JPH08301948A - Unsaturated polyester resin composition, bulk molding compound, and sheet molding compound - Google Patents

Abstract

PURPOSE: To obtain a molded article which is excellent in water resistance and clarity and does not discolor in brown by compounding a resin compsn. comprising an unsatd. polyester (A), a copolymerizable monomer (B), an unsatd. alcohol (C), and a styrene-maleic anhydride compolymer (D) with an epoxy resin. CONSTITUTION: The component A is obtd. by reacting a dihydric alcohol component essentially contg. a hydrogenated bisphenol A with an α,β-ethylenically unsatd. dibasic acid. An example of the component B is methyl methacrylate. The component C is an alcohol copolymerizable with the components A and B, 2-hydroxyethyl methacrylate being an example. And, the component D used is obtd. from styrene and maleic anhydride in a molar ratio of (3/1)-(7/1) by a known polymn. method and has a number average mol.wt. lower than 5,000. The compounding ratios by wt. of C/B, A/(B+C), and D/(A+B+C) are (1/99)-(50/50), (30/70)-(70/30), and (10/90)-(40/60), respectively.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an unsaturated polyester resin composition particularly suitable for artificial marble, and more particularly to a marble-like composition having excellent water resistance and transparency by heat compression molding in a mold. The present invention relates to an unsaturated polyester resin composition which is capable of obtaining a molded article of 1. and has excellent thickening properties, a bulk molding compound and a sheet molding compound using the same.

[0002]

2. Description of the Related Art Conventionally, as a method for obtaining an artificial marble-like molded product, a sheet molding compound or a bulk molding compound is compression molded at a molding pressure of ³ to 150 kgf / cm ² using a mold having a temperature of 100 to 160 ° C. A press forming method is known. These compounds are thickened with magnesium oxide or the like for the purpose of obtaining workability at the time of molding and proper fluidity in the mold, but at the time of thickening, the acid value, molecular weight, and compound of the unsaturated polyester are used. There is a problem in that workability is poor because proper management of the amount of water in the interior is required.
Also known is a method in which isocyanates are added to the compound and a hydroxyl group at the terminal of the unsaturated polyester is reacted to increase the viscosity, but foaming easily occurs due to the water in the compound, and the resulting molded product becomes brownish brown. It has a drawback that it cannot be used for marble-like molded products.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and makes it possible to efficiently obtain a molded article excellent in water resistance and transparency by a heat compression molding method with a short molding cycle. The present invention also provides an unsaturated polyester resin composition which has excellent thickening properties and is particularly suitable for artificial marble, and a bulk molding compound and a sheet molding compound using the same.

[0004]

The unsaturated polyester resin composition according to the present invention is obtained by using a dihydric alcohol containing hydrogenated bisphenol A as an essential component and an α, β-ethylenically unsaturated dibasic acid. Saturated polyester
(I), the copolymerizable monomer (II), the unsaturated alcohol (III) copolymerizable with the components (I) and (II), and the molar ratio of styrene and maleic anhydride (styrene / maleic anhydride) are Styrene-maleic anhydride copolymer having a number average molecular weight of less than 5000 in the range of 3/1 to 7/1.
(IV), and the blending ratio [(III) / (II)] by weight of component (III) and component (II) is in the range of 1/99 to 50/50, and component (I) and component (II) The weight blending ratio [(I) / ((II) + (III))] of the total amount of II) and (III) is 30/70 to 70/30.
Of the component (IV) and the components (I), (II) and (III)
Of the total amount of [(IV) / ((I) + (II) + (III))] in the resin composition in the range of 10/90 to 40/60 is soluble in the component (II). It contains an epoxy resin (V). The unsaturated polyester resin composition preferably contains a tin compound (VI) soluble in the copolymerizable monomer (II). Further, it is preferable that these unsaturated polyester resin compositions contain imidazoles (VII) soluble in the copolymerizable monomer (II). Furthermore, it is preferable that these unsaturated polyester resin compositions contain glass powder and / or aluminum hydroxide. The bulk molding compound or sheet molding compound in the present invention is obtained by adding glass fiber and a polymerization catalyst to this unsaturated polyester resin composition and aging it at a temperature of preferably room temperature to 60 ° C. to increase the viscosity. It is a thing.

