JPH0129365B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an unsaturated polyester resin composition having a small curing shrinkage rate. The shrinkage rate of unsaturated polyester resin compositions largely depends on the amount of polymerizable monomer, and when 50-30% styrene monomer is used, the shrinkage rate is 7-10%. This is undesirable because it causes defects such as cracks in the product and deformation of the FRP product. One method of reducing this shrinkage rate is to use a dicyclopentadiene derivative as a raw material for unsaturated polyester (Japanese Patent Publication No. 40-25900), but the shrinkage rate in this case is 6 to 9%, about 1. % is only improved. Additionally, a method is generally known in which a thermoplastic polymer such as polystyrene is dissolved in an unsaturated polyester resin composition, but in this case, the thermoplastic polymer phase undergoes phase separation, resulting in poor pigment dispersibility and poor molded appearance. A new disadvantage of inferiority arises, which is not desirable. As described above, no method has yet been proposed to sufficiently reduce the shrinkage rate without degrading other properties. The present inventors added tricyclodecenyl maleate and/or tricyclodecenyl fumarate, which is one of the dicyclopentadiene derivatives, to 20 to 20% of the total acid component.
Using 85 mol%, the terephthalic acid component is 15 to 15% of the acid component.
It has been found that an unsaturated polyester resin composition using an unsaturated polyester with an acid value of 55 to 40 obtained by using 80 mol% has a turbidity of 40 or more and a small shrinkage rate of 3.5 to 6%. The present invention uses tricyclodecenyl maleate and/or tricyclodecenyl fumarate as an acid component.
Using 85 mol%, the terephthalic acid component is 15 to 15% of the acid component.
The present invention relates to a low-shrinkage unsaturated polyester resin composition containing an unsaturated polyester having an acid value of 55 to 40 obtained by using 80 mol % and a polymerizable monomer. In the present invention, the amount of tricyclodecenyl maleate and/or tricyclodecenyl fumarate used, the amount of terephthalic acid component used, and the acid value of the resulting unsaturated polyester are within the above ranges, This is to maintain the turbidity of the low-shrinkage unsaturated polyester resin composition at 40 or higher, thereby obtaining desirable mechanical strength and shrinkage of the resulting cured product. Tricyclodecenyl maleate and/or tricyclodecenyl fumarate in an amount of 20 to 85 mol% of the acid component
However, when the terephthalic acid component is not used in combination, the turbidity is usually as low as 30 or less, and the shrinkage rate is 6 to 9%, which is not sufficient as described above. Furthermore, if the acid value of the unsaturated polyester is made higher than 55, the mechanical strength of the cured product will decrease. Furthermore, if the acid value is increased to 80 or higher, the turbidity becomes 40 or higher, but the compatibility with the styrene monomer becomes extremely poor and the product separates into two phases. On the other hand, when the terephthalic acid component is used in an amount less than 15 mol %, the acid value of the unsaturated polyester becomes higher than 55 in order for the turbidity to become 40 or more, and the mechanical strength of the cured product decreases. Further, even when 15 to 80 mol% of the terephthalic acid component is used, if the acid value of the unsaturated polyester is less than 40, transparency will rapidly recover and the shrinkage rate will increase.
Furthermore, if the acid value of the unsaturated polyester is greater than 55, the mechanical strength of the cured product will decrease. Next, the materials will be explained. Tricyclodecenyl maleate and tricyclodecenyl fumarate can be obtained, for example, by the method described in Japanese Patent Application No. 107607/1983. Moreover, the terephthalic acid component refers to polymers such as terephthalic acid, dimethyl terephthalate, and polyethylene terephthalate, which are cracked by adding glycol. In addition to these acid components, unsaturated dibasic acids such as maleic anhydride, fumaric acid, itaconic acid, and muconic acid, and saturated dibasic acids such as phthalic anhydride, isophthalic acid, succinic acid, adipic acid, sebacic acid, and tetrahydrophthalic anhydride, One type or two or more types of basic acids can be used. Alcohol components include propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and alkylene oxide adducts of bisphenol A. , glycerin, etc. can be used. As the polymerizable monomer, styrene, vinyltoluene, t-butylstyrene, chlorostyrene, divinylbenzene, etc. can be used alone or in combination, and methyl (meth)acrylate (hereinafter referred to as methyl methacrylate and methyl acrylate) can be used. same), ethyl (meth)acrylate,
Butyl (meth)acrylate, diallyl phthalate, triallyl cyanurate, vinyl acetate, trimethylolpropane di- or tri(meth)acrylate, and the like can be used in combination with the above polymerizable monomer. The amount used is determined by the type of product, the curing method of the composition, the required workability, etc., and is not particularly limited. Further, the synthesis of unsaturated polyester may be carried out by a commonly used method and is not particularly limited. When curing the low-shrinkage resin composition of the present invention, it is cured using a catalyst such as peroxide and, if necessary, a curing accelerator such as metal soap. The composition may also contain known additive components such as a polymerization inhibitor, an antifoaming agent, a filler such as calcium carbonate, a pigment, and a dye, if necessary. The present invention will be explained below with reference to Examples and Comparative Examples. In the Examples and Comparative Examples, turbidity was measured using a turbidity meter AUD-CH-GV ₃ -H manufactured by Suga Test Instruments Co., Ltd.
