuring method described in Measurement & Evaluation>.

0.8 is preferable, the upper limit of the peeling strength (kgf / cm) of the hardened | cured material of the resin composition of this invention has more preferable 0.9, 1.0 is still more preferable, 1.1 is still more preferable, 1.2 is especially preferable, 2 Is particularly preferred. The lower limit of the peel strength (kgf / cm) of the cured product of the resin composition of the present invention is preferably 0.4, more preferably 0.5, and still more preferably 0.6.

Surface roughness of the hardened | cured material of the resin composition containing (A) component, (B) component, (C) component, (D) component of this invention, and (E) component is the <surface roughness (Ra value) after a roughening mentioned later. It can grasp | ascertain by the measuring method of measurement and evaluation>.

700 is preferable, 500 is still more preferable, 400 is still more preferable, 300 is still more preferable, 200 is especially preferable, 200 is especially preferable in the upper limit of the surface roughness (nm) of the hardened | cured material of the resin composition of this invention. desirable. The lower limit of the surface roughness (nm) of the cured product of the resin composition of the present invention is preferably 150, more preferably 120, still more preferably 90, still more preferred, 50 is particularly preferred, and 30 is particularly preferred. desirable.

[Rubber particles]

The resin composition of this invention can contain a solid rubber particle for the purpose of a stress relaxation effect etc. which improve the mechanical strength of hardened | cured material. It is preferable that a rubber particle does not melt | dissolve in the organic solvent at the time of preparing a resin composition, is not compatible with the component in resin compositions, such as an epoxy resin, and exists in a dispersion state in the varnish of a resin composition. 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 and making it into a particulate form. As a rubber particle, a core cell type rubber particle, a crosslinked acrylonitrile butadiene rubber particle, a crosslinked styrene butadiene rubber particle, an acryl rubber particle, etc. are mentioned, for example. The core cell rubber particles are rubber particles in which the particles have a core layer and a cell layer. For example, a two-layer structure in which the cell layer of the outer layer is made of a glass polymer, and the core layer of the inner layer is made of a rubbery polymer, or the cell layer of the outer layer is glass. And a three-layer structure in which the type polymer, the intermediate layer are rubber-like polymers, and the core layer are composed of a glass type polymer. The glass layer is made of, for example, a polymer of methyl methacrylate, or the like, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber) or the like. Specific examples of the core cell rubber particles include starpiroid AC3832, AC3816N, (Kantzugasei Co., Ltd. brand name), and metabrene KW-4426 (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 metabrene W300A (average particle diameter: 0.1 µm) and W450A (average particle diameter: 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, the rubber particles are uniformly dispersed by an ultrasonic wave or the like in a suitable organic solvent, the particle size distribution of the rubber particles is prepared on a mass basis using FPRA-1000 (manufactured by Otsuka Denshi Co., Ltd.) It can measure by making diameter into an average particle diameter.

It is preferable that it is the range of 1-10 mass% with respect to 100 mass% of non volatile matters in a resin composition, and, as for content in the case of mix | blending rubber particle, it is more preferable that it is the range which is 2-5 mass%.

[Other thermosetting resins]

The resin composition of this invention can mix | blend other thermosetting resins, such as a maleimide compound, a bisaryl nadiiimide compound, a vinyl benzyl resin, a vinyl benzyl ether resin, in the range in which the effect of this invention is exhibited as needed. You may use these thermosetting resins in mixture of 2 or more types. As maleimide resin, BMI1000, BMI2000, BMI3000, BMI4000, BMI5100 (manufactured by Yamato Kasei Kogyo Co., Ltd.), BMI, BMI-70, BMI-80 (manufactured by Keikaisei Co., Ltd.), ANILIX-MI (Mitsuiga As Baku-M, BANI-X (manufactured by Maruzen Seki Yugagaku Kogyo Co., Ltd.), as vinyl benzyl resin, V5000 (manufactured by Showa Kobunshi Co., Ltd.), As vinyl benzyl ether resin, V1000X and V1100X (made by Showa Kobunshi Co., Ltd.) is mentioned.

