JPS60248771A - Flame-retardant fiber-reinforced thermosetting resin article having high transparency - Google Patents

Abstract

PURPOSE:To provide a molded article having excellent transparency and weather resistance, and low smoking tendency in combustion, by impregnating a composition composed of a specific unsaturated polyester resin, a vinyl ester resin, alumina white and a curing agent in a specific fibrous reinforcing material, and curing and forming the composition. CONSTITUTION:(A) 100pts.(wt.) of an unsaturated polyester resin and/or vinyl ester resin giving a cured product having a refractive index of 1.51+ or -0.03 at 15 deg.C is compounded with (B) >=30pts. of alumina white of formula [Al2SO4(OH)4. XH2O.2Al(OH)3]n, and the obtained resin composition is impregnated in a fibrous reinforcing material having a refractive index of 1.51+ or -0.03, preferably 1.51+ or -0.02 at 15 deg.C. The impregnated product is cured and formed. The alumina white is preferably the one having a refractive index of 1.51+ or -0.03.

Description

DETAILED DESCRIPTION OF THE INVENTION Compositions prepared by adding aluminum hydroxide to unsaturated polyester resins and products reinforced with glass fibers are flame retardant and are commonly used.

The present invention utilizes a specific unsaturated polyester resin and/or vinyl ester resin and the general formula [A12SO4(OH)
4.XH2O-2AI(OH)3). It is obtained by impregnating a specific fibrous reinforcing material with a resin composition consisting of alumina white and a hardening agent, and then curing and molding it as a single piece. Fiber-reinforced thermosetting resin (hereinafter referred to as F
It's called RP. ) provides goods.

That is, in the present invention, the general formula is A resin composition consisting of 30 parts by weight or more of alumina white and a curing agent is impregnated into a fibrous reinforcing material having a refractive index of 1.51 ± 0.03 at 15°C and cured as one body. The present invention relates to an FRP article obtained by molding that is highly transparent, flame retardant, produces little smoke when burned, and has excellent weather resistance.

The unsaturated polyester resin and/or vinyl ester resin used in the present invention can be freely used as long as it has a refractive index in the range of 1.51±0.03 at 15°C when cured. . Therefore, even if an unsaturated polyester resin or vinyl ester resin has a refractive index that is not within the range of 1.51±0.03 at 15°C when cured, the refractive index of a cured resin that is a combination of these resins is If it is in the range of 1.51±0.03 at 15°C, it can be used. Among them, the following examples (1) and (It) can be cited as preferred embodiments.

(I) An acid component containing maleic anhydride and/or fumaric acid as an essential component and mainly containing an aliphatic polybasic acid and/or an alicyclic polybasic acid and an aliphatic polyhydric alcohol and/or an alicyclic polybasic acid. Unsaturated polyester which is a polycondensate with alcohol component whose main component is alcohol 90~
The refractive index of the cured product is in the range of 1.51 ± 0.03 at 15°C with the unsaturated polyester resin and the 110 to 90 weight ratio of the 1O superimposed part and the vinyl monomer. thing. Furthermore, among these, maleic anhydride and/or fumaric acid 10 to 60 molar, other aliphatic polybasic acids and/or
or an unsaturated polyester (a) which is a polycondensate of an acid component of an alicyclic polybasic acid having a mole ratio of 90 to 40 and an alcohol component of an aliphatic polyhydric alcohol and/or an alicyclic polyhydric alcohol (40 to 700) Monomer composition (b) consisting of ~70% by weight aromatic vinyl monomer 30-70% by weight and 70-30% by weight (meth)acrylate monomer 60
An unsaturated polyester resin containing up to 30% by weight is preferable because the final FRP article obtained has a particularly good balance of transparency and other physical properties.

Examples of the acid component and alcohol component used in the unsaturated polyester resin are, for example, Polyester Resin by Eiichi Takiyama (Nikkan Kogyo Shimbun, August 3, 1980).
Table 2 and 1 of Glass Materials Course 10), published 9th edition on 0th
(a) (page 25) and Table 2.z (bl (page 26)). Among them, aliphatic or alicyclic polybasic acids and polyhydric alcohols are listed. As mentioned above, it is preferable to use it extensively.