The unsaturated polyester (I) comprises a dihydric alcohol containing hydrogenated bisphenol A as an essential component and α,
It can be obtained by synthesizing β-ethylenically unsaturated dibasic acid by a known method, but if necessary, saturated dibasic acid, alcohol other than hydrogenated bisphenol A and the like can be used in combination. As the α, β-ethylenically unsaturated dibasic acid,
Maleic acid, fumaric acid, itaconic acid, citraconic acid and their anhydrides are used. Examples of the saturated dibasic acid used in combination as necessary include adipic acid, sebacic acid, succinic acid, gluconic acid, phthalic anhydride, orthophthalic acid, isophthalic acid, terephthalic acid, and tetrahydrophthalic acid.

Examples of the dihydric alcohol other than hydrogenated bisphenol A include alkanediol, oxaalkanediol, and diol obtained by adding ethylene oxide or propylene oxide to bisphenol A. In addition to these, monohydric or trihydric alcohols are used. May be used. As the alkane diol, ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentadiol, 1,6-hexanediol, cyclohexanediol, etc. Can be mentioned. Examples of the oxaalkane diol include diethylene glycol and trioxyethylene glycol. Examples of monohydric or trihydric alcohols used in combination with these dihydric alcohols include octyl alcohol, oleyl alcohol, and trimethylolpropane. These acids or alcohols may be used in combination.

In the above dihydric alcohol, the mixing ratio of hydrogenated bisphenol A and alcohols other than hydrogenated bisphenol A is usually a molar ratio (hydrogenated bisphenol A / alcohol other than hydrogenated bisphenol A due to characteristics such as water resistance). ) 0.10 / 0.90 to 0.50 /
The range of 0.5 is preferable, and the range of 0.20 / 0.80 to 0.40 / 0.60 is more preferable in terms of gloss and workability. The mixing ratio of the dihydric alcohol and the α, β-ethylenically unsaturated dibasic acid is usually 0 in terms of the molar ratio (dihydric alcohol / α, β-ethylenically unsaturated dibasic acid) due to the characteristics such as water resistance. The range of .90 / 1.00 to 1.20 / 1.00 is preferable, and 1.00 / 1.00 to 1.10 / 1.00
Is more preferable. In addition, saturated dibasic acid and α, β-
The mixing ratio of the ethylenically unsaturated dibasic acid is usually a molar ratio (saturated dibasic acid / α, β-ethylenically unsaturated dibasic acid).
The range of 0 / 1.00 to 0.70 / 0.30 is preferable, and the range of 0 / 1.00 to 0.55 / 0.45 is more preferable.

The number average molecular weight of the unsaturated polyester (I) is usually in the range of 1000 to 600 in view of workability and water resistance.
The range is 0. This number average molecular weight is a standard polystyrene conversion value measured by gel permeation chromatography (GPC). Unsaturated polyester (I)
In the production of, a monovalent or trivalent alcohol may be used in combination as the alcohol component. If you use these,
The amount of the α, β-ethylenically unsaturated dibasic acid and the saturated dibasic acid and the monohydric or trihydric alcohol used is the molar ratio [monohydric or trihydric alcohol / (α, β
-Ethylenically unsaturated dibasic acid + saturated dibasic acid)].
It is preferably in the range of less than 05 / 1.00.

The copolymerizable monomer (II) used in the present invention includes styrene, p-chlorostyrene, vinyltoluene, divinylbenzene, acrylic acid or methacrylic acid and an alcohol having 1 to 18 carbon atoms. Examples thereof include esters (for example, methyl methacrylate, butyl acrylate, trimethylolpropane trimethacrylate) and the like. You may use these in combination of 2 or more types.