[Flame retardant]

The resin composition of this invention may contain a flame retardant in the range in which the effect of this invention is exhibited. You may use a flame retardant in mixture of 2 or more type. 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. As an organophosphorus flame retardant, phosphorus containing benzoxazine compounds, such as HCA, HCA-HQ, HCA-NQ, and HFB-2006M by Showa Kobunshi Co., Ltd. make, and Ajinomoto Fine Techno ( Leopard 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, Hokogakuku Kogyo Co., Ltd. Phosphate ester compounds, such as OP930 manufactured by Daihachi Chemical Co., Ltd., PX200 by Daihachi Chemical Co., Ltd., Phosphorus containing epoxy resins, such as FX289 and FX310 by Totogasei Co., Ltd., ERF001 by Totogsei Co., Ltd. Phosphorus containing phenoxy resin etc. are mentioned. Examples of the organic nitrogen-containing phosphorus compound include phosphate ester imide 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. As the metal hydroxide, magnesium hydroxides such as UD65, UD650, and UD653 manufactured by Ube Materials, Inc., B-30, B-325, B-315, B-308, B-303, manufactured by Tomoe Kogyo Co., Ltd., Aluminum hydroxide, such as UFH-20, etc. are mentioned.

[Resin additive]

The resin composition of this invention may arbitrarily contain various resin additives other than the above 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-based, fluorine-based, antifoaming agents or leveling agents, silane coupling agents, triazole compounds, thiazole compounds, Adhesion-providing agents, such as a triazine compound and a porphyrin compound, Coloring agents, such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, carbon black, etc. are mentioned. Moreover, imidazole compounds, such as curazole 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2MZ-OK, 2MA-OK, 2PHZ (Shikoku Chemical Co., Ltd. brand name); Amine adduct compounds such as Asahi Kasei Kogyo Co., Ltd., Fujicure (Fuji Kasei Kogyo Co., Ltd. brand name); 1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter DBU) Tertiary amine compounds such as tetraphenylborate salts; Amine-type hardening accelerators, such as these, etc. are mentioned.

The preparation method of the resin composition of this invention is not specifically limited, For example, the method of adding a solvent etc. as needed and mixing using a rotary mixer etc. are mentioned.

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 part embedding resin, etc. It can be used extensively for the use which a composition requires. Among these, it is preferable to apply | coat on a support body, to form a resin composition layer, and to make an adhesive film, or to impregnate the said resin composition in the sheet-like fiber base material which consists of fibers, and to make it a prepreg. Although the resin composition of this invention may be apply | coated to a circuit board in a varnish state, and may form an insulating layer, industrially, it is generally used in formation of an insulating layer in the form of a sheet-like laminated material, such as an adhesive film or a prepreg. It is preferable.

[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 a person skilled in the art, for example, apply | coats this resin varnish on a support body, and heat | fever or hot air jet etc. It can manufacture by drying 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, acetate esters such as propylene glycol monomethyl ether acetate, carbitol acetate, cellosolve, butyl Carbitols, such as carbitol, Aromatic hydrocarbons, such as toluene and xylene, Amide type solvents, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, etc. are mentioned. 1 type may be used for an organic solvent and may be used for it in combination of 2 or more type.

Although dry conditions are not specifically limited, 10 mass% or less is preferable, and, as for the content rate of the organic solvent with respect to a resin composition layer, it is made to dry so that it may become 5 mass% or less more preferably. Drying conditions are appropriate by simple experiments, and suitable drying conditions can be set. Although it changes also with the amount of the organic solvent in a varnish, for example, the varnish containing 30-60 mass% organic solvent can be dried at 50-150 degreeC for about 3 to 10 minutes.

It is preferable to make the thickness of the resin composition layer formed in an adhesive film more than the thickness of a conductor layer. 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 the thickness of a resin composition layer has a thickness of 10-100 micrometers. The resin composition layer may be protected by a protective film described later. By protecting with a protective film, adhesion and scratches such as dust on the surface of the resin composition layer can be prevented.

