KR101203156B1 - Epoxy resin composition, an adhesive film and a multi-layered printed circuit board prepared by using the same - Google Patents

Abstract

The present invention relates to an epoxy resin composition comprising a mixture of a phenoxy resin and a rubber-modified epoxy resin and a polyfunctional acid anhydride curing agent as a roughening agent having excellent surface anchor formation, and an epoxy resin composition having high heat resistance and high peel strength properties, and using the same. It relates to an adhesive film and a multilayer printed wiring board produced by.

Phenoxy resin, rubber modified epoxy resin, polyfunctional acid anhydride, epoxy resin, heat resistance, peel strength, multilayer printed wiring board

Description

Epoxy resin composition, an adhesive film and a multi-layered printed circuit board prepared by using the same}

The present invention relates to an epoxy resin composition, and an adhesive film and a multilayer printed wiring board manufactured using the same. More specifically, the present invention relates to an epoxy resin composition having high heat resistance and high peel strength properties, including a roughening agent having excellent surface anchor formation and a polyfunctional acid anhydride curing agent, and an adhesive film and a multilayer printed wiring board manufactured using the same. will be.

In general, a multi-layered printed circuit board includes a plurality of prepreg sheets obtained by impregnating a glass cross substrate with an epoxy resin and semi-cured on an inner layer circuit board on which a circuit is formed, and overlapping copper foil thereon. It is manufactured by the process of heating, pressurizing, and shape | molding by a hotplate press. However, the use of prepreg sheets containing glass crosses leads to an increase in the cost of wiring board manufacture, the problem of peeling or cracking at the interface of the glass crosses, the thickness between the circuit layers is regulated by the glass crosses, and multilayered printing There existed a problem that ultrathinning of the whole wiring board was difficult.

In order to solve this problem, a build-up method for manufacturing a substrate by alternately stacking an organic insulating layer on a conductor layer of an inner circuit board has been proposed.

In Japanese Patent Laid-Open Nos. 7-304931 and 7-304933, an epoxy resin composition is applied to a circuit-formed inner layer circuit board, an anchor is formed on the surface by a roughening agent after heat curing, and a multilayer printed wiring board is formed by a plating method. A manufacturing method is disclosed. In the epoxy resin composition used at this time, an amine curing agent such as a dicyandiamide or an imidazole compound has been generally used as the curing agent. However, in recent years, a curing agent excellent in heat resistance with an increase in mounting density has become preferred.

Accordingly, Japanese Laid-Open Patent Publication No. 2003-127313 proposes an epoxy resin composition for an interlayer insulating material in which a triazine structure-containing phenol-based curing agent is used, and high heat resistance and compatibility with an oxidizing agent are achieved. However, in the case of such a composition, the heat resistance was improved, but a good roughening surface was not obtained, and the peel strength with the conductor layer was weak.

The present invention is to provide an epoxy resin composition for producing a multilayer printed wiring board having high heat resistance and high peel strength and an adhesive film comprising the same.

The inventors of the present invention continued to manufacture a multilayer printed wiring board having high heat resistance and high peel strength, and as a result, an epoxy resin composition was prepared by using a roughening agent composed of a phenoxy resin and a rubber-modified epoxy resin and a polyfunctional acid anhydride curing agent. The present invention has been found to have a high glass transition temperature and peel strength due to its excellent harmonic properties, thus completing the present invention.

In the present invention, by using an epoxy resin composition having a high glass transition temperature and peel strength, including a roughening agent composed of a mixture of a phenoxy resin and a rubber-modified epoxy resin and a polyfunctional acid anhydride curing agent, excellent heat resistance and peel strength are achieved. It has the effect of providing the adhesive film for multilayer printed wiring boards, and a multilayer printed wiring board.

The present invention provides an epoxy resin composition comprising a roughening agent composed of a polyfunctional epoxy resin, a phenoxy resin and a rubber-modified epoxy resin, a polyfunctional acid anhydride, and a curing accelerator.

In one embodiment of the present invention, (A) 20 to 40 parts by weight of polyfunctional epoxy resin, (B) phenoxy resin and rubber modified epoxy resin 30 to 60 parts by weight, (C) 20 to 50 parts by weight of polyfunctional acid anhydride And (D) provides an epoxy resin composition comprising 0.1 to 5 parts by weight of the curing accelerator.

