JP3221921B2 - Thermoplastic resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer, which has improved impact resistance, good weather resistance and chemical resistance, and further has another property. The present invention relates to a thermoplastic resin composition having a good balance of physical properties and a method for producing the same.

[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 drawback of low impact resistance. Conventionally, as a method of improving such a defect, grafting of a diene rubber has been performed (Japanese Patent Publication No. 34-3341,
Nos. 42-13616, 42-19330 and 46-26865). However, the copolymer resins improved by these have poor weather resistance due to having double bonds. As described above, the copolymer resin obtained by grafting the diene rubber to the aromatic vinyl monomer and the vinyl cyanide monomer can improve the impact resistance, but decreases the weather resistance. Met.

[0003]

SUMMARY OF THE INVENTION The present invention has solved the above-mentioned drawbacks. An object of the present invention is to provide a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer. A resin composition of a copolymer improved with a vinyl monomer and a modified polyolefin-based polymer, and further, by adding a weathering agent, is excellent in impact resistance, weather resistance and chemical resistance. Another object of the present invention is to provide a thermoplastic resin composition having a good balance of physical properties and a method for producing the same.

[0004]

In summary, the present invention relates to a resin composition and a method for producing the same, comprising: (I) an aromatic vinyl monomer and a vinyl cyanide monomer; A copolymer of a vinyl monomer containing an epoxy group (A),
Or 60 to 95% by weight of a composition of the copolymer (A) and a copolymer (B) of an aromatic vinyl monomer and a vinyl cyanide monomer, and (II) 20 to 90 mol% of ethylene, α- Olefin only
10 to 80 mol% of monomer and 0 to 10 mol of other monomers
% Glass transition temperature (Tg) below -30 degrees Celsius
The glass transition temperature (T) obtained by modifying the rubber-like polyolefin-based copolymer with 0.1 to 10% by weight of an unsaturated dicarboxylic acid anhydride monomer group or an unsaturated carboxylic acid monomer group
g) comprises 5 to 40% by weight of a modified polyolefin polymer of a rubbery substance having a temperature of not more than -30 degrees Celsius , and the copolymer (A)
When the copolymer (B) is not contained, the amount of the vinyl monomer containing an epoxy group copolymerized therein is as follows when the copolymer (A) is contained in 100 parts by weight of the copolymer (A). the copolymer from 0.1 to 10 parts by weight der each total amount of 100 parts by weight of (a) and the copolymer (B) is, and the copolymer (a)及
Vinyl monomer and vinyl cyanide in copolymer and copolymer (B)
The ratio of the vinyl monomer is 50 to 90 weight of the aromatic vinyl monomer.
% And the vinyl cyanide monomer 50 to 10% by weight (however,
The total amount of the aromatic vinyl monomer and the vinyl cyanide monomer is 1
A thermoplastic resin composition comprising 0.01 to 5 parts by weight of a weathering agent with respect to 100 parts by weight of a composition ( 00% by weight) , and a method for producing the same.

The thermoplastic resin composition of the present invention comprises (I) a copolymer (A) of an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer containing an epoxy group (hereinafter referred to as copolymer). (A), or a copolymer (B) of the copolymer (A) with an aromatic vinyl monomer and a vinyl cyanide monomer.
(Hereinafter referred to as copolymer (B)) and (II) a modified polyolefin-based polymer modified with an unsaturated dicarboxylic anhydride monomer group or unsaturated carboxylic acid monomer group. And an appropriate weathering agent.

Specific examples of the aromatic vinyl monomer used in the copolymer (A) and the copolymer (B) of the present invention include styrene, α-methylstyrene, vinyltoluene and t-butylstyrene. Yes, specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.

Further, specific examples of the vinyl monomer containing an epoxy group include glycidyl methacrylate, glycidyl methyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether and methallyl glycidyl ether.

Further, the copolymer (A) and the copolymer (B) of the present invention may contain other copolymerizable monomers as required.