Examples of the support in the present invention include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and the like. Plastic films; Especially as a plastic film, PET is preferable. Metal foil, such as copper foil and aluminum foil, can be used as a support body, and it can also be set as the adhesive film with metal foil. It is preferable to use the same plastic film as a protective film. In addition, a support body and a protective film may perform a mold release process other than a mat process and a corona treatment. In addition, the mold release treatment may be performed with a mold release agent such as a silicone resin mold release agent, an alkyd resin mold release agent, or a fluororesin mold release agent.

Although the thickness of a support body is not specifically limited, The range of 10-150 micrometers is preferable, It is more preferable to be able to use in the range of 25-50 micrometers. Moreover, although the thickness of a protective film is not restrict | limited in particular, The range of 1-40 micrometers is preferable, It is more preferable to be able to use in the range of 10-30 micrometers.

The support body in this invention peels after laminating an inner circuit board etc. or after forming an insulating layer by heat-hardening. When a support body is peeled 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 support body is previously performed to a support body. Moreover, it is preferable to form the resin composition layer formed on a support body so that the area of a layer may become smaller than the area of a support body. Moreover, an adhesive film can be wound up in roll shape, and can be preserve | saved and stored.

[Manufacturing methods, such as a multilayer printed wiring board using an adhesive film]

Next, the method of manufacturing circuit boards, such as 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 off, it laminates on one side or both sides of an inner layer circuit board so that a resin composition layer may directly contact an inner layer circuit board. In the adhesive film of this invention, the method of laminating to an inner layer circuit board under reduced pressure by the vacuum lamination method is used suitably. The method of lamination may be batch type, or may be continuous by a roll. In addition, before performing lamination, you may heat (preheat) an adhesive film and an inner layer circuit board as needed.

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 which consists of a conductor layer (circuit) patterned on one side or both surfaces, alternately layering a conductor layer and an insulation layer, also the intermediate | middle product to which an insulation layer and a conductor layer should be formed is also seen. It is contained in the inner layer circuit board in the invention. In the inner circuit board, it is preferable that the surface of the conductor circuit layer is subjected to a roughening process in advance by a roughening process or the like from the viewpoint of the adhesion of the insulating layer to the inner circuit board.

Condition of the laminate is preferably 70 to 140 ℃, preferably from 1 to 11kgf / ㎠ (9.8 × 10 ⁴ to 107.9 × 10 ⁴ N / ㎡) in, and the air pressure is 20 the contact pressure for contact bonding temperature (lamination temperature) It is preferable to laminate under reduced pressure which is mmHg (26.7 hPa) or less.

Vacuum lamination can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, Nichigo Moton Co., Ltd. product application, a vacuum press type laminator by Meiki Seisakusho Co., Ltd., Hitachi Industries Co., Ltd. roll type dry coater, Hitachi AIC Co., Ltd. make And a vacuum laminator.

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 a support body layer side.

As a press condition, 1 * 10 <^-2> MPa or less is preferable and, as for a pressure reduction degree, 1 * 10 <^-3> MPa or less is more preferable. Although heating and pressurization may be performed in one step, it is preferable to divide conditions into two or more steps from a viewpoint of controlling that resin permeates. For example, the press of the first stage has a temperature in the range of 70 to 150 ° C., the pressure of 1 to 15 kgf / cm 2, and the press of the second stage has a temperature of 150 to 200 ° C. and a pressure of 1 to 40 kgf / cm 2. It is preferable to carry out. The time of each step is preferably carried out in 30 to 120 minutes. Commercially available vacuum hot press machines include MNPC-V-750-5-200 manufactured by Meiki Seisakusho, VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

Thus, after laminating an adhesive film to an inner layer circuit board, when peeling a support body, it can peel, and an insulating layer can be formed in an inner layer circuit board by thermosetting a resin composition. The conditions of heat-hardening are selected in the range of 20 minutes-180 minutes at 150 degreeC-220 degreeC, More preferably, they are 30 minutes-120 minutes at 160 degreeC-200 degreeC.

After forming an insulating layer, when a support body is not peeled off before hardening, it peels off here. Next, through holes are formed in the insulating layer formed on the inner circuit board to form via holes and through holes. The drilling can be carried out by a known method such as a drill, a laser, a plasma, or a combination of these methods as necessary, but the drilling is performed by a laser such as a carbon dioxide laser or a YAG laser. to be.

