JPH0551493A - Polymer composition having excellent chemical resistance and heat-resistance - Google Patents

Abstract

PURPOSE:To provide a polymer composition having excellent chemical resistance, appearance of injection molded article, impact strength, rigidity, etc., and suitable for various industrial parts such as interior trim of automobile, general domestic goods such as container for microwave oven, etc. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of a polymer composed of (A1) 5-95wt.% of a maleic anhydride- styrene copolymer produced by polymerizing maleic anhydride, a styrene compound and, as necessary, other polymerizable compounds and/or a rubber- modified maleic anhydride-styrene copolymer produced by graft-polymerizing maleic anhydride, a styrene compound and optionally other polymerizable compounds to a rubbery polymer and (A2) 95-5wt.% of an olefin polymer with (B) 0.1-20 pts.wt. of an olefin polymer grafted with an unsaturated dicarboxylic acid anhydride. The balance of the physical properties of the composition can be further improved by compounding (C) 0.1-20 pts.wt. (based on 100 pts.wt. of the component A) of one or more elastomers selected from styrene-ethylene- butylene-styrene block copolymer elastomer, etc., to the above composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention does not cause whitening, crazing or cracking even when immersed in an organic solvent, especially oils and fats.
Further, the present invention relates to a polymer composition which does not generate a pearl pattern or a streak pattern during injection molding and is excellent in mechanical strength, moldability, heat resistance and heat stability.

[0002]

2. Description of the Related Art Conventionally, maleic anhydride-styrene copolymers and rubber-modified maleic anhydride-styrene copolymers are known as polymers having high rigidity, dimensional stability and heat resistance. However, since the copolymer is poor in thermal stability, it undergoes thermal decomposition during molding and produces silver streaks on the surface of the molded product. Furthermore, the copolymer is poor in chemical resistance, particularly oil resistance, and when contacted with oils and fats such as coconut oil, salad oil and MCT oil and fat, the surface is attacked,
Whitening, crazing, cracks, etc. occur and cannot be used. Olefin polymers such as propylene polymers have excellent chemical resistance, and even if they come into contact with fats and oils such as coconut oil, salad oil, and MCT fats and oils, the appearance of molded articles does not deteriorate. However, it is inferior in moldability, dimensional stability and rigidity. Further, a maleic anhydride-styrene copolymer and an olefin polymer are melt-kneaded to obtain a polymer composition, but the compatibility is poor and it cannot be put to practical use. A method for improving the compatibility of this polymer composition has also been investigated, and for example, a styrene-butadiene block copolymer elastomer (Japanese Patent Laid-Open No. 63-2).
No. 05341), an epoxy group-containing olefin polymer (JP-A-61-95052) and the like are known, but a pearl pattern or a streak pattern showing poor compatibility is generated during injection molding to improve the compatibility. Is not fully satisfied.

[0003]

An object of the present invention is to provide a polymer composition which is excellent in mechanical strength, moldability, heat resistance and compatibility even when immersed in an organic solvent, particularly oils and fats. It is in. Specifically, the compatibility between the maleic anhydride-styrene copolymer and / or the rubber-modified maleic anhydride-styrene copolymer and the olefin polymer is improved, and chemical resistance, moldability, rigidity and mechanical properties are improved. It is to provide a polymer composition having both excellent mechanical strength.

[0004]

The present inventors have reached the present invention as a result of intensive studies to solve the above problems. That is, the present invention is a maleic anhydride and a styrene compound, or a maleic anhydride-styrene copolymer obtained by polymerizing these and another polymerizable compound different from these, and / or a maleic anhydride and a styrene compound. , Or 5 to 95% by weight of a rubber-modified maleic anhydride-styrene copolymer and 95 to 5% by weight of an olefin polymer obtained by graft-polymerizing these or other polymerizable compounds different from these with a rubber-like polymer. It is a polymer composition excellent in chemical resistance and heat resistance, which is obtained by blending 0.1 to 20 parts by weight of an unsaturated dicarboxylic acid anhydride grafted olefin polymer with 100 parts by weight of the combined product.