The proportion of each component of the copolymer (A) of the present invention is not particularly limited as long as it is within a copolymerizable range. Preferably, the proportion of an aromatic vinyl monomer and a vinyl cyanide monomer is preferably one. The total amount is 99.9-70% by weight, more preferably 99.9%
To 90% by weight, and the amount of the vinyl monomer containing an epoxy group is preferably 0.1 to 30% by weight, more preferably 0.1 to 30% by weight.
~ 10% by weight.

The ratio between the aromatic vinyl monomer and the vinyl cyanide monomer is preferably 50 to 90% by weight, more preferably 65 to 85% by weight as the aromatic vinyl monomer. If the ratio of the aromatic vinyl monomer is out of this range, the chemical resistance and the fluidity decrease, which is not preferable.

Next, the ratio of the aromatic vinyl monomer to the vinyl cyanide monomer in the copolymer (B) of the present invention is not particularly limited. 9090% by weight, more preferably 65-85% by weight. If the ratio of the aromatic vinyl monomer is out of this range, the chemical resistance and the fluidity decrease, which is not preferable.

The amount of the copolymerized vinyl monomer having an epoxy group in the copolymer (A) of the present invention is 100% of that of the copolymer (A) when the copolymer (B) is not contained. 0.1 to 10 parts by weight per part by weight, and the copolymer (B)
When containing, the total amount of the copolymer (A) and the copolymer (B)
0.1 to 10 parts by weight per 100 parts by weight,
The mixing ratio of the copolymer (A) and the copolymer (B) is not limited as long as the amount of the vinyl monomer containing an epoxy group is within the above range.

When the amount of the epoxy group-containing vinyl monomer is less than 0.1 part by weight, the impact strength of the resin composition is poor, and when it exceeds 10% by weight, the impact strength of the resin composition is poor. , The fluidity becomes extremely low.

The modified polyolefin polymer used in the present invention includes ethylene and α-olefin monomer and other
It refers to a modified product of a rubber-like substance composed of 0 to 10 mol% of a monomer. As a specific example of the α- olefin monomer used,
Is flop propylene, 1-butene, Isobuchire down, 3 - methyl-1-butene, 4-methyl-1-butene, 4-methyl-1-pent down, 1 - hexene down, 1 - octene, 1-decene and 1-dodecene and the like.

[0015] Then, the modified polyolefin-based polymer,
20-90 mol% of ethylene, α-olefin monomer 10
~ 80 mol% and other monomers 0 ~ 10 mol%, the ethylene content is 50 ~ 85 mol%,
Particularly preferred.

The glass transition temperature of these modified polyolefin polymers is not higher than -30 degrees Celsius.

Specific examples of the unsaturated dicarboxylic anhydride monomer group for modifying the modified polyolefin polymer include maleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic anhydride, ethylmaleic anhydride and There are phenylmaleic anhydride and the like, and maleic anhydride is particularly preferred.

Further, specific examples of the unsaturated carboxylic acid monomer group include acrylic acid and methacrylic acid.

The modified polyolefin polymer of the present invention comprises:
It is modified with 0.1 to 10% by weight of an unsaturated dicarboxylic acid anhydride monomer group or unsaturated carboxylic acid monomer group. If the amount of modification is less than 0.1% by weight, the impact strength of the composition is reduced. When the content exceeds 10% by weight, the impact resistance of the composition becomes poor, and the fluidity becomes low.

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 known techniques such as polymerization and graft polymerization. The denaturation method is not particularly limited.For example, JP-B-39-6810, JP-B-52-43677, JP-B-53-5716, JP-B-56-9925 and JP-A-58-445.
The denaturation can be carried out according to the method disclosed in Japanese Patent Application Publication No.

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

The molecular weight of the modified polyolefin polymer is as follows:
Although there is no particular limitation, the balance between impact resistance and formability is 5%.
It is preferably from 100,000 to 500,000, particularly preferably from 100,000 to 300,000. Examples of these modified polyolefin-based polymers include commercially available Tuffmer MP-0620 (trade name, manufactured by Mitsui Petrochemical Industries, Ltd.).

