JPH05170840A - Unsaturated polyester resin composition, preparation of cured article, and molding material - Google Patents

Abstract

PURPOSE:To reduce the change with time in normal-temp. gelation time of the title compsn. without detriment to the quick curability as well as to the light color and clarity. CONSTITUTION:The title compsn. comprising an unsatd. polyester prepd. by reacting an acid component with an alcohol component, a crosslinking monomer, a vanadium compd., an alkyl phosphate, and a quaternary ammonium salt is provided together with a method for curing the compsn. and a molding material comprising the compsn.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an unsaturated polyester resin composition suitable for reinforced plastics, casting, buttons, decorative boards, coating, etc., a method for producing a cured product using the same, and a molding material. Regarding

[0002]

2. Description of the Related Art Conventionally, curing of an unsaturated polyester resin composition has been carried out by adding a polymerization initiator and heating the mixture at room temperature or at room temperature, and adding a polymerization initiator together with an accelerator. The method of curing at room temperature is not only economically desirable, but is a method particularly necessary for the production of processed products such as wood products in which heating should be avoided, and various methods using a combination of an accelerator and a polymerization initiator. Is proposed. As a combination of an accelerator and a polymerization initiator, cobalt naphthenate or a combination thereof with a dialkylaniline or toluidine derivative and methyl ethyl ketone peroxide, or a combination of dialkylaniline or toluidine derivative and benzoyl peroxide is known.

However, when these accelerators are used,
It has the drawback that the color of the cured product is yellowish brown or light reddish purple, and it cannot be used for products in which the hue of the cured product is particularly problematic, such as buttons and decorative boards, and it can be used outdoors in winter. There has been a problem that the curing rate is lowered during FRP molding at low temperature. In order to solve such a problem, an accelerator combining a vanadium compound and a dialkyl phosphate ester (British Patent 907363)
No.), an accelerator combining a vanadium compound and a reducing sulfur compound (Publication No. 39-29195), and the like. When these accelerators are used, the curability at room temperature or low temperature improves, but the polymerization reaction partially progresses over time, and a gelled product is formed, resulting in a markedly poor storage stability and industrial production. There was a problem that it was difficult.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, has an excellent curing speed at room temperature, has a light curing hue, and is an unsaturated polyester resin containing a vanadium compound and an alkyl compound. It is intended to provide an unsaturated polyester resin composition having a small time-dependent gelation time at room temperature even when an accelerator combined with a phosphoric acid ester is added, a method for producing a cured product using the same, and a molding material.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above problems, and as a result, the presence of a quaternary ammonium salt in the unsaturated polyester resin causes the unsaturated polyester resin to contain a vanadium compound, It has been found that an accelerator combined with an alkyl phosphate can be added to maintain rapid curing and light-color transparency of the color of the cured product, while significantly reducing the change in gelling time with time.
That is, the present invention provides (A) an unsaturated polyester obtained by reacting an acid component and an alcohol component, (B) a crosslinkable monomer, (C) a vanadium compound, (D) an alkyl phosphate and (E) a fourth Unsaturated polyester resin composition containing a primary ammonium salt, a method for producing a cured product by curing the unsaturated polyester resin composition in the presence of a polymerization initiator, and a molding material using the unsaturated polyester resin composition Regarding

The unsaturated polyester (A) used in the present invention is obtained by reacting an acid component, an alcohol component and, if necessary, a modifying component by a known method. Examples of the acid component include unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid, phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, benzoic acid and trimellitic acid. Saturated acids such as acids, vegetable oil fatty acids such as linseed oil, soybean oil, tall oil, castor oil, derivatives thereof, mixtures thereof and the like can be used.

As alcohol components, ethylene glycol, propylene glycol, diethylene glycol,
Dipropylene glycol, neopentyl glycol,
1,3-propanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,6-hexanediol, glycol, cyclopentanediol, cyclohexanediol , Diols such as xylene glycol and 2,2-bis (4-hydroxyphenyl) propane, and polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol can be used.

As the modifying component, cyclopentadiene,
Dicyclopentadiene or the like can be used.

Crosslinkable monomer (B) used in the present invention
Examples thereof include styrene, vinyltoluene, chlorostyrene, α-methylstyrene, divinylbenzene, methyl methacrylate, methyl acrylate, ethyl acrylate, vinyl acetate, diacrylic phthalate and the like. The amount of the crosslinkable monomer (B) to be blended is not particularly limited and can be adjusted according to reactivity, workability and various other purposes. The total amount is 100 parts by weight, and it is preferable to use 30 to 60 parts by weight of the crosslinkable monomer (B) with respect to 70 to 40 parts by weight of the unsaturated polyester (A).

