JPH1060203A - Thermoplastic resin molding product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin molding product useful for automobile parts excellent in weatherability, mechanical strength, appearance and qualities, by simultaneously feeding a specific resin composition and an AS-based resin in a specific ratio and molding. SOLUTION: (A) A resin composition in an amount of 10-90wt.% comprising (i) 60-95 pts.wt. of a copolymer which is a copolymer of an aromatic vinyl monomer such as styrene, a vinyl cyanide monomer such as acrylonitrile and a vinyl monomer such as glycidyl methacrylate and has 0.1-10wt.% of an epoxy group-containing vinyl monomer in the copolymer and (ii) 5-40wt.% of a modified polyolefinic polymer modified with 0.1-10wt.% of an unsaturated dicarboxylic acid (anhydride) monomer and (B) 10-90 wt.% of an ABS-based resin are fed to a molding machine at the same time and molded. Preferably, in the molding, a fatty acid glycerol ester and a weathering agent are added to the composition and molded.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding machine for a resin composition comprising a specific copolymer containing an epoxy group and a specific modified polyolefin polymer and an AS resin simultaneously without prior kneading. And a molded product (hereinafter referred to as direct molding).

[0002]

2. Description of the Related Art Copolymers of an aromatic vinyl monomer and a vinyl cyanide monomer are widely and generally used, but have a disadvantage of low impact resistance. Conventionally, as a method for improving this disadvantage, a diene rubber is grafted and used. However, although the copolymer resin obtained by this method was able to improve the impact resistance, it had poor weather resistance due to having a double bond.

[0003] In response to the demand for a resin molded article having excellent weather resistance, a method of applying a paint to the surface of a molded article has been used. However, the coating process is costly and environmental pollution due to a solvent for the paint is required. There is a problem.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a direct molded article having excellent weather resistance and strength by using a specific resin composition and an AS resin.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by directly molding the following specific resin composition and an AS-based resin,
It has been found that a direct molded article having both excellent weather resistance and strength can be obtained, and the present invention has been completed. That is, the present invention is a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer and a vinyl monomer containing an epoxy group, and a vinyl monomer containing an epoxy group in the copolymer. Copolymer (A) 60 in an amount of 0.1 to 10% by weight
-95 parts by weight and 5-40 parts by weight of a modified polyolefin polymer (B) modified with 0.1-10% by weight of an unsaturated dicarboxylic acid anhydride monomer group or an unsaturated dicarboxylic acid monomer group. 10 to 90% by weight of the resin composition (I)
An object of the present invention is to provide a thermoplastic resin molded article obtained by simultaneously supplying 10 to 90% by weight of the system resin (II) to a molding machine and molding. Further, the present invention provides a resin composition (I) containing 0.2 to 5 parts by weight of a fatty acid glycerin ester (C) based on a total of 100 parts by weight of a copolymer (A) and a modified polyolefin-based polymer (B). The present invention provides the above-mentioned thermoplastic resin molded article using Further, the present invention relates to 10 to 90 parts by weight of the resin composition (I) and 10 to 9 parts by weight of the AS resin (II).
The present invention provides a thermoplastic resin molded article obtained by simultaneously supplying 0.01 to 5 parts by weight of a weathering agent (III) to a molding machine based on 100 parts by weight of a total of 0 parts by weight.

Hereinafter, the present invention will be described in detail. Specific examples of the aromatic vinyl monomer used in the copolymer (A) of the present invention include styrene, α-methylstyrene, vinyltoluene and t-butylstyrene, and specific examples of the vinyl cyanide monomer Examples include acrylonitrile and methacrylonitrile.

The proportion of the aromatic vinyl monomer in the copolymer (A) is preferably from 50 to 90 as the aromatic vinyl monomer.
%, More preferably 65 to 85% by weight. If the proportion of the aromatic vinyl monomer is out of this range, the appearance of the molded article is unfavorably deteriorated.

Specific examples of the epoxy group-containing vinyl monomer used in the copolymer (A) of the present invention include glycidyl methacrylate, glycidyl methyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether and methallyl glycidyl ether. There is.

The amount of the vinyl monomer having an epoxy group copolymerized in the copolymer (A) of the present invention is 0.1 to 10% by weight based on 100 parts by weight of the copolymer (A). is there.
0.1% by weight of vinyl monomer containing epoxy group
If it is less than 10%, the impact resistance of the molded article will be poor, and if it exceeds 10% by weight, the appearance of the molded article will be poor.