Examples of the styrene compound used in the present invention include styrene, α-methylstyrene, pt-butylstyrene, vinyltoluene and chlorostyrene.
The maleic anhydride-styrene copolymer is a copolymer obtained by copolymerizing one or more of the styrene compounds with maleic anhydride, such as a maleic anhydride-styrene copolymer, and maleic anhydride-styrene. As a copolymer, Dailark # 232 (manufactured by Arco Chemical Co., Ltd.) was used. As the rubber-modified maleic anhydride-styrene copolymer, a graft copolymer obtained by graft-copolymerizing one or more of the styrene compound and maleic anhydride on a butadiene polymer rubber, for example, maleic anhydride-styrene. As a graft copolymer, maleic anhydride-styrene graft copolymer, Dailark # 250 (manufactured by Arco Chemical Co., Ltd.) was used. These are manufactured by methods well known to those skilled in the art and are commercially available. Further, as a copolymer obtained by polymerizing another polymerizable compound, a copolymer obtained by copolymerizing one or more of the styrene compound, maleic anhydride and acrylonitrile, for example, acrylonitrile-maleic anhydride-styrene. It is a copolymer. These are obtained by a known bulk polymerization method or bulk-suspension polymerization method. Examples of the olefin polymer used in the present invention include ethylene polymers, propylene polymers, propylene-ethylene polymers,
Examples include butene polymer and methylpentene polymer, and Mitsui Noblene EB-G [manufactured by Mitsui Toatsu Chemicals, Inc.] was used as the olefin polymer. These are manufactured by methods well known to those skilled in the art and are commercially available.

The unsaturated dicarboxylic acid anhydride-grafted olefin polymer used in the present invention can be obtained by graft-polymerizing an unsaturated dicarboxylic acid anhydride onto an olefin polymer. The olefin polymer used here may be one having crystallinity. As the unsaturated dicarboxylic acid anhydride, maleic anhydride, itaconic anhydride, etc. were used, and as the unsaturated dicarboxylic acid anhydride grafted olefin polymer, Mitsui Rompray GPP (manufactured by Mitsui Toatsu Chemicals, Inc.) was used. These can be manufactured by methods well known to those skilled in the art.

Styrene-ethylene-used in the present invention
Butylene-styrene block copolymer elastomer (S
EBS) comprises an olefin polymer (ethylene / butylene) block which is a soft segment in the middle of a styrene polymer block at both ends which is a hard segment, and is a butadiene polymer of a styrene-butadiene-styrene block copolymer elastomer. Obtained by adding hydrogen. Examples of the styrene-based polymer used here are styrene, α-methylstyrene, paramethylstyrene,
It is a polymer of vinyl xylene and a copolymer thereof.
Further, maleic anhydride is grafted onto the copolymer elastomer (SEBS) to obtain a maleic anhydride-modified styrene-ethylene-butylene-styrene block copolymer elastomer. As SEBS, Kraton G-1652
[Shell Chemical Co., Ltd.], maleic anhydride modified SEBS
Craton FG-1901X (manufactured by Shell Kagaku Co., Ltd.) was used. These are manufactured by methods well known to those skilled in the art and are commercially available.

Styrene-ethylene-used in the present invention
Propylene block copolymer elastomer (SEP)
Is composed of a styrene-based polymer block and an olefin polymer (ethylene / propylene) block.
It is obtained by adding hydrogen to the isoprene block copolymer elastomer. Further, the copolymer elastomer (SE
Maleic anhydride is grafted onto P) to obtain a maleic anhydride-modified styrene-ethylene-propylene block copolymer elastomer. KL-1001 (manufactured by Kuraray Co., Ltd.) as SEP and K as maleic anhydride-modified SEP
L-01M-2 (manufactured by Kuraray Co., Ltd.) was used. These are manufactured by methods well known to those skilled in the art and are commercially available.

