JPH07133379A - Thermoplastic olefin elastomer composition - Google Patents

Abstract

PURPOSE:To obtain the title stabilized composition which does not cause plate- out during molding and can give a molding having excellent processability and appearance by mixing a thermoplastic olefin elastomer with a specified compound in a specified ratio. CONSTITUTION:100 pts.wt. thermoplastic olefin elastomer resin (e.g. ethylene/ propylene random copolymer) is mixed with 0.001-5 pts. wt. at least one compound having at least two acid anhydride groups in the molecule (e.g. 3,3',4,4'- benzophenonetetracarboxylic dianhydride).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an excellent novel olefinic thermoplastic elastomer composition capable of stably producing molded products, sheets, films and the like by calendering, extrusion, injection and the like.

More specifically, a molding obtained by blending a compound having two or more acid anhydride groups with an olefinic thermoplastic elastomer, which does not cause plate-out during molding, is excellent in processability, and has excellent appearance. The present invention relates to an olefin-based thermoplastic elastomer composition from which a product is obtained.

[0003]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Generally, olefinic thermoplastic elastomer resins are excellent in mechanical properties, physical properties, chemical properties, etc., and are therefore used as automobile parts such as bumper parts and instruments. It is widely used for panels, door trims, other interior materials, and parts for electric products, wire coating, building materials, and outdoor seats.

However, there is a problem of sticking and sticking to the metal surface during processing and a problem of appearance due to blooms and bleeds after molding, so that the production and use thereof are greatly limited. In particular, in the calendar processing, the plate-out phenomenon occurs so violently that mass production has not been possible.

[0005]

[Means for Solving the Problems] In view of the above situation, the present inventors have conducted extensive studies to obtain a novel olefinic thermoplastic elastomer composition, and as a result, have two acid anhydride groups in the molecule. It was found that the olefinic thermoplastic elastomer composition obtained by adding the compound having the above gives a product excellent in processability and appearance by suppressing the plate-out phenomenon in various processing methods, and completed the present invention. .

According to the present invention, therefore, 0.001 to 5 parts by weight of at least one compound having two or more acid anhydride groups in the molecule is added to 100 parts by weight of the olefinic thermoplastic elastomer resin. Provided is an olefin-based thermoplastic elastomer composition, which is obtained by adding a compound and does not cause plate-out during molding and has excellent workability and an excellent appearance.

The compound having two or more acid anhydride groups is
General formula

[0008]

[Chemical 1] It is an organic compound having two or more partial structures.

Typical examples of such compounds having two or more acid anhydride groups include pyromellitic dianhydride and 5-
(2,5-dioxotetrahydro-3-furanyl) -3
-Methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,4-dicarboxy-1,2,
3,4-tetrahydronaphthalene-1-succinic dianhydride, cis, cis, cis, cis
-1,2,3,4-Cyclopentanetetracarboxylic acid dianhydride, 2,2-bis (3,4-anhydride dicarboxyphenyl) propane, 2,2-bis (3,4-
Anhydrodicarboxyphenyl), hexafluoropropane, bis (3,4-anhydrodicarboxyphenyl) sulfone, isobutylene maleic anhydride copolymer, styrene-maleic anhydride copolymer trimellitic anhydride dimer, and the like. To be

In addition to the above, compounds having one or more acid anhydride groups, such as succinic anhydride, maleic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, citraconic anhydride, 2,3-Pyridinedicarboxylic anhydride, 2-phenylglutaric anhydride, trimellitic anhydride, 1,8-naphthalic anhydride, 2,3-dimethylmaleic anhydride, diglycolic anhydride, cis-
Another example is a reaction using a compound such as 1,2-cyclohexanedicarboxylic acid anhydride, and an organic compound whose reaction product has two or more acid anhydride groups. Furthermore, an organic compound or the like whose reaction product has two or more acid anhydride groups in the reaction by dehydration of a polybasic acid of tetrabasic acid or more is also exemplified.

The olefinic thermoplastic elastomer resin is usually obtained by cross-linking a crystalline olefin polymer and a non-crystalline olefin polymer, or by melt-mixing them.

Crystalline olefin polymers include polypropylene, low density or high density polyethylene. Furthermore,
Polypropylene, polyethylene and ethylene or other alpha
-Propylene containing 1 to 30% by weight of olefin and α
A random or block copolymer with an olefin, a random or block copolymer of ethylene and an α-olefin containing 1 to 30% by weight of another α-olefin,
Polybutene-1 etc. are mentioned.

As the amorphous olefin polymer, a copolymer of ethylene and another α-olefin such as propylene, butene-1, hexene-1, 3-methylpentene-1 or the like and a third component thereof Examples of the non-conjugated dienes include, for example, terpolymers obtained by copolymerizing ethylidene norbornene and cyclopentadiene.

The mixing ratio of the crystalline olefin polymer and the amorphous olefin polymer is generally about 5 to 50 parts by weight of the amorphous olefin polymer to about 50 to 95 parts by weight of the crystalline olefin polymer. Is the ratio.