Below, the structural component of a resin composition is demonstrated more concretely.

(A) polyfunctional epoxy resin

Polyfunctional epoxy resins are thermosetting resins having excellent electrical, thermal properties, and chemical stability, including, but not limited to, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, and cresol furnaces. As at least one epoxy compound selected from the group consisting of a ballolac epoxy resin, an alkylphenol novolac epoxy resin, a bisphenol epoxy resin, a naphthalene epoxy resin, a dicyclopentadiene epoxy resin, triglycidyl isocyanate and acyclic epoxy resin, Preferably, the weight average molecular weights 200-2,000 can be used. Specific examples of the commercially available Zepen Epoxy Resin Co., Ltd. Epicoat 152, 154, 828, YX-4000, Dainippon Ink Chemical Co., Ltd. Epikron N-660, N-673, N-695, Kukdo Chemical Co., Ltd. YDCN -500-4P, YDCN-638, YH-300, YH-325 and the like.

The polyfunctional epoxy resin is used in the range of 20 to 40 parts by weight, but if the content is less than 20 parts by weight, heat resistance, chemical resistance, and electrical properties are insufficient, and if it exceeds 40 parts by weight, flame retardancy and adhesion decrease.

(B) phenoxy resin and rubber modified epoxy resin

The phenoxy resin and the rubber-modified epoxy resin according to the present invention have good adhesion as well as chemical resistance and solvent resistance as roughening components that are soluble or decomposed in an aqueous solution of an oxidizing agent. In particular, the phenoxy resin not only improves the mechanical strength of the cured coating film, but also facilitates the control of the resin melt viscosity of the adhesive film, and exhibits an effect of preventing cratering.

The phenoxy resin may be prepared by reacting a bifunctional epoxy resin with bisphenol S or by reacting a bisphenol S-type epoxy resin with bisphenol, preferably having a weight average molecular weight of 10,000 to 70,000. In particular, in the case of the phenoxy resin produced by reacting a biphenyl type bifunctional epoxy resin with bisphenol S, not only the glass transition point is high but also a dense roughened surface is most preferable. Specific examples of the phenoxy resin include bisphenol A epoxy resin (Dongdo Chemical Co., Ltd. YP-50, YP-70, YP-50-EK35, ZX-1356-2) and biphenyl type epoxy resin (Zeppen Epoxy Resin Co., Ltd.). YX-4000, YX-4000H), YX-6954BH30, YL-6746H30, YL-6747H30, InChemRez Co., Ltd. PKHH, PKHJ, PKHB etc. which are phenoxy resins which consist of reaction products with a bisphenol compound.

The rubber-modified epoxy resin is a resin selected from polybutadiene rubber, rubber-modified epoxy resin, or urethane-modified epoxy resin, and preferably has a weight average molecular weight of 500 to 10,000. Examples of the rubber-modified epoxy resin include polybutadiene rubber (R-45EPI and R-45HT of Idemis Petrochemical Co., Ltd.), PB3600, PB4700, D.C. Co., Ltd., and rubber modified epoxy resin (Kukdo Chemical Co., Ltd. KR-207). And KR-208, KR-909) and urethane-modified epoxy resins (Kukdo Chemical Co., Ltd. UME-305, UME-330).

In the present invention, high peel strength is obtained by appropriately adjusting the contents of the phenoxy resin and the rubber-modified epoxy resin. In the present invention, the ratio of the phenoxy resin and the rubber-modified epoxy resin is preferably 1: 0.2 to 2 by weight. If the ratio of the rubber-modified epoxy resin is too high, the roughness of the surface becomes large and a uniform roughening surface cannot be obtained.

Phenoxy resin and rubber-modified epoxy resin are used in the resin composition of 30 to 60 parts by weight. If the content is less than 30 parts by weight, the heat resistance or mechanical strength is lowered. If the content exceeds 60 parts by weight, the resin varnish itself causes phase separation or thermal fluidity. It is not desirable to get worse.

