JPH01105735A - Manufacture of fiber reinforced phenol resin molded object - Google Patents

Abstract

PURPOSE:To obtain the fiber reinforced phenol resin molded object passing the incombustibility standard of the Ministry of Transport, while ignition, flaming, carburetion and deformation in flame test do not occur by using a specified primer. CONSTITUTION:A gel coat layer is the material in which 50-100pts.wt. of aluminum hydrate is compounded with 100pts.wt. of unsaturated polyester resin. A primer layer is the material in which 50-100pts.wt. of aluminum hydrate is added to 100pts.wt. of vinyl ester resin, and further 10-40wt.% in the weight of aluminum to the total weight of a molded object of any one kind or more of aluminum powder, aluminum grain, aluminum fiber or the glass fiber coated with aluminum is compounded with said vinyl ester resin. As the phenol resin layer of a backing layer, the material in which 10-30pts.wt. of clay and 20-60 pts.wt. of semiaqueous plaster to 100pts.wt. of phenol resin are added to glass fiber base material, is used. After the gel coat layer, the primer layer and the backing layer have been successively laminated on a mold surface and cured, the molded object made of flame retardant fiber reinforced phenol resin is obtained by its mold release.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing highly flame-retardant fiber-reinforced phenolic resin molded products (hereinafter referred to as phenol FRP), and in particular to ducts, scrubbers, and corrosion-resistant pipes. It is useful for various uses such as walls, ceilings, aircraft parts, vehicle parts, and shelters.

(Conventional technology) Conventional unsaturated polyester gel coated phenol FR
In order to make P flame retardant, there is a method of adding aluminum hydroxide to gel coat, an inorganic filler such as calcined gypsum, clay, aluminum hydroxide to phenol FRP, and a method of adding antimony dioxide and chlorinated paraffin, and a method of adding decabromodiphenyl. There is a way to add it. However, with these combinations, gas generation due to heat from the phenolic resin layer causes surface blistering, deformation due to repelling, ignition, etc. It was not possible to find a formulation that met the "sexual" standards.

(Problems to be Solved by the Invention) Therefore, in order to eliminate the above-mentioned drawbacks of phenol FRP and pass the Ministry of Transport's "non-flammability" standard, the inventors of the present invention conducted extensive research and found that a specific primer was used. We have completed a method for manufacturing fiber-reinforced phenolic resin moldings that does not ignite, flame, carbonize, or deform in combustion tests, and passes the Ministry of Transportation's ``nonflammability'' standards.

(Means for Solving the Problems) That is, the present invention uses 50 to 1 part of aluminum hydroxide as a gel coat layer to 100 parts by weight of unsaturated polyester resin.
00 parts by weight is used.

The primer layer used in the present invention is phenol FR.
Considering adhesion with P and heat diffusion and conduction during combustion, 50~50~ of aluminum hydroxide is added to 100 parts by weight of vinyl ester resin.
100 parts by weight is added, and one or more of aluminum powder, aluminum grains, aluminum fibers, or aluminum-coated glass fibers is added in an amount of 10 to 40% by weight of aluminum based on the total amount of the molded product. For the phenolic resin layer of the backing layer, use is made of a glass fiber base material to which 10 to 30 parts by weight of clay and 20 to 60 parts by weight of gypsum are added to 100 parts by weight of phenol resin. In this way, the gel coat layer, primer layer, and backing layer are sequentially laminated and cured on the mold surface, and then removed from the mold to obtain a highly flame-retardant fiber-reinforced phenolic resin molded product, which meets the Ministry of Transport's "Nonflammable" standards. passed the gender standard.

(Function) The phenol resin used in the present invention is a resol type phenol resin precondensation product obtained by reacting 1 mole of phenols and 0.3 to 3.0 moles of aldehydes in the presence of an alkaline catalyst. . This condensate may be partially neutralized with an acid. Alternatively, the water may be replaced with a suitable solvent after dehydration. Examples of phenols include phenol and its homologs such as cresol, xylenol, and alkylphenol. Formaldehyde as an aldehyde,
Examples include acetaldehyde and furfural.

The vinyl ester resin used in the present invention is obtained by reacting an epoxy resin with an unsaturated monocarboxylic acid, or a modified product obtained by substituting a part of an unsaturated monocarboxylic acid with a saturated carboxylic acid or a derivative thereof. etc., and are generally commercially available. Among these, non-wax air-curing types are preferred because they have a hard coating film, good adhesion, and particularly good adhesion to phenol resins.

In addition, the unsaturated polyester resin used in the present invention is
It is obtained by reacting an unsaturated polybasic acid and, if necessary, a saturated polybasic acid with a polyhydric alcohol, and is widely commercially available. Among these, so-called iso-based materials using isophthalic acid as a saturated polybasic acid are particularly suitable as gel coats.

The primer layer has good heat diffusion during combustion.

Aluminum powder and aluminum grains have good thermal conductivity, and aluminum fibers and aluminum coated glass fibers are blended to prevent surface blistering and repellency.