The unsaturated alcohol (II used in the present invention
I) is unsaturated polyester (I) and copolymerizable monomer (II)
The unsaturated alcohol (III) is a copolymerizable alcohol with 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate and the like, 2-hydroxyethyl methacrylate, 2 -Hydroxypropyl methacrylate such as hydroxypropyl methacrylate and 2-hydroxybutyl methacrylate, methyl maleate (2-hydroxyethyl), ethyl maleate (2-hydroxyethyl), propyl maleate (2-
Hydroxyethyl), butyl maleate (2-hydroxyethyl), methyl maleate (2-hydroxypropyl), ethyl maleate (2-hydroxybutyl) and other maleic acid alkyl (hydroxyalkyl) esters, methyl itaconate (2 -Hydroxyethyl), ethyl itaconate (2-hydroxyethyl), propyl itaconate (2-hydroxyethyl), ethyl itaconate (2-hydroxypropyl), methyl itaconate (2-
Itaconic acid alkyl (2-hydroxyalkyl) esters such as hydroxybutyl), alcohols having an aryl group such as allyl alcohol, amides such as hydroxymethyl acrylamide and hydroxymethyl methacrylamide,
Examples thereof include hydroxyalkyl styrenes such as hydroxymethyl styrene and hydroxyethyl styrene. Of these, 2-hydroxyethyl methacrylate and 2-hydroxypropyl acrylate are preferable in terms of price and availability. You may use these unsaturated alcohols in combination of 2 or more type.

The styrene-maleic anhydride copolymer (IV) used in the present invention has a molar ratio of styrene and maleic anhydride (styrene / maleic anhydride) in the range of 3/1 to 7/1, preferably 4 / 1 to 5/1, and the number average molecular weight is less than 5000, preferably 1 by a known polymerization method.
It is obtained by adjusting to 500 to 3000. This number average molecular weight is a value converted into standard polystyrene by GPC measurement. The blending molar ratio of the above styrene and maleic anhydride is 3 /
If it is less than 1, the compatibility with the unsaturated polyester (I) is poor,
Since the phase separation occurs, the properties of the obtained marble-like molded product deteriorate. Further, when the molar ratio exceeds 7/1, the transparency of the obtained molded article is lowered. When the number average molecular weight is 5,000 or more, the unsaturated polyester (I) and the copolymerizable monomer (I
The compatibility with I) and unsaturated alcohol (III) is poor, and these cause phase separation, resulting in deterioration of the properties of the obtained molded article. As the copolymer (IV), for example, commercially available products such as GSM-503 and CSM-505 manufactured by Gifu Shellac Manufacturing Co., Ltd. can be used.

In the present invention, unsaturated alcohol (III)
The mixing ratio of the copolymerizable monomer (II) and the copolymerizable monomer (II) is a weight ratio [(III) / (I
I)] is 50/50 to 1/99, preferably 1/99 to 1
The range is 5/85. If this weight ratio exceeds 50/50, the water resistance of the resulting molded article decreases and
When it is less than 9, the compatibility of the styrene-maleic anhydride copolymer (IV) with the unsaturated polyester (I), the copolymerizable monomer (II) and the unsaturated alcohol (III) becomes poor, and these are phase separated. As a result, the characteristics of the obtained molded product deteriorate. Further, unsaturated polyester (I) and copolymerizable monomer (II)
And the blending ratio with the total amount of unsaturated alcohol (III) is 30/70 to 70/3 by weight ratio [(I) / ((II) + (III))].
The range is 0, preferably 45/55 to 65/35. If this weight ratio is less than 30/70, the curing shrinkage rate becomes large, cracking occurs in the molded product, and 70 to 3
If it exceeds 0, the properties of the obtained molded article deteriorate.

Further, styrene-maleic anhydride copolymer
The compounding ratio of (IV) to the total amount of unsaturated polyester (I), copolymerizable monomer (II) and unsaturated alcohol (III) is a weight ratio [(IV) / ((I) + (II) + (III))] 10 / 90-40
The range is / 60, preferably 15/85 to 30/70. If this weight ratio is less than 10/90, the molded product will crack, and if it exceeds 40/60, the properties of the molded product obtained will deteriorate. Further, if the compatibility with the unsaturated polyester (I), the copolymerizable monomer (II) and the unsaturated alcohol (III) is good, in addition to styrene and maleic anhydride, the above-mentioned copolymerizable monomer The molar ratio of (II) [(styrene +
(II)) / maleic anhydride] A copolymer having a number average molecular weight of less than 5000 obtained by blending in the range of 3/1 to 7/1 is used in the same proportion as the styrene-maleic anhydride copolymer. Can be used. This number average molecular weight is GP
It is a value converted into standard polystyrene by C measurement.

