JPH01242627A - Production of nonburning fiber reinforced laminate impregnated with resol phenol resin - Google Patents

Abstract

PURPOSE:To obtain the title laminate having high mechanical strengths and being suited as a construction material, by releasing a nonburning fiber reinforced laminate impregnated with an acid-curable resol phenol resin from a mold in mid course of curing and immersing it in a silanol-containing syrupy liquid. CONSTITUTION:An acid-curable resol phenol resin and a basic inorganic filler such as aluminum hydroxide are added to a nonburning laminate formed by laminating a plurality of glass fiber nonwoven cloth mats and cured by heating in a mold. After the surface is cured enough to release the molding from the mold, the molding is released from the mold and immersed in a silanol- containing syrupy liquid to obtain a nonburning fiber reinforced laminate. Said syrupy liquid can be obtained by treating a silicate mineral such as kaolin or bentonite with sodium hydroxide or by hydrolyzing chlorosilane. According to this process, the methylol groups derived from the resin react with the silanol groups to form methylene bonds, so that the mechanical strengths are increased and the nonburning property is ensured.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to architectural materials such as interior materials for buildings, wall materials for fireproof partitions, etc., and more particularly, to architectural materials made of fiber-reinforced foamed resol-based phenolic resin materials. Regarding.

(Prior art) Conventionally, resol-based phenolic resins have been used as molding materials for building materials, and fiber-reinforced molded products made from resol-based phenolic resins have also been seen, which include aluminum hydroxide. A laminate that is reinforced with a noncombustible material such as glass fiber and in which a noncombustible material such as a noncombustible filler is used in combination is attracting attention.

[Problems with conventional technology]

However, although this material may have appropriate nonflammability, the current situation is that the mechanical strength of the material is still not sufficient.

Namely, (1) This type of material manufactured by the conventional method has the disadvantage that the hydrogen ion concentration when the laminate absorbs water is not neutral, and is slightly biased towards the acid side, so that metal corrosion is likely to occur during construction.

■ A sufficient amount of organic acids such as phenolsulfonic acid and balatoluenesulfonic acid, which are curing mediums, are used as catalysts, but since the filler added is basic, this neutralizes the acidity of the organic acids. Therefore, this catalytic action tends to be insufficient, and therefore the curing reaction of the resin system tends to be delayed, and it is difficult to obtain a cured product with sufficiently high mechanical strength even when molded at high temperatures. In addition, in such a situation, the curing time becomes longer, so the molding speed must also be reduced, and the manufacturing process is therefore time-consuming.

(2) It is also possible to add a large amount of inorganic filler to promote unidirectional neutralization, but this is not preferable in terms of maintaining the mechanical strength of the material, and the added proportion does not improve the nonflammability.

[Problem to be solved by the invention]

In view of the above-mentioned problems, the present invention has been developed to fully perform the function of curing organic acids such as phenolsulfonic acid and valatoluenesulfonic acid as curing catalysts during the resin molding process, and therefore to prevent curing of the resin. A resol-based material that is sufficiently hardened and has sufficient mechanical strength, so that the catalyst works quickly and can be done in a short time, and also avoids metal corrosion that is likely to occur during use and construction. This was done for the purpose of obtaining a method for manufacturing a phenolic resin fiber-reinforced noncombustible laminate.

[Technology to solve problems]

That is, the method for producing a fiber-reinforced noncombustible laminate based on a resol-based phenolic resin of the present invention uses a substance obtained by mixing an acid-curable resol-based phenolic resin with a basic inorganic filler substance to produce a fiber-reinforced noncombustible laminate and the same foam. In the manufacturing method, the laminate molded in a mold is removed from the mold at the minimum time when it can be released from the mold, and then a silanol-containing syrup-like product obtained by silanolizing a silicate mineral with sodium hydroxide is added to the laminate. It is characterized by being impregnated with a substance.

[Effect]

As soon as the curing reaction of the resol-based phenolic resin, that is, the polycondensation reaction in this system, has progressed to a certain extent and the laminate can be removed from the mold, it is removed from the mold, and immediately after that, it is made of natural silicic acid such as kaolin or bentonite. Immersion in syrup-like silanol-containing liquids, such as those obtained by adding caustic soda to salt-based minerals and modifying some of the resulting crystals to silanol groups, or substances obtained by hydrolyzing chlorosilane. However, if silanol is sufficiently permeated into the cells of the laminate or foam, the acid remaining in the resol-based phenolic resin will be sufficiently neutralized.

Afterwards, it is dried.

〔Example〕

Next, this invention will be explained in detail.

Multiple layers of glass fiber non-woven mats are stacked inside the mold,
Next, a mixture prepared by adding (aluminum hydroxide) as a basic inorganic filler to an acid-curable resol type phenolic resin was supplied and cured by heating and foaming.

Normal demolding is done at (15) minutes after pressurization, but after the surface has hardened to the touch, that is, after (10), the above-mentioned molded body is carefully demolded, and then this is converted into the syrup modified with silanol groups as shown in the table below. It was immersed in a liquid to impregnate it.

After drying, the surface pH of the molded bodies was measured, and it was confirmed that all of them had a pH of 7, indicating that they were neutral.

〔effect〕

As mentioned above, by properly contacting a silanol-based liquid after mold release, the methylol groups derived from the resin system react with the silanol groups to form a methylene bond, which undergoes dehydration condensation polymerization, and then The effect of this can be obtained.

(2) The chemical bonding of inexpensive natural inorganic substances allows the condensation reaction of the resin to be carried out easily, quickly, and safely, thereby increasing the mechanical strength of the resin and ensuring nonflammability.

(2) By controlling the amount of acid that serves as a catalyst for polymerization and the amount of base and silanol base solution as fillers, the catalytic action can be sufficiently performed and residual acid can be kept to a minimum.

Claims (1)

[Claims] (1) In a method for producing fiber-reinforced noncombustible laminates and foams using a mixture of an acid-curable resol-based phenolic resin and a basic inorganic filler substance, the laminate molded in a mold is released from the mold. A resol-based phenolic resin fiber-reinforced noncombustible laminate, characterized in that the laminate is demolded at the minimum possible time and then impregnated with a silanol-containing syrup obtained by silanolizing a silicate mineral with caustic soda. How the body is manufactured.