In addition, as the vinyl monomer (■), those listed in Table 2.1 (Q (page 27)) of "Polyester Resin" by Eiichi Takiyama mentioned above can be mentioned. As mentioned above, the monomer composition (b) containing an aromatic vinyl monomer and a (meth)acrylic acid ester monomer is a preferred book.Aromatic vinyl monomer The most common monomers are styrene and vinyltoluenes, and examples of (meth)acrylic acid ester monomers include methyl (meth)acrylate and butyl (meth)acrylate.
Acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentynyloxyethyl (meth)acrylate, hydroxyethyl (
meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, etc. It is also possible to use (meth)acrylic acid in a small proportion.

(1) Reaction product of an epoxy compound whose main component is an aliphatic epoxy resin and/or an alicyclic epoxy resin and an acid component whose main component is (meth)acrylic acid (090-
A vinyl ester resin consisting of 10 parts by weight and 10 to 90 parts of the vinyl placing monomer a3, which has a refractive index in the range of 1.51±0.03 at 15°C when cured.

An example of an epoxy compound that is a component of reaction product 0 used in vinyl ester resin is "Epoxy Resin" by Kuniyuki Hashimoto (Plastic Materials Course ■, published by Nikkan Kogyo Shimbun, October 30, 1964, 2nd edition). Epoxy resin and hydrogenated hisphenol A described on pages 43 to 47, 1.6-
・Cysandio/L1 Polyhydric glycidyl ethers obtained by polycondensation of epichlorohydrin with polyhydric alcohols such as polypropylene glycol and neopentyl glycol, and glycidyl esters of polyhydric carboxylic acids. As mentioned above, it is preferable to use as many aliphatic or alicyclic polyepoxy compounds as possible.

Furthermore, as the vinyl monomer 0 used in the vinyl ester resin, those listed as the vinyl monomer (B) can be used.

Use of unsaturated polyester in Embodiment Example (1) or reaction product 0 in Embodiment Example (11) may cause problems such as a uniform composition or foaming due to excessive heat generation during polymerization. Conversely, if the viscosity is set higher than the above range, the viscosity becomes too high, making molding operations difficult and making it impossible to use a sufficient amount of filler.

Alumina white is represented by the above general formula and has a refractive index of about 1.47 to 1.56 at room temperature, but is an amorphous compound according to X-ray diffraction.

The refractive index is preferably in the range of 1.51±0.03 at room temperature, and when a refractive index in this range is used, the resulting article will have excellent translucency.

The ratio of unsaturated polyester resin and/or vinyl ester resin to alumina white is 100 parts by weight of the former and 30 parts by weight or more of the latter.

If the amount of alumina white is less than 30 parts by weight, the flame resistance will be insufficient, so it is preferable to use as much as possible as long as it does not interfere with the molding operation.

Curing agents include polymerization initiators such as organic peroxides and diazo compounds. A combination of an organic peroxide and an accelerator is particularly effective when curing at medium to low temperatures. Organic peroxides include L-benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, methyl in butyl ketone peroxide, cyclohexanone peroxide, etc. Diazo compounds include 2.2'-azobisin butyronitrile and 2.2' -azobis(2,4-dimethylbaleonitrile L2,2'-azobis(4-methylhaleonitrile),],]1'-azobiscyclohexane-1
-Carbonitrile), etc., as promoting culm, tertiary amines, quaternary ammonium salts, cobalt, manganese, etc.
Soluble metal soaps such as copper and calcium may be used alone or in combination.

The fibrous reinforcement material has a refractive index of 1.51± at 15°C.
Any material, organic or inorganic, can be used as long as it has a refractive index of 0.03, but particularly preferred is B glass, which has a refractive index of 1.51±0.02 at 15°C. It provides excellent translucency. The reinforcing material can be used in various forms such as roving, chopped strands, chopped strand mats, and cloth, but the fiber length is 5 fibers or more, and the unsaturated polyester resin and/or vinyl ester resin has a weight of 100%. It is preferable to use 5 parts by weight or more. This is to maintain the properties of FRP such as impact resistance of the product.

A typical embodiment of the present invention is as follows.

30 parts by weight or more of the alumina white is mixed with 100 parts by weight of the unsaturated polyester resin and/or vinyl ester resin, and then 0.5 to 0.5 parts by weight of the above curing agent is added to 100 parts by weight of the resin. A resin composition is prepared by adding 3.0 parts by weight and, if necessary, also adding the above-mentioned accelerator. This resin composition is degassed if necessary, impregnated into the aforementioned fibrous reinforcing material mat or cloth, as well as preformed roving or roving chops, and then molded and hardened by the usual FRP molding method to achieve the purpose. can be reached. For example, the fibrous reinforcing material in the form of a mat is continuously supplied, and the material is sandwiched between the release film together with the resin composition while defoaming, impregnated, and then introduced into a curing furnace to form a corrugated shape. When solidified, a transparent, flame-retardant FRP corrugated sheet with excellent weather resistance is continuously obtained. Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples, but these do not include all of the present invention.

