JPH04180984A - Adhesive composition for chemical plating, adhesive film for chemical plating, and method for producing printed wiring board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a chemical plating phase adhesive composition, a chemical plating adhesive film, and a method for producing a printed wiring board.

(Prior Art) Conventionally, in the manufacturing method of printed wiring boards in which circuits are formed on the surface of an insulating substrate by electroless plating, a method is known in which a base adhesive for electroless plating is formed on the surface of the insulating substrate in advance. ing. This adhesive is 1% Kosho 45
-9843 publication.

Japanese Patent Publication No. 58-57776 9% Publication No. 59-6268
As described in Publications No. 3, IJJ Kaisho Kaikai-248291, etc., there are known materials whose main components are epoxy resin, synthetic rubber, and phenol resin. Also, 1% Publication No. 58-30760, 1% Publication No. 1983
-5079 publication.

Japanese Unexamined Patent Publication No. 63-213676 1% Publication No. 63-213
No. 677, etc., describes an adhesive whose main components are synthetic rubber and phenolic resin.

In these methods, known thermosetting catalysts such as imidazoles, amines, acid anhydrides, and novolanc phenol resins are used as curing agents for epoxy resins, and resol type phenols, sulfur compounds, etc. are used for vulcanization of synthetic rubber. Zinc oxide, magnesium oxide, etc. are used as sulfur aids. On the other hand, these adhesives have improved roughening efficiency with a chromium sulfuric acid mixture,
In order to improve beer strength and solder heat resistance with plating film,
Inorganic fillers such as calcium carbonate, calcium silicate, silicon oxide, zirconium silicate, and titanium oxide are used.

The above-mentioned adhesive components are dissolved in a solvent and applied to an insulating substrate by a dip method, roll coating method, curtain coating method, etc.
Alternatively, fc can be obtained by coating and drying the fc adhesive film on a support film in advance, then laminating the fc adhesive film with the adhesive side facing the insulating substrate, and then heating and curing it. The curing conditions for the adhesive shown above are set at a temperature of 150 to 200° C. for 30 to 120 minutes, as described in the above-mentioned Japanese Unexamined Patent Publication No. 62-248291. However, under the conditions of 150°C for 30 minutes, the thermosetting component does not react sufficiently, and as a result, the insulation resistance of the cured adhesive is low, and the adhesive film swells due to the precipitation stress of the plating during electroless plating. Generates fc6. There is a problem of sipping due to decreased beer strength & f solder heat resistance with the plating film. For this reason.

- For boat fishing, as described in the examples of JP-A No. 62-248291, curing conditions are applied at 160° C. or higher and for 60 minutes or longer.

By the way, in recent years, the thickness of printed wiring boards has become thinner year by year, and the insulating base material used is paper phenol board with a thickness of 0.8 to 1.0 -
For glass epoxy plates, a thickness of 0.5 to 1.0 t has come to be used.

If the above-mentioned adhesive is formed on a thin insulating substrate and cured for 60 minutes or more at 160°C or higher, reaction force and twisting will occur on the insulating substrate, and the plating resist before electroless plating will be damaged. In the formation process, problems arise in printing the resist ink and forming the Menki resist using a dry film, and in fact, it becomes impossible to form fine circuits.

(Problems to be Solved by the Invention) The present invention solves the problems of the prior art described above, namely, the reaction, twisting, and thermal deterioration of paper phenol plates when using a thinned insulating base material. .

The present invention provides an adhesive composition for chemical plating that hardens in a short period of time, and a method for producing an adhesive film for chemical plating and a printed wiring board using the same.

(Means for Solving the Problems) The present invention comprises nine epoxy resin rubbers, phenolic resins,
Adhesive composition for chemical plating containing a noble metal compound and a photosensitive aromatic onium salt as a catalyst for chemical plating 1. The present invention relates to an adhesive film for chemical plating in which a layer of this adhesive composition is formed on a transparent support film, and to a method for manufacturing a printed wiring board using the adhesive film.

The present invention is preferably applied to a thin laminate having a thickness of α61 Im or less.

The adhesive composition for chemical plating and the adhesive film for chemical plating of the present invention will be explained in detail below.

1% as the photosensitive aromatic onium salt used in the present invention
Aromatic onium salt of group ■a element described in Japanese Patent Publication No. 52-14277, 1% aromatic onium salt of group ■a element described in Japanese Patent Publication No. 52-14278
Aromatic onium salts of Group VJI elements described in Publication No. 9 can be used.