Subsequently, a roughening process is performed on 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, the composition is prepared by using an alkaline permanganate solution (for example, potassium permanganate and sodium permanganate aqueous solution of sodium permanganate), which is an oxidizing agent that is generally used for roughening the insulating layer in the manufacture of a multilayer printed wiring board by a built-up method. desirable.

It is preferable that the roughness of the roughening surface which roughened the insulating layer surface is 0.05-0.5 micrometer by Ra value when forming a fine wiring. In addition, Ra value is a kind of numerical value which means surface roughness, and is called an 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, it can obtain | require by the numerical value obtained by making a measurement range 121 micrometer x 92 micrometers by VSI contact mode and a 50x lens using WYKO NT3300 by Vico Instruments.

Next, a conductor layer is formed on the surface of the resin composition layer in which the uneven anchor was formed by the roughening process by the method which combined 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. Moreover, after forming a conductor layer, the peel strength of a conductor layer can further be improved and stabilized by annealing at 150-200 degreeC for 20 to 90 minutes. It is preferable that the peeling strength of a conductor layer is 0.6 kgf / cm or more.

In addition, as a method of pattern-processing a conductor layer and forming a circuit, the subtractive method, the semiadditive method, etc. which are well-known to a person skilled in the art can be used, for example.

[Prepreg]

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. That is, it can be set as the prepreg which becomes the state which the resin composition of this invention impregnated the sheet-like fiber base material which consists of fibers.

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

The hot-melt method does not dissolve the resin in an organic solvent and coats the resin with a resin and a coated paper having good peelability, and then laminates the sheet-like fibrous base material or directly coats it with a die coater to produce a prepreg. It is a way. The solvent method is a method of immersing a sheet-like fibrous substrate in a resin varnish in which resin is dissolved in an organic solvent, like an adhesive film, and impregnating the resin varnish into a sheet-like fibrous substrate, followed by drying.

[Manufacturing method of multilayer printed wiring boards using prepreg]

Next, the method to manufacture circuit boards, such as 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 superimposed on the inner 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 392 × 10 ⁴ N / m 2), and the temperature is preferably molded in the range of 20 to 100 minutes at 120 to 200 ° C. Moreover, after laminating to an inner layer circuit board by the vacuum lamination method similarly to an adhesive film, it can manufacture also by heat-hardening. Then, after roughening the surface of the prepreg hardened with the oxidizing agent like the above-mentioned method, a circuit board, such as a multilayer printed wiring board, can be manufactured by forming a conductor layer by plating.

[Example]

Hereinafter, although an Example and a comparative example are demonstrated in detail according to this invention, these do not limit this invention in any meaning. In addition, in the following description, "part" means a "mass part."

(Example 1)

35 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, Japan epoxy resin Co., Ltd. "jER828EL") and 35 parts of biphenyl type epoxy resin (Epoxy equivalent 269, Nihon Kayaku Co., Ltd. "NC3000H"), 40 parts of phenoxy resin (weight average molecular weight 38000, methyl ethyl ketone (hereinafter abbreviated as "MEK") and cyclohexanone of 30 mass% of non volatile matters made by Japan Epoxy Resin Co., Ltd. "YX6954" non-volatile content) MEK 40 parts It melt | dissolved by stirring, stirring 10 parts and 3 parts of cyclohexanone. (4- which is 45 parts of MEK solution of 60 mass% of non volatile matters, phenolic hydroxyl group equivalent 124), quaternary phosphonium-type hardening accelerator (4- of phenol novolak-type hardening | curing agent (DIC Corporation make "LA-7054") Methylphenyl) triphenylphosphonium thiocyanate (Hokko Chemical Co., Ltd. make, dimethylformamide (hereinafter abbreviated as "DMF") solution of 10 mass% of non volatile matter "TPTP-SCN") 2 parts, spherical silica ( An average particle diameter of 0.5 µm, 70 parts of an aminosilane-treated "SOC2" manufactured by Admatex Co., Ltd.) and a high speed rotary mixer were uniformly dispersed to prepare a resin varnish. Next, such a resin varnish is applied on a polyethylene terephthalate (thickness 38 占 퐉, hereinafter abbreviated as "PET") with a die coater so that the resin thickness after drying is 40 占 퐉, and 80 to 120 占 폚 (average 100 占 폚). It dried for 6 minutes at (about 2 mass% 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 thereby obtain a sheet-shaped adhesive film having a size of 507 × 336 mm.