Examples of the epoxy resin (V) soluble in the copolymerizable monomer (II) used in the present invention include a bisphenol type epoxy resin. The epoxy resin (V) is preferably liquid at room temperature and has a molecular weight of 300 to 1
The range of 000 is preferable. The amount of the epoxy resin (V) used depends on the water resistance and weather resistance of the resulting molded product, the viscosity increase of the resin composition, the unsaturated polyester (I), and the copolymerizable monomer.
5 to 20 parts by weight is preferable with respect to 100 parts by weight of the resin composition consisting of (II), unsaturated alcohol (III) and styrene-maleic anhydride copolymer (IV), and the range of 5 to 10 parts by weight is further preferable. preferable.

The tin compound (VI) soluble in the copolymerizable monomer (II) used in the present invention accelerates the esterification reaction. Examples of such tin compounds (VI) include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin malate, dilauryltin diacetate, dioctyltin diacetate, and the like. The amount of the tin compound (VI) used is the amount of the unsaturated polyester resin composition 1
The range of 0.1 to 1.0 parts by weight is preferable with respect to 00 parts by weight. The imidazoles (VII) soluble in the copolymerizable monomer (II) used in the present invention are usually used as a curing accelerator when the epoxy resin is cured with an acid anhydride, for example, 5-membered ring compound containing two nitrogens produced from glyogizal and ammonia 2-methylimidazole having a substituent introduced at the 2,4 position, 2-ethyl-4-
Methylimidazole, 2-phenylimidazole, etc. are used. The amount of the imidazole (VII) used is 1.0 to 100 parts by weight of the unsaturated polyester resin composition.
A range of 5.0 parts by weight is preferred.

The glass powder and / or aluminum hydroxide used in the present invention is not particularly limited, and the amount used, the particle size and the particle size distribution are appropriately selected according to the characteristics of the marble-like molded product to be obtained. . The amount of glass powder or aluminum hydroxide used is 1 for 100 parts by weight of the total resin content.
It is preferably from 0.00 to 300 parts by weight. The unsaturated polyester resin composition according to the present invention, glass fiber used in the bulk molding compound and sheet molding compound, a polymerization catalyst, a release agent, if necessary,
A polymerization inhibitor, a silane coupling agent, an ultraviolet absorber, a pigment, an accelerator, a chain transfer agent, and the like are appropriately added. As the polymerization inhibitor, an organic peroxide such as tert-butyl peroxybenzoate is used, and normally, 0.5 to 3% by weight is preferably used based on 100 parts by weight of the total resin content. Further, the unsaturated polyester resin composition of the present invention may be used in combination with polystyrene, polymethylmethacrylate, polyvinyl acetate, a copolymer thereof, or the like, if necessary. These polystyrenes and the like are preferably used in an amount of 30 parts by weight or less based on 70 parts by weight of the styrene-maleic anhydride copolymer in view of the transparency of the obtained artificial marble.

The bulk molding compound according to the present invention generally comprises unsaturated polyester (I), copolymerizable monomer (II), unsaturated alcohol (III), styrene-maleic anhydride copolymer (IV) and After adding a polymerization catalyst, and optionally a tin compound (VI) and an imidazole (VII) to a composition containing an epoxy resin (V), glass powder and / or aluminum hydroxide, preferably having a length of 0. 5-6
Add components such as glass fiber of about mm and knead well, preferably with deaeration, and add 3 to 3 at room temperature to 60 ° C.
It is obtained by allowing it to stand for 5 days for aging and thickening. Glass fiber is 10 to 100 parts by weight of total resin content
It is preferable to use 50 parts by weight. The thus obtained bulk molding compound having good workability is heated and compression molded in a mold and cured by radical polymerization to obtain an artificial marble having excellent water resistance and transparency. The temperature is 100-150 ° C,
The pressure is preferably in the range of ^{20 to} 150 kg / cm ² .