(C) polyfunctional acid anhydrides

The polyfunctional acid anhydride according to the present invention is selected from pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitic anhydride, glycerol tris trimellitic anhydride, and maleic methylcyclohexene tetracarboxylic anhydride As a hardening | curing agent used, Preferably the weight average molecular weights are 170-17,000. Specific examples include pyromellitic dianhydride (PMDA), benzophenon tetracarboxylic dianhydride (BTDA), ethylene glycol bis-trimellitic dianhydride (TMEG), glycerin tris-trimellitic dianhydride (TMTA), and MCTC (5- (2,5-dioxotetrahydropryle) -3-methyl -3-cyclohexene-1,2-dicarboxylic anhydride), TDA ((2,5-dioxotetranhydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride), zefen epoxy resin (Note YH-308, and the like.

In the present invention, heat resistance, electrical insulation, and mechanical strength can be improved by using a polyfunctional acid anhydride. 20 to 50 parts by weight of the polyfunctional acid anhydride is included in the resin composition, but if the content of the polyfunctional acid anhydride is less than 20 parts by weight, the heat resistance is lowered, and if it exceeds 50 parts by weight, the unreacted active hydrogen group remains and the insulation is lowered. do.

The amount of the curing agent depends on the type and the amount of use of the epoxy resin, it is added to the equivalent relative to the epoxy resin.

(D) curing accelerator

The curing accelerator according to the present invention is imidazole such as 2-methyl imidazole, 2-ethyl-4-methyl imidazole, benzyl dimethyl amine, 1,8-diazabicyclo (5,4,0) undecene- Amines such as 7, organic phosphines such as phenyl phosphine and tetraphenylborate are used.

In addition to the said essential components (A)-(D), one or more of the usual additives can be mix | blended with the resin composition of this invention to an appropriate content in the range which does not impair the effect of this invention.

Typical additives include, for example, silica, alumina, barium sulfate, talc, mud, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, calcium titanate, Inorganic fillers such as magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, organic fillers such as silicon powder, nylon powder, fluorine powder, thickeners such as asbestos, orbene, benton, silicone, fluorine, polymer Adhesion-providing agents, such as a defoaming agent of a type | system | group, a leveling agent, an imidazole type, a dental zortho type, a triazole type, and a silane coupling agent, etc. are mentioned.

Preparation of Adhesive Film

Another aspect of the present invention is an adhesive film formed by dissolving the epoxy resin composition according to the present invention in an organic solvent, applying it on a support base film, and then drying the solvent by hot air to provide an adhesive film suitable for a printed wiring board. It is.

Organic solvents include ketones such as acetone, methanol, ethanol, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, aromatic hydrocarbons such as toluene and xylene, dimethyl formamide, dimethyl One or two or more organic solvents selected from acetamide and N-methyl pyrrolidone can be used in combination.

Examples of the supporting base film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonates, and polyimides.

In one embodiment of the present invention, the epoxy resin composition according to the present invention dissolved in an organic solvent is formed on a support base film having a thickness of 10 to 100 µm to a thickness in the range of 10 to 100 µm. At this time, if the thickness of the epoxy resin composition layer is too thin, a good peel value cannot be obtained, and if it is too thick, there is a problem that the electric capacity falls. If the amount of residual solvent in the resin layer after drying is too small, the flexibility of the film may be inferior and cracks may occur in the resin portion, and if the amount is too high, voids are generated in the resin when heat curing is performed in the presence of the supporting base film. There is a case. In general, the residual solvent amount of the resin layer after drying is preferably 5% by weight or less based on the total weight of the resin composition.

It is preferable to further laminate | stack a 10-50 micrometers protective film on the other surface of a crude resin layer, wind up, and store on a roll.

Fabrication of Multilayer Printed Wiring Boards

Another aspect of the present invention is to provide a multilayer printed wiring board made from the epoxy resin composition according to the present invention.

According to the present invention, the step of forming an epoxy resin composition according to the present invention as a resin layer on the copper foil layer material formed with an inner layer circuit and thermosetting; Forming a roughened surface on the surface of the resin layer by roughening treatment with an aqueous solution of an oxidizing agent; And forming a conductor layer on the roughened surface to manufacture a multilayer printed wiring board.

In one embodiment, the protective film is removed from the adhesive film formed from the epoxy resin composition according to the present invention and then laminated to the circuit processed circuit board under pressure and heating. The lamination step is a step of laminating under reduced pressure at a compression temperature of 80 to 130 ° C. and a compression pressure of 1 to 10 kgf / cm 2. The circuit board on which the adhesive film is laminated is cooled to around room temperature, the supporting film is peeled off, and then heat cured to form an insulating layer. Heat curing takes place for 30 minutes to 120 minutes at a temperature of 150 ° C to 200 ° C.