[0010] The copolymer (A) of the present invention may contain other copolymerizable monomers as necessary.

The modified polyolefin-based polymer (B) used in the present invention refers to a polymer or copolymer of an olefin monomer which is an unsaturated dicarboxylic anhydride monomer group or an unsaturated dicarboxylic acid monomer group. 0.1 to 10% by weight. Specific examples of the olefin monomer used include ethylene, propylene, 1-butene, isobutylene, 2-butene, cyclobutene, 3-methyl-1-butene, 4-methyl-1-butene, and 4-methyl-1-. Examples include pentene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene and 1-dodecene.

The preferred composition range of the olefin polymer constituting the modified polyolefin polymer (B) is exemplified by 20 to 90 mol% of ethylene, 10 to 80 mol% of α-olefin monomer, and The ethylene content is preferably 50 to 85 mol%, particularly preferably 50 to 80 mol%.

The glass transition temperature of the modified polyolefin polymer (B) is -10 ° C. or lower, preferably -30 ° C. or lower.

Specific examples of the unsaturated dicarboxylic anhydride monomer group that modifies the polyolefin polymer include maleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic anhydride, ethylmaleic anhydride and ethylmaleic anhydride. Examples include phenylmaleic acid, and maleic anhydride is particularly preferred.

Specific examples of unsaturated carboxylic acid monomer groups include acrylic acid and methacrylic acid.

The modified polyolefin-based polymer (B) of the present invention is characterized in that the polyolefin-based polymer has an unsaturated dicarboxylic anhydride monomer group or unsaturated carboxylic acid monomer group of 0.1%.
When the amount of modification is less than 0.1% by weight, the impact strength of the molded article is inferior, and when it exceeds 10% by weight, the impact resistance of the molded article is inferior. Worse.

The term "modified" as used in the present invention means that a monomer group used for the modification, for example, a maleic anhydride group, is present in the main chain or side chain of the polyolefin polymer. Modification can be performed by a known technique such as merging or graft copolymer. The modification method is not particularly limited. For example, JP-B-39-6810 and JP-B-52-4.
Nos. 3677, 53-5716, 56-9
Modification can be performed according to the methods disclosed in JP-A-925-925 and JP-A-58-445.

The modification is preferably carried out as a grafted product in terms of low-temperature impact value and the like, rather than being introduced into the main chain. The amount of unreacted monomer residues is 0.5% by weight. The following are preferable in terms of physical properties.

The weight average molecular weight of the olefin polymer constituting the modified polyolefin polymer (B) is not particularly limited, but is preferably 50,000 to 500,000, more preferably 100,000, from the impact resistance and appearance of the molded product. ~ 300,000 is preferred. As these modified polyolefin-based polymers, for example, commercially available Tuffmer MP-0620 (manufactured by Mitsui Petrochemical Industries, Ltd.)
Product name).

The amount of the modified polyolefin-based polymer (B) in the total of 100 parts by weight of the copolymer (A) of the resin composition (I) and the modified polyolefin-based polymer (B) is 5 to 40 parts by weight. . If the modified polyolefin-based polymer is less than 5 parts by weight, the impact resistance of the molded article is inferior.

The AS resin (II) used in the present invention is a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer. Specific examples of the aromatic vinyl monomer include styrene and α.
-Methylstyrene, vinyltoluene, t-butylstyrene and the like, and specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.

The ratio of the aromatic vinyl monomer to the vinyl cyanide monomer in the AS resin (II) is preferably 50 to 90% by weight as the aromatic vinyl monomer, and more preferably 6 to 90% by weight.
5 to 85% by weight. If the proportion of the aromatic vinyl monomer is out of this range, the appearance of the molded article is unfavorably deteriorated.

The composition of the thermoplastic resin molded article of the present invention is 10 to 90% by weight of the resin composition (I) and 1 part of the AS resin (II).
0 to 90% by weight is good. 10% by weight of resin composition (I)
If the amount is less than 90%, the impact resistance of the molded article is low. If the amount exceeds 90% by weight, appearance defects are likely to occur, and the heat resistance and rigidity are reduced.