The sheet molding compound according to the present invention usually comprises unsaturated polyester (I), copolymerizable monomer (II), unsaturated alcohol (III), styrene-maleic anhydride copolymer (IV) and To a composition containing an epoxy resin (V), a polymerization catalyst, and optionally a tin compound (VI) and an imidazole (VII) are added, and then glass powder and / or aluminum hydroxide is added and well stirred, preferably Is impregnated into glass fiber with a length of about 25 mm,
It is obtained by leaving it in an atmosphere of 0 ° C. for 3 to 5 days. 50 to 50 parts by weight of glass fiber based on 100 parts by weight of total resin content
It is preferable to use 100 parts by weight. The thus obtained sheet molding compound having good workability is subjected to heat compression molding in a mold and cured by radical polymerization to obtain artificial marble having excellent water resistance and transparency. The temperature is 100-150 ° C,
The pressure is preferably in the range of 20 to 150 kg / cm.

[0019]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. Example 1 1410 g of hydrogenated bisphenol A, 250 g of neopentyl glycol, 370 g of propylene glycol and 1490 g of isophthalic acid were placed in a 5-liter four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen gas introducing tube and a thermometer, and the temperature was adjusted to 190 from room temperature. The temperature was raised to 1 ° C. in 1 hour and then to 215 ° C. in 5 hours to continue the reaction. When the acid value became 5 mgKOH / g or less, the temperature was lowered to 120 ° C, 810 g of neopentyl glycol and 1070 g of maleic anhydride were charged, and 160 ° C in 1 hour.
Then, the temperature was raised to 215 ° C. for 4 hours and the reaction was continued to obtain an unsaturated polyester (A) having an acid value of 22 mgKOH / g.

Next, unsaturated polyester (A) 600
Resin composition (B) in which 350 g of styrene is dissolved in 350 g of styrene and 50 g of 2-hydroxyethyl methacrylate, GS
M-505 [styrene-maleic anhydride copolymer: styrene / maleic anhydride = 5/1 (molar ratio), number average molecular weight 2500, product name manufactured by Gifu Shellac Manufacturing Co., Ltd.] 600
resin composition (C) having g dissolved in 400 g of styrene,
Epicoat 828 (bisphenol A type epoxy resin,
Yuka Shell Epoxy Co., Ltd.) and dibutyltin dilaurate and 1-cyano-2-ethyl-4-methylimidazole in a weight ratio of [resin composition (B) / resin composition (C) / Epicoat 828 / dibutyl]. [Tindilaurate / 1-cyano-2-ethyl-4-methylimidazole] 60/40/81 / 0.5 / 12.0 and sufficiently stirred and mixed to prepare an unsaturated polyester resin composition. (D) was obtained.

Then, the components shown in Table 1 (the compounding amount is parts by weight) are compounded and 260 mmH is applied by using a planetary mixer.
After kneading under a reduced pressure of g, the mixture was allowed to stand in an atmosphere of 40 ° C. for 48 hours to obtain a thickened bulk molding compound (E) having good workability. The obtained bulk molding compound (E) was applied to a flat plate mold (250 mm × 50
0 mm) was used to obtain a molded product (F) having a thickness of 8 mm. The molding conditions were a mold temperature of 130 ° C., a molding pressure of 100 kg / cm, and a molding time of 10 minutes. The obtained molded product (F) had excellent transparency, and the linear shrinkage ratio (measured from the size of the mold at room temperature and the size of the molded product) was 0.3%. Further, the molded product (F) was immersed in hot water at 90 ° C. for 300 hours, and then the appearance was visually evaluated. No blister, crack, or remarkable whitening was observed in the molded product (F). It is shown in Table 2 together with other test results.

