JPS6017340B2 - Manufacturing method for flame-resistant laminates - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a thermosetting resin laminate having excellent flame resistance, electrical properties, and punching workability.

With the recent remarkable development of the electronic equipment industry, the demand for laminates and printed wiring boards used as insulators is increasing, especially with the development and sophistication of high-end electronic equipment.
From the standpoint of safety, there is a call for parts used in these devices to be made inflammable, and as a result, requirements for the flame retardancy of the substrates themselves have become even more stringent.

In addition, as printed wiring boards used in electronic devices have recently become larger and the automatic insertion rate of parts has rapidly increased, higher dimensional accuracy is required in printed wiring board processing.To meet this demand, low-temperature punching is Processing is about to take place. Conventionally, in order to improve punching workability, external plasticizers have been added to thermosetting resins, or resins have been modified with internal plasticizers.

On the other hand, the method of flame retardation of thermosetting resins is carried out by adding nitrogen compounds, phosphorus compounds and halogen compounds alone or in combination to the thermosetting resin to be made flame retardant.

In particular, the combustion method for paper-based laminates involves adding a retardant to the thermosetting resin for laminates, such as triphenyl phosphate, chlorinated paraffin, tetrapromobisphenol A, etc. for ferre resin, and adding a retardant to epoxy resin. These are made by using tetrabromohisphenol A, tetrachlorophthalic anhydride, etc., and for polyester resins, tricresyl phosphate, phthalic anhydride, etc. alone or in combination with antimony trioxide. However, when a large amount of plasticizer is used to improve punching workability, solvent resistance, water resistance, thermal stability, and electrical properties deteriorate.

Moreover, since a flame retardant is further added to impart flame resistance, the deterioration of solvent resistance, water resistance, thermal stability, and electrical properties becomes significant. In addition, there is a problem in the balance between the plasticizer-added resin and the flame retardant used, and it is very difficult to maintain this balance.

The present invention was made in view of these points, and involves reacting dimer acid, which is effective as a plasticizer, with halogenated bisphenol A diglycidyl ether, which is effective as a retardant, and partially containing epoxy as a reactive group. Reactive type flame retardant that retains the group * By adding plasticity to thermosetting resin, it has flame resistance and improves punching workability. This invention relates to a method for producing a laminate having excellent solvent resistance, water resistance, thermal stability, and electrical properties.

That is, the present invention uses a reaction product obtained by subjecting a halogenated bisphenol A diglycidyl ether to a dimer acid as a main flame retardant, if necessary in combination with other flame retardants such as triphenyl phosphate. This resin varnish is added to a thermosetting resin, and a predetermined amount of this resin varnish is adhered to a base material such as paper, and after drying, the required number of base materials are pressurized and heated to form a heat-resistant and hammerable varnish. This method produces a laminate with good punchability.

The novel flame retardant of the present invention contains halogenated pisphenol A diglycidyl ether and dimer acid in a molar ratio of 2 to 3.
mol/1 to 1.5 mol (preferably 2.5 to 3 mol/
1 mol), preferably an organic amine as a catalyst,
It is a reaction product having an epoxy equivalent of 650 to 1,200, which is obtained by using 1 to 3 weight percent of an alkali metal hydroxide or the like and reacting at a reaction temperature of 80 to 150 pm to an acid value of 1 or less.

Halogenated bisphenol A diglycidyl ether is bisphenol A diglycidyl ether in which 1 to 4 hydrogen atoms of the phenyl group are substituted with halogen, and there is no particular restriction on the epoxy equivalent molecular weight. Commercially available products include DER-Ko2 (product name manufactured by Dow Chemical Company), Shodyn 821 (product name manufactured by Showa Denko Company), and ESB-40.
0, ESB-milk 0 (trade name manufactured by Sumitomo Chemical Co., Ltd.), etc.

Dimer acid has a dimer acid content of 50 to 97% and an acid value of 180 to 200. Commercially available products include Enpol 1022, Enpol 1024 (trade name manufactured by Emery), Versadim 210, and Versadim 2.
88 (product name manufactured by Daiichi General Co., Ltd.).

The catalysts used in the present invention include organic amines such as N,N-dimethylcyclohexylamine, benzyldimethylamine, tolu-n-butylamine, triethylamine, and NN.
'-dimethylamine, N-(B-hydroxyethyl)amine, alkali metal hydroxides such as caustic potash,
Examples include lithium hydroxide, lithium chloride, and sodium hydroxide.

As phenol resins, tricresyl phosphate, triphenyl phosphate, chlorinated paraffin, tetrabromobisphenol A, etc. are used as scale retardants when used in combination with this new retardant and added to the impregnating resin as an auxiliary agent. It will be done.

Similarly, for epoxy resins, tris(beta-chloroethyl) phosphate, chlorinated paraffin, tetrabromobisphenol A, tetrabromophthalic anhydride, etc. are used. Similarly, for polyester resins, tetrabromo phthalic anhydride, tetrachlorophthalic anhydride, chlorinated polyphenyl phosphate, etc. are used.
Phenolic resins for impregnation include tung oil, dehydrated castor oil,
A liquid resin produced by reacting a drying oil such as Oiticica oil with phenols such as carbolic acid, cresol, or alkyl-substituted phenol under an acidic catalyst such as paratoluenesulfonic acid or sulfuric acid, followed by a resolization reaction with paraformaldehyde under an alkaline catalyst. can be used.

