JPS62192420A - Production of thermosetting resin for laminate - Google Patents

Abstract

PURPOSE:To obtain a thermosetting a resin for laminates excelling in solvent resistance, moisture resistance, interlayer adhesion and flexibility and having heat resistance, by reacting, a specified organopolysiloxane with an epoxy compound by heating in the presence of oxalic acid while blowing carbon dioxide gas into the reaction system. CONSTITUTION:An organopolysiloxane having a reactive ethoxy group is reacted with an epoxy compound having an epoxy group by heating in the presence of oxalic acid while carbon dioxide gas is being blown into the reaction system. The amount of oxalic acid used is preferably 2-4pts.wt. per 100pts.wt. resin which takes part in the reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a thermosetting resin for laminates having heat resistance and flexibility.

Conventional technology Resins for heat-resistant laminates include polyimide thread resins and silicone resins, with the latter being widely used. Silicone resins are generally derivatives obtained by hydrolyzing chlorosilane. The organopolysiloxane is impregnated into a heat-resistant base material in the presence of a basic catalyst, and the materials are stacked and heated under pressure (two-layered heat-resistant laminates are obtained).

However, in terms of heat resistance, these laminates are superior to paper-based phenolic resins and glass cloth-based epoxy resins (2-based laminates), but they have poor solvent resistance. It is inferior in terms of hardness, moisture resistance, interlayer adhesion, and flexibility.For this reason, in the field of laminates of 0.6mm to 2.0cm, which require resistance to decomposition agents and willowability, 1.History fields were restricted.

Therefore, as a means of improving performance by mixing with a resin that has excellent solvent resistance, we conducted a preliminary study and found that
Apart from solvent resistance, it was not possible to improve moisture resistance, interlayer adhesion, and flexibility.

An object of the present invention is to provide a thermosetting resin for MM boards that is heat-resistant with one needle and has excellent solvent resistance, moisture resistance, interlayer adhesive strength, and flexibility.

As a means to solve the problem, we obtained a cocondensate by reacting the epoxy group of the boxy resin with the ethoxy group of the reactive organopolysiloxane, which had poor solvent resistance and interlayer adhesion. We investigated ways to obtain molecular control compounds that have the features of both.

However, this co-condensate? In order to obtain C2, it is necessary to use a catalyst to promote the reaction and an operation to prevent the equilibrium reaction state, that is, a reaction in a carbon dioxide gas stream, but after various studies, we found that it is convenient. It was found that there are two differences in the properties of the polymer compound obtained depending on the catalyst used.

As a result, an epoxy compound in which an organopolysiloxane having an ethoxy group and an epoxy group are combined in the presence of a 7-well acid catalyst can be used as a resin for laminates by heating and stirring while blowing carbon dioxide gas. ++'a, and was able to obtain a heat-resistant thermosetting resin that was more flexible than resins obtained under other catalysts.

Action: Add methyl ethyl ketone to the above resin to make a face.
This is impregnated into glass cloth (thickness 0.18W), heated and dried to make a prepreg with a fat content of about 50%, and a laminate is obtained by kneading all the prepregs together and heat-pressing them. The board is a conventional laminate board (compared to the previous one), which has better solvent resistance, moisture resistance, and interlayer adhesion, and is a similar type of board that has been polymerized using #L acid or para-toluene sulfonic acid as a catalyst. It has superior flexibility compared to glass cloth-based bulkhead boards that use co-condensate as a face.

The organopolysiloxane used in the present invention may have only ethoxy groups or a mixture of ethoxy groups and methoxy groups. In addition, the amount of hydrochloric acid used in the reaction is preferably 2 to 4 parts, and 1
．． If it is less than 5 parts, the reaction rate will be rough and slow, and if it exceeds 5 parts, the reaction rate will increase and the sinterability of the resulting resin will be poor. -Blowing carbon dioxide gas is extremely effective in promoting the reaction and making it uniform.

The reaction proceeds satisfactorily at a reaction temperature of 140°C or higher;
A temperature of 60°C to 200°C is advantageous for controlling the reaction.

In parallel with the present invention, a glass cloth substrate laminate was prototyped using a fest prepared by stirring and mixing 100 parts of organopolysiloxane and 50 parts of bisphenol-type epoxy resin at 40°C for 1 hour, and adding a basic catalyst to it. Although the properties were confirmed, no improvement in solvent resistance or interlayer adhesion was observed.

In addition, after carrying out a condensation reaction between organopolysiloxane having an ethoxy group and bisphenol-type epoxy resin Ftlyfe in a carbon dioxide gas stream at 160°C under an acid catalyst, the obtained polymer compound was made into a glass cloth substrate laminate. Prototype and characteristics? I checked and found out that the solvent resistance, moisture resistance, and interlayer adhesion are the same as those of the above-mentioned mixed festival? Although this was an improvement over the case in which it was used, flexibility could not be obtained.

As mentioned above, the present invention relates to organopolysiloxane.

Xane and epoxy compounds are reacted under certain conditions, and by using a special catalyst, it has properties that were previously unobtainable and a material that is better than similar laminates.
Laminated board with T flexibility? You can get it.

Example The present invention will be described in detail.

Example 1 Phenylethoxypolysiloxane 100r and bisphenol type epoxy resin (manufactured by Shell, product name KPON 82)
8) 5(l) and aqueous acid solution (3t/10canto)
'&4 Tulo flask (:), stirred while blowing carbon dioxide gas, and reacted by heating at 160°C for 90 minutes. As the reaction progressed, the epoxy value and ethoxy value decreased, and a resinous substance was obtained.

Methyl ethyl ketone was added to this resinous material to form a face, which was impregnated into a glass cloth having a thickness of 0.18 Iu+ and dried to obtain a prepreg with a resin content of 50%. Eight sheets of this prepreg were stacked together and molded using a laminate press using a conventional method (temperature: 160-170°C, pressure: 80°C, 9 parts m, time: 80°C).
) to obtain a laminate with a thickness of 1.6 centimeters.

Examples 2 to 6 In Example 1, when the reaction tube If was set to 140°C and 200°C, and the reaction temperature was 160°C, catalyst # was added to 1.5.3 parts per 100 parts of resin participating in the reaction.
．． The reaction when each of the 5 parts was added was tracked.

Comparison (flJl) A prepreg was obtained using fest added to 0.1 part of a basic catalyst (triethanolamine) to 100 parts of silicone resin for laminates, and glass cloth substrate silicon was prepared under the same conditions as in Example 1. A resin laminate was obtained.

Comparative Example 2 Phenylethoxypolysiloxane 100f and bisphenol type epoxy side fat (shell split, product name KPON828
) 50F Tohala toluenesulfonic acid water bath C (2y/4c
ghbo) was placed in a 4-tube flask, stirred while blowing carbon dioxide gas, and reacted by heating at 160° C. for 90 minutes to obtain a resinous substance 'IN'. This material was coated with methylethylgtone as a varnish, and 8 prepregs were obtained under the same conditions as in Example 1. Eight sheets were stacked and heated and pressed to form a laminate with a thickness of 1.6 m. .

Performance of resin reactants and laminates in Examples and Comparative Examples? 'O
It is shown in Table 51 and the second column.

*1 Table ◎Good ΔMinor BL The resulting resin has excellent heat resistance, moisture resistance, interlayer adhesive strength, and flexibility, and is widely used in the field of heat-resistant laminates.

Claims (1)

[Claims] A method for producing a thermosetting resin for a laminate, which comprises heating an organopolysiloxane having a reactive ethoxy group and an epoxy compound having an epoxy group in the presence of oxalic acid while blowing carbon dioxide gas into the reaction.