The vanadium compound (C) used in the present invention is a trivalent to pentavalent vanadium or vanadyl compound such as vanadium chloride (Vcl ₃ ), vanadyl chloride (VOcl ₃ ), vanadium pentoxide (V ₂ O).
₅ ), vanadyl sulfuric acid (VOSO ₄ nH ₂ O, n = 0 to
5), salts of inorganic or organic acids such as vanadyl-p-toluene sulfonic acid, vanadyl acetic acid, vanadyl oxalic acid,
Examples thereof include organic acid complex compounds containing vanadyl complex salts of amino acids such as tartaric acid, malic acid, citric acid or glutamic acid, and soluble compounds such as vanadium and vanadyl complex salts of β-diketone compounds such as acetylacetone and acetoacetic acid esters. The blending amount of the vanadium compound (C) is preferably 0.0001 to 0.05% by weight based on the total amount of the unsaturated polyester (A) and the crosslinkable monomer (B).

Examples of the alkyl phosphate (D) used in the present invention include dibutyl phosphate, tributyl phosphate, triethyl phosphate and the like. The compounding amount of the alkyl phosphate ester (D) is
Unsaturated polyester (A) and crosslinkable monomer (B)
0.1 to 2.0% by weight is preferable with respect to the total amount.

As the quaternary ammonium salt (E) used in the present invention, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkylbenzyldimethylammonium chloride, alkylbicolinium chloride and the like are used. By using the quaternary ammonium salt (E), the change with time in the room temperature gelation time can be significantly reduced. The amount used is preferably 0.01 to 0.5% by weight based on the total amount of the unsaturated polyester (A) and the crosslinkable monomer (B).

Hydroquinone, methylhydroquinone, nitrophenol, pt-butylcatechol, and 2,5-di-t are used as long as they do not affect the object of the present invention.
-Butyl hydroquinone, mono-t-butyl hydroquinone, p-benzoquinone, naphthoquinone, para-xyloquinone 2,5-diphenyl-p-benzoquinone, 2,6
-Di-t-butyl-p-cresol, α-naphthol,
A polymerization inhibitor such as copper naphthenate may be used in combination.

The vanadium compound (C) and the alkyl phosphate ester (D) can be practically dissolved in a solvent before use. As the solvent, those having good compatibility with the unsaturated polyester resin obtained by dissolving an unsaturated polyester in a crosslinkable monomer and having no influence on the curability and the hue of the cured product are preferable, for example, methyl alcohol, ethyl alcohol, propyl alcohol. And aliphatic and aromatic alcohol compounds such as butyl alcohol and benzyl alcohol, glycol compounds such as triethylene glycol and hexylene glycol, and glycol monoether compounds such as methyl cellosolve and ethyl cellosolve. Of these, methyl cellosolve is particularly preferable for practical use. The amount of the solvent used is preferably 0.1 to 1.0% by weight based on the total amount of the unsaturated polyester (A) and the crosslinkable monomer (B).

Upon curing of the unsaturated polyester resin composition, for example, a ketone peroxide compound such as methyl ethyl ketone peroxide, cyclohexane peroxide, etc., a hydroperoxide compound such as cumene hydroperoxide, benzoyl peroxide, tertiary butyl peroxide, etc. A polymerization initiator such as a perester compound such as benzoate or a dialkyl peroxide compound such as dicumyl peroxide is used. The amount of the polymerization initiator used is usually 0.5 to 3.0% by weight with respect to the unsaturated polyester composition, and although it varies depending on the kind, it is generally cured in the range of 5 ° C or higher to 150 ° C or so. ..

The unsaturated polyester resin composition of the present invention contains a polymerization initiator and a reinforcing material and / or a filler to prepare a molding material. A reinforcing material such as glass fiber and a filler such as calcium carbonate are used, but a thixotropic agent such as erogel and a surface drying property-imparting agent such as wax may be contained.

[0017]