In addition, in the examples, "1 part" generally refers to "parts by weight."

Example l 3.6 moles of propylene glycol, 1.5 moles of hydrogenated bisphenol A, 3.3 moles of acynic acid, and 1.6 moles of maleic anhydride were heated to 200 to 210 moles under an inert gas flow.
The mixture was diesterized by a melting method at .degree. C. to obtain an unsaturated polyester having an acid value of 30 (hereinafter referred to as polyester (1)). 20 parts of styrene and 10 parts of methyl methacrylate were blended with 70 parts of polyester (1) to obtain an unsaturated polyester resin (hereinafter referred to as resin ()). The refractive index of the cured product of resin (1) at 15° C. was 1.50.

Resin (1) 100 parts, alumina white (manufactured by Bunmei Kagaku Kogyo Co., Ltd., refractive index i, s 1) ty s parts, dimethylaniline 0.2 parts, and benzoyl peroxide 0.6
After defoaming, 25 parts of B glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) was impregnated with 75 parts of the resulting composition. An FRP board (1) with a thickness of 2.7 # was obtained. The FRP board (1) was flame retardant and transparent enough to read a newspaper that was closely attached to the back side.

Comparative Example l Comparative FR was made in the same manner as in Example 1 except that aluminum hydroxide was used instead of alumina white in Example 1.
A P plate (1) was obtained. Although the comparison FRP board (1) was flame retardant, it was slightly inferior to the FRP board (1), and was milky white, making it impossible to read a newspaper that was closely attached to the back.

Example 2 3.6 mol of propylene glycol, 1.5 mol of phthalic anhydride
An unsaturated polyester having an acid value of 25 (hereinafter referred to as polyester (2)) was obtained in the same manner as in Example 1 using 1.5 moles of fumaric acid and 1.5 moles of fumaric acid. Polyx Stell (1)
40 parts, Ho9 ester (2) 20m, styrene 20
1 part and 20 parts of methyl methacrylate were blended to obtain an unsaturated polyester resin (hereinafter referred to as resin (2)). The refractive index of the cured product of resin (2) at 15° C. was 1.54.

Resin (Z) aS part, alumina white (manufactured by Bunmei Kagaku Kogyo Co., Ltd., refractive index z, s 1) s s part, benzoyl peroxide 0.3 part and 1 part B glass fiber cut into 4 inch pieces (Nippon Electric Glass ■ Knead 10 parts of (manufactured by) in a kneader until uniform and heat the premix mixture to a thickness of 3wm.
An FRP board (2) was obtained. The FRP board (2) is flame retardant, and the FRP board (1) can be used to read newspapers that are placed close to the back.
Although the contrast was slightly lower than in the case of , it was sufficiently transparent.

Example 3 320 parts of an epoxide of liquid polybutadiene, which is an aliphatic epoxy resin, and 87 parts of methacrylic acid were mixed with 9 parts of styrene.
A vinyl ester resin (hereinafter referred to as resin (3)) was obtained by reacting according to a conventional method using 3 parts as a solvent. The refractive index of the cured product of resin (3) at 15°C is 1.4
It was 9.

Resin (3) 60 parts, azobisisobutyronitrile 0.1
8 parts and 40 parts of alumina white (manufactured by Ozeki Kagaku Kogyo Co., Ltd., refractive index 1.sl) and a roving made of B glass were used to conduct a pretreatment process carried out in the unsaturated polyester resin industry. The helmet was molded according to the 7 ohm mated metal die method. The obtained helmet was flame retardant and had excellent transparency.

Claims (1)

[Claims] 1.Refractive index when cured is 1.51±0 at 15℃
．． 03 and the general formula [Al 2804
(OH) A resin composition in which alumina white represented by xazo・2Al(OH)3) is essential and the ratio of the latter is 30 parts by weight or more to 100 parts by weight of the former is 1
A highly transparent flame-retardant fiber-reinforced thermosetting resin article obtained by impregnating a fibrous reinforcing material with a refractive index in the range of 1.51±0.03 at 5° C. and curing and molding the product as one piece.