In the polymer composition of the present invention, the compounding ratio of the maleic anhydride-styrene copolymer and / or the rubber-modified maleic anhydride-styrene copolymer is 5 each.
To 95% by weight, 95 to 5% by weight, preferably 20
-80% by weight and 80-20% by weight. If the maleic anhydride-styrene copolymer and / or the rubber-modified maleic anhydride-styrene copolymer is less than 5% by weight, the rigidity is poor, and if it exceeds 95% by weight, the chemical resistance is unfavorably lowered. The blending ratio of the unsaturated dicarboxylic acid anhydride grafted olefin polymer is such that the polymer of the maleic anhydride-styrene copolymer and / or the rubber-modified maleic anhydride-styrene copolymer and the polymer of the olefin polymer is 100. 0.1 to 20 parts by weight, preferably 5 to 5 parts by weight
15 parts by weight. If it is less than 0.1, the compatibility decreases,
It is not preferable because the chemical resistance decreases. If it exceeds 20 parts by weight, the mechanical strength is deteriorated, which is not preferable. Further, a styrene-ethylene-butylene-styrene block copolymer elastomer (SEBS), a styrene-ethylene-propylene block copolymer elastomer (SEP), and a maleic anhydride-modified copolymer elastomer obtained by grafting maleic anhydride onto these elastomers. The compounding ratio of the one or more elastomers selected from the following is 100% by weight of a maleic anhydride-styrene copolymer and / or a rubber-modified maleic anhydride-styrene copolymer and an olefin polymer.
It is 0.1 to 20 parts by weight, preferably 5 to 15 parts by weight, based on parts by weight. By adding the copolymer elastomer within this range, a composition having a better balance of physical properties can be obtained. If it is less than 0.1, the effect of addition is not exhibited, and if it is 20 or more, the rigidity is poor, which is not preferable.

The method for producing the polymer composition of the present invention is not particularly limited and can be produced by a known method. That is, maleic anhydride-styrene copolymer and / or rubber-modified maleic anhydride-styrene copolymer and olefin polymer, unsaturated dicarboxylic acid anhydride grafted olefin polymer, styrene-ethylene-butylene-styrene block Copolymer elastomer (SEBS) and / or styrene-ethylene-propylene block copolymer elastomer (SEP) and / or maleic anhydride-modified copolymer elastomer obtained by grafting maleic anhydride onto these elastomers is used as a tumbler or a Henschel mixer. Examples of the method include uniform mixing using a high speed stirrer, etc., and then melt kneading with a Banbury mixer, an extruder, or the like. Of course, in the polymer composition of the present invention, if necessary, various additives used in ordinary thermoplastic polymers, for example, colorants, lubricants, plasticizers, antioxidants, stabilizers, antistatic agents, and ultraviolet absorbers. Agents and the like may be added.