(Example 2)

2 parts of (4-methylphenyl) triphenylphosphonium thiocyanate (DMF solution of 10 mass% of non-volatile matters manufactured by Hokogagaku Kogyo Co., Ltd., "TPTP-SCN") which is a quaternary phosphonium-based hardening accelerator of Example 1 Similarly, except changing into 4 parts of tetraphenyl phosphonium thiocyanate (the DMF solution of 5 mass% of TPP-SCN non-volatile matters) by a quaternary phosphonium system hardening accelerator, it is completely the same. To obtain an adhesive film. Next, using such a resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

(Example 3)

18 parts of liquid bisphenol A type epoxy resins (epoxy equivalent 180, Japan epoxy resin Co., Ltd. "jER828EL") and 20 parts of biphenyl type epoxy resin (epoxy equivalent 269, Nihon Kayaku Co., Ltd. "NC3000L"), Of naphthalene-type tetrafunctional epoxy resin (epoxy equivalent 162, DIC Corporation "HP-4700") 6 parts, phenoxy resin (weight average molecular weight 38000, Japan epoxy resin Co., Ltd. "YL7553" nonvolatile matter 30 mass% 12 parts of a 1: 1 solution of MEK and cyclohexanone) was dissolved by heating while stirring with 8 parts of MEK and 8 parts of cyclohexanone. Here, 13 parts of phenol novolak-type hardening | curing agents (DIC Corporation make "LA-7054" non-volatile content 60 mass% MEK solution, phenolic hydroxyl group equivalents 124), and active ester type hardening | curing agent (DIC Co., Ltd. product " EXB-9460 "Toluene solution of 65 mass% of non volatile matters, 20 parts of active ester equivalents 223), tetrabutyl phosphonium decanoate which is a quaternary phosphonium system hardening accelerator (Hokko Chemical Co., Ltd. product," TBP-DA " ) 0.2 parts, spherical silica (average particle diameter: 0.5 µm, aminosilane treatment "SOC2" admatex company) 75 parts, polyvinyl butyral resin solution (glass transition temperature 105 degreeC, Sekisui Chemical Co., Ltd. product " 18 parts of 1: 1 solution of ethanol and toluene of 15 mass% of non volatile matters were mixed, it was disperse | distributed uniformly by the high speed rotary mixer, and the resin varnish was produced. Next, using such a resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

(Example 4)

25 parts of liquid bisphenol A type epoxy resin (Epoxy equivalent 180, Japan epoxy resin Co., Ltd. product "jER828EL") and 25 parts of biphenyl type epoxy resin (Epoxy equivalent 269, Nihon Kayaku Co., Ltd. product "NC3000L"), Of naphthalene-type tetrafunctional epoxy resin (epoxy equivalent 162, DIC Corporation "HP-4700") 6 parts, phenoxy resin (weight average molecular weight 38000, Japan epoxy resin Co., Ltd. "YL7553" nonvolatile matter 30 mass% 12 parts of a 1: 1 solution of MEK and cyclohexanone) was dissolved by heating while stirring with 5 parts of MEK and 5 parts of cyclohexanone. Here, 36 parts of phenol novolak-type hardening | curing agents (MEK solution of 60 mass% of non volatile matters, "LA-7054" DIC Corporation make, phenolic hydroxyl group equivalent 124), butyl triphenyl which is a quaternary phosphonium-type hardening accelerator 2 parts of phosphonium thiocyanate (Hokko Chemical Co., Ltd. product, DMF solution of 10 mass% of "TPPB-SCN" non volatile matter), spherical silica (0.5 micrometer in average particle diameter, aminosilane treatment "SOC2" admatex company Manufacture) 190 parts, 12 parts of polyvinyl butyral resin solution (glass transition temperature 105 degreeC, 1: 1 solution of ethanol and toluene of 15 mass% of non-volatile matters manufactured by Sekisuga Chemical Co., Ltd. "KS-1" non-volatile content) And it disperse | distributed uniformly by the high speed rotary mixer, and produced the resin varnish. Next, using such a resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