After heat-hardening, it drills in the insulating layer formed on a circuit board, and then forms a via hole and a through hole. Although drilling can be performed by well-known methods, such as a drill, a laser, and a plasma, for example, drilling by a laser is most preferable.

Then, the surface of the insulating layer is subjected to a roughening treatment with an oxidizing agent. At this time, if necessary, physical polishing may be performed to stabilize the adhesiveness before the roughening treatment. Examples of the oxidizing agent include sodium permanganate (such as potassium permanganate and sodium permanganate), dichromate, ozone, hydrogen peroxide / sulfuric acid and acetic acid.

Thereafter, the conductor layer is formed on the surface of the adhesive film layer on which the uneven anchor is formed by roughening treatment by electroless plating and electrolytic plating. As a pattern formation method after that, a well-known subtractive method, a semiadditive method, etc. can be used specifically ,. After forming the conductor layer, the annealing treatment may be performed at 150 to 200 ° C. for 20 to 90 minutes to further improve the peel strength of the conductor layer.

Hereinafter, the present invention will be described in detail with reference to Examples, but the following Examples are only intended to illustrate the present invention, and thus the scope of the present invention is not limited thereto.

Example

<Examples 1-4>

According to the composition described in Examples 1 to 4 of Table 1, an epoxy resin composition was prepared by the following method: After dissolving the epoxy resin in a methyl ethyl ketone solvent, each component was uniformly mixed in a resolver. Resin varnishes were prepared. The resin varnish was applied on a polyethylene terephthalate film having a thickness of 38 μm in a comma coater so as to have a thickness of 35 μm, and dried at 100 ° C. for 10 minutes to obtain an adhesive film. The circuit board was laminated with a vacuum laminator. After curing at 160 ° C. for 60 minutes, it was roughened with potassium permanganate, and then a conductor layer of about 25 microns was formed by electroless plating and electroplating.

After annealing the prepared specimens for 60 minutes at 180 ° C., the glass transition temperature and peel strength were measured, and the results are shown in Table 2.

How to measure property

Tg: glass transition temperature (TMA method)

Peel Strength: JIS-C-6481 (N / cm)

<Comparative Example 1-4>

Epoxy resin compositions were prepared according to the compositions described in Comparative Examples 1-4 of Table 1. Preparation of the specimen using the resin composition and measurement of the physical properties were carried out according to Examples 1 to 4 and the results are shown in Table 2.

Table 1

Furtherance Example Comparative example One 2 3 4 One 2 3 4 (A) component KDP-540 15 10 30 15 30 YH-300 20 30 20 20 20 EP-828 10 15 25 15 10 EPPN-520H 25 Component (B) YL6954BH30 20 40 20 10 YP-70 20 35 25 20 R-45 EPT 10 15 10 25 10 40 YPB40-PXM40 50 PES5003P 50 (C) Component PMDA 20 BTDA 18 25 25 TMEG 20 TMTA 20 20 MCTC 15 YH-308 10 15 15 10 YLH-808 40 TD-2090-60M 90 (D) component 1,8-ziazabicyclo (5,4,0) undecene-7 One 2E4MZ 0.5 0.5 0.5 0.5 0.5 0.5 0.5

(Content unit: parts by weight)

KDP-540: Kukdo Chemical Co., Ltd., Multifunctional Flame Retardant Epoxy Resin

YH-300: Kukdo Chemical Co., Ltd., polyfunctional epoxy resin

EP-828: Zefen Epoxy Resin, Bisphenol A Type Epoxy Resin

N-690: Nippon Ink Chemical Co., Ltd., cresol novolac type epoxy resin

EPPN-502H: Nippon Kayaku Co., Ltd., trisphenol type epoxy resin

YL6954BH30: ZEPPEN Epoxy Resin Co., Ltd., biphenyl type phenoxy resin

YP-70: Dongdo Chemical Co., Ltd., phenoxy resin

R-45 EPT: Nagase Chemical Co., Ltd., rubber modified epoxy resin

YPB40-PXM40: Toto Hwasung Co., Ltd., canceled phenoxy resin varnish

PES5003P: Sumimoto Chemical Industries Co., Ltd., Polyether Sulfone Varnish

PMDA: Misumibi Gas Chemical Co., Ltd., pyromellitic anhydride

BTDA: Daicel Chemical Co., Ltd., benzophenone tetracarboxylic anhydride

TMEG: Nippon Ewha Co., Ltd., ethylene glycol bis trimellitic anhydride

TMTA: Nippon Ewha Co., Ltd., Glycerol Tris Trimellitic Anhydride

MCTC: Japan Ink Chemical Industry Co., Ltd., maleic methylcyclohexene tetracarboxylic anhydride

