JPH09307240A - Manufacture of multilayer wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayer wiring board having heat resisting property, moisture resisting property and close contact property without using a halogen as a non-flammable method and without generation of hydrogen bromide, which is poisonous gas, when a burning operation is conducted. SOLUTION: In the manufacturing method of a multilayer wiring board using a build-up method, a process in which a red phosphorus containing photosensitive resin composition is formed at least on one surface of an inner layer wiring board where a non-halogen containing resin composition is used, and a process in which a wiring pattern is formed on the layer insulating film by etching a conductive layer after formation of a conductive layer by non- electrolytic plating and electric plating, are repeated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention does not use halogen as a flame-retardant technique and provides a plurality of layers of conductor patterns on an insulating substrate without generating hydrogen bromide which is a toxic gas during flame retardation. And a method for manufacturing a multilayer wiring board.

[0002]

2. Description of the Related Art The flame-retardant regulation required for electric and electronic parts is shifting to low pollution, low toxicity, and safety along with global environmental problems and increasing concern about human safety. In addition to being difficult to burn, there is a growing demand for reducing toxic gases and fumes.

Even in the multilayer printed wiring board by the built-up method, most of the halogen-containing substances used as flame retardants are bromine-based and tetrabromobisphenol A.
Derivatives centered on (such as brominated epoxy resin) are widely used. Therefore, the demand for dehalogenation is increasing. Examples of non-halogen flame retardants include nitrogen-based, phosphorus-based, and inorganic compounds. When used as a raw material for printed wiring boards, nitrogen-based compounds generally affect the effect of resin curing and phosphorus-based compounds. However, it is difficult to put it into practical use because of problems such as reduced moisture resistance.

[0004]

SUMMARY OF THE INVENTION The object of the present invention was made in view of the above-mentioned circumstances. It does not use halogen as a flame retardant method and produces hydrogen bromide which is a toxic gas during combustion. The present invention intends to provide a built-up multilayer wiring board having excellent heat resistance, moisture resistance, and adhesiveness.

[0005]

As a result of intensive research aimed at achieving the above object, the inventors of the present invention did not use halogen as a flame retardant for an interlayer insulating film, and did not use a phosphorus-based compound as a flame retardant. Use phosphorus. In particular, the inventors have found that the above-mentioned object of the built-up multilayer wiring board can be achieved by using an inorganic filler together, and completed the present invention.

That is, according to the present invention, in a method for manufacturing a multilayer wiring board by a built-up method, a photosensitive layer containing red phosphorus for interlayer insulation is provided on at least one surface of an inner layer wiring board using an epoxy resin composition containing no halogen. A multi-layer characterized by repeating a step of forming a resin composition and a step of forming a conductor layer by electroless plating and electroplating on the interlayer insulating film and then etching the conductor layer to form a wiring pattern. It is a method of manufacturing a wiring board. Also,
A method for producing a multilayer wiring board, wherein an epoxy resin composition containing red phosphorus is also used as the epoxy resin composition of an inner layer wiring board.

The present invention will be described in detail below.

The epoxy resin composition used in the present invention is
(A) epoxy resin, (B) curing agent, (C) curing accelerator, (D) red phosphorus, (E) inorganic filler as essential components,
The red phosphorus of (D) is added to the entire resin composition in an amount of 0.5 to
The content is 20% by weight. Each of these components will be described.

The epoxy resin (A) is not particularly limited and can be widely used as long as it can be usually used for laminated boards. Specific examples include glycidyl ether type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolac epoxy resin, or glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, and complex. Examples thereof include cyclic epoxy resins, and these epoxy resins can be used alone or in combination of two or more kinds.

The curing agent (B) is not particularly limited as long as it is one usually used as a curing agent for epoxy resins. Examples of amine curing systems include dicyandiamide and aromatic amines, and examples of phenol curing systems include phenol novolac resins, cresol novolac resins, and bisphenol A type novolac resins. These may be used alone or in combination of two or more. be able to.

