JP3131243B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a copolymer of an aromatic vinyl monomer and a vinyl cyanide monomer having improved impact resistance, good weather resistance and chemical resistance, and other physical properties. The present invention relates to a thermoplastic resin composition having a good balance.

[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, a diene rubber has been grafted (Japanese Patent Publication Nos.
-19330, 42-13616, 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. there were.

[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 modified with a vinyl monomer and a modified polyolefin-based polymer is excellent in impact resistance, weather resistance and chemical resistance, and has a good balance of other physical properties. An object of the present invention is to provide a plastic resin composition.

[0004]

SUMMARY OF THE INVENTION In general, the present invention relates to a resin composition, which comprises (I) an aromatic vinyl monomer, a vinyl cyanide monomer and an epoxy group. Copolymer of vinyl monomer (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- Glass transition temperature (Tg) composed of 10 to 80 mol% of olefin monomer and 0 to 10 mol% of other monomers is -30 ° C or less.
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
(00% by weight) .

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 polymer modified with an unsaturated dicarboxylic acid anhydride monomer group or an unsaturated carboxylic acid monomer group.

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 of the aromatic vinyl monomer to the vinyl cyanide monomer is 50 to 90% by weight, 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.
It is 50 to 90% by weight, preferably 65 to 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 containing an epoxy group in the copolymer (A) of the present invention is 100 parts by weight when the copolymer (B) is not contained. When the copolymer (B) is contained, the total amount of the copolymer (A) and the copolymer (B) is 0.1 to 10 parts by weight per 100 parts by weight of the copolymer (B). For example, the ratio of the copolymer (A) to the copolymer (B) is not limited.

When the amount of the vinyl monomer containing an epoxy group is less than 0.1 part by weight, the impact resistance of the resin composition is poor, and when it exceeds 10 parts by weight, the impact resistance of the resin composition is poor. Further, the fluidity becomes extremely low.

The modified polyolefin-based polymer used in the present invention is defined as 20 to 90 mol% of ethylene and α-olefin unit.
10 to 80 mol% of monomer and 0 to 10 mol of other monomers
% Glass transition temperature (Tg) below -30 degrees Celsius
Refers to a modified product of gum, specific examples of are 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
And 1 -octene, 1-decene and 1-dodecene. By way of example the preferred range, it is particularly preferable et styrene content of from 50 to 85 mol%. These modified polyolefin polymers have a glass transition temperature ( T
g ) is not more than -30 degrees Celsius.

Specific examples of the unsaturated dicarboxylic anhydride monomer group that modifies 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 preferable. Specific examples of the unsaturated carboxylic acid monomer group include acrylic acid and methacrylic acid.

The modified polyolefin polymer of the present invention comprises
An unsaturated dicarboxylic acid anhydride monomer group or an unsaturated carboxylic acid monomer group, modified with 0.1 to 10% by weight;
If the modified amount is less than 0.1% by weight, the impact strength of the composition is poor, and if it exceeds 10% by weight, the impact strength of the composition is poor and the fluidity is low. In the present invention, the term "modification" refers to the presence of a monomer group used for modification in the main chain or side chain of the polyolefin polymer, for example, the presence of a maleic anhydride group. Modification can be performed by a known technique such as polymerization. The method of denaturation is not particularly limited, and is described, for example, in JP-B-39-681.
No. 0, JP-A-52-43677 and JP-A-53-571.
No. 6, No. 56-9925 and No. 58-445.
The denaturation can be carried out according to the method disclosed in Japanese Patent Application Publication No. In addition, the modification is preferably performed as a graft rather than the introduction into the main chain in terms of low-temperature impact value and the like, and the residual amount of unreacted monomer is 0.5% by weight or less. It is preferable in terms of physical properties. Although the molecular weight of the modified polyolefin-based polymer is not particularly limited, it is preferably 50,000 to 500,000, particularly preferably 100,000 to 300,000 from the balance of impact resistance and moldability. Examples of these modified polyolefin-based polymers include commercially available Tuffmer MP-0620 (trade name, manufactured by Mitsui Petrochemical Industries, Ltd.).

The thermoplastic resin composition of the present invention comprises 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,
If the impact resistance of the resin composition is inferior, and if it exceeds 40% by weight, heat resistance and rigidity are undesirably reduced.

The thermoplastic resin composition of the present invention can be made into a resin composition by adding other additives or modifiers depending on the use. Specifically, glass fiber, carbon fiber, and the like can be used. There are reinforcing fibers such as aramid fibers, fillers such as talc, silica, clay, mica and calcium carbonate, as well as flame retardants, lubricants and coloring agents. Further, the addition of a weathering agent further improves the weather resistance.

