JP3163710B2 - Room temperature low shrinkage unsaturated polyester resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cold-shrinkable unsaturated polyester resin composition for molding materials.

[0002]

2. Description of the Related Art Unsaturated polyester resins have a viscosity of 7 to
Shrink volume by 11%. For this reason, defects such as die sink occur in the FRP molded product and the like, which is not preferable. As a method of reducing the shrinkage, generally, two liquids of an unsaturated polyester resin and a thermoplastic polymer resin such as polystyrene are mixed to expand the thermoplastic polymer due to heat generated during curing of the unsaturated polyester resin, or Methods are known which utilize phenomena such as expansion of α, β-ethylenically unsaturated monomers in a polymer and specific volume difference due to agglomeration of a thermoplastic polymer.

[0003]

The above-described method of mixing the two liquids of the unsaturated polyester resin and the thermoplastic polymer is mainly used for high-temperature curing, and the low-temperature shrinkage effect is small in normal-temperature curing. . In addition, since the thermoplastic polymer phase aggregates during curing to cause phase separation, there has been a problem that color unevenness occurs when a coloring agent is added, and the mechanical strength of a molded article is reduced. The present invention has been made in view of these points, and an object of the present invention is to provide a room-temperature, low-shrinkable unsaturated polyester resin composition which exhibits a low-shrinkage effect without phase separation in a room-temperature curing system. Things.

[0004]

SUMMARY OF THE INVENTION The present invention relates to 100 parts by weight of a crystalline unsaturated polyester obtained by reacting an unsaturated acid, a symmetric dibasic acid and a symmetric glycol, and a dicyclopentadiene-modified unsaturated polyester. 100 parts by mass of the α, β-ethylenically unsaturated monomer 10 to 300
The present invention relates to a room-temperature low-shrinkable unsaturated polyester resin composition completely dissolved in parts by mass. In the present invention, the symmetric dibasic acid and the symmetric glycol are used as the materials for the crystalline unsaturated polyester in order to make the polymer of the crystalline unsaturated polyester exhibit crystallinity. , The low shrinkage effect is increased. The use of the dicyclopentadiene-modified unsaturated polyester is such that the crystalline unsaturated polyester alone is α,
This is because it is difficult to dissolve in the β-ethylenically unsaturated monomer, and the presence of the dicyclopentadiene-modified unsaturated polyester enhances the low shrinkage effect.

Next, the materials will be described. Crystalline unsaturated polyesters include unsaturated acids such as maleic acid and maleic anhydride, symmetric dibasic acids such as terephthalic acid, adipic acid and sebacic acid, and ethylene glycol, diethylene glycol, neopentyl glycol and 1,3-propanediol. , 1,4-butanediol, 1,6-hexanediol, hydrogenated bisphenol A and the like. Two or more of the above unsaturated acids, symmetric dibasic acids and symmetric glycols may be used.

Here, if necessary, unsaturated acids such as fumaric acid, itaconic acid, citraconic acid, endmethylenetetrahydrophthalic anhydride, saturated acids such as phthalic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and linseed oil Propylene glycol, dipropylene glycol, 1,3-butanediol, 1,2-propanediol, 1,2-propanediol, -Aliphatic glycols such as butanediol, 1,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,2-hexanediol, 1,4-hexanediol, and 2,3-hexanediol , Cyclopentanediol, cyclohexanediol, etc., alicyclic diols, xylene glyco Le, aromatic diols such as dimethyl xylene glycol, bis propylene glycol ethers, ethers such as bis butylene glycol ethers,
Polyhydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol, or a mixture thereof may be used as the alcohol component. However, the amount used is within the range in which the crystalline unsaturated polyester exhibits crystallinity.