Tung oil 10-35% modified phenolic resin is preferred. In addition, there are melamine-modified phenol resins and the like. Similarly, there are no particular limitations on the epoxy equivalent molecular weight, etc. of the epoxy resin. Other resins for immersion include polyester resin, thermosetting acrylic resin, etc., and commercially available products are sufficient. The novel descaling agent of the present invention is a product made by reacting halogenated bisphenol A diglycidyl ether with dimer acid, which is effective as a plasticizer, and the reaction product has an epoxy group, so it has low reactivity. have. If necessary, this and other auxiliary retardants are used in combination with an impregnating resin, impregnated into a base material such as paper that has been previously treated with a water-soluble melamine-modified phenol resin, etc., and laminated under heat and pressure. , this new retardant is incorporated into a part of the structure of the thermosetting resin. Therefore, deterioration of solvent resistance, heat resistance, water resistance, electrical properties, etc. that inevitably occurs due to plasticization is prevented. Furthermore, a laminate having sufficient flame resistance can be provided.

A paper base material is impregnated with a varnish containing 100 parts by weight of 10 to 35% tung oil modified phenolic resin, 15 to 3 parts by weight of triphenyl phosphate and 25 to 4 parts by weight of the flame retardant of the present invention. Pressed laminates show good results.

The resin varnish according to the present invention can also be impregnated and dried on a paper substrate that has been previously treated with a water-repellent melamine-modified phenolic resin.

Example 1 Tetrabromobisphenol A diglycidyl ether (epoxy equivalent: 395-410) 76 parts (parts by weight, same hereinafter), 21 parts of dimer acid (acid value 195,197), 2 parts of penzyldimethylamine as a catalyst were mixed and reacted at 9000 for 4 hours.

After the reaction was completed, the mixture was cooled to obtain a solidified light brown product, a flame retardant. The acid value of this synthetic retardant is 0.4 and the bromine content is 38.
It was %. 100 parts of a resolized resin with a tung oil modification amount of 15% (100 parts of tung oil modified with 15%), which was obtained by reacting tung oil and synthetic carbolic acid under an acidic catalyst and then resolizing it with paraformaldehyde and an alkaline catalyst.
3 parts of the above synthetic nada retardant and 25 parts of triphenyl phosphate are mixed with the solid content) to make an impregnating varnish, and a craft base material is previously treated with a water-soluble melamine-modified phenol resin, and the above impregnation is applied to a 10% resin coating. The prepreg was impregnated with varnish to a resin adhesion of 50% and dried, and eight sheets of the prepreg were combined with adhesive-coated copper foil and laminated under heat and pressure to obtain a single-sided copper-clad laminate with 1.6 marks.

The characteristics of this copper-clad laminate are shown in the attached table. Example 2 3 parts of the synthetic retardant of Example 1 and 25 parts of triphenyl phosphate were blended with 10 parts of resol-formed resin (solid content) with 30% tung oil modification obtained by the same manufacturing method as in Example 1. As a varnish for impregnation, a craft base material was previously treated with water-soluble melamine-modified ferre resin, and the above-mentioned varnish for building impregnation was impregnated with a resin adhesion of 50% on a material with a resin adhesion of 10%. A single-sided copper-clad laminate with 1.6 ribs was obtained by combining 8 sheets of prepreg and copper foil with adhesive and heating and pressing the head layer.

The characteristics of this copper-clad laminate are shown in the attached table. Comparative Example 1 10 parts (solid content) of a resolized resin with a copper oil modification amount of 30% obtained by the same manufacturing method as in Example 1, 9 parts of tetrabromobisphenol AI, and 25 parts of triphenyl phosphate. A varnish for impregnation is prepared by blending the varnish, and the craft substrate is treated with a water-soluble melamine-modified phenol resin in advance to achieve a resin adhesion of 1
0% impregnation varnish was impregnated with the above-mentioned impregnating varnish to a resin adhesion of 50% and dried, and the 8 pieces of Bripreg and copper with adhesive were combined with < and laminated under heat and pressure to form 1.6 ribs of single-sided copper. A stretched laminate was obtained.

The characteristics of this copper-clad laminate are shown in the attached table. G: Excellent F:
Good P: Bad test method JIS06481, UL-208ヱ492,
ASTM D617-44 As is clear from the examples described above, the laminate of the present invention has flame resistance, solvent resistance, heat resistance,
It showed excellent values for water absorption, insulation resistance, and punching workability, and other properties were also very good.

The punching temperature conditions for punching workability were heating at each temperature for 3 minutes.

Claims (1)

[Claims] 1 Dimer acid (acid value 180-200,
Dimer acid content 50-97 PHR) 1-1.5 mol is blended and heated to react until the acid value is 1 or less, and the resulting reaction product is blended with a thermosetting resin as a flame retardant. A method for producing a flame-resistant laminate, which comprises impregnating and adhering a flame-resistant laminate, and heating and pressing a required number of base materials after drying.