JPS5842456A - Uninflammable reinforced plastic shape - 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 The present invention relates to a nonflammable reinforced plastic molded article.

Conventionally, methods for making reinforced plastic molded products flame retardant include:
The methods used include using a chlorinated or brominated resin, or adding a flame retardant such as antimony trioxide or chlorinated paraffin, or an inorganic filler containing water of crystallization such as hydrated alumina or gypsum.

However, when a reinforced plastic molded product with a gel coat formed using these methods is burned, heat accumulates in the exposed areas, and after a certain amount of time, the gel coat layer cracks and separates from the reinforcing layer. There was a problem with ignition and ignition.

An object of the present invention is to provide a non-combustible reinforced plastic molded product that prevents heat from accumulating in areas exposed to grains during combustion, that is, disperses heat, and prevents cracking, peeling, ignition, and flaming of the gel coat layer. There is a particular thing.

The present invention provides a gel coated reinforced plastic molded article (hereinafter referred to as gel coated FRP) using unsaturated polyester resin or vinyl ester resin, in which the gel coat layer is made of metal powder or/and metal oxide without crystal water. 50 parts or more per 100 parts by weight of the resin (hereinafter abbreviated as "parts"), and the reinforcing layer contained 25 parts or more of a metal powder or/and a metal oxide having no crystal water per 100 parts of the resin. This relates to a non-combustible reinforced plastic molded product consisting of a glass fiber reinforced layer, and the molded product is in good condition, with no cracks, ignition, or flaming, except for slight discoloration on the surface of the gel coat layer that is exposed to flame during combustion. can bring.

Examples of the metal powder used in the present invention include iron, aluminum, zinc, copper, magnesium, silicon, chromium, manganese, cobalt, nickel, molybdenum, silver, cadmium, antimony, tungsten, platinum, gold, etc. Examples of metal oxides without crystal water include oxides of the metal powders mentioned above.

In addition, other inorganic fillers such as aqueous alumina, gypsum, calcium carbonate, zinc silicate, alum, calcium hydroxide, clay, etc., vinyl chloride resin powder, polyethylene resin powder, etc. may be used in the gel coat layer and reinforcing layer in the present invention. There is no problem even if a thermoplastic resin of 100% is added.

The unsaturated polyester resin used in the present invention is obtained by suitably combining polyhydric alcohols, unsaturated polycarboxylic acids, saturated polycarboxylic acids, etc. and subjecting them to a condensation reaction at high temperatures in an inert atmosphere. The unsaturated polyester is dissolved together with a polymerization inhibitor in a polymerizable monomer such as styrene, methyl methacrylate, and a mixture of styrene and methyl methacrylate.

Vinyl ester resin is also called epoxy acrylate-1 resin or unsaturated epoxy resin, (A) an epoxy compound having at least one epoxy group in the molecule (B) an unsaturated basic acid (C) a saturated Alternatively, an unsaturated dibasic acid alone or an oligodibasic acid obtained from a saturated or unsaturated dibasic acid and a glycol (A) and CB) or (B) and (C) are suitably esterified. The resulting vinyl ester is dissolved in a polymerizable monomer together with a polymerization inhibitor.

The gel coat layer in the present invention contains metal powder and/or a metal oxide without water of crystallization in an amount of 50 parts or more, preferably 80 to 400 parts, based on 100 parts of the resin. It is appropriate to use 25 parts or more, preferably 50 to 100 parts, of the powder and/or metal oxide without crystal water per 100 parts of the resin.

The glass fiber in the reinforcing layer of the present invention is usually used in glass mat, glass roving cloth, glass roving, etc.
% is preferred.

The molded product of the present invention usually has gel coat layers laminated to a thickness of 0.3 to 1 mm. Incidentally, the gel coat layer and reinforcing layer in the present invention may be mixed with additives such as a coloring agent, a flame retardant, and an anti-shrinkage agent, if necessary.

The molded product of the present invention not only has excellent nonflammability but also excellent mechanical strength, so it can be used as interior wall materials, ceilings, unit baths, vehicle-related parts, such as under-floor storage equipment cylinders,
It is used for tanks, ducts, etc., and is particularly suitable for vehicle-related parts.

Next, the present invention will be explained with reference to examples, in which ``chi'' represents weight %.