The fatty acid glycerin ester (C) used in the present invention is, for example, a fatty acid monoglyceride, a fatty acid diglyceride, a fatty acid triglyceride, which are widely used, and a combination thereof may be used. Among them, fatty acid triglyceride is particularly preferred, and 12-hydroxystearic acid triglyceride is more preferred.

The fatty acid glycerin ester (C) preferably contains 0.2 to 5 parts by weight based on 100 parts by weight of the total of the copolymer (A) and the modified polyolefin-based polymer (B). By adding the fatty acid glycerin ester, the impact resistance and appearance of the molded article can be further improved. If the added amount is less than 0.2 parts by weight, the effect of improving them is small, and if it exceeds 5 parts by weight, the impact strength, heat resistance and appearance of the molded article are undesirably reduced.

The resin composition (I) of the present invention may contain, depending on the purpose, a weathering agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a plasticizer, a lubricant, a coloring agent, a flame retardant, and a glass fiber. ,
Reinforcing fiber such as carbon fiber and aramid fiber, talc,
Fillers such as silica, clay, mica and calcium carbonate can be added.

The mixing method for obtaining the resin composition (I) of the present invention is not particularly limited, and it can be carried out using a usual melt kneading apparatus. Suitable melt-kneading apparatuses include a screw extruder, a Banbury mixer, a co-kneader, and a mixing roll.

The molding machine used in the present invention includes, but is not limited to, an injection molding machine, a sheet molding machine, a blow molding machine, and an injection-blow molding machine.

As a method of supplying the resin composition (I) and the AS resin (II) of the present invention to a molding machine, a method of supplying a pre-blended material using a known device such as a tumbler mixer or a V blender is used. Or in the supply port of the molding machine,
A method of supplying both materials separately and quantitatively can also be adopted. It is not particular about the supply method. Further, depending on the purpose, a weathering agent, a weathering agent masterbatch, a coloring agent, a coloring agent masterbatch, or the like can be simultaneously supplied. Weathering agent (III) used in the present invention
For example, a widely used combination of an ultraviolet absorber, a light stabilizer, and an antioxidant can be used.

Specific examples of the ultraviolet absorber include 2- (5-
Methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] benzotriazotriazole, 2- (3,5-di-t-butyl- 2-hydroxyphenyl) benzotriazotriazole, 2- (3-t-
Butyl-5-methyl-2-hydroxyphenyl) -5
Chlorobenzotriazotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazotriazole, 2- (3,5-di-t-
Amyl-2-hydroxyphenyl) benzotriazotriazole, 2-ethoxy-2'-ethyloxacacid bisanilide, 2-ethoxy-5-t-butyl-
2'-ethyloxazac acid bisanilide and 2-
And hydroxy-4-n-octoxybenzophenone.

Specific examples of the light stabilizer include bis (2,2,2).
6,6-tetramethyl-4-piperidyl) separate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) separate, dimethyl succinate / 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidyl polycondensation Object, poly [[6, (1,
1,3,3-tetramethylbutyl) amino-1,3,5
-Triazine-2,4-diyl] [(2,2,6,6-
Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] and 1- [2- [3- (3,5-di-t)
-Butyl-4-hydroxyphenyl) propionoxy] ethyl] -4- [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionoxy] -2,
2,6,6-tetramethylpiperidine and the like.

Specific examples of the antioxidant include triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,
4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityltetrakis [3- (3
5-di-t-butyl-4-hydroxyphenyl) propinate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propinate, 2,2-
Thiobis (4-methyl-6-t-butylphenol) and 1,3,5-trimethyl-2,2,6-tris (3
5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

In the present invention, the weatherability can be further improved by adding a weathering agent. The weathering agent is a total of 10 of the resin composition (I) and the AS-based resin (II).
It is preferable to add 0.01 to 5 parts by weight of the weathering agent (III) to 0 parts by weight.
If it is less than 5 parts by weight, uniform mixing is insufficient during direct molding and the improvement effect is small. If it exceeds 5 parts by weight, the impact strength is undesirably reduced.

The optimum value for the cylinder setting temperature of the molding machine is determined by the respective compositions of the resin composition (I) and the AS-based resin (II) and the supply ratio thereof. Specifically, in the case of the present invention, 220 ° C. to 280 ° C. is preferable.

In the case of injection molding, a known static mixer, for example, a sluser type, a Kenix type, a Toray engineering type, or the like is installed between a molding machine cylinder and a nozzle to provide higher quality. A molded article having appearance can be obtained.