[0007] Dicyclopentadiene-modified unsaturated polyesters include unsaturated acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, endmethylenetetrahydrophthalic anhydride, terephthalic acid, adipic acid, and the like.
Sebacic acid, phthalic acid, phthalic anhydride, isophthalic acid,
Saturated acids such as trimellitic acid, linseed oil, soybean oil, tall oil, vegetable oil fatty acids such as castor oil, acid components such as one or more of these derivatives or mixtures thereof, ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,2-propanediol, 1,2-butanediol, Aliphatic glycols such as 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,2-hexanediol, 1,4-hexanediol, 2,3-hexanediol, cyclopentanediol, Alicyclic diols such as cyclohexanediol, hydrogenated bisphenol , Xylene glycol, aromatic diols such as dimethylxylene glycol, ethers such as bispropylene glycol ether and bisbutylene glycol ether, one or more or a mixture of polyhydric alcohols such as glycerin, trimethylolpropane and pentaerythritol, or a mixture thereof And a modified component such as dicyclopentadiene and cyclopentadiene.

This synthesis method comprises a one-step synthesis method in which an acid component, an alcohol component and a modified component are simultaneously charged and modified simultaneously with a condensation reaction, and a method in which an acid component and an alcohol component are subjected to a condensation reaction and a modified component is charged and modified during the reaction. Any of the step synthesis methods or a combination thereof may be used. Here, the dicyclopentadiene-modified unsaturated polyester may be one in which cyclopentadiene generated by decomposition of dicyclopentadiene is included in the polymer skeleton. Further, a material obtained by previously reacting dicyclopentadiene and / or cyclopentadiene with an acid component and / or an alcohol component may be used as a part of the acid component and / or the alcohol component.

As the α, β-ethylenically unsaturated monomer, styrene, vinyltoluene, t-butylstyrene,
Chlorostyrene, divinylbenzene, diallyl phthalate and the like can be used alone or in combination. Methyl (meth) acrylate (meaning methyl methacrylate and methyl acrylate; the same applies hereinafter), ethyl (meth) acrylate, butyl (meth) Acrylate,
Diallyl phthalate, triallyl cyanurate, vinyl acetate, trimethylolpropane di or tri (meth) acrylate may be used in combination with the aforementioned α, β-ethylenically unsaturated monomer.

The above-mentioned crystalline unsaturated polyester, dicyclopentadiene-modified unsaturated polyester and α, β-
They are used in the above proportions in order to completely dissolve the ethylenically unsaturated monomers. The molecular weight and acid value of the crystalline unsaturated polyester and the dicyclopentadiene-modified unsaturated polyester are determined by the type of the product, the curing conditions of the composition and the required workability, and are not particularly limited. The method for synthesizing the crystalline unsaturated polyester may be a commonly used method and is not particularly limited.

For curing the room temperature low shrinkage resin composition of the present invention, a catalyst such as a peroxide is used, and the composition may be used, if necessary, with a polymerization inhibitor, an antifoaming agent, calcium carbonate or the like. Known additives such as fillers, pigments and dyes may be included.

[0012]

Embodiments of the present invention will be described below. Example 1 (1) Maleic anhydride 9 was placed in a 2-liter four-necked flask equipped with a reflux tube, an inert gas introduction tube, a thermometer, and a stirrer.
80 g, 682 g of ethylene glycol and 0.17 g of hydroquinone were charged and subjected to a condensation reaction at 210 ° C. for 11 hours in an inert gas stream to obtain a crystalline unsaturated polyester UP-I having an oxidation of 30. (2) 310 g of maleic anhydride in a device similar to (1),
592 g of phthalic anhydride, 456 of propylene glycol
g, 310 g of ethylene glycol, 268 g of dicyclopentadiene, and 0.1 g of hydroquinone, and subjected to a condensation reaction at 210 ° C. for 12 hours in an inert gas stream to obtain a dicyclopentadiene-modified unsaturated polyester UP-A having an acid value of 30.
I got (3) 50 parts by mass of UP-A was added to 100 parts by mass of styrene at 70 ° C. and dissolved while stirring at 2,000 rpm of a stirrer, and 100 parts by mass of UP-I was added thereto and completely dissolved. A resin composition RI was obtained. The obtained R-
I was filled into a test tube having an outer diameter of 18 mm from the bottom to 100 mm from the bottom and allowed to stand for 2 hours, and then visually observed. A transparent and non-separable one was good, a turbid one was turbid, and a separated one was separated. Those that did not dissolve during mixing were evaluated as insoluble.
The results are shown in Table 1 as a compatibility test. (4) RI: 250 parts by mass of cobalt naphthenate 1.2 dissolved in xylene so as to have a cobalt content of 6%
5 parts by mass, 2.50 parts by mass of methyl ethyl peroxide and 2.50 parts by mass of carbon black were added, and the mixture was stirred for 3 minutes at a rotation speed of a stirrer of 2,000 rpm. Next, the foam was removed and poured into a flat mold (200 × 200 × 4 mm), gelled at room temperature, and after-cured at 40 ° C. for 24 hours.
Thereafter, the mixture was cooled and allowed to stand at room temperature for 12 hours to produce a cured product. Using this cured product, color unevenness, volume shrinkage, flexural strength and flexural modulus were evaluated. The results are shown in Table 1. Here, the color unevenness is visually observed for the cured product, ◎ indicates no color unevenness,
は represents slight color unevenness, Δ represents color unevenness, and × represents marked color unevenness. The volumetric shrinkage was calculated by calculating the specific gravity of the mixed solution and the specific gravity of the cured product by the JIS-K6901 specific gravity bottle method, and calculating as (specific gravity of the cured product−specific gravity of the mixture) ÷ specific gravity of the mixed solution × 100. The flexural strength and flexural modulus are JIS-K6
911 was measured.