[0011]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The invention is not limited to these examples. The chemical resistance and the physical properties described in Examples and Comparative Examples were evaluated according to the following methods. (1) chemical resistance ^{X 2/12 2 + Y 2} /4.5 1/4 elliptical jig represented by ² = 1, 150 × 50m created by injection molding
m, 1mm thick flat plate fixed, coconut oil, salad oil, M
After applying CT oil and fat and leaving it at 23 ° C for 24 hours, the test piece is observed and a critical strain (minimum strain) in which a crack is generated
Was evaluated and evaluated using the symbols shown below. Symbol Content ○: No appearance defect or critical strain of 0.3 or more △: Critical strain of 0.15 or more and less than 0.3 ×; Critical strain of less than 0.15 or whitening, swelling, dissolution, etc.
Poor appearance. (2) Izod impact strength Based on JIS K-7110. (3) Heat distortion temperature It was based on JIS K-7207. (4) Flexural strength and flexural modulus Based on JIS K-7203. (5) Appearance A flat plate having a size of 150 × 50 mm and a thickness of 3 mm was prepared by injection molding, the surface of the molded product was observed with the naked eye, and the amount of pearl pattern or streak pattern was used for the determination. No .: No pearl pattern or streak pattern △: Less than 10% pearl pattern or streak pattern can be confirmed on the surface of the molded product ×; 10% or more pearl pattern or streak pattern can be confirmed on the surface of the molded product Example 1 Maleic anhydride 50% by weight of Dailark # 232 (manufactured by Arco Chemical Co., Ltd.) as a styrene-based copolymer,
As an olefin polymer, Mitsui Noblene EB-G [manufactured by Mitsui Toatsu Chemicals, Inc.] is 50% by weight, and as an unsaturated dicarboxylic acid anhydride grafted olefin polymer, Mitsui Rompley GPP [manufactured by Mitsui Toatsu Chemicals, Inc.] ] 10 parts by weight were mixed, mixed using a tumbler, and extruded at 230 using a twin-screw extruder to form pellets. Test pieces were prepared from the pellets by injection molding (molding temperature: 220 ° C., mold temperature: 50 ° C.), and the above-described evaluation was performed. The results are shown in Table 1. All of them are excellent in chemical resistance, impact resistance, heat resistance, rigidity and moldability, and have sufficient practical value. Example 2 The same procedure as in Example 1 was carried out except that Dailark # 250 (manufactured by Arco Chemical Co., Ltd.), which was a rubber-modified maleic anhydride-styrene copolymer, was used instead of Dailark # 232, and the results were It is shown in Table 1. Example 3 The same procedure as in Example 1 was carried out except that acrylonitrile-maleic anhydride-styrene copolymer was used as the maleic anhydride-styrene copolymer instead of Dailark # 232, and the results are shown in Table 1. Shown in. Example 4 Example 1 was repeated except that the compounding ratios of Dailark # 232 and Mitsui Noblene EB-G were changed to 75% by weight and 25% by weight, and the results are shown in Table 1. Example 5 Example 1 was repeated except that the compounding ratios of Dailark # 232 and Mitsui Noblene EB-G were changed to 25% by weight and 75% by weight, and the results are shown in Table 1. Example 6 Example 1 was repeated except that the compounding ratios of Dailark # 250 and Mitsui Noblene EB-G used in Example 2 were changed to 75% by weight and 25% by weight, and the results are shown in Table 1. .. Example 7 Example 1 was repeated except that the compounding ratios of Dailark # 250 and Mitsui Noblene EB-G used in Example 2 were changed to 25% by weight and 75% by weight, and the results are shown in Table 1. .. Example 8 Example 1 was repeated except that 10 parts by weight of Kraton G-1652 (manufactured by Shell Kagaku Co., Ltd.) was added as the styrene-ethylene-butylene-styrene block copolymer elastomer (SEBS) in Example 1. The same procedure as in Example 1 was performed, and the results are shown in Table 1. Example 9 In Example 1, as a styrene-ethylene-propylene block copolymer elastomer (SEP), KL-
Example 1 was repeated except that 10 parts by weight of 1001 (manufactured by Kuraray Co., Ltd.) was blended, and the results are shown in Table 1. Example 10 Example 1 was repeated except that 10 parts by weight of Kraton FG-1901X (manufactured by Shell Chemical Co., Ltd.) was blended as the maleic anhydride-modified styrene-ethylene-butylene-styrene block copolymer elastomer in Example 1. The results are shown in Table 1. Example 11 Same as Example 1 except that 10 parts by weight of KL-01M-2 (manufactured by Kuraray Co., Ltd.) was blended as the maleic anhydride-modified styrene-ethylene-propylene block copolymer elastomer. The results are shown in Table 1. Example 12 In Example 1, 5 parts by weight of Kraton G-1652 (manufactured by Shell Chemical Co., Ltd.) and Kraton FG-1901 were used.
Except that 5 parts by weight of X [manufactured by Shell Chemical Co., Ltd.] was blended,
The same procedure as in Example 1 was performed, and the results are shown in Table 1. Example 13 The same procedure as in Example 1 was carried out by using the compounding ratios of Dailark # 232 and Dailark # 250 in combination with 25% by weight and 25% by weight, and the results are shown in Table 1. Example 14 Example 13 was repeated except that 10 parts by weight of SEBS was added, and the results are shown in Table 1. Example 15 The compounding ratio of Dailark # 232 and acrylonitrile-maleic anhydride-styrene copolymer was 25% by weight and 2% by weight.
The same procedure as in Example 14 was carried out in combination with 5% by weight, and the results are shown in Table 1. Comparative Examples 1 to 7 The same procedure as in Examples 1 to 7 except that the unsaturated dicarboxylic acid anhydride grafted olefin polymer was not used, and the results are shown in Table 2. The chemical resistance is remarkably reduced and the appearance of the molded product is inferior as compared with the examples. Comparative Example 8 The same procedure as in Example 1 was carried out using only Dilark # 232, and the results are shown in Table 2. The impact resistance and chemical resistance are inferior to those of the examples. Comparative Example 9 Only Mitsui Noblen EB-G was performed in the same manner as in Example 1,
The results are shown in Table 2. Excellent in chemical resistance as compared with Examples, but inferior in impact resistance and rigidity. Comparative Example 10 The procedure of Example 1 was repeated, except that the unsaturated dicarboxylic acid anhydride grafted olefin polymer was blended in a proportion outside the range of the present invention, and the results are shown in Table 2. It is inferior in heat resistance and rigidity as compared with the examples. Comparative Examples 11 to 14 Comparative Examples 11 to 14 were carried out in the same manner as Examples 8 to 11 except that SEBS and the like were blended at a ratio outside the range of the present invention, and the results are shown in Table 2. It is inferior in heat resistance and rigidity as compared with the examples. Comparative Example 15 Example 8 was repeated except that the unsaturated dicarboxylic acid anhydride grafted olefin polymer was not used, and the results are shown in Table 2. The chemical resistance is remarkably reduced and the appearance of the molded product is inferior as compared with the examples.