Further, as the screw of the injection molding machine, a full-flight screw having the highest versatility can be used, but a screw of a dalmage type, a pin type or a Maddock type having higher kneading properties can also be used.

[0037]

The present invention will be described in more detail with reference to the following examples, which are merely illustrative and do not limit the present invention.

The respective copolymers, polymers, resins and raw materials used in the present invention are as follows. (1) Copolymer of aromatic vinyl monomer, vinyl cyanide monomer and vinyl monomer containing epoxy group (A) The polymerization ratio of styrene, acrylonitrile and glycidyl methacrylate is 73/24/3 (a -1), 74/25 /
A copolymer of 1 (a-2) and 75/25/0 (a-3) was used.

(2) Modified polyolefin polymer (B) The polymerization ratio of the ethylene / propylene copolymer and maleic anhydride is 100/0 (b-1), 99.1 / 0.9 (b-
2), 98.7 / 1.3 (b-3) and 98.0 / 2.
0 (b-4) was used. All of these had a weight average molecular weight of 200,000.

For example, b-2 is an ethylene-containing 80 mol%
8.0k of ethylene / propylene copolymer pellets
g, 96 g of powdered maleic anhydride and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-
8.0 g of No. 3 was charged into a 20-liter Henschel mixer through which nitrogen was passed, and stirred for 5 minutes to be uniformly blended.
This was extruded into a 40 mmφ extruder (flowing nitrogen, L / T = 28,
(Dharmage type), the cylinder temperature is set to 2
The temperature was adjusted to 40 ° C. to obtain a graft reaction product, which was formed into a pellet.

(3) Fatty acid glycerin ester (c) Commercially available K-3 wax (Kawaken Fine Chemical Co., Ltd.)
(Product name, product name).

(4) AS-based resin (II) A standard commercially available styrene-acrylonitrile copolymer resin having a polymerization ratio of styrene to acrylonitrile of 75/25 was used to give (II-1).

(5) Weathering agent (III) 2- (5-methyl-2-hydroxyphenyl) benzotriazole and bis (2,2,6,6-tetramethyl-4)
-Piperidyl) separate and octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
A mixture of propionate at a weight ratio of 40/40/20 was used, and the mixture was defined as (III-1).

Example 1 Table 1 shows a copolymer (A) of an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer containing an epoxy group, and a modified polyolefin-based polymer (B). 2 at the indicated ratio
After blending into a 0 liter Henschel mixer,
Using an EM35B extruder (Toshiba 2-axis same direction), temperature 21
The mixture was extruded at 0 ° C. and pelletized to obtain a resin composition (I). Each of the resin composition (I) and the AS-based resin (II) was supplied to an injection molding machine at a ratio of 73:27 by a quantitative feeder to form a test piece. The molding is performed by an injection molding machine K-125 manufactured by Kawaguchi Iron Works Co., Ltd. and a static mixer (mixing nozzle) TMN-16-06 manufactured by Toray Engineer Co., Ltd.
Was carried out. Other molding conditions are as follows. Cylinder set temperature: 240 ° C, injection pressure: minimum filling pressure + 5 kg / cm ² G Injection speed: 40%, mold temperature: 60 ° C Screw: full flight type Using the test pieces thus obtained, various physical properties Measurement and appearance evaluation were performed. Table 1 shows the results.

Example 2 A copolymer of an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer containing an epoxy group (A), a modified polyolefin polymer (B), and a fatty acid glycerin ester ( C) was charged into a 20-liter Henschel mixer at the ratio shown in Table 1, blended, and extruded at a temperature of 210 ° C. with a TEM35B extruder (Toshiba two-axis same direction) to pelletize the resin composition (I). I got The same operation as in Example 1 was performed except that the resin composition (I) and the AS-based resin (II) were blended as shown in Table 1. Table 1 shows the results.

Example 3 The same operation as in Example 1 was performed except that the resin composition (I) and the AS-based resin (II) were mixed as shown in Table 1. Table 1 shows the results.

Example 4 Resin composition (I), AS resin (II) and weathering agent (I)
The same operation as in Example 1 was performed except that II) was supplied to the injection molding machine at the compounding ratio shown in Table 1. Table 1 shows the results.

Example 5 The same operation as in Example 4 was performed. Table 1 shows the results.