The (C) curing accelerator may be any one usually used as a curing accelerator for epoxy resins,
There is no particular limitation. Specific examples include 2-ethyl-4-methylimidazole and 2-phenyl-
Examples include imidazole derivatives such as 4-methylimidazole and 2-methylimidazole, cyanoethyl compounds thereof, azine compounds, benzyldimethylamine, 1,8-diazabicyclo (5,4,0) undecene, etc. A mixture of two or more species can be used.

As the red phosphorus (D), in addition to using red phosphorus alone, inorganic compounds such as aluminum hydroxide, magnesium hydroxide and titanium oxide are dispersed or coated in red phosphorus, or red phosphorus is a resin. Examples thereof include coated materials, and these may be used alone or in combination of two or more kinds. It is desirable to mix the red phosphorus so that it is contained in an amount of 0.5 to 20% by weight of the entire resin composition. If the blending amount is less than 0.5% by weight,
Insufficient flame retardancy and adhesion are not obtained, and 20% by weight
If it exceeds the range, the electrical characteristics deteriorate, which is not preferable.

Examples of the inorganic filler (E) include talc, silica, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate and the like.
A mixture of two or more species can be used. It is desirable to mix the inorganic filler so as to be contained in a proportion of 10 to 50% by weight based on the total resin composition. The amount
If it is less than 10% by weight, sufficient flame retardance, heat resistance and moisture resistance cannot be obtained, and if it exceeds 50% by weight, the resin viscosity increases,
It is not preferable because coating unevenness occurs, resulting in voids and defective plate thickness.

The epoxy resin composition comprises (A) epoxy resin, (B) curing agent, (C) curing accelerator, (D) red phosphorus,
(E) An inorganic filler is used as an essential component, but other components such as a color pigment, a defoaming agent, a leveling agent, and an antioxidant are added and blended as necessary within the range not deviating from the object of the present invention. be able to.

This epoxy resin composition is used as an epoxy resin varnish, which is applied, impregnated and dried on a glass cloth or a glass non-woven fabric to form a prepreg. A copper foil is laminated on at least one surface of a plurality of the prepregs and integrally molded by heating and pressuring to manufacture a glass epoxy laminate. A circuit is formed on the copper foil surface of this laminate to form an inner layer substrate.

The photosensitive resin composition used in the present invention is
(1) Epoxy acrylate resin, (2) Diluent,
(3) sensitizer, (4) epoxy resin, (5) curing agent,
(6) Curing accelerator, (7) Red phosphorus, (8) Inorganic filler are essential components, and 0.5 to 20% by weight of the above-mentioned (7) red phosphorus is contained in the whole photosensitive resin composition. It is contained. Each of these components will be described.

(1) As the epoxy acrylate resin, a reaction of an epoxy resin with an unsaturated monocarboxylic acid or a reaction of an epoxy resin with an unsaturated monocarboxylic acid and further addition of a polybasic acid anhydride The product is not particularly limited and can be widely used as long as it is a product. These epoxy acrylate resins can be used alone or in combination of two or more.

(2) The diluent may be an unsaturated compound having at least two ethylene bonds in the molecule, an organic solvent and the like, and is not particularly limited and can be widely used.

(3) The sensitizer is not particularly limited as long as it is a compound usually used for photocuring an epoxy acrylate resin. Specific sensitizers include, for example, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, p-phenylbenzophenone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-Isopropylthioxanthone, benzoin ethyl ether and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

(4) Epoxy resin, (5) Curing agent,
Regarding (6) curing accelerator, (7) red phosphorus, and (8) inorganic filler, (A) epoxy resin, (B) curing agent, (C) curing accelerator, which are components of the epoxy resin composition described above. , (D) red phosphorus, and (E) inorganic filler can be used.