Example 1 Unsaturated polyester resin (manufactured by Inu Nippon Ink Chemical Industry ■,
Polylye) FG・190) 100 parts and zinc powder 600
Part 6- was mixed. After adding 0.5% of 6% cobal naphthenate as an accelerator and 1.0% of 55% methyl ethyl ketone peroxide as a hardening agent to this composition, it was applied to the surface of a glass plate that had been surface-treated with a mold release agent in advance. did. After gelling by leaving it as it is at room temperature, it was cured in a hot air dryer at 40 to 50°C to form a gel coat layer.

Next, 100 parts of unsaturated polyester resin, 10 parts of zinc powder
0 parts and 50 parts of hydrated alumina were mixed. This composition contains 6% cobalt naphthenate 0.5% as an accelerator and 1.0% 55 dimethyl ethyl ketone peroxide as a hardener.
(Glass chopped strand pine)
(45 oz), and a reinforcing layer was laminated on the surface of the gel coat layer by a hand lay-up method so that the amount of glass fiber was 20 inches.

Thereafter, it was gelled and cured in a hot air dryer at 60 to 70°C.

Test plates for the Ministry of Transport type combustion test (B-5 size) were cut out from the FRP board created in this way, and a combustion test for non-metallic materials for railway vehicles standardized by the Ministry of Transport was conducted. There was no flame formation, and only slight discoloration was observed on the surface of the gel coat layer that was exposed to the flame.
The nonflammability test was passed.

Comparative Example 1 In Example 1, when zinc powder and hydrated alumina were added to a firing test, they ignited violently and ignited into flames, failing the test for nonflammability.

Comparative Example 2 An FRP board was obtained in the same manner as in Example 1 except that a reinforcing layer containing 100 parts of hydrated alumina without containing zinc powder was used, and a Ministry of Transport combustion test was conducted. However, cracks appeared on the surface of the gel coat, and the nonflammability test was rejected.

Comparative Example 6 In Example 1, the gel coat layer was made of 100 parts of water phase alumina without adding zinc powder, and the reinforcing layer was also made of 100 parts of water phase alumina without adding zinc powder. An FRP board was prepared in the same manner as in Example 1, except that the board was subjected to a Ministry of Transport combustion test. Cracks, ignition, and flaming occurred in the gel coat layer, and the nonflammability test was rejected.

Example 2 A gel coat layer was obtained in the same manner as in Example 1 except that 150 parts of aluminum powder was used instead of zinc powder and hydrated alumina, and 100 parts of aluminum powder was used instead of zinc powder.
An FRP board was prepared in accordance with Example 1 using the same reinforcing layer as in Example 1 except for using the following. This FRP board passed the Ministry of Transport standard 9-flammability test for nonflammability.

Comparative Example 4 A gel coat layer was obtained in the same manner as in Example 1 except that 50 parts of aluminum powder was used instead of zinc powder, and Example 1 except that 25 parts of aluminum powder was used instead of zinc powder.
F R according to Example 1 using the reinforcing layer obtained in the same manner as
l) A board was prepared and a combustion test according to the Ministry of Transport standards was conducted at t7, and it failed to pass the test for nonflammability.

Comparative Example 5 FR was produced in the same manner as in Example 1, except that in Example 2, the amount of aluminum powder in the gel coat layer was changed to 30 parts, and the amount of aluminum powder in the reinforcing layer was changed to 20 parts.
When a P board was prepared and subjected to a Ministry of Transport standard combustion test, it was found to have a small rank without ignition, and failed the test for nonflammability.

=10- Example 6 Example 1 except that 150 parts of iron oxide was used instead of zinc powder in the gel coat layer, and 100 parts of iron oxide was used instead of zinc powder in the reinforcing layer. An FRP board was obtained by pressing in the same manner as above, and when a Ministry of Transport combustion test was conducted, it passed the nonflammability test.

Example 4 FRP made in the same manner as in Example 2 using vinyl ester resin (Inu Nippon Ink Chemical Industry Dick Light UE-5210) instead of the unsaturated polyester resin.
When the board was subjected to a Ministry of Transport combustion test, there were no cracks, peeling, ignition, or flames, and it passed the test as nonflammable.

Patent applicant Nippon Ink Chemical Industry Co., Ltd. 11-

Claims (1)

[Claims] (1) A gel coat layer comprising 100 parts by weight of an unsaturated polyester resin or vinyl ester resin and 50 parts by weight or more of a metal powder or/and a metal and oxide without water of crystallization; and (II) an unsaturated polyester resin or vinyl ester. A nonflammable reinforced plastic molded article formed by laminating 1.00 parts by weight of a resin, 25 parts by weight or more of a metal powder or/and a metal oxide free of water of crystallization, and a reinforcing layer containing glass fiber.