JPS5857776A - Method of producing adhesive coated insulating substrate - 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] Unexploded TXR! The present invention relates to a method of manufacturing an insulating board with a small amount of adhesive used to form a printed wiring board by using chemical plating or a combination of chemical plating and electroplating to form a FIT supporting circuit.

The method of manufacturing a printed circuit board by forming a carbon layer using chemical plating or a combination of chemical plating and electroplating is as follows: Method of manufacturing a printed wiring board by forming a circuit and forming a circuit on chemical plating 0 (2) Applying a chemical layer 11 on the entire surface of the insulation layer 1k41 and forming an electric layer resist on the area other than the part where one circuit is formed. , a circuit is formed in an electrometallurgical process, and a circuit is formed by electroplating resist peeling. .

Conventionally, when chemical plating is performed on the surface of an insulating substrate, a layering agent is applied to the surface of the insulating substrate, dried and hardened, and then the surface is treated with an oxidizing roughening liquid, etc., to achieve good bonding with the plated metal! Maintains layeredness. Adhesives for this purpose are usually acrylonitrile and butadiene (combined as a product component, and phenolic resin as the product component).

Thermosetting side fat components such as epoxy resins, and if necessary, curing accelerators, rubber vulcanizing agents, vulcanization accelerators, fillers,
Pigment, plating catalyst, cold 711J toilet, etc.
What they have in common is that the acrylonitrile-butadiene copolymer accounts for 30% or more by weight of the organic material components excluding bath additives.

When the acrylonitrile-butadiene copolymer is treated with an oxidizing roughening solution, the 21MI portion is cut off, the amount of solubility increases due to lower molecular weight and generation of functional groups, and unevenness occurs on the surface of the adhesive. The anchoring effect of the plated metal increases and the adhesive strength increases. (2) The adhesive strength increases with the large hexapolar acrylonitrile group in the molecule and the amount of functional groups generated in (1). It has the following effects, and the standard 1.2 kg/c
In order to safely obtain a wiring board with an adhesive force of more than m, it is necessary to use acrylonitrile-butadiene rubber with a content of 301% or more. Since then, there has been a desire to improve the electrical properties of adhesives, such as electrical insulation resistance, spinning rate, and high-frequency properties of Kakudensho. Among the molecules, it belongs to the material with 8% poor electrical properties even after vulcanization,
It should be better if it is dredged with styrene-butadiene rubber, polybutadiene, etc., or the adhesive strength is low and it is difficult to put it into practical use! do not have.

- Study of lowering the content of tcr, 7-acrylonitrile-butadiene copolymer [conducted] By lowering the co-IIL copolymer content and increasing the epoxy 11-fat content, Phase separation occurs in ◇ (2) It is used as an impact-resistant agent for hardening of epoxy resin.

A liquid acrylonitrile-butadiene copolymer containing amine groups, etc.) is mixed with a conventional 7-acrylonitrile-butadiene conjugate, which causes phase separation even in an organic solvent solution (3) Low rubber-containing layer agent In this case, the amount of epoxy resin is inevitably increased, and there are problems such as the epoxy resin curing agent, class 81, which greatly affects the characteristics of the wiring board and the heat resistance of the board.

The present invention was made in view of these points, and involves adding an acrylonitrile-butadiene copolymer having a functional group and a double M and an epoxy resin to an organic solvent solution of a thermosetting W resin. The reaction product of the acrylonitrile-butadiene copolymer component is mixed in an amount of 2 to 201% in organic materials excluding bath additives, and the inorganic filler dissolved in the chemical roughening solution is mixed in the organic material excluding the solvent. 5 to 50 points per 100 parts of the material are mixed with a layer agent t% insulation group 8i It is to be applied on the surface to give a t value 〇Functional group and acrylonitrile with two wheels M unit and t. Butadiene co-X compound and epoxy resin are reacted in advance/S-sweetened epoxy resin arrangement and cutting is 40 to 95]Lit for the sum of acrylonitrile-butadiene compound and epoxy resin. Perform within %.