Comparative Examples 1 and 2 Resin composition (I), AS resin (II) and weathering agent (I)
The procedure was performed in the same manner as in Example, except that II) was used at the ratio shown in Table 2. Table 2 shows the results.

Comparative Examples 3 and 4 Except that the amount of the vinyl monomer containing an epoxy group in the copolymer (A) was out of the range, or the amount of modification of the modified polyolefin polymer (B) was out of the range. Was performed in the same manner as in the example. Table 2 shows the results.

Comparative Example 5 Various physical properties were measured using an ABS resin having a ratio of styrene / acrylonitrile / butadiene of 61/21/18. Table 2 shows the results.

Comparative Example 6 Resin composition (I), AS resin (II) and weathering agent (I)
II) at the ratio shown in Table 3 and then TEM-35B
The mixture was extruded at a temperature of 210 ° C. by an extruder to obtain pellets. The pellets were molded under the above-described injection molding conditions, and various physical properties were measured. Table 2 shows the results.

[0053]

[Table 1]

[0054]

[Table 2]

The methods for measuring various physical properties in the examples are as follows. 1) Heat resistance: 1/4 thickness according to ASTM D-648
Using an inch injection molded product, load 18.6kg / cm
^{In 2} , the heat distortion temperature (HDT) was measured. 2) Impact strength: according to ASTM D-256, thickness 1 /
Notched IZOD impact values were measured on 4-inch injection molded articles. 3) Elongation: Measured according to ASTM D-638 using an injection molded product having a thickness of 1/8 inch. 4) Rigidity: Flexural modulus was measured using an injection molded product having a thickness of 1/4 inch according to ASTM D-790. 5) Weather resistance: Using a fade meter, when the temperature is 63
° C, the elongation after irradiating with ultraviolet light for 1200 hours is AST
According to MD-638, measurement was performed using an injection molded product having a thickness of 1/8 inch, and a retention ratio before irradiation was determined. 6) Appearance: A square plate having a length of 127 mm, a width of 127 mm, and a thickness of 2 mm was molded with side gates (two points) under the above-described injection molding conditions, and the appearance of the molded article was visually observed and judged according to the following criteria. ：: No defect phenomenon (flow mark, silver streak) occurred on the surface. ×: A defect phenomenon (flow mark, silver streak) has occurred on the surface.

As shown in the examples of Table 1, a molded product obtained by directly molding the resin composition (I) and the AS resin (II) of the present invention has excellent weather resistance, strength and high quality appearance. I have.
On the other hand, as shown in the comparative examples in Table 2, a molded product deviating from the scope of the present invention cannot maintain these excellent qualities. Further, as is apparent from the comparison between Comparative Example 6 and Example 5, the direct molding has a higher impact strength because of the smaller thermal history.

[0057]

As described above, the thermoplastic resin molded article obtained by directly molding the resin composition (I) and the AS resin (II) of the present invention has excellent weather resistance, strength and high quality appearance. It is useful for a wide range of applications such as automobile front grills, air spoilers, outdoor units of air conditioners, antennas for satellite broadcasting, and signboards. In addition, because an economically superior process of direct molding can be adopted,
The industrial utility value is extremely large.

Claims (3)

[Claims] 1. A copolymer of an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer containing an epoxy group, and a copolymer of the vinyl monomer containing an epoxy group in the copolymer. Copolymer (A) 60 in an amount of 0.1 to 10% by weight
-95 parts by weight and 5-40 parts by weight of a modified polyolefin polymer (B) modified with 0.1-10% by weight of an unsaturated dicarboxylic acid anhydride monomer group or an unsaturated dicarboxylic acid monomer group. 10 to 90% by weight of the resin composition (I)
A thermoplastic resin molded article obtained by simultaneously supplying 10 to 90% by weight of the base resin (II) to a molding machine and molding. 2. The resin composition (I) comprises 0.2 to 5 parts by weight of a fatty acid glycerin ester (C) based on 100 parts by weight of the copolymer (A) and the modified polyolefin-based polymer (B) in total. The thermoplastic resin article according to claim 1, further comprising: 3. A resin composition (I) of 10 to 90% by weight and A
Claims characterized in that 0.01 to 5 parts by weight of the weathering agent (III) is simultaneously supplied to a molding machine and molded with respect to 100 parts by weight in total of 10 to 90% by weight of the S-based resin (II). Item 3. The thermoplastic resin article according to Item 1 or 2.