The photosensitive resin composition used in the present invention is
(1) Epoxy acrylate resin, (2) Diluent,
(3) sensitizer, (4) epoxy resin, (5) curing agent,
(6) Curing accelerator, (7) Red phosphorus, (8) Inorganic filler as essential components, but other components such as a color pigment, a defoaming agent, and a leveling agent within the range not deviating from the object of the present invention. An antioxidant and the like can be added and blended as necessary.

A photosensitive resin composition for interlayer insulation is formed into a film on at least one surface of the above-mentioned circuit-formed inner layer substrate,
A via hole necessary for interlayer connection is formed through UV exposure and development treatment, and subsequently, heat curing treatment, surface roughening treatment, electroless plating and electroplating are performed to form a conductor layer and a wiring pattern. A multilayer wiring board can be manufactured by repeating the steps of forming a conductive layer by electroless plating and electroplating a film of a photosensitive resin composition and forming a wiring pattern.

Since the present invention does not use any halogen compound as a flame retardant method, it does not generate hydrogen bromide, which is a toxic gas at the time of combustion, and is excellent in heat resistance, moisture resistance and adhesion. It has become possible to manufacture a multilayer wiring board by the up method.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be specifically described with reference to Examples. The present invention is not limited by these examples. In the following Examples and Comparative Examples,
"Parts" means "parts by weight".

Example 1 Epoxy acrylate resin (Novolak K-48C,
Acid value 63, solid content 60 parts by weight 100 parts, epoxy resin (CN
E200EL, epoxy equivalent 200) 40 parts, trimethylolpropane triacrylate 10 parts, Irger Cure 9
07 (manufactured by Ciba Geigy, trade name) 8 parts, dicyandiamide 1 part, 2-ethyl-4-methylimidazole 0.25 part,
Barium sulfate 10 parts, aluminum hydroxide 10 parts, red phosphorus (phenol resin coating, red phosphorus content 85% by weight) 25 parts were mixed and further uniformly mixed with a three-roll mill to produce a photosensitive resin composition. .

Next, a glass-based epoxy resin copper-clad laminate TLC-7 using red phosphorus as a flame retardant for the inner layer substrate.
51 TRG (Toshiba Chemical Co., Ltd., trade name) was prepared, and a solution of the above-mentioned photosensitive resin composition was applied by screen printing to a film thickness of 60 μm on the inner layer substrate on which a circuit was formed. The inner layer substrate coated with the photosensitive resin composition is dried by a hot air circulation dryer at 80 ° C for 25 minutes, the organic solvent is volatilized, and then UV irradiation with an exposure amount of 300 mJ is performed through a desired pattern mask, and 1% carbon dioxide is added. Sodium (30 ℃, spray pressure 1.0kg
/ Cm @ 2) for 60 seconds. Then, it was dried for 60 minutes with a hot air circulation dryer at 150 ° C. to obtain a resin film.

After that, the resin coating was buffed, etched with a potassium permanganate solution, and electroless copper plated and electrolytic copper plated to form a conductor layer. Next, the conductor layer was patterned by etching to produce a multilayer wiring board.

Example 2 Epoxy acrylate resin (Novolak K-48C,
Acid value 63, solid content 60% by weight) 100 parts, epoxy resin (CN
E200EL, epoxy equivalent 200) 40 parts, trimethylolpropane triacrylate 10 parts, Irger Cure 9
07 (manufactured by Ciba Geigy, trade name) 8 parts, dicyandiamide 1 part, 2-ethyl-4-methylimidazole 0.25 part,
Barium sulfate 10 parts, aluminum hydroxide 10 parts, red phosphorus (phenol resin coating, red phosphorus content 85% by weight) 50 parts were mixed and further uniformly mixed with a three-roll mill to produce a photosensitive resin composition. . Then, a multilayer wiring board was manufactured in the same manner as in Example 1.