As the weathering agent used in the present invention, those widely used, for example, a 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] benzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole, 2-ethoxy-2'-ethyloxacacid bisanilide, 2-ethoxy-5-t-butyl-2'-ethyloxacacid bisanilide and 2-hydroxy-4-n-octoxybenzophenone .

As a specific example of the light stabilizer, bis (2,
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-pepyridyl) sebacate, dimethyl succinate 1- (2-
(Hydroxyethyl) -4-hydroxy-2,2,6,6
A polycondensate of tetramethylpiperidine, poly [[6,
(1,1,3,3-tetramethylbutyl) amino-1,
3,5-triazine-2,4-diyl] [(2,2,2
6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] and 1- [2- [3- (3,5,
Di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]
-2,2,6,6-tetramethylpiperidine and the like.

Specific examples of the antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,
4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-
Triazine, pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], octadecyl-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-t-butylphenol) and 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

The composition constituting the main part of the present invention is a copolymer (A) or a composition of the copolymer (A) and the copolymer (B).
A mixture of 60 to 95% by weight and 5 to 40% by weight of a modified polyolefin polymer modified with an unsaturated dicarboxylic anhydride monomer group or an unsaturated carboxylic acid monomer group. If the polyolefin polymer is less than 5% by weight,
The impact strength of the thermoplastic resin composition is poor, and 40
Exceeding the weight percentage is not preferred because the heat resistance and rigidity decrease.

The thermoplastic resin composition of the present invention can contain other additives or modifiers depending on the application.
Specifically, there are reinforcing fibers such as glass fiber, carbon fiber and aramid fiber, fillers such as talc, silica, clay, mica and calcium carbonate, as well as flame retardants, lubricants and coloring agents.

Next, the mixing for obtaining the thermoplastic resin composition of the present invention can be carried out by using an ordinary melt kneading apparatus. Examples of the melt kneading apparatus that can be suitably used include a screw extruder and a Banbury. There are mixers, co-kneaders and mixing rolls.

As a method of adding the weathering agent in obtaining the thermoplastic resin composition, a two-stage melt mixing method in which the weathering agent is melt-mixed into a main component obtained by melt-mixing in advance is preferable.

The specific method of melt-mixing the composition constituting the main part and the weathering agent is, for example, the copolymer (A) or the copolymer (A) and the copolymer (B) and the modified polyolefin-based polymer. A method in which a weathering agent is added to a pellet obtained by melt-extruding a coalesced mixture with a composition and melt-extruded and mixed, copolymer (A)
A method in which a weathering agent is added during melt extrusion of the copolymer (A) and the copolymer (B) with the modified polyolefin-based polymer and melt-mixed, and the copolymer (A) or Various methods such as a method of adding and mixing a weathering agent during the melt mixing of the copolymer (A) and the copolymer (B) with the modified polyolefin-based polymer can be used. , Not limiting.

The thermoplastic resin composition of the present invention is useful for applications such as front grills and air spoilers of automobiles, outdoor units of air conditioners, and antennas for satellite broadcasting.

[0033]

The present invention will be described in more detail with reference to the following examples. These are all examples and do not limit the content of the present invention.

The methods for measuring various properties are as follows. Heat resistance: Heat distortion temperature (HDT) was measured according to ASTM D-648 using an injection molded product having a thickness of 1/4 in under a load of 18.6 kg / cm ² . Impact strength: According to ASTM D-256, a notched IZOD impact value was measured using an injection molded product having a thickness of 1/4 inch. Fluidity: The melt flow rate was measured according to JISK-6874 at a temperature of 220 ° C. and a load of 10 kg. Elongation: Measured according to ASTM D-638 using an injection molded product having a thickness of 1/8 inch. Rigidity: According to ASTM D-790, a flexural modulus was measured using an injection molded product having a thickness of 1/4 inch. Weather resistance: Using a fade meter, the temperature was 63 ° C. and the elongation after irradiating with ultraviolet light for 1200 hours was determined according to ASTM D-638.
Measurement was performed using an injection molded product having a thickness of 1/8 inch, and the retention ratio before irradiation was determined.