Determine the transmittance of light using pure water as a standard solution, and 100% transmission is considered 0 turbidity, and 0% transmission is turbidity.
It was set as 100. The shrinkage rate was calculated by determining the specific gravity of the liquid and the specific gravity of the cured product using the JIS K 6901 Hubbard pycnometer method, and calculating the specific gravity of the cured product - specific gravity of the liquid/specific gravity of the liquid x 100.
The flexural strength and flexural modulus were determined by adding and mixing 1.5 parts by weight of cobalt naphthenate and 3 parts by weight of methyl ethyl ketone peroxide to 300 parts by weight of an unsaturated polyester resin composition, and mixing this into a 30 x 30 cm chopped strand mat ( FEM manufactured by Fuji Fiber Glass Co., Ltd.
-G450) After impregnation and degassing in 3 layers and curing at 25℃
The FRP board obtained by after-curing at 50°C for 12 hours was measured according to JIS K 6911. Example 1 355 g of terephthalic acid was placed in a 2-four-necked flask equipped with a solvent reflux tube, a nitrogen inlet tube, a thermometer, and a stirrer.
(26 mol%), 325 g of propylene glycol, 0.4 g of dibutyltin oxide and 200 g of xylene were charged, and the temperature was raised to 200°C over 6 hours under a nitrogen stream.
After reacting at this temperature for 5 hours, when the acid value reached 14, the temperature was lowered to 100°C, and 493 g (26 mol%) of tricyclodecenyl maleate, 280 g of maleic anhydride,
159g phthalic anhydride and propylene glycol
244g was charged and the temperature was raised to 210°C in 3 hours. The reaction proceeded at this temperature, and when the acid value was 50, the temperature was lowered to 190°C, and xylene was distilled off to obtain unsaturated polyester 1 with an acid value of 45. Unsaturated polyester resin composition 1 was obtained by dissolving 65 parts by weight of this unsaturated polyester 1 in 35 parts by weight of styrene in which 0.02% of hydroquinone was dissolved. The properties of this unsaturated polyester resin composition 1 are shown in Table 1. Example 2 In the same flask as in Example 1, 411 g (26 mol%) of dimethyl terephthalate and propylene glycol were added.
325 g of methanol and 0.4 g of zinc acetate were charged, heated to 200°C over 6 hours under a nitrogen stream, reacted at this temperature for 8 hours, and when 120g of methanol had been distilled off, the temperature was lowered to 100°C, and tricyclodecenyl 493 g (26 mol %) of acid, 280 g of maleic anhydride, 159 g of phthalic anhydride, 244 g of propylene glycol, and 200 g of xylene were charged, and the temperature was raised to 210° C. over 3 hours. Proceed the reaction at this temperature, and at an acid value of 50, 190℃
The temperature was lowered to , and xylene was distilled off to obtain unsaturated polyester 2 having an acid value of 43. Using this unsaturated polyester 2, an unsaturated polyester resin composition 2 was obtained in the same manner as in Example 1, and its properties are shown in Table 1. Example 3 Into the same flask as in Example 1, 411 g of polyethylene terephthalate (26 mol % with the repeating unit as one molecule), 217 g of propylene glycol, and 0.4 g of dibutyltin oxide were charged, and the mixture was heated under a nitrogen stream.
