JPH0249042A - Inorganic filler-containing polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent thermal oxidation stability and light stability by blending a composition comprising a polyolefin and an inorganic filler with a specific phenolic antioxidant and a specific compound. CONSTITUTION:(A) A composition comprising 100 pts.wt. polyolefin and 1-100 pts.wt. inorganic filler is blended with (B) 0.01-1 pt.wt. phenolic antioxidant such as tetrakis[methylene 3-(3,5-di-tertiary butyl-4-hydroxyphenyl) propionate]methane, 2,2-thio-diethylenebis[3-(3,5-di-tertiary butyl-4-hydroxyphenyl) propionate] or triethylene glycol-bis[3-(3-tertiary butyl-5-methyl-4-hydroxyphenyl) propionate] and (C) 0.01-1 pt.wt. compound shown by formula I and/or formula II (R1 is 7-17C alkyl, etc.; R2 is H or acyl; R3 is 8-18C alkyl, etc.; m+n=2-10) to give the aimed composition.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an inorganic filler-containing polyolefin composition having excellent thermal oxidative stability and photostability G.

<Prior Art> In order to improve mechanical properties such as rigidity, impact resistance, one-dimensional stability, and heat resistance of polyolefins, methods of blending inorganic fillers are widely used.

However, the inclusion of an inorganic filler has the disadvantage that the thermal oxidation stability and light stability are significantly lower than those without the filler, and an improvement has been desired.

From this point of view, two different methods have been proposed to improve thermal oxidative deterioration and photodegradation (for example, Japanese Patent Laid-Open No. 52-4
9254, JP 52-80345, JP 53-79938, JP 56-90844, JP 56-118437, JP 56-
No. 141339). However, these known methods are not sufficiently improved.

The cause of the decrease in thermal oxidative stability and photostability of systems containing inorganic fillers is that the thermal oxidative stabilizers and optical stabilizers added to prevent thermal oxidative deterioration and photodegradation are affected by the inorganic fillers. Since it is inactivated, it is thought that its effect is not fully exhibited.

<Problems to be Solved by the Invention> Under the present circumstances, the problem to be solved by the present invention, that is, the purpose of the present invention is to solve the problem by adding a specific thermal oxidation stabilizer and/or light stabilizer to a polyolefin blended with an inorganic filler. The object of the present invention is to provide an inorganic filler-containing polyolefin composition that has excellent thermal oxidative stability and optical stability by blending specific compounds together.

<Means for Solving the Problems> That is, the present invention provides a composition comprising 100 parts by weight of a polyolefin and 1 to 100 parts by weight of an inorganic filler, and 0.01 to 1.0 parts by weight of a specific Hinderdoff-Sole antioxidant. , and the general formula (wherein R4 represents an alkyl group or alkenyl group having 7 to 17 carbon atoms. R2 is H or acyl (R-Co), and R' is an alkyl group or alkenyl group having 7 to 17 carbon atoms. R5 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms.

m and n are integers in the relationship m+n=2 to 10. ] This invention relates to an inorganic filler-containing polyolefin composition characterized by blending 0.01 to 1.0 parts by weight of the compound represented by the formula (1) and exhibiting excellent thermal oxidative stability.

Further, the polyolefin composition may contain 0.01 to 1.0 parts by weight of a sulfur-based antioxidant and/or 0.01 to 2.0 parts by weight of a light stabilizer to achieve thermal oxidative stability and/or Alternatively, the present invention relates to an inorganic filler-containing polyolefin composition having excellent photostability.

The polyolefin used in the present invention is a homopolymer of α-olefin such as ethylene, propylene, phthene-1, hexene-1,4-methyl-pentene-1, or a random or block copolymer consisting of two or more types. Yes, polyethylene, polypropylene, polybutene-11 polyisobutyne, poly-3-methyl-butene-
1, Poly-4-methyl-pentene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer, propylene-4-methyl-pentene-i #i polymer flobylene-butene-1 copolymer , decene-1-4-phthylbentene-1 copolymer, ethylene-propylene-butene-1 copolymer, and the like. In the case of copolymerization, α-
Also included are polyunsaturated compounds such as conjugated dienes and non-conjugated dienes, or those containing acrylic acid, methacrylic acid, vinyl acetate, etc. as copolymerization components with olefins. These polymers may be acid-modified, for example, polymers graft-modified with α,β-unsaturated fatty acids, alicyclic carboxylic acids, or derivatives thereof, and have rubbery, fatty, Also includes waxy polymers.