Further, each copolymer, polymer and weathering agent are
It is as follows. (1) Copolymer of aromatic vinyl monomer, vinyl cyanide monomer and epoxy-containing vinyl monomer (A) The polymerization ratio of styrene, acrylonitrile and glycidyl methacrylate is 73/24/3 ( a-1), 78/19/3 (a-2), 71/24/5 (a-
3) and 66/22/12 (a-4).

(2) Copolymer of aromatic vinyl monomer and vinyl cyanide monomer (B) Standard commercially available standard styrene-acrylonitrile copolymer having a weight ratio of styrene to acrylonitrile of 76/24 Resin (b-1).

(3) Modified polyolefin copolymer (C) The polymerization ratio of the ethylene / propylene copolymer and maleic anhydride is 100/0 (c-1), 99.5 / 0.5 (c-2), 99.1 / 0.9 (c-3) and
A polymer having a ratio of 98.0 / 2.0 (c-4).

For example, c-3 has an ethylene content of 80 mol%
Ethylene / propylene copolymer pellets at 8.0K
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 with a 40 mmφ extruder (flowing nitrogen, L / T-28, dalmage type). , In the form of pellets. The cylinder temperature was adjusted so that the polymer temperature became 240 ° C., to obtain a graft reaction product.

(4) Weathering agent (D) 2- (5-methyl-2-hydroxyphenyl) benzotriazole and bis (2,2,6,6-tetramethyl-
4 piperidyl) sebacate and octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
A mixture of propionate in a weight ratio of 45/45/10 (D).

Example 1 Copolymer of an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer containing an epoxy group (A) 2.12
1.08 kg of a copolymer (B) of Kg, an aromatic vinyl monomer and a vinyl cyanide monomer and 0.80 kg of a modified polyolefin-based polymer (C) are charged into 20 liter Henschel, blended, and then blended with a TEM35B extruder. (Toshiba, 2 axis same direction)
The mixture was extruded at 230 ° C. into pellets. next,
3 kg of the pellets and 34.5 g of the weathering agent (D) were charged into a 20-liter Henschel and blended.
Extruded pellets were obtained at a temperature of 230 ° C. Using the pellets, test specimens for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. Table 1 shows the results.

Examples 2 to 7 Example 1 was repeated except that the copolymer (A), the copolymer (B), the modified polyolefin polymer (C) and the weathering agent (D) were blended as shown in Table 1. The same operation as described above was performed. Table 1 shows the measurement results of various physical properties.

Comparative Examples 1 to 5 Copolymer (A), copolymer (B), modified polyolefin polymer (C) and weathering agent (D) are shown in Table 2
Comparative Examples 1 and 4 set the amount of the vinyl monomer containing an epoxy group out of the range, Comparative Examples 2 and 3 set the amount of the modified polyolefin-based copolymer out of the range, and Comparative Example 5 set the modified polyolefin The same operation as in Example 1 was performed except that the amount of modification of the system copolymer was out of the range. Table 2 shows the measurement results of various physical properties.

Comparative Example 6 Various physical properties were obtained by using an ABS resin having styrene / acrylonitrile / butadiene components of 61/21/18 and a weathering agent (D) added in the same manner as in Example 1. Was measured. Table 2 shows the measurement results.

[0044]

[Table 1]

[0045]

[Table 2] The molding temperature was set at 240 ° C. as a standard, and was slightly modified depending on the condition of the molded product.

Example 8 The copolymer (A), the copolymer (B), the modified polyolefin polymer (C) and the weathering agent (D) were combined with 53 (a-1) / 27 (b-1) /
The same operation as in Example 1 was performed except that the compounding ratio was 20 (c-3) /0.58 (D). Various physical properties, IZOD impact value: 25Kg
・ Cm / cm, elongation: 20%, HDT: 90 ° C., MFR: 8.
The flexural modulus was 20900 kg / cm ² , the elongation after the weather test was 15%, and the retention was 75%.