Example 2 Using the unsaturated polyester resin composition (D) obtained in Example 1 and applying the composition shown in Table 1 by a conventional method, 40 ° C.
It was left for 48 hours under the atmosphere described above to obtain a sheet molding compound (G) having good workability. Using a flat plate mold (250 mm × 500 mm), a molded product (H) having a thickness of 8 mm was obtained. The molding conditions were a mold temperature of 130 ° C., a molding pressure of 100 kg / cm ² , and a molding time of 10 minutes. The obtained molded product (H) had excellent transparency and had a linear shrinkage of 0.1%. Further, the molded product (H) was immersed in hot water at 90 ° C. for 300 hours, and then the appearance was visually evaluated. Molded product (H)
No swelling, cracks or significant whitening was observed. It is shown in Table 2 together with other test results.

Comparative Example 1 The unsaturated polyester resin composition (B) obtained in Example 1,
Similarly, unsaturated polyester resin composition (C) and Millionate MR-100 (polymethylene polyphenyl polyisocyanate, trade name of Nippon Polyurethane Industry Co., Ltd.)
60/40/8 in terms of weight ratio [resin composition (B) / resin composition (C) / millionate MR-100], respectively.
To obtain a resin composition (I). Next, the components shown in Table 1 were mixed and kneaded using a planetary mixer under a reduced pressure of 260 mmHg, and then left in an atmosphere of 40 ° C. for 48 hours to obtain a thickened bulk molding compound (I) having good workability. ) Got. A bulk molding compound (I) was used to obtain a molded product (J) having a thickness of 8 mm using a flat plate mold (250 mm × 500 mm). The molding conditions were a mold temperature of 140 ° C., a molding pressure of 100 kg / cm ² , and a molding time of 10 minutes. The obtained molded product had a dark brown color. It is shown in Table 2 together with other test results.

[0024]

[Table 1]

[0025]

[Table 2] The light transmittance was measured according to JIS K 7105.
Regarding the boiling characteristics, the appearance of the molded product after continuous immersion at 90 ° C. for 300 hours was visually observed. The linear shrinkage was calculated from the difference between the size of the flat plate mold at room temperature and the size of the molded product.

[0026]

According to the unsaturated polyester resin composition of the first aspect of the present invention, it is possible to obtain a molded article which is excellent in water resistance and transparency and which is not colored dark brown. According to the unsaturated polyester resin composition of the second aspect, it is possible to obtain a marble-like molded article which is excellent in water resistance and transparency and which is not colored dark brown. According to the compound of claim 3 or 4, the heat compression molding method with a short molding cycle makes it possible to efficiently obtain a marble-like molded article which is excellent in water resistance and transparency and is not colored brown.

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Claims (4)

[Claims] 1. An unsaturated polyester (I) and a copolymerizable monomer (II) obtained by using a dihydric alcohol containing hydrogenated bisphenol A as an essential component and an α, β-ethylenically unsaturated dibasic acid. The unsaturated alcohol (III) copolymerizable with the components (I) and (II) and the molar ratio of styrene to maleic anhydride (styrene / maleic anhydride) is 3 /
A styrene-maleic anhydride copolymer (IV) having a number average molecular weight of less than 5000 in the range of 1 to 7/1 is included, and the weight mixing ratio of the component (III) and the component (II) [(III ) /
(II)] in the range of 1/99 to 50/50, and the component (I)
And the total weight ratio of the components (II) and (III) [(I) / ((I
I) + (III))] is in the range of 30/70 to 70/30,
The weight ratio [(IV) / ((I) + (II) + (III))] of the total amount of the component (IV) and the components (I), (II) and (III)] is 10/90 to 4
An unsaturated polyester resin composition comprising an epoxy resin (V) soluble in component (II) in a resin composition in the range of 0/60. 2. An unsaturated polyester resin composition comprising the resin composition for unsaturated polyester according to claim 1 containing glass powder and / or aluminum hydroxide. 3. A bulk molding compound obtained by adding glass fiber and a polymerization catalyst to the unsaturated polyester resin composition according to claim 2 and aging it to increase the viscosity. 4. A sheet molding compound obtained by adding glass fiber and a polymerization catalyst to the resin composition according to claim 4 and aging it to increase the viscosity.