Furthermore, in the present invention, a mixture of these polyolefins and synthetic rubber may be used depending on the purpose. As the synthetic rubber that can be used in the present invention, ethylene-α olefin copolymer rubber is preferred. Ethylene-α-olefin copolymer rubbers include ethylene and monoolefins, such as propylene and butene-olefins.
1, copolymer rubber such as hexene-1, or terpolymer rubber (hereinafter referred to as rEPDMJ
), etc. Among these, ethylene-propylene copolymer rubber or EPDM is preferred.

Inorganic fillers that can be used in the present invention include talc, mica, wollastonite, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, cal/lamb sulfate, carbon fiber, glass fiber, metal fiber, (・Sand, opalescent stone, carbon blank, titanium oxide, magnesium hydroxide, asbestos, zeolite, molybdenum, diatomaceous earth, sericite, shirasu, calcium hydroxide, calcium sulfite, sodium sulfate, ben I/night, graphite, etc.) can be given.

Among these, talc, mica, glass fiber, wollastonite, etc. are preferable as materials that improve low-temperature impact resistance, moldability, and paintability.

As the 2-nol antioxidant used in the present invention,
Tetrakis [methylene-3-(35-di@3butyl-4-hydroquinphenyl)propioid-tocomethano,
2,2-thiodiethylenenobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)probioate], triethyleneglyph-rubisC3-(3-tert-tert-butyl-5-methyl- 4-hydroxyphenyl) flobionate], 2,6-hexanediol bisC3 (3,5
-:/''-tert-butyl-4-hydroxyphenyl)propione-)], 1,3.5-tris(3,5;-tert-butyl-4-hydroxyphenyl)isocyasate, 1
, 3.5-)LisCC3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, ], 3.5-tris(2,6-dimethyl-3-hydroxyphenyl) 3rd) methylbenzylsocyanurate, 1,3.5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-'2,4.

6-drimethylbenzene and the like are preferred.

Examples of the sulfur-based antioxidants used in the present invention include lauryl-thiodiglobionate, dimyristyl-thio-dipropionate, distearyl-thio-dipropionate, pentaerythritol tetrakis (β-laurylthiopropionate), etc. can be given.

Further, as the light stabilizer used in the present invention, compounds such as salicylic acid ester type, hensifhenone type, benzotriazole type, nickel gyrate type, hindered amine type, etc. are used alone or in combination. Specific examples of these compounds include 2,4;-tert-butylphenyl-3.5-di-tert-butyl-4-hydroxybenzoate, 4-octylphenyl-3.5-di-tert-butyl-4 -Hydroxybenzoate, 2-hydroxy4-methoxybenzophenone, 2-hydro-4-octoxybenzophenone, 2(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chloropenttriazole, 2( 2-
Hydroxy-3:5-di-tert-butylphenyl]-5-
Chloropenttriazole, bis(2,2.

6.6-titranotyl-4-piperinor) sebacate,
Dimethyl-1-(2-hydroxyethyl)-4 succinate
-Hydroxy-2,2,6,6-titramethylbiperinone polycondensate, Bo'JC(6-(11,3,3-tetramethylbutyl)imino-1,1,3゜5-triazine-2
,4-diyl+ + 2.2,6.6-tetramethyl-
4-piperidyl)imino)hexamethylene+(2,2,
6,6-tetramethyl-4-piperidyl)imino)],
Nickel bis(35-cy 3-phthyl-4-hydroxybenzyl)-2-n-butyl malonate, C2,
2-thiobis(4-tertiary octylphenolate))-n
-butylamine nickel ■ etc.

Note that a light stabilizer and a sulfur-based antioxidant may be used in combination.

Specific examples of compounds represented by the general formula used in the present invention 92 include (m+n-2) ゝ(CH2CH20)nH (m+r+=:2) (m+n=10) (mn=2) (m+n=2 ) (m+n=10), etc., but in the present invention, especially (m+n=10), etc.
=2) Also, it is preferable to add a phosphorous antioxidant because it improves thermal oxidative stability and light stability.

Specific examples of phosphorous antioxidants include distearyl pentaerythritol diphosphite, tris(2,4-di-
tert-butylphenyl) phosphite, bis(2,4-;
-tert-butylphenyl) pentaerythritol diphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4-biphenylenodiphosphonite, trinonylphenyl phosphite, and the like.

Other additives may be added to the composition of the present invention, as long as they do not impair its properties, such as process oils, plasticizers, lubricating oils, neutralizing agents, antioxidants, heavy metal deactivators, lubricants, nucleating agents, Antistatic agents, mold release agents, pigments, fungicides, etc. can be added.