[0012]

[Table 1]

[0013]

[Table 2]

[0014]

INDUSTRIAL APPLICABILITY The polymer composition of the present invention is excellent in chemical resistance and appearance at the time of injection molding, and is also excellent in impact resistance, rigidity, moldability and heat stability. Can be used for various industrial parts, general household products such as microwave oven containers, and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08L 51:04 51:06 23:26) (72) Inventor Yoko Nakamura Kasama Town, Sakae Ward, Yokohama City, Kanagawa Prefecture 1190 Mitsui Toatsu Chemicals, Inc.

Claims (2)

[Claims] 1. A maleic anhydride and a styrene compound,
Alternatively, a maleic anhydride-styrene copolymer obtained by polymerizing these and another polymerizable compound different from these, and / or a maleic anhydride and a styrene compound, or a polymerizable compound different from these and a rubber is used. Modified rubber-modified maleic anhydride-styrene copolymer (5 to 95% by weight) and olefin polymer (9)
Unsaturated dicarboxylic acid anhydride grafted olefin polymer 0.1 to 100 parts by weight of 5 to 5% by weight of polymer
A polymer composition excellent in chemical resistance and heat resistance, which is prepared by mixing 20 parts by weight. 2. The polymer composition according to claim 1, which is based on 100 parts by weight of a compound of a maleic anhydride-styrene copolymer and / or a rubber-modified maleic anhydride-styrene copolymer and an olefin polymer. , Styrene-ethylene-
Butylene-styrene block copolymer elastomer (S
EBS) and / or one or more elastomers selected from styrene-ethylene-propylene block copolymer elastomers (SEP) and maleic anhydride-modified copolymer elastomers obtained by grafting maleic anhydride onto these elastomers. The polymer composition according to claim 1, which comprises 1 to 20 parts by weight.