Example 2 (1) A device similar to (1) of Example 1 was charged with 686 g of maleic anhydride, 498 g of terephthalic acid, 682 g of ethylene glycol, and 0.17 g of hydroquinone, and placed in an inert gas stream at 210 ° C. for 12 hours. The condensation reaction was carried out to obtain a crystalline unsaturated polyester UP-II having an acid value of 30. (2) 50 parts by mass of UP-A was added to 100 parts by mass of styrene at 70 ° C. and dissolved while stirring at 2,000 rpm of a stirrer, and 100 parts by mass of UP-II was added thereto and completely dissolved. A resin composition R-II was obtained. A compatibility test was performed for the obtained R-II, and the results are shown in Table 1. (3) A cured product was prepared in the same manner as in (3) of Example 1 using R-II and R-I instead of color unevenness, volume shrinkage, flexural strength and flexural modulus. Table 1 shows the results.
It was shown to.

Example 3 (1) A device similar to (1) of Example 1 was charged with 980 g of maleic anhydride, 496 g of ethylene glycol, 228 g of propylene glycol, and 0.17 g of hydroquinone.
Condensation reaction at 210 ° C for 11 hours in an inert gas stream, acid value 3
Thus, a crystalline unsaturated polyester UP-III was obtained. (2) 50 parts by mass of UP-A was added to 100 parts by mass of styrene at 70 ° C. and dissolved while stirring at 2,000 rpm of a stirrer, and 100 parts by mass of UP-III was added thereto and completely dissolved. A resin composition R-III was obtained. A compatibility test was performed for the obtained R-III, and the results are shown in Table 1. (3) A cured product was prepared in the same manner as in (3) of Example 1, using R-III instead of R-I, and evaluated for color unevenness, volumetric shrinkage, flexural strength, and flexural modulus. Table 1 shows the results.
It was shown to.

Comparative Example 1 (1) A device similar to (1) of Example 1 was charged with 980 g of maleic anhydride, 836 g of propylene glycol and 0.17 g of hydroquinone, and heated at 210 ° C. in an inert gas stream at 11 ° C.
Time-condensation reaction, unsaturated polyester UP with acid value 30
-IV was obtained. (2) 50 parts by mass of UP-A was added to 100 parts by mass of styrene at 70 ° C. and dissolved while stirring at 2,000 rpm of a stirrer, and 100 parts by mass of UP-IV was added thereto and completely dissolved. A resin composition R-IV was obtained. The obtained R-IV was subjected to a compatibility test, and the results are shown in Table 1. (3) Using R-IV instead of R-I, a cured product was prepared in the same manner as in (3) of Example 1, and color unevenness, volumetric shrinkage, flexural strength, and flexural modulus were evaluated. Table 1 shows the results.
It was shown to.