As a hardening agent, use a novolac type phenolic resin or vinyl phenol resin or epoxy resin with a hardening resistance of 15 to 50%. 2nd year middle school
If it exceeds 0m%, there will be no young rice that is prone to rotting due to the reduction of electricity in the rubber, and if it is less than 2%, the roughening liquid soluble inorganic filler will be packed in and the surface of the adhesive will be roughened. Even if the degree of unevenness is increased, the adhesion strength will not exceed 2 kg/cn+. If the epoxy resin is used at a concentration of 40% or more and heated before use, it will not phase separate even if stored for a long time due to the solubility. If it is less than 40311%, it will separate during storage, so it will be necessary to constantly stir when applying the layering agent. If the amount of epoxy resin distributed exceeds 951 it%, unreacted 7
It may be necessary to add acrylonitrile-butadiene copolymer to make a layering agent, which may cause phase separation and result in an incommunicable color. I/il￥, bath salts'
It can also be carried out by heating while stirring in a reaction vessel without adding rIIS, or it can be applied with a suitable curing agent for epoxy resin to lower the heating temperature.
- Can the introduced acrylonitrile-butadiene copolymer be used? It is easy to glue during the preliminary reaction with the epoxy resin, and W! Due to the ammonia odor when applying the crusher and curing, it is practical to use a carboxyl group-containing copolymer.
Addition of acrylonitrile-butadiene copolymer to TVM, and by roughening, the unevenness of the surface of the skin agent created becomes smaller and the ILF strength decreases. The am of the 0 inorganic additive improves with the addition of 0 inorganic additives, and the 4f mechanical material 100 mukura sVc is less than 511[mold part, which has no effect on increasing the contact force, and if it exceeds 50 dwarf part, the soldering heat resistance deteriorates. Calcium carbonate, calcium silicate, or calcium carbonate is preferable as a zero-roughening ffi, #decomposable, uncontaminated agent due to its properties, electrolyte properties, or particle shape. In other words, if calcium silicate is present on the surface of the adhesive in the form of crystals, it will cause cracking, elongated depressions, and circuit chipping during plating. On that point, carbonic acid power runum does not have elongated particles, so choose one with a branch according to the prescription of 1 circuit width for mixed use. ! [1, Iwao, do soldering to attach parts, etc.n, father, rounding of heat generated during use #resulting force is required・Mi with a high rubber content: resol type for electrodynamic layer agent Dicyandiamide is generally used for the fattening of alkyl 7S alcohol or acrylonitrile-butadiene rubbers, and in the case of epoxy resins with no rubber content.

In the relatively small amount of rubber-containing adhesive of the present invention.

The above-mentioned curing system can also be used if the usage conditions are selected.

Soldering heat resistance is improved when using Novo 2 Tsuku, phenolic resin, and vinyl phenol resin.OWhen using Novo 2 Tsuku type phenolic resin, the amount of epoxy resin (epoxy resin content during preliminary reaction with acrylonitrile-butadiene copolymer and unused amount) 15 to 50% by weight, preferably 25 to 25% by weight of the total amount of reacted epoxy resins) plus 7 enol fallen fat
401 Doushi is good. 15 [If less than 111%, the solder heat resistance is poor due to insufficient curing.
There is no difficult rowing force.

Vinyl 2-enol resin is also preferably used at a concentration of 15 to 50% by weight, and for growth of 25 to 40% by weight. 15. If it is less than 1% m, the soldering heat resistance will be poor, and if it exceeds 50 It%r, the bonding strength will be poor.To roughen the surface of adhesive #, use an organic bath agent such as methyl ethyl ketone, acetic acid ether, dimethyl formand, etc. After moistening, dissolve in oxidizing roughening solution 4).

As the oxidizing roughening liquid, elR-forming V) chromium mixed acid is used.

Contain chloroA acid, hydrofluoric acid solution, etc.