Example 3 Epoxy acrylate resin (triphenol methane type T
CR1025, acid value 103, solid content 60% by weight) 100 parts, epoxy resin (CNE200EL, epoxy equivalent 200) 40
Part, trimethylolpropane triacrylate 10 parts, Irger Cure 907 (manufactured by Ciba Geigy, trade name) 8
Part, dicyandiamide 1 part, 2-ethyl-4-methylimidazole 0.25 part, barium sulfate 10 parts, aluminum hydroxide 10 parts, red phosphorus (phenol resin coating, red phosphorus content
85 parts by weight) was mixed and further uniformly mixed with a three-roll mill to produce a photosensitive resin composition. Then, a multilayer wiring board was manufactured in the same manner as in Example 1.

Comparative Example 1 Epoxy acrylate resin (Novolak K-48C,
Acid value 63, solid content 60% by weight) 100 parts, brominated epoxy resin (BREN-S, epoxy equivalent 285) 60 parts, trimethylolpropane triacrylate 10 parts, Irger Cure 907 (Ciba Geigy, trade name) 8 Part, dicyandiamide 1 part, 2-ethyl-4-methylimidazole 0.25
Parts, 10 parts of barium sulfate and 20 parts of aluminum hydroxide were mixed, and further uniformly mixed with a three-roll mill to produce a photosensitive resin composition.

Next, a glass substrate epoxy resin copper clad laminate TLC using a brominated epoxy resin for the inner layer substrate.
-751 (manufactured by Toshiba Chemical Co., Ltd., trade name) was prepared, and the solution of the above-mentioned photosensitive resin composition was applied to a circuit-formed inner layer substrate by screen printing to a film thickness of 60 μm. afterwards,
A multilayer wiring board was manufactured in the same manner as in Example 1.

Comparative Example 2 Epoxy acrylate resin (Novolak K-48C,
Acid value 63, solid content 60% by weight) 100 parts, epoxy resin (CN
E200EL, epoxy equivalent 200) 40 parts, trimethylolpropane triacrylate 10 parts, Irger Cure 9
07 (manufactured by Ciba Geigy, trade name) 8 parts, dicyandiamide 1 part, 2-ethyl-4-methylimidazole 0.25 part,
Mix 10 parts of barium sulfate and 20 parts of aluminum hydroxide,
Further, the mixture was uniformly mixed with a three-roll mill to produce a photosensitive resin composition. Then, a multilayer wiring board was manufactured in the same manner as in Comparative Example 1.

Table 1 shows the characteristic evaluation results of the multilayer wiring boards manufactured in Examples 1 to 3 and Comparative Examples 1 and 2. In all cases, the present invention was excellent, and the effects of the present invention could be confirmed.

[0034]

[Table 1] * 1: Measured according to UL-94 flame retardancy test. * 2: The adhesion between the plated conductor layer and the photosensitive resin composition layer was measured according to JIS-C-6481. * 3: Thermal deterioration conditions, 180 ° C, 200 hours. * 4: A ... Boiled for 4 hours, B ... 120 ° C, steam at 2 atm for 2 hours. After the treatment of A or B, it was immersed in a solder bath at 260 ° C. for 30 seconds and observed for blisters. ◎: No blisters, ○: Some blisters, △: Most blisters. * 5: Measured according to JIS-C-6481.

[0035]

As is apparent from the above description and Table 1, according to the method for manufacturing a multilayer wiring board of the present invention, since it does not contain a halogen compound, no toxic gas is generated during combustion, heat resistance, It is possible to manufacture a multilayer wiring board having excellent moisture resistance, adhesion, and flame retardancy.

Claims (2)

[Claims] 1. A method for manufacturing a multilayer wiring board by a build-up method, wherein a photosensitive resin composition containing red phosphorus for interlayer insulation is provided on at least one surface of an inner layer wiring board using a halogen-free epoxy resin composition. Manufacture of a multilayer wiring board characterized by repeating a step of forming a film and a step of forming a conductor layer by electroless plating and electroplating on the interlayer insulating film and then etching the conductor layer to form a wiring pattern Method. 2. The method for producing a multilayer wiring board according to claim 1, wherein an epoxy resin composition containing red phosphorus is used as the halogen-free epoxy resin composition.