Here, the crystalline olefin polymer has a crystallinity of, for example, 15% or more, and the amorphous olefin polymer has a crystallinity of, for example, less than 15%. Crystallinity is density method, X-ray diffraction method, infrared method, NMR
Method, thermal analysis method, etc.

In the olefinic thermoplastic elastomer of the present invention, a phenolic antioxidant, if necessary,
By adding an organic phosphorus-containing compound, an ultraviolet absorber, a hindered amine light stabilizer, and a thioether antioxidant, the oxidation stability and light stability thereof can be further improved.

Phenolic antioxidants that can be used in the present invention include 2,6-di-tert-butyl-p-cresol,
2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenol) propionate, distearyl (3,5
-Di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-ditert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2 ′ -Methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3′-bis (hydroxy-3-tert-butylphenyl) ) Butyric acid] glycol ester, 4,4′-butylidene bis (6-tert-butyl-m-cresol), 2,2′-
Ethylidene bis (4,6-di-tert-butylphenol),
2,2'-ethylidene bis (4-tert-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,
Bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-) Hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trismethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl) -4
-Hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5)
-Di-tert-butyl-4-hydroxyphenol) propionate] methane, 2-tert-butyl-4-methyl-6-
(2-Acroyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [ 5,5] undecane-bis [β- (3
-Tert-butyl-4-hydroxy-5-methylphenol) propionate], triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

The amount of the phenolic antioxidant added is 0.001 to 5 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the olefinic thermoplastic elastomer resin.
3 parts by weight.

Examples of the organic phosphorus-containing compound include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tridecylphosphite, di (tridecyl) pentaerythritol diphosphite,
Distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4)
-Methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4-n
-Butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,
1,3-tris (3-tert-butyl-4-hydroxy-5)
-Methylphenyl) butanetriphosphite, 2,2 '
-Methylenebis (4,6-di-tert-butylphenyl) octadecylphosphite, 2,2'-methylenebis (4,4
6-di-tert-butylphenyl) fluorphosphate, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite and the like can be mentioned.

The amount of the organic phosphorus-containing compound added is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the olefinic thermoplastic elastomer resin.

As the ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-hydroxy-).
2-methoxybenzophenones such as 4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-)
3,5-di-tert-butylphenyl) benzotriazole,
2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-
Chlorobenzotriazole, 2- (2-hydroxy-5)
-Tertiary octylphenyl) benzotriazole, 2-
(2-Hydroxy-3,5-dimethylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiaryoctyl-6-benzotriazolylphenol), 3- (3
2- (2-hydroxyphenyl) benzotriazoles such as tert-butyl-4-hydroxy-3-benzotriazolylphenyl) propionic acid-polyethylene glycol ester; phenyl salicylate, resorcinol monobenzoate, 2,4-di-primary Tributylphenyl-3,
Benzoates such as 5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4 '. -Substituted oxanilides such as dodecyl oxanilide; and cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate. To be

The amount of these ultraviolet absorbers added is 0.0 with respect to 100 parts by weight of the olefinic thermoplastic elastomer.
The amount is 01 to 5 parts by weight, preferably 0.01 to 3 parts by weight.

As the hindered amine light stabilizer, 2,
Ester compound of mono- or divalent carboxylic acid of 2,6,6-tetramethyl-4-piperidinol or 1,2,2,6,6-pentamethyl-4-piperidinol [2,
2,6,6-tetramethyl-4-piperidyl laurate, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,6,6-pentamethyl-4-piperidyl stearate, Bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (2,2
2,6,6-Tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-)
Piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,
2,2,6,6-Pentamethyl-4-piperidyl) sebacate], 2,2,6,6-Tetramethyl-4-piperidinol or 1,2,2,6,6-pentamethyl-4
1,2,3,4-butanetetracarboxylate of piperidinol, 2,2,6,6-tetramethylpiperidinol or 1,2,2,6,6-pentamethyl-4-
Condensate of piperidinol with 1,2,3,4-butanetetracarboxylic acid and tridecyl alcohol, 2,2,6
6-tetramethyl-4-piperidinol or 1,2,
2,6,6-pentamethyl-4-piperidinol and 1,
2,3,4-butanetetracarboxylic acid and β, β, β ′,
Condensate with β'-tetramethyl-3,9- (2,4,8,10-tetraoxapyro [5,5] undecane) diethanol, poly [[6- (1,1,3,3-tetra Methylbutyl) amino-1,3,5-triazine-2,4-
Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino]], poly [(6-morpholino-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]], N, N′-bis (3-aminopropyl) ethylenediamine Condensate with 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine, 1, 6,11-triaminoundecane and 2,4-bis [N-butyl-N- (1,2,2,6,6)
-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate and the like.

The amount of the hindered amine compound added is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the olefinic thermoplastic elastomer.
Parts by weight.

Examples of the thioether antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl and distearyl esters of thiodipropionic acid, and β-of a polyol such as pentaerythritol tetra (β-dodecylmercaptopropionate). Examples thereof include alkyl mercaptopropionic acid esters.