Actual hga 1 Epit 1004 (Shell Chemical Exhibition epoxy resin) and carboxyl group-functionalized acrylonitrile-butadiene copolymer (Hiker CTBN130θ x 13) tNjIt ratio is 5
Stir in a flask at 1180℃ with 10 portions open at 3 o'clock)J
D heating was carried out to prepare a P17 react copolymer.

NoriReact Kyotei Seven +6nm part, Epicort 1c1
04, 541ii$, 5b-6600 (novolac type phenolic resin manufactured by Schenectady Chemical Co.) 3 ohm parts, calcium carbonate 15M rod, plating catalyst (PEC-8 manufactured by Hitachi Chemical Co., Ltd.) 6 electric bar parts, silica powder ( A foil layer was prepared by dispersing a foil layer of 5M (Erosyl) 5M chlorine acetate to prepare a layer of adhesive. The adhesive was dried to a thickness of 40μ, and then heat-cured at 170°C for 60 minutes.The laminated laminate to which the adhesive was applied was dimethylformia mixed in a 1:1 mixture of 1:1 and Improvil alcohol. After swelling by immersion in K for 2 minutes in decomposition, it was roughened by edging with an oxidizing chromium mixed acid, and chemically plated to produce a steel plated laminate with a copper thickness of 30μ.Acrylonitrile-butadiene rubber content in the adhesive used is 4% by weight of organic materials excluding solvents.

Actually 7M? IJ2 In Example 1, the pre-react copolymer was t40 parts, and the unreacted Ebico) was 1004? A printed wiring board was obtained in the same manner as in Example 1 except that rfjFc was used.

0 m force required by rubber content Fitoxt% 6 In Example 1, sp ~ 6600't Resistance 7M (vinylphenol @ resin manufactured by Maruzen Sekiyu KK) was replaced with a dressing agent, and the rest was the same as in Example 1. 〇Example 4 In Example 1, 150.5 parts of dicyandiamide r1.
5m, benzyldimethylamine 2 parts 'tme% adhesive r
A printed wiring board was produced in the same manner as in Example 1.

Comparative example Acrylonitrile/butadiene rubber (Hiker 1052
) 45 parts% 5p-660010 parts, 5p-126 (Schenectady Chemical Co. resol type phenol folding sword ¥1) 20ffB, Ebiko) 1004. 25 parts, 45 parts of zirconium silicate, 3 parts of zirconium silicate, 6 parts of catalyst
Disperse Ceronlube Acetate VC bath waste lol! A steel plated laminate was prepared using the same method as in Example 1, and then a steel plated laminate was prepared.

In addition, the solvent immersion during the process and the embedding were omitted, and the upper opening was the first through-hole of the firs 1, which was obtained in Examples and Comparative Examples. [Bu I] 1st fitting Bone extraction M button mouth n1Fi Audience transmission conversation, # is the dielectric constant.

As mentioned above, we have developed a convenient stone for manufacturing printed wiring boards that has high dielectric constant, dielectric loss tangent, etc., and has good solder heat resistance and bonding strength. It is possible to manufacture an insulating substrate coated with a lubricant.

Claims (1)

[Scope of Claims] 1. Thermosetting 1m fat organic solvent solution containing a functional group and 21l
Reaction product of acrylonitrile-butadiene copolymer and epoxy resin
2 to 2 butadiene components in organic materials excluding solvents
01% by weight, and organic materials other than the fl@Kikkoyoko tm agent dissolved in the chemical coarsening agent 10O] 1
A method for manufacturing an insulating substrate to be coated with a bonding agent, in which 5 to 50 parts by weight of a bonding agent is added to the surface of the insulating substrate. 2 Is it an acrylonitrile-butadiene copolymer? Claim 1, which is an acrylonitrile-butadiene copolymer having a carboxyl group! Adhesive described in J *A Manufacturing method for extremely fine substrate
Epoxy resin or 40-95% by weight and 7! , 6, the adhesive 41 according to claim 1331, which is reacted in the manner
1a! Insulated substrate manufacturing method/