Specifically, triphenylphenacylphosnium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, etc. can be used. The amount of these photosensitive aromatic onium salts is preferably 0.2 to 5% by weight as a solid content in the composition from the viewpoint of curing the epoxy resin.

When this photosensitive aromatic onium salt is irradiated with ultraviolet light (365 nm) -1=N? 0.5 to 3. ．． OJ/3
It decomposes (degree) and releases Lewis alcohol, which is a curing species of epoxy resin, and then or simultaneously cures the epoxy resin.
Low temperature curing at ℃ is possible.

As the epoxy resin used in the present invention, bisphenol type, novolank type, talesol novolak type alicyclic epoxy resins, etc. can be used. Epoxy equivalent is 450-2
, 100g/eq of bisphenol A type epoxy resin has excellent heat resistance! It is more preferable from the viewpoint of properties, and the blending amount is preferably 15 to 40% by weight as a solid content in the composition from the viewpoints of insulation resistance of the adhesive film and beer strength.

Examples of the synthetic rubber used in the present invention include acrylonitrile butadiene rubber, isoprene-containing acrylonitrile butadiene rubber, carboxyl-containing acrylonitrile butadiene rubber, and styrene butadiene rubber. The amount to be blended is preferably 4-0 to 60% by weight based on the solid content of the composition from the viewpoint of beer strength of the plating film and insulation resistance of the resulting printed wiring board. The insulation resistance of the cured adhesive film is 1
gl! There is a tendency for the value to be lower than Ω.

Examples of the phenol resin used in the present invention include resol type phenol resin, pure phenol resin, alkyl-modified phenol resin, and cashew-modified phenol resin. The amount of the phenol resin to be blended is preferably 20 to 40% by weight based on the solid content of the composition from the viewpoints of reactivity with the 9 synthetic rubber and beer strength of the plating film.

The noble metal compounds used as catalysts for chemical plating used in the present invention include palladium compounds such as palladium chloride, rhodium compounds such as rhodium chloride, etc., and they can be used in the form of fine particles adsorbed on an inorganic filler or dispersed in a resin solution. Can be used as a solution. An example of a commercial product is PEC-8, manufactured by Hitachi Chemical Co., Ltd. The amount to be blended is preferably 0.01 to 2% by weight based on the solid content of the composition from the viewpoint of the precipitation properties of the plating film and the insulation resistance of the printed wiring board obtained. Epoxy resin 9 composition rubber, phenolic resin.

Two or more kinds of noble metal compounds and photosensitive aromatic onium salts that serve as catalysts for chemical plating can be used as necessary.

In the present invention, furthermore, known synthetic rubber vulcanization aids such as nitrite oxide, magnesium oxide, cobalt oxide, etc. can be used.
i! Silicon oxide, which has a large surface area, is used as a runoff prevention agent during construction, and calcium carbonate and calcium silicate are used to facilitate roughening during chemical roughening.

Fine powder fillers such as zirconium silicate can also be used. Other additives 1. Colorants, thermosetting catalysts, etc. can also be used.

The adhesive composition of the present invention can be produced by a conventional method using a known device such as two rolls or a kneader.

Inorganic materials are dispersed with synthetic rubber etc. using these devices, and organic materials are dispersed with ketones.

A solution of the adhesive composition of the present invention can be obtained by dissolving it in a solvent such as cellosolve.

As a method for applying the solution of the adhesive composition onto the laminate, known methods such as a roll printing method, a curtain coating method, a tip method, and a screen printing method are used. At this time, the coating thickness can be adjusted by adjusting the concentration of the adhesive solution and the coating method, but the thickness of the adhesive composition layer after drying is determined from the viewpoint of beer strength of the plating film and curing of the epoxy resin. ~
A thickness of 70 μm is preferred.

The adhesive film of the present invention can be produced by a conventional method. For example, a solution of the adhesive composition described above may be applied to a support such as a polypropylene film, a polyethylene film, a triacetate film, a vinyl fluoride film, a polyester film treated with silicone mold release, a polyester film treated with olefin mold release, or an unstretched polymethylpentene film. It is applied by knife coating, roll coating, etc. onto the body film and drying. As the support film, an olefin release-treated polyester film is preferable in terms of heat resistance during coating, release properties, and non-transferability of the release agent.◎ When producing a long adhesive film, the production In the final step, the adhesive film is wound up into a roll. In this case, using a method known in the production of pressure-sensitive adhesive tapes, etc., a protective film with a smaller adhesion force to the adhesive layer than the support film is placed on the exposed surface of the adhesive composition layer (the opposite side of the support). It is preferable to coat with. By covering the adhesive composition layer with a protective film, it is possible to prevent the adhesive composition layer from transferring to the back surface of the support film when it is wound up into a roll. It is also possible to prevent dust from adhering. Examples of the protective film include polyethylene film, polypropylene film, and Teflon film.