In addition, the olefinic thermoplastic elastomer resin of the present invention includes inorganic fillers such as talc, calcium carbonate, mica and silica, glass fiber, carbon fiber,
Reinforcing agents such as metal whiskers, flame retardants, lubricants, antistatic agents, calcium stearate, metal soaps such as calcium stearyl lactate, aluminum-p-tertiary butyl benzoate, dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol, Nucleating agents such as bis (4-tert-butylphenyl) phosphate sodium salt and 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate sodium salt, and additives such as pigments and dyes are added as desired. May be added.

The composition of the present invention can be molded by conventionally known methods such as calender molding, injection molding, extrusion molding and blow molding, and is not limited by the molding method or its form.

The surface characteristics of the composition of the present invention can be improved by subjecting it to a well-known treatment such as low temperature plasma treatment after molding.

[0029]

EXAMPLES Next, the effects of the present invention will be specifically shown by examples, but the present invention is not limited by the following examples.

The test compounds used in the examples having two or more acid anhydride groups are shown below.

No. Test Compound 1-1 Pyromellitic anhydride 1-2-5- (2,5-dioxotetrahydro-3-phenyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride 1 -3 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride 1-4 4,3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene -1 succinic dianhydride 1-5 cis , Cis, cis, cis-1,2,3,4-cyclopentane tetracarboxylic acid dianhydride 1-6 2,2-bis (3,4-anhydride dicarboxyphenyl) propane 1-7 2,2 -Bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane 1-8 Bis (3,4-anhydrodicarboxyphenyl) sulfone 1-9 Isobutylene maleic anhydride Coalescing 1-10 styrene - Structure of maleic anhydride copolymers 1-11 dimer test compound trimellitic anhydride is as follows.

[0032]

[Chemical 2]

[0033]

[Chemical 3]

Example 1 A sheet was prepared according to the following formulation by processing with an 8-inch roll at 175 ° C. Press the sheet with a press machine (condition 1
A test piece having a thickness of 1 mm was prepared at 80 ° C.-100 kg / cm ² -5 minutes).

The plate-out (P.O.) was judged by visually observing stains on the roll during sheet production. Further, using this test piece, the appearance after 30 days was visually observed and judged.

The judgment was performed by the following evaluation method.

⊚: No stain ○: Some stain was observed Δ: Stain was observed ×: Stain was noticeable (blended) Mirastomer 5030N 100 parts by weight Irganox 1010 0.1 parts by weight Test compound 0.3 Weight part Mirastomer 5030N: Mitsui Petrochemical Irganox 1010: Ciba Geigy

[0038]

[Table 1] Example 2 A sheet having the following composition was kneaded with an 8-inch roll at 175 ° C. for 5 minutes to prepare a sheet. Press the sheet (1
A test piece having a thickness of 1 mm was prepared at 80 ° C.-100 kg / cm ² -5 minutes).

Table 2 shows the results of this test according to Example 1 for evaluation and judgment of plate-out (PO) and appearance.

(Compounding) Ethylene-propylene random copolymer 70 parts by weight EPR 30 parts by weight Calcium stearate 0.1 parts by weight Irganox 1010 0.2 parts by weight Distearyl pentaerythritol diphosphite 0.2 parts by weight 2- ( 2-Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole 0.2 parts by weight 1,6,11-triaminoundecane and 2,4-bisN-butyl-N- (1, Condensate of 2,2,6,6-piperidyl) amino-6-chloro-1,3,5-triazine 0.1 part by weight Test compound Variable

[0041]

[Table 2] Example 3 A sheet was prepared by kneading with an 8-inch roll at 175 ° C. for 5 minutes according to the following formulation. Press the sheet (18
A test piece having a thickness of 1 mm was prepared at 0 ° C.-100 kg / cm ² -5 minutes).

The evaluation and judgment of the plate-out (PO) and the appearance were the same as in Example 1. The test results are shown in Table 3.

(Compounding) Ethylene-propylene random copolymer 60 parts by weight EPR 40 parts by weight Calcium stearate 0.05 parts by weight Irganox 1010 0.05 parts by weight Distearyl pentaerythritol diphosphite 0.1 parts by weight 2- ( 2-Hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole 0.05 part by weight 1,6,11-triaminoundecane and 2,4-bis N-butyl-N- (1, Condensate with 2,2,6,6-pentamethyl-4-piperidyl) amino-6-chloro-1,3,5-triazine 0.05 parts by weight Test compound Variable

[0044]

[Table 3]

[0045]

From the results of Examples 1 to 3, the olefinic thermoplastic elastomer composition stabilized by adding the acid anhydride of the present invention exhibits excellent effects in improving processability and appearance, and is stable. It can be seen that it will be possible to provide a product with an excellent appearance as well as to enable mass production. From these points, it is clear that the effects of the present invention are extremely unique and useful.

Claims (1)

[Claims] 1. Stabilized by mixing 0.001 to 5 parts by weight of at least one compound having two or more acid anhydride groups in the molecule with 100 parts by weight of an olefinic thermoplastic elastomer resin. Olefin-based thermoplastic elastomer composition.