The temperature was raised to 200°C over time, and after reacting at this temperature for 4 hours, the temperature was lowered to 100°C. Tricyclodecenyl maleate 493g (26 mol%), maleic anhydride
280g, phthalic anhydride 159g, propylene glycol 190g and xylene 200g in 3 hours.
The temperature was raised to 210℃. The reaction proceeds at this temperature and the acid value
At 50°C, the temperature was lowered to 190°C, and xylene was distilled off to obtain unsaturated polyester 3 with an acid value of 45. Using this unsaturated polyester 3, an unsaturated polyester resin composition 3 was obtained in the same manner as in Example 1. Table 1 shows its characteristics.
It was shown to. Example 4 In the same flask as in Example 1, 632 g (40 mol%) of dimethyl terephthalate and propylene glycol were added.
188g, dipropylene glycol 331g and zinc acetate 0.4g were prepared and heated to 210g over 6 hours under a nitrogen stream.
The temperature was raised to 100°C, and when 182g of methanol was distilled out, the reaction was continued at this temperature for 8 hours, and the temperature was lowered to 100°C.
Tricyclodecenyl fumarate 568g (30 mol%), maleic anhydride 161g, phthalic anhydride 122g,
194g propylene glycol and 200g xylene
The temperature was raised to 210°C in 3 hours. The reaction proceeded at this temperature, and when the acid value was 50, the temperature was lowered to 190°C, and xylene was distilled off to obtain unsaturated polyester 4 with an acid value of 44.
Using this unsaturated polyester 4, an unsaturated polyester resin composition 4 was obtained in the same manner as in Example 1. Its characteristics are shown in Table 1. Comparative Example 1 The reaction of unsaturated polyester 1 of Example 1 was further advanced to obtain unsaturated polyester 5 having an acid value of 28.
Using this unsaturated polyester 5, an unsaturated polyester resin composition 5 was obtained in the same manner as in Example 1. Its characteristics are shown in Table 1. Comparative Example 2 The reaction proceeded in the same manner as in Example 1 using the same flask and synthetic raw materials, and when the acid value was 70, the temperature was lowered to 190°C and xylene was distilled off to obtain unsaturated polyester 6 with an acid value of 61. Using this unsaturated polyester 6, an unsaturated polyester resin composition 6 was prepared in the same manner as in Example 1.
I got it. Its characteristics are shown in Table 1. Comparative Example 3 In the same flask as in Example 1, 534 g of isophthalic acid was added.
489 g of propylene glycol, 0.5 g of dibutyltin oxide, and 200 g of xylene were charged and the temperature was raised to 200°C over 6 hours under a nitrogen stream.
When the acid value reached 10 after a period of reaction, the temperature was lowered to 100℃, and 493g of tricyclodecenyl malate was added.
(26 mol%), 280 g of maleic anhydride, and 81 g of propylene glycol were charged, and the temperature was raised to 210° C. over 3 hours. The reaction proceeded at this temperature, and when the acid value reached 50, the temperature was lowered to 190°C, and the xylene was distilled off, yielding unsaturated polyester 7 with an acid value of 44. Using this unsaturated polyester 7, an unsaturated polyester resin composition 7 was obtained in the same manner as in Example 1. Its characteristics are shown in Table 1. Comparative Example 4 Phthalic anhydride 740 was added to the flask used in Example 1.
g, 490 g of maleic anhydride and 798 g of propylene glycol and heated under a nitrogen stream for 5 hours.
Raise the temperature to 210℃ and react at this temperature for 6 hours to increase the acid value.
35 unsaturated polyester 8 was obtained. Using this unsaturated polyester 8, an unsaturated polyester resin composition 8 was obtained in the same manner as in Example 1. Its characteristics are shown in Table 1.

[Table] The unsaturated polyester resin composition of the present invention has a shrinkage rate of the cured product that is about 3% smaller than that of ordinary unsaturated polyester resin compositions, and there is no two-phase separation over time, and the cured product can be easily machined. It is an unsaturated polyester resin composition with comparable properties.

Claims (1)

[Claims] 1 An acid value of 55 to 40 obtained by using tricyclodecenyl maleate and/or tricyclodecenyl fumarate in an amount of 20 to 85 mol% of the acid component and a terephthalic acid component of 15 to 80 mol% of the acid component. A low shrinkage unsaturated polyester resin composition comprising an unsaturated polyester and a polymerizable monomer.