JP2002080706A - Unsaturated polyester-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated polyester-based resin composition capable of keeping not only excellent moldability but also flame retardance at the time of processing. SOLUTION: This resin composition is characterized in that the unsaturated polyester resin contains one or more kinds of hydrotalcite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a novel unsaturated polyester resin composition. More specifically, an object of the present invention is to provide excellent water resistance without lowering the moldability of a product during processing of an unsaturated polyester resin.

[0002]

[Prior art]

2. Description of the Related Art At present, flame-retardant unsaturated polyester resin compositions are used as molding materials for electric / electronic equipment parts and automobile parts, and the use of such resin compositions is expected to increase more and more in the future. ing. However, as the functions used for molded articles have increased, the performance requirements for molding materials have increased and have become stricter. For this reason, in order to satisfy various required performances, various additions are added to the unsaturated polyester resin. For example, an epoxy resin is added for the purpose of preventing decomposition of the flame-retarded thermoplastic polyester resin at the time of molding or improving hydrolysis resistance (JP-A-54-149756, JP-A-57-1979). −
No. 5745), triaryl phosphate and glass fiber are added to unsaturated polyester resin for the purpose of improving heat resistance (boiling water resistance). Japanese Patent Application Laid-Open No. 56-161452) discloses that an unsaturated polyester resin contains a carbodiimide compound, an epoxy compound and glass fiber in order to improve the above.

[0003] By the way, under high temperature, especially in an environment under high pressure and high temperature due to steam pressure such as a polyester resin molded part used for a rice cooker or a car hood (in many cases, a high temperature and high humidity environment). When the polyester resin molded part is used for a long time, the physical properties of the polyester resin molded part are significantly reduced due to hydrolysis. In order to prevent the hydrolysis and improve the moisture resistance, it is common to use the above-mentioned epoxy compound or a combination of the epoxy compound and the carbodiimide compound. However, the epoxy compound does not have a sufficient effect of improving the hydrolysis resistance, and the melt viscosity of the material becomes high, so that the moldability is deteriorated and the epoxy compound is not practical. In addition, the effect of improving the hydrolysis resistance is not sufficient even when a carbodiimide compound is used in combination. In addition, triaryl phosphate alone did not show an effect of improving moisture resistance.
For this reason, it has been quite difficult with conventional techniques to obtain a flame-retardant unsaturated polyester resin composition having good moldability and excellent moisture resistance.

[0004]

The object of the present invention is to provide a flame-retardant unsaturated polyester resin composition which has good moldability and does not adversely affect the water resistance of the product when processing the unsaturated polyester resin. With the goal. In general, equation (1)

^{Embedded image} [M 2 ⁺ _{1 -X} M ³⁺ _X (OH) ₂ ] ^{X +} [A ⁿ⁻
_{x / n} · yH ₂ O] ^X-

FIG. ( ^Where M ²⁺ is a divalent cation, M ³⁺ is a trivalent cation,
A ^n- represents an anion, and 0 ≦ x ≦ 0.5, n ≧ 1, y> 0), specifically, hydrotalcite-type layered metal double water Called oxide, as shown in FIG.

FIG. 2 [M 2 ⁺ _{1 -X} M ³⁺ _x (OH) ₂ ] The octahedral layer (double hydroxide layer) formed by the portion of ^{X +} has a positive charge,
Negative charge of ^n- supported anion A in the interlayer is commensurate with the positive charge, electrical neutrality is maintained.

The hydrotalcite compound (1) has an anion-exchange property and can take in large anions in a short time and with high efficiency, and thus has an advantage that the production process can be simplified. It is.
Generally, it traps chlorine in PVC, so that it is often used as a stabilizer for PVC. However, there are not many examples of use for unsaturated polyester-based resins such as polyesters, and the present study was conducted.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the problems have been solved by incorporating one or more of the above hydrotalcites into an unsaturated polyester resin. The present invention was completed, and the present invention was completed.

The unsaturated polyester resin according to the present invention includes an unsaturated polyester resin obtained by subjecting a saturated dibasic acid and an unsaturated dibasic acid to a condensation reaction with a dihydric alcohol and mixing a vinyl monomer. Specifically, the composition is composed of a glycol, a saturated dibasic acid such as adipic acid, phthalic anhydride, tetrachlorophthalic anhydride, nadic anhydride, and heptic acid; an unsaturated dibasic acid such as maleic acid and fumaric acid; Dihydric alcohols such as propylene glycol, ethyl glycol, 1.3-butylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, bisphenol dioxyethyl ether, and vinyl polymers such as styrene, diallyl phthalate, triallyl isocyanate, methyl methacrylate, and diallyl Examples thereof include vinyl monomers such as benzenephosphonate, but are not limited thereto.