EXAMPLES The present invention will be described in detail below with reference to examples. The parts in the examples mean parts by weight unless otherwise specified. Example 1 0.50 mol of maleic anhydride, 0.50 mol of phthalic anhydride, 0.8 mol of propylene glycol and 0.3 mol of ethylene glycol were used as a heating device, thermometer, nitrogen gas blowing device, and condensed water distilling device. The mixture was placed in a reaction kettle equipped with a reactor and heated to 150 ° C. under stirring in a nitrogen atmosphere for half-esterification, and then reacted at 210 ° C. until the acid value reached about 25 to synthesize an unsaturated polyester. 65 parts of this unsaturated polyester was dissolved in 35 parts of styrene monomer in which 0.03 part of methylhydroquinone was dissolved to obtain a resin composition (I). To 100 parts of this resin composition (I), 0.3 parts of a 50% by weight solution of alkylbenzyldimethylammonium chloride in hexylene glycol and 0.4 parts of a solution of vanadyl sulfuric acid in methylselve (0.2% by weight of vanadyl metal, the same applies hereinafter). An unsaturated polyester composition I was prepared by dissolving 0.4 part of di-n-butyl phosphate ester. This unsaturated polyester resin composition I was treated at 60 ° C.,
After leaving it for 20 hours and at 25 ° C for 14 days,
Cumene hydroperoxide (active oxygen content 7.
7%) to 1.% of unsaturated polyester resin composition I.
Table 1 shows the results obtained by examining the gelation time at room temperature when adding 0% by weight and curing at room temperature and the hue of the cured product visually. The room temperature gelation time was measured by the method of JIS-6901. Comparative Example 1 Unsaturated polyester resin composition II in which the 50% by weight hexylene glycol solution of alkylbenzyldimethylammonium chloride in Composition I of Example 1 was not added
Was adjusted. With respect to this unsaturated polyester resin composition II, the room temperature gelation time and the hue of the cured product were examined in the same manner as in Example 1 and the results are shown in Table 1.

[0018]

[Table 1]

From Table 1, unsaturated polyester composition I containing alkylbenzyldimethylammonium chloride I
Shows that the cured product is light-colored and has a significantly smaller change in the room temperature gelation time with time as compared with the unsaturated polyester resin composition II.

Example 2 100 parts of the resin composition (I) of Example 1 was added to hexylene glycol 50 of alkylbenzyl ammonium chloride.
After 0.2 part by weight of a solution was added and dissolved, 0.8 part of a thixotropic agent (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) was added and sufficiently mixed to obtain a resin composition II. To 100 parts of this resin composition II, 0.5 part of a solution of vanadyl sulfuric acid in methyl cellosolve and di-n-butyl phosphate ester was added.
An unsaturated polyester resin composition III was prepared by dissolving 3 parts. This unsaturated polyester resin composition III6
0 parts of cumene hydroperoxide at 25 ° C. and 15 ° C. with unsaturated polyester resin composition III
1.0% by weight to the size of 150 × 1
Glass mat cut into 50 mm square (FEM-G45
FRP was prepared by impregnating 3 layers of 0, Fuji Fiber Glass Co., Ltd.), wrapping in cellophane, defoaming and curing. The curing time, hardness and hue of the cured product of the obtained FRP were investigated, and the results are shown in Table 2.

Comparative Example 2 0.8 part of the thixotropic agent was added to 100 parts of the resin composition (I) of Example 1 and mixed thoroughly to obtain a resin composition (III). To 100 parts of this resin composition (III), 0.3 part of cobalt octenoate (cobalt metal content 6.0%) and 0.05 part of dimethylaniline were added to prepare an unsaturated polyester resin composition IV. This unsaturated polyester resin composition I
To 60 parts of V, 1.0 wt% of methyl ethyl ketone peroxide (active oxygen content 10.0%) was added to the unsaturated polyester resin composition IV at 25 ° C. and 15 ° C., and FRP was added in the same manner as in Example 2. The curing time, hardness, and hue of the cured product were examined, and the results are shown in Table 2.

[0022]

[Table 2] (Note) Using a Barcol hardness tester (Barcor 935),
Time to reach hardness 60

From Table 2, in Example 2 using the unsaturated polyester resin composition of the present invention, although the curing time of FRP is long, the time to reach hardness 60 is short and the hue of the cured product is also high. It is shown to be excellent.

[0024]

According to the unsaturated polyester resin composition of the present invention, the accelerator containing the vanadium compound maintains the rapid curability and the light-color transparency of the hue of the cured product, and the presence of the quaternary ammonium salt. This makes it possible to reduce the change with time in the room temperature gelation time, which is sufficient for practical use in industrial production. The unsaturated polyester resin composition of the present invention has FR
It is particularly useful for P, casting, buttons, decorative boards, and painting.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 67/06 MSD 8933-4J

Claims (3)

[Claims] 1. An unsaturated polyester obtained by reacting (A) an acid component and an alcohol component, (B) a crosslinkable monomer, (C) a vanadium compound, (D) an alkyl phosphate and (E) a quaternary compound. An unsaturated polyester composition containing an ammonium salt. 2. A method for producing a cured product, which comprises curing the unsaturated polyester resin composition according to claim 1 in the presence of a polymerization initiator. 3. A molding material containing the unsaturated polyester resin composition according to claim 1, a polymerization initiator and a reinforcing material and / or a filler.