The thickness of the adhesive composition layer of the adhesive film of the present invention is I
Although not limited to #, as mentioned above, 20 to 70μ
m is preferred.

9. A solution of the adhesive composition for chemical plating of the present invention is applied on the laminate, and then the adhesive composition is cured to cover areas other than the wiring pattern forming area with a plating resist, and then chemical plating is applied to the wiring pattern forming area. A printed wiring board is manufactured by depositing plating on the substrate.

A chemical plating adhesive film of the present invention is placed on a laminate,
The adhesive composition layer is placed on the laminate side and laminated under heat and pressure, and then the adhesive composition is cured.

A printed wiring board is fabricated by covering areas other than the wiring pattern forming area with a plating resist, and then depositing plating on the wiring pattern forming area by chemical plating.

A method for laminating a laminate with the chemical plating adhesive film of the present invention will be explained.

These steps are carried out by the known methods described in JP-A-50-15876 and 1% JP-A-63-277772. It is easy to laminate adhesive films to laminates, paper substrates, phenolic resin laminates, etc.

In other words, if there is no protective film such as polyethylene, then heat and pressure laminate on both sides or the other side of the laminate, with the adhesive side facing the laminate, or with the protective film peeled off or while peeling it off. .

Heat-pressure lamination is carried out using a hot roll laminator under normal pressure or a 52-527 % opening lamination machine, which is well known in printed wiring board manufacturers.
This can be carried out using a laminator under reduced pressure or vacuum as described in Japanese Patent Publication No. 03, Japanese Patent Publication No. 55-13341, and the like.

The adhesive film laminated laminate is then cured to cure the adhesive composition layer, with or without peeling off the KFi support film if necessary.

The adhesive film obtained by applying the adhesive composition to the substrate is
It will harden as it is. Curing Fi is performed by heating at 100 to 150° C. simultaneously with or after the step of irradiating ultraviolet rays.

Next, a plating resist is formed on areas other than the areas to be chemically plated of the laminate on which the adhesive film has been formed by a conventional method, the adhesive is chemically roughened, and plating nuclei are precipitated and activated. Roughening of the plating resist forming adhesive, precipitation of plating nuclei, and activation may be performed first.

Next, a chemical plating film is deposited by a conventional method on the part to be chemically plated by electroless plating.

The laminated board on which the adhesive layer of the present invention was formed was one sheet.

Since no twisting occurs, it is easy to print plating resists and laminate dry film plating resists.
Fine circuits can be stably formed.

(Example) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. In addition, "part" in one example indicates the quantity [Ii] unless otherwise specified.

Example 1.2 and comparative example As shown in Table 1 using a knife coater.

Polyester film subjected to olefin release treatment as a support film, manufactured by Konjin, Tetron Film FLO2
An adhesive composition solution having the composition shown in Table 1 was applied to the mold release surface (38 μm thick) so that the dry film thickness of the adhesive layer was 30 μm, and then dried (60 to 110°C for 5 minutes). After that, mining film, polyethylene film (30μm
An adhesive film for chemical plating was obtained by winding it up into a cover sheet and roll shape. Next, the adhesive composition layer of two rolls of adhesive film (width 500 m, length 100 m) was applied to the laminate to form a paper-based epoxy resin laminate containing a chemical plating catalyst (manufactured by Hitachi Chemical Co., Ltd., commercial product). Name LE-144,0
, 8m thick, 500an x 500m), while peeling the polyethylene film, laminate it with a Hontrol laminator (manufactured by Hitachi Chemical Co., Ltd., trade name HLM-1500 model). The adhesive film was cut to the size of a laminate (4 kgf/am", lamination speed 1 m/min).

Next, an 80W/Cl11 high-pressure mercury lamp 2 has a parallel light irradiation type reflector that emits ultraviolet and infrared rays simultaneously.
Ultraviolet irradiation machine with book (manufactured by Oak Seisakusho N, product name H)
MW-514 type) using an e 365 nm sensor.
2 J/- of ultraviolet light was irradiated. Regarding Comparative Example 1.