Comparative Example 2 (1) The same apparatus as in (1) of Example 1 was charged with 588 g of maleic anhydride, 644 g of phthalic anhydride, 456 g of propylene glycol, 310 g of ethylene glycol, and 0.1 g of hydroquinone. At 210 ° C. for 12 hours to obtain an unsaturated polyester UP- having an acid value of 30.
B was obtained. (2) 50 parts by mass of UP-B was added to 100 parts by mass of styrene at 70 ° C. and dissolved while stirring at a rotation speed of a stirrer of 2,000 rpm, and 100 parts by mass of UP-I was added thereto.
After stirring for 0 minutes, no dissolved product was obtained and a cured product could not be produced.

Comparative Example 3 (1) 50 parts by mass of UP-B was added to 100 parts by mass of styrene at 70 ° C. and dissolved while stirring at a rotation speed of a stirrer of 2,000 rpm, and 100 parts by mass of UP-IV was added thereto. The mixture was completely dissolved to obtain a resin composition R-VI. A compatibility test was performed on the obtained R-VI, and the results are shown in Table 1. (2) Using R-VI instead of R-I, a cured product was prepared in the same manner as in (3) of Example 1, and color unevenness, volume shrinkage, flexural strength and flexural modulus were evaluated. Table 1 shows the results.
It was shown to.

Comparative Example 4 (1) Polystyrene 50 having a number average molecular weight of 100,000
100 parts by mass of styrene was added to 70 parts by mass of 70 ° C. and dissolved while stirring at a stirrer rotation speed of 2,000 rpm, and 100 parts by mass of UP-IV was added and completely dissolved to obtain a resin composition R-VII. Was. A compatibility test was performed on the obtained R-VII, and the results are shown in Table 1. (2) Using R-VII instead of R-I, a cured product was prepared in the same manner as in (3) of Example 1, and color unevenness, volume shrinkage, bending strength, and flexural modulus were evaluated. Table 1 shows the results.
It was shown to.

Comparative Example 5 (1) 150 parts by mass of UP-I was used at 70 ° C. in styrene 100
In addition to the parts by mass, the mixture was stirred for 10 minutes at a rotation speed of a stirrer of 2,000 rpm, but no dissolved product was obtained and a cured product could not be produced.

[0020]

[Table 1]

[0021]

According to the present invention, the room-temperature low-shrinkable unsaturated polyester resin composition of the present invention has the same volume shrinkage ratio as that of a mixed resin composition of unsaturated polyester and polystyrene, and can be used in a conventional unsaturated polyester resin. About 4 more than the composition
%small. In addition, because of good compatibility, no phase separation occurs and no color unevenness is observed. Further, it is a room-temperature low-shrinkable unsaturated polyester resin composition having a mechanical strength equal to or higher than that of a normal unsaturated polyester resin composition and more than twice as high as that of a mixed resin composition of unsaturated polyester and polystyrene.

Continuation of the front page (56) References JP-A-58-2315 (JP, A) JP-A-64-69615 (JP, A) JP-A-56-53120 (JP, A) JP-A-58-108218 (JP) JP-A-3-103416 (JP, A) JP-A-3-200821 (JP, A) JP-A-61-42564 (JP, A) JP-A-58-225112 (JP, A) JP-A-58-225112 JP-A-53-146789 (JP, A) JP-A-58-198514 (JP, A) JP-A-58-156592 (JP, A) JP-A-50-51188 (JP, A) A) JP-A-58-21459 (JP, A) JP-A-52-39785 (JP, A) JP-A-54-144013 (JP, A) JP-B-38-14823 (JP, B1) (58) Survey Field (Int.Cl. ⁷ , DB name) C08F 299/00-299/08 C08F 283/00-283/01 C08F 290/00-290/14 C08L 67/00-67/07 C08G 63/00-63 / 91

Claims (1)

(57) [Claims] 1. A method according to claim 1, wherein 100 parts by mass of a crystalline unsaturated polyester obtained by reacting an unsaturated acid, a symmetric dibasic acid and a symmetric glycol, and 1 to 100 parts by mass of a dicyclopentadiene-modified unsaturated polyester are α, β -A room-temperature low-shrinkable unsaturated polyester resin composition dissolved in 10 to 300 parts by mass of an ethylenically unsaturated monomer.