(Comparative Example 1)

Except not adding the quaternary phosphonium-type hardening accelerator of Example 1, it carried out exactly the same and the adhesive film was obtained. Next, using such a resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

(Comparative Example 2)

2 parts of (4-methylphenyl) triphenylphosphonium thiocyanate (DMF solution of 10 mass% of non-volatile matters manufactured by Hokogagaku Kogyo Co., Ltd., "TPTP-SCN") which is a quaternary phosphonium-based hardening accelerator of Example 1 Similarly, except for changing to two parts of DBU-based tetraphenyl borate salt (manufactured by San-Apro Co., Ltd., MEK solution of 10 mass% of non-volatile content of "U-CAT 5002") which is a quaternary phosphonium-type hardening accelerator, An adhesive film was obtained. Next, using such a resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

(Comparative Example 3)

0.2 parts of tetrabutylphosphonium decanoate (Hokko Chemical Co., Ltd. product, "TBP-DA") which is a quaternary phosphonium-type hardening accelerator of Example 3 is similarly triphenylphosphine which is a quaternary phosphonium-type hardening accelerator Except having changed into 2 parts of triphenyl boranes (The DMF solution of 10 mass% of "TPP-S" non volatile matter manufactured by Hokogagaku Kogyo Co., Ltd.), it carried out similarly and the adhesive film was obtained. Next, using such a resin varnish, it carried out exactly the same as Example 1, and obtained the adhesive film.

(Comparative Example 4)

2 parts of (4-methylphenyl) triphenylphosphonium thiocyanate (DMF solution of 10 mass% of non-volatile matters manufactured by Hokogagaku Kogyo Co., Ltd., "TPTP-SCN") which is a quaternary phosphonium-based hardening accelerator of Example 1 Similarly, except that it changed to 0.2 part of tetraphenyl phosphonium tetraphenyl borate (Hokko Chemical Co., Ltd. product, "TPP-K") which is a quaternary phosphonium-type hardening accelerator, it carried out completely similarly, and obtained the adhesive film. Next, using such a 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 inner layer circuit board

Both surfaces of the glass cloth base material epoxy resin double-sided copper-clad laminated board [18 micrometers of copper foil, substrate thickness 0.3mm, Matsushita Denko Co., Ltd. R5715ES] which formed the inner layer circuit were immersed in MEC Co., Ltd. CZ8100, Harmonic treatment was performed.

(2) Lamination of Adhesive Film

The adhesive film produced by the Example and the comparative example was laminated on both surfaces of an inner layer circuit board using the batch type vacuum pressurization laminator MVLP-500 (made by Meiki Corporation). Lamination was performed by depressurizing for 30 second, making atmospheric pressure 13 hPa or less, and pressing at 100 degreeC and pressure 0.74 Mpa for 30 second after that.

(3) curing of the resin composition

PET film was peeled from the laminated adhesive film, the resin composition was hardened on 180 degreeC and 30 minutes of curing conditions, and the insulating layer was formed.

 (4) coordination treatment

The inner circuit board having the insulating layer formed thereon was immersed in Swelling Dip Secure Gun P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd., which is a swelling liquid, at 60 ° C. for 5 minutes. Immersion Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) of Tec Japan Co., Ltd. for 20 minutes at 80 ° C. Finally, Atotech Japan Co., Ltd. reduction solution It was immersed in security gun P at 40 degreeC for 5 minutes. The surface roughness (Ra value) of the surface of the insulating layer after roughening process was measured using this board | substrate.

(5) Plating by semiadditive process

In order to form a circuit on the insulating layer surface, the inner layer circuit board was immersed in the electroless plating solution containing PdCl ₂ , and then immersed in the electroless copper plating solution. After heating at 150 degreeC for 30 minutes and performing an annealing process, after forming an etching resist and pattern-forming 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 plating conductor layer was measured for this circuit board.