This ultraviolet irradiation step was not performed. After that, the polyester film was peeled off and heated for 30 minutes in a curing oven with an ambient temperature of 150°C.

Furthermore, as Comparative Example 2, another substrate was heated for 60 hours in a curing furnace with an ambient temperature of 160°C without UV irradiation.
It was prepared by heating for a minute.

Next, on the surface of the substrate on which this adhesive layer was formed, one width 1a was applied.
Beer strength measurement pattern of nX length 10cm and width 2.
Except for the 260°C solder heat resistance measurement pattern of 5 an The lever plating resist ink was cured. Both of the patterned areas where the adhesive layer is exposed were treated with 65g/l of anhydrous acid and sulfurized at W1250m!
Roughen with a chemical roughening solution consisting of / / at 50°C for 7 minutes.

Washing edge e CuS 04 ・5 H*O150f4 /
l * Ethylenediaminetetraacetic acid 309//, 37 t HCHO aqueous solution 10 dll, sodium cyanide 25
/J and adjusted to pH 12.5 with NaOH for 15 hours at 70° C. to form a copper plating film about 30 μm thick on each pattern forming part. Next, after washing with water, it was dried at 150°C for 30 minutes.

Using the obtained printed wiring board, the beer strength and solder heat resistance of the copper plating film in the pattern forming area were measured according to the JIS-C6481 method. The results are summarized in Table 2.

Beer strength was determined by peeling off a 1a1-wide plating film using a rheometer at a rate of 50.7 minutes with the tensile direction at 90° to the laminate.

Solder heat resistance is measured by contacting the surface of a printed wiring board with a flow solder bath at 260°C and measuring the blistering of the plating film.

It is expressed as the time until peeling, etc. occurs.

Both Examples 1 and 2 were able to be cured at a low temperature of 150°C using ultraviolet rays, so the warp and twist of the substrate was reduced to 1.0 m.
There are no problems with printing, etc. as shown below.

A printed wiring board with good beer strength and heat resistance of plated steel was obtained. On the other hand, in the comparative example, curing at 150°C resulted in insufficient curing of the epoxy resin, causing only 1 crack and less twisting, but resulting in beer strength.

There is a problem with solder heat resistance. In addition, those cured by heating at 160°C for 60 minutes have no problems with beer strength and heat resistance, but are extremely resistant to cracking.

It was often necessary to correct wrinkles before printing with racist ink.

Margins below (Effects of the Invention) The chemical plating adhesive composition and chemical plating adhesive film of the present invention can produce printed wiring boards with less warping and twisting of the substrate, and with high beer strength and solder heat resistance of the plating film. can get.

Agent Patent Attorney Kuni Wakabayashi Hikoichi

Claims (6)

[Claims] 1. An adhesive composition for chemical plating comprising an epoxy resin, a synthetic rubber, a phenolic resin, a noble metal compound serving as a catalyst for chemical plating, and a photosensitive aromatic onium salt. 2. The solid content of the epoxy resin in the composition is 15 to 40
40-60% by weight of synthetic rubber, 20-40% by weight of phenolic resin, 0.01-2% by weight of a noble metal compound that serves as a catalyst for chemical plating, and 0.2-5% by weight of a photosensitive aromatic onium salt. The adhesive composition for chemical plating according to claim 1, which is % by weight. 3. An adhesive film for chemical plating comprising a layer of the adhesive composition for chemical plating according to claim 1 or 2 formed on a transparent support film. 4. 4. An adhesive film for chemical plating according to claim 3, wherein the transparent support film is a polyester film subjected to olefin release treatment. 5. A solution of the adhesive composition for chemical plating according to claim 1 or 2 is applied onto the laminate, and then the adhesive composition is cured to cover areas other than the wiring pattern forming area with a plating resist. A method for manufacturing printed wiring boards that deposits plating on the wiring pattern forming area. 6. The adhesive film for chemical plating according to claim 3 or 4 is laminated on the laminate under heat and pressure with the adhesive composition layer facing the laminate, and then the adhesive composition is cured to form a wiring pattern. A method of manufacturing printed wiring boards in which areas other than the wiring pattern area are coated with a plating resist, and then plating is deposited on the wiring pattern forming area using chemical plating.