The mixing of the composition can be carried out using a conventional melt kneading apparatus, and preferred melt kneading apparatuses include a screw extruder, a Banbury mixer, a co-kneader, and a mixing roll.

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.

[0021]

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 at a load of 18.6 kg / cm ² using a 1/4 ″ thick injection molded article according to ASTM D-648. Impact strength: Thick according to ASTM D-256 Notched IZOD impact values were measured on 1/4 "injection molded articles. Fluidity: 220 degrees Celsius according to JISK-6874,
The melt flow rate was measured under a load of 10 kg. Elongation: Measured using an injection molded product having a thickness of 1/8 "according to ASTM D-638. Stiffness: Flexural modulus using an injection molded product having a thickness of 1/4" according to ASTM D-790 Was measured. Weather resistance: Injection molded product with a thickness of 1/8 ″ according to ASTM D-638, using an i-Super UV tester to irradiate light at a temperature of 63 degrees Celsius and a wavelength of 295 to 450 nm for 20 hours. And the retention ratio before irradiation was determined.

The respective copolymers and polymers are as follows. (1) Copolymer of aromatic vinyl monomer, vinyl cyanide monomer and vinyl monomer containing epoxy group (A) The weight ratio of styrene, acrylonitrile and glycidyl methacrylate is 73/24/3 ( a-1), 78/19/3 (a-2), 71/24/5 (a-
3), 66/22/12 (a-4).

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

(3) Modified polyolefin polymer (C) The weight ratio of the ethylene / propylene copolymer to maleic anhydride is 100/0 (c-1), 99.5 / 0.5 (c-2), 99.1 / 0.9 ( c-3), 9
A polymer having a ratio of 8.0 / 2.0 (c-4). For example, c-3 is 8.0 kg of ethylene-propylene copolymer pellets having an ethylene content of 80 mol%, 96 g of powdered maleic anhydride, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-
3 8.0 g was charged into a 20-liter Henschel mixer through which nitrogen was passed, and stirred for 5 minutes to be uniformly blended.
Pelletize with a 40 mmφ extruder (flowing nitrogen, L / T-28, dalmage type). The cylinder temperature was adjusted so that the polymer temperature was 240 ° C. to obtain a graft reaction product.

Example 1 A copolymer (A) of an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer containing an epoxy group (2.12 kg), an aromatic vinyl monomer and a vinyl cyanide monomer 1.08 kg of copolymer (B) and modified polyolefin polymer (C)
0.80 kg is charged into 20 liter Henschel and blended, then TE
Temperature of 230 degrees Celsius with M35B extruder (Toshiba, same direction on two axes)
And extruded into pellets. Using the pellets, test specimens for measuring physical properties were prepared by an injection molding machine, and various physical properties and the like were measured. Table 1 shows the results.

Examples 2 to 7 The same operation as in Example 1 was carried out except that the copolymer (A), the copolymer (B) and the modified polyolefin polymer (C) were blended as shown in Table 1. Was. Table 1 shows the measurement results of various physical properties.
Shown in

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

Comparative Example 6 Each component of the ABS resin was styrene / acrylonitrile /
Various physical properties were measured using 61/21/18 butadiene. Table 2 shows the measurement results.

[0030]

[Table 1]

[0031]

[Table 2]

The molding temperature was set at 240 degrees Celsius as a standard, and the temperature was slightly modified depending on the condition of the molded product.

The following is clear from the results of the examples and 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 become low.

From Example 1 and Comparative Example 2, when the amount of the modified polyolefin polymer is small, the impact value is low. Also, as in Comparative Example-3, when the amount of the modified polyolefin-based polymer is too large, 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. From Example 1 and Comparative Example 6, when a diene rubber is used, the weather resistance is extremely poor.

As described above, an epoxy group-containing copolymer has an epoxy group, and a modified polyolefin-based polymer has an unsaturated dicarboxylic acid anhydride monomer group or an unsaturated carboxylic acid monomer group. Only when it is contained, it can be seen that the weather resistance and impact resistance are excellent and the balance of physical properties is good.

[0037]

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

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 25/00-25/18 C08L 51/04-51/06

Claims (1)

(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, (II) 20 to 90% by mole of ethylene, 10 to 80% by mole of an α-olefin monomer and others Glass transition temperature (T
g) a glass obtained by modifying a polyolefin-based copolymer of a rubbery substance having a temperature of -30 ° C. or lower with 0.1 to 10% by weight of an unsaturated dicarboxylic acid anhydride monomer group or an unsaturated carboxylic acid monomer group. Rubber with transition temperature (Tg) of -30 degrees Celsius or less
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
The total amount of the body is 100% by weight) . "