Preferably, the aluminum powder used in the present invention has a particle size of 100 .mu.I or less, and the aluminum grains have a particle size of 100 to 1000 .mu.m produced by melting and coating an aluminum base metal, and both have a purity of 99% or more. Aluminum fibers are directly spun from molten aluminium, have a fiber diameter of about 70 to 250 μm, and are commercially available in the form of mats, (dis)continuous fibers, short fibers, and nonwoven fabrics. Further, the aluminum coated glass fiber is made by melting and bonding 40% by weight of aluminum to E glass (15μ diameter) and has a specific gravity of about 2.6. The amount of aluminum needs to account for 10 to 40 weight percent of the total molded product. If the amount is less than 10%, heat diffusion will be insufficient;
If the amount is more than %, the adhesion of the primer will be poor and the workability will be poor. Moreover, the weight also increases, which is undesirable. The primer layer and gel coat layer each contain 50 to 100 parts by weight of aluminum hydroxide per 100 parts by weight of the resin to improve flame retardancy. If the amount is less than 50 parts by weight, the combustion effect will not be sufficient, and if the amount is more than 100 parts by weight, the surface strength will decrease and adhesion will deteriorate.

It is desirable to use a combination of clay and gypsum hemihydrate as fillers in the backing layer of phenolic FRP. In particular, when gypsum hemihydrate is used, it reacts with the water in the phenol resin and prevents repelling during combustion. Due to repellency during combustion, workability, etc., 10 to 30 parts of clay should be added to 100 parts of phenolic resin.
It is desirable to combine 20 to 60 parts by weight of gypsum hemihydrate.

The molded product of the present invention can be molded by a known molding method such as a hand lay-up method, a spray-up method, a mated die method, or a vacuum bag method.

Although the molding temperature varies depending on the amount of curing agent, curing cycle, and molding method, it can be arbitrarily selected from room temperature to 90°C, and if necessary, post-curing can be performed at 60 to 120°C.

As the fiber reinforcing material used in the present invention, the above-mentioned aluminum powder, aluminum particles, aluminum fiber, aluminum coated glass fiber and the reinforcing material shown below are used in combination. Examples of the fiber reinforcing material include glass fibers such as chopped strand mats, glass cloths, glass rovings, continuous mats, and surface mats, inorganic fibers such as carbon fibers and whiskers, and organic fibers such as aramid fibers.

(Example) The present invention will be explained in more detail with reference to Examples below.

Examples 1 to 4, Comparative Examples 1 to 3 [Example 1] An unsaturated polyester resin was applied as a gel coat layer according to the formulation shown in Table 1, and cured. As a primer layer, 100 parts of vinyl ester resin, 60 parts of aluminum hydroxide, and 168 parts of aluminum particles (17.2% based on the total molded product) were mixed, coated and cured on the gel coat layer, and 200 parts of phenol resin was added on top of it. , 67 parts of clay, 100 parts of Hanmizu stone
30 parts of hardening agent and glass mat (450g/
a#) Two layers (100 parts) of 250 x 250 mm were laminated, heated and cured, and a flat plate with a thickness of 5 mm was formed and a combustion test was conducted. The results are shown in Table 1.

[Examples 2 to 6] Laminate molding was carried out in the same manner as in Example 1, and a combustion test was conducted.

The formulation and combustion test results are shown in Table 1.

[Comparative Example 1] A gel coat prepared by adding 30 parts of aluminum hydroxide to 100 parts of unsaturated polyester resin was applied onto a glass plate and cured. Glass mat (450g/box) impregnated with a mixture of 200 parts of phenolic resin, 20 parts of clay, 40 parts of baked stone kola, and 30 parts of hardening agent 25
Two layers of 0 x 250 mm were laminated and cured by heating to form a flat plate with a thickness of 5 m+n, and a combustion test was conducted. The results are shown in Table 1.

[Comparative Examples 2 to 3] In the same manner as in Comparative Example 1, but using the formulations shown in Table 1, a gel coat and a primer layer of unsaturated polyester resin were respectively applied onto a glass plate and cured. Next, a phenol FRP layer was formed as a backing layer according to the formulation shown in Table 1. The results are shown in Table 1.

(Effects of the Invention) As is clear from the results in Table 1, according to the formulation according to the present invention, a product that passed the "nonflammability" standard of the Ministry of Transport was obtained. It can be used in railway vehicles, especially Shinkansen washbasin units and toilet units.

Claims (1)

[Claims] On the mold surface, (A) a gel coat layer containing 50 to 100 parts by weight of aluminum hydroxide to 100 parts by weight of an unsaturated polyester resin, (B) a reaction between an epoxy resin and an unsaturated monocarboxylic acid. 50 to 100 parts by weight of aluminum hydroxide and 10 to 40 parts by weight of any one or more of aluminum powder, aluminum grains, aluminum fibers, or aluminum coated glass fibers are blended into 100 parts by weight of the vinyl ester resin obtained by the method. A backing layer is formed by impregnating the primer layer and (C) a glass fiber base material with a phenolic resin composition consisting of 100 parts by weight of phenolic resin, 10 to 30 parts by weight of clay, and 20 to 60 parts by weight of gypsum hemihydrate. A method for producing a fiber-reinforced phenolic resin molded product, which comprises sequentially laminating and curing the molded product, and then removing the mold.