Example 9 The copolymer (A), the copolymer (B), the modified polyolefin-based polymer (C) and the weathering agent (D) were combined with 53 (a-1) / 27 (b-1) /
The same operation as in Example 1 was performed, except that the compounding ratio was 20 (c-3) /2.30 (D). Various physical properties, IZOD impact value: 23Kg
・ Cm / cm, elongation: 19%, HDT: 89 ° C., MFR: 9.
The flexural modulus was 21000 kg / cm ² , the elongation after the weather test was 15%, and the retention was 100%.

The following is clear from the results of the examples and the comparative examples. From Example 1 and Comparative Example 1, the impact value was low when no vinyl monomer containing an epoxy group was included. Further, as in Comparative Example 4, when the amount of the vinyl monomer containing an epoxy group is too large, the impact value and the fluidity are lowered.

From Example 1 and Comparative Example 2, when the amount of the modified polyolefin polymer is small, the impact value is low. Comparative Example 3
If the amount of the modified polyolefin-based polymer is too large, the heat resistance and rigidity are lowered.

From Example 1 and Comparative Example 5, the impact value is low when an unmodified polyolefin polymer is used. According to Example 1 and Comparative Example 6, when a diene rubber is used, the weather resistance is extremely poor.

As described above, the epoxy group-containing copolymer has an epoxy group, and the modified polyolefin-based polymer has an unsaturated dicarboxylic anhydride monomer group or an unsaturated carboxylic acid monomer group. Each contains a proper amount, and only when a weathering agent is added, the weather resistance and impact resistance are excellent,
Further, it can be seen that the balance of other physical properties is improved.

[0052]

The resin composition of the present invention is excellent in weather resistance, impact resistance and chemical resistance, has a good balance of physical properties such as heat resistance, elongation and rigidity, has good moldability, and is capable of being molded. The product has a beautiful appearance and has extremely high practical value as an industrial material.

Continuation of front page (56) References JP-A-4-18441 (JP, A) JP-A-4-55456 (JP, A) JP-A-4-132754 (JP, A) (58) Fields investigated (Int) .Cl. ⁷ , DB name) C08L 25/08-25/14 C08L 51/06 C08L 23/26

Claims (2)

(57) [Claims] 1. A copolymer (A) of an aromatic vinyl monomer, a vinyl cyanide monomer and an epoxy group-containing vinyl monomer (A), or the copolymer (A) and an aromatic vinyl monomer 60 to 95% by weight of a composition of a copolymer (B) of a vinyl monomer and a vinyl cyanide monomer, and (II) 20 to 90 mol of ethylene
%, Α-olefin monomer 10 to 80 mol% and other
Glass transition temperature (T
g) Polyolefin, a rubbery substance having a temperature of not more than -30 degrees Celsius
Rubber copolymer having a glass transition temperature (Tg) of -30 ° C. or less obtained by modifying a copolymer based on 0.1 to 10% by weight of an unsaturated dicarboxylic acid anhydride monomer group or unsaturated carboxylic acid monomer group.
The amount of the vinyl monomer containing an epoxy group copolymerized in the copolymer (A) is 5 to 40% by weight of the modified polyolefin polymer of the substance. When the copolymer (B) is contained in 100 parts by weight of the copolymer (A), the total amount of the copolymer (A) and the copolymer (B) is 100.
Each 0.1-10 parts by der in parts by weight is, and co
Aromatic vinyl monomer in polymer (A) and copolymer (B)
The ratio of the monomer to the vinyl cyanide monomer is
50 to 90% by weight of a vinyl cyanide monomer
% By weight (but aromatic vinyl monomer and vinyl cyanide monomer
A thermoplastic resin composition comprising 0.01 to 5 parts by weight of a weathering agent based on 100 parts by weight of a composition whose total amount is 100% by weight. 2. A method for producing a thermoplastic resin composition, comprising: melt-mixing a composition comprising (I) and (II) according to claim 1;