When 3 to 20 parts by weight of hydrotalcite is added to 100 parts by weight of the unsaturated polyester resin composition, hydrotalcite releases crystal water from about 200 ° C., thereby exhibiting a flame retardant effect. For the purpose of the flame retardant effect, the addition amount of the hydrotalcite is suitably 3 to 20% by weight in the flame retardant composition. When the amount is 0.01 to 5% by weight, sufficient thermal stability can be obtained, and the mechanical strength of the flame retardant composition is reduced and the migration of components to the surface (bleeding phenomenon) is small. However, if the amount is more than 5 parts by weight, the water resistance deteriorates. Also, the viscosity tends to increase according to the amount added. There are grades in the particle size, but for uniform dispersibility in resin and transparency, the particle size is desirably 3 μm or less. If it is more than 5 microns, the dispersibility is poor, which adversely affects moldability, transparency and flame retardancy.

Further, various additives such as a curing agent (peroxides) and an accelerator (cobalt naphthenate) which are usually contained during the processing of the unsaturated polyester resin may be appropriately contained depending on the purpose and application. good.

[0010] Various additives are added to the unsaturated polyester resin. Among them, fillers, thickeners, coloring agents, foaming agents, and release agents are typical ones. Further, the compositions of the present invention also include reinforced flame retardant compositions reinforced with the following fillers. Known and commonly used reinforcing fillers can be used as necessary. Among them, typical ones are glass fiber, carbon fiber, potassium titanate fiber, metal fiber, ceramic fiber, aramid fiber, PPS fiber, Calcium carbonate, calcium silicate,
Magnesium silicate, calcium sulfate, barium sulfate,
Examples include iron oxide, graphite, carbon black, mica, asbestos, ceramic powder, metal flake, and glass peas.

The present invention will be specifically described below with reference to examples.

[0011] hydrotalcite used in Example This example average particle size is of aluminum ^magnesium, as ^{M 3 +} is as ^{M 2+} is of 0.3 to 1.5 microns. As A ^n- is CO ₃ ^- it is. The hydrotalcite used as a comparative example has an average diameter of 8 microns.

[Table 1] The compositions shown in Table 1 were mixed in a stainless steel beaker in a stainless steel beaker for 5 minutes in an atmosphere at a temperature of 25 ° C., and left for 5 minutes for defoaming to prepare a liquid composition. The viscosity was measured with a B-type viscometer.

1) Formability Each liquid composition is 3 cm square and 3 m thick on a photographic ferroplate.
m, and after gelation, put it in a 110 ° C shelf dryer.
hr to complete cure. When cooled to room temperature, the moldability was evaluated based on the degree of peeling from the ferroplate. 2) Water resistance Further, each of the above liquid compositions was poured into a test tube, and a test piece, which was similarly gelled and completely cured, was placed at 80 to 90 ° C. for 100 hours.
The surface state of the hrs dough was visually observed to evaluate the water resistance.

3) Flame retardancy: Based on a test of the surface of a quasi-incombustible material described in Ministry of Construction Notification No. 1231. 4) Weather resistance Sunshine weather meter: room temperature 40 ° C, panel temperature 63 ° C, cycle 120 minutes, spray 18 minutes Water pressure: 0.8 kg / cm ³ Evaluation method ○ No change △ Some change × Some change

[0014]

As can be seen from the examples, the composition of the present invention has excellent water resistance and moldability of products, and can be effectively used in fields requiring water resistance. It also has excellent flame retardancy. In addition, when an artificial marble pigment is used, it is possible to produce a marble-like bathtub or the like having a texture and appearance close to that of an extremely high-grade natural stone. Further, it is understood that the weather resistance required for the resin composition is excellent.

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[Procedure amendment]

[Submission date] January 25, 2001 (2001.1.2)
5)

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[0004]

SUMMARY OF THE INVENTION The present invention provides a flame-retardant unsaturated polyester resin composition which has good moldability and does not adversely affect the water resistance of the product when processing the unsaturated polyester resin. With the goal. In general, equation (1)

Embedded image [M²⁺ _1-XM³⁺ _X(OH)_Two]^{X +}[A^n-
_{x / n}・ YH₂O]^X-  (Where M²⁺Is a divalent cation, M³⁺Is a trivalent cation,
A^n-Represents an anion, and 0 ≦ x ≦ 0.5, n ≧ 1, y> 0
The hydrotalcite compounds represented by
Called hydrotalcite-type layered metal double hydroxide
As shown in FIG.

Embedded image [M 2 ⁺ _{1 -X} M ³⁺ _x (OH) ₂ ] The octahedral layer (double hydroxide layer) formed by the portion of ^{X +} has a positive charge,
Negative charge of ^n- supported anion A in the interlayer is commensurate with the positive charge, electrical neutrality is maintained.

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[Brief description of the drawings]

Fig. 1 General structure of hydrotalcite

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FIG.

Claims (2)

[Claims] 1. A resin composition obtained by adding at least one kind of hydrotalcites to an unsaturated polyester resin. 2. The resin composition according to claim 1, which is hydrotalcite having an average particle size of 3 μm or less.