YH-308: Zefen epoxy resin Co., Ltd., trialkyl tetrahydrophthalic anhydride

YLH-808: Acetylated Modified Product of Zefen Epoxy Resin Co., Ltd., Phenol Novolak Resin

TD-2090-60M: Nippon Ink Chemical Co., Ltd., phenol novolak resin varnish

2E4MZ: Japan Chrysanthemum Co., Ltd., 2-ethyl-4-methyl imidazole

Table 2

Example Comparative example One 2 3 4 One 2 3 4 Tg (占 폚) 198 205 190 187 152 185 190 172 Peel Strength (N / cm) 13 14 16 11 8 7 7 9

As can be seen in Table 2, the specimen prepared by using the epoxy resin composition according to the present invention of Examples 1 to 4 exhibits high glass transition temperature and good peel strength, and thus has high heat resistance and high peeling strength due to roughening. It is possible to form a conductor layer. However, the epoxy resin composition of Comparative Example 1 obtained according to Japanese Patent Application Laid-Open No. 2003-127313 had both a low glass transition temperature and a peel strength, and in the case of Comparative Examples 2 to 4 outside the composition range of the present invention, a low glass transition temperature or There was a problem of low peel strength.

Claims (8)

In order to give favorable roughening property to the surface which apply | coated and hardened the epoxy resin composition on the board | substrate, the roughening agent which mixed the polyfunctional epoxy resin, the phenoxy resin, and the rubber modified epoxy resin, a polyfunctional acid anhydride, and a hardening accelerator As an epoxy resin composition comprising The phenoxy resin is a resin prepared by reacting bifunctional epoxy resin with bisphenol S or a resin produced by reacting bisphenol S type epoxy resin with bisphenol, and the rubber modified epoxy resin is made of polybutadiene rubber or urethane modified epoxy resin. The resin is selected and the roughening agent comprises a phenoxy resin to a rubber modified epoxy resin in a weight ratio of 1: 0.2 to 2, The polyfunctional acid anhydride is selected from the group consisting of pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitic anhydride, glycerol tris trimellitic anhydride, and maleicmethylcyclohexene tetracarboxylic anhydride It is more than one kind, The polyfunctional epoxy resin is 20 to 40 parts by weight, The roughening agent which is a mixture of the phenoxy resin and the rubber-modified epoxy resin is 30 to 60 parts by weight, The polyfunctional acid anhydride is 20 to 50 parts by weight, The curing accelerator is 0.1 to 5 parts by weight of the epoxy resin composition. delete delete delete The method of claim 1, wherein the silica, alumina, barium sulfate, talc, mud, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, calcium titanate, magnesium titanate, At least one inorganic filler selected from the group consisting of bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate; At least one organic filler selected from the group consisting of silicone powder, nylon powder, and fluorine powder; One or more thickeners selected from the group consisting of asbestos, orbene, and benton; Epoxy further comprising at least one additive selected from at least one adhesion imparting agent selected from the group consisting of silicone-based, fluorine-based, anti-foaming agents, leveling agents, imidazole-based, dental-based, triazole-based, and silane coupling agents Resin composition. An adhesive film formed by applying the epoxy resin composition according to claim 1 on a support base film. Forming an epoxy resin composition according to claim 1 as a resin layer on a copper foil layer material having an inner layer circuit and thermally curing the epoxy resin composition; Forming a roughened surface on the surface of the resin layer by roughening treatment with an oxidizing agent aqueous solution; And Forming a conductor layer on the roughened surface: Method of manufacturing a multilayer printed wiring board comprising a. The multilayer printed wiring board obtained by hardening the epoxy resin composition of Claim 1.