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

A cutting line 10 mm in width and 100 mm in length is inserted into the conductor layer of the circuit board by using a cutter, and one end is peeled off to remove the handle (Kaisha Shi, S, E, Autocom Tester AC-50C-SL). The load at the time of peeling 35 mm in the vertical direction at the speed of 50 mm / min was measured at room temperature. When the load is 0.75 kgf / cm or more, "◎" is used, when 0.72 kgf / cm or less is 0.62 kgf / cm or more "○", and when 0.62 kgf / cm or less is 0.40 kgf / cm or more, it is set as "△". , The case of less than 0.40 kgf / cm was evaluated as "x".

<Measurement and Evaluation of Surface Roughness (Ra Value) After Harmonization>

Using a non-contact surface roughness meter (WYKO NT3300, manufactured by Vico Instruments), the numerical value obtained by measuring the measurement range as 121 micrometers x 92 micrometers by VSI contact mode and a 50x lens was measured. And it was set as Ra value by calculating | requiring the average surface roughness of 10 points. When Ra value is 500 nm or more, it is set as "xx", when less than 500 nm is 420 nm or more, and when less than 420 nm is 380 nm or more, when it is less than 380 nm and 300 nm or more Was made into "(circle)", the case below 300 nm and 200 nm or more was made into "(◎)", and the case below 200 nm was evaluated as "(◎)".

Table 1 below shows the results of the peel strength and surface roughness (Ra value) of the plated conductor layer of the evaluation sample using the varnish obtained in the examples and the comparative examples. As is clear from Table 1, in the resin composition of the Example, although the surface roughness of the insulating layer was low, the conductor layer which has high peeling strength was formed. Thus, in this invention, since low surface roughness is achieved, it turns out that it is advantageous for fine wiring. In Comparative Example 1, in which a quaternary phosphonium-based curing accelerator was not added, roughness for obtaining equivalent peel strength was increased. In Comparative Example 2, an amine curing agent was used, but the result was that the roughness was also increased. In Comparative Examples 3 and 4, the same triphenylphosphine-based curing accelerator was used as the curing accelerator. However, in comparison with the examples, compatibility of low light and high peel was not achieved.

TABLE 1

Industrial availability

Even if the roughness of the surface of the insulating layer obtained by hardening a resin composition was low, the resin composition, adhesive film, prepreg, and multilayer printed wiring board in which the conductor layer which has high peeling strength can be formed can be provided. In addition, electric appliances such as computers, cellular phones, digital cameras, and televisions mounted thereon, and vehicles such as motorcycles, automobiles, trams, ships, and aircrafts can be provided.

Claims (9)

(A) polyfunctional epoxy resin, (B) phenolic curing agent and / or active ester curing agent, (C) thermoplastic resin, (D) inorganic filler, (E) tetrabutylphosphonium decanoate, (4-methylphenyl) tri A resin composition containing at least one quaternary phosphonium-based curing accelerator selected from phenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyl triphenylphosphonium thiocyanate. The said component (E) in Claim 1 whose ratio of the mass of the said component (E) with respect to the total mass of the non volatile matter of the said component (A) and the said component (B) becomes 100: 0.05-100: 2. Resin composition containing). The component (B) according to claim 1 or 2, wherein the proportion of the epoxy group present in the resin composition and the reactor of the curing agent of the component (B) is 1: 0.3 to 1: 1 in molar ratio. Resin composition. The resin composition of any one of Claims 1-3 whose content of the said component (C) is 1-20 mass% when the non volatile matter of the said resin composition is 100 mass%. The resin composition of any one of Claims 1-4 whose content of the said component (D) is 10-70 mass% when the non volatile matter of the said resin composition is 100 mass%. The peeling strength is 0.4 kgf / cm-2 kgf / cm, and surface roughness is 30 nm-400 nm, The resin composition of any one of Claims 1-5 characterized by the above-mentioned. The adhesive film in which the resin composition in any one of Claims 1-6 is layered on a support body. The prepreg in which the resin composition in any one of Claims 1-6 is impregnated in the sheet-like fiber base material. The circuit board in which the insulating layer is formed of the hardened | cured material of the resin composition of any one of Claims 1-6.