The composition of the present invention can be obtained by kneading in a heated molten state using a conventional kneading machine such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll, or a ferrule/turn kneader.

As described above, the products obtained from the inorganic filler-containing polyolefin composition of the present invention have extremely excellent thermal oxidative stability and light stability.

<Example> EXAMPLES The present invention will be explained in more detail with reference to Examples below.

The testing methods for thermal oxidation stability and photostability in the Examples are as follows.

(Thermal Oxidation Stability Test Method) Evaluation was conducted in accordance with JIS K 72], 2C Heat Aging Test Method (Open Method) General Rules for Thermoplastic Plastics]. Using a gear oven made by Toyo Seiki Seisakusho 1
Measured at 50°C. Then, the time (GO life) until the test piece (a pressed sheet with a thickness of 11) completely deteriorated, in other words, the tensile strength became zero, was measured.

(Photostability Test Method) An accelerated double-light test was conducted using a Sunshine Super Long Cruyff Weather Meter (WEL-9UN-DC model) manufactured by Sumi Test M■. Then, the time required for appearance abnormalities such as cracks to occur on the surface of the test piece was measured. The test conditions are shown below.

(1) Test piece dimensions: 70R11X25mX1m (thickness) press sheet (2) Black panel temperature: 83℃ (3) Spray/dry cycle: 18 minutes/120
(4) Humidity in the testing machine tank: 50% RH (5) Observation of appearance abnormalities such as cracks: Observation using a microscope (x50) f Examples 1 to 7 Crystalline ethylene-propylene block copolymer (ethylene content; 7゜2% by weight, Melt Indenokunu: 3.O
100 parts by weight of the powder (100 parts by weight) was melt-kneaded in a Bamba'J-mixer at 180°C for 10 minutes using the formulation shown in Table 1, and then cooled with a roll into a sheet with a thickness of 5 ms. After solidification, it was cut into l-beleft. The obtained pellet was heated to 230°C and pressed into a 14-thick press sheet (
This was molded. A disk with a diameter of 25 cm was punched out from this sheet and its 150' CGO life was measured. The measurement results at this time are shown in Table 1.

Comparative Examples 1 to 9 Samples were prepared using the formulations shown in Table 2 in the same manner as Examples 1 to 7, and their 150°C Go lives were measured. The measurement results at this time are shown in Table-2.

Examples 8 to 11 Crystalline ethylene-propylene block copolymer (near ethylene content, 2% by weight, melt index: 3.0
710 minutes) was melted and kneaded for 10 minutes in a banohary mixer at 180°C using the formulation shown in Table 3, and then cooled and solidified using a roll into a sheet with a thickness of 5 cm. After that, it was cut and pelletized. The obtained pellet was molded at 230° C. into a breath notebook with a thickness of 1 mm. A 70w x 25mm test piece was cut out from this sheet and subjected to an accelerated double light test, and the time required for appearance abnormalities such as cracks to occur was measured. The measurement results at this time are shown in Table 3.

Comparative Example 10 ~] 4 Samples were prepared using the formulation shown in Table 4 in the same manner as in Examples 8 to 11, and an accelerated double-light test was conducted to measure the time required for appearance abnormalities such as cracks to occur.

The results at this time are shown in Table 4.

<Effects of the Invention> Polyolefins have the disadvantage that their thermal oxidative stability and light stability are significantly lowered by adding inorganic fillers compared to those without fillers. By combining a specific compound with a sulfur-based antioxidant and/or a sulfur-based antioxidant and/or a light stabilizer, it was possible to significantly improve thermal oxidative stability and light stability.

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Claims (3)

[Claims] (1) 100 parts by weight of polyolefin and 1 part of inorganic filler
~100 parts by weight of tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 2,2-thio-diethylenebis[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4
-hydroxyphenyl)propionate], 1,6-hexanediolbis[3-(3,5-di-tert-butyl-
4-hydroxyphenyl)propionate], hindered phenols with an isocyanuric acid ester group, and 1,3,5-tris(3,5-di-tert-butyl-4-
0.01 to 1.0 parts by weight of at least one phenolic antioxidant selected from (hydroxybenzyl)-2,4,6-trimethylbenzene and general formula ▲ Numerical formula, chemical formula, table, etc. ▼ and/or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 represents an alkyl group or alkenyl group having 7 to 17 carbon atoms. R_2 is H or acyl (R'-CO)
and R' represents an alkyl group or alkenyl group having 7 to 17 carbon atoms. R_3 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms. m and n are m+n=2-10
is an integer in the relationship. ) An inorganic filler-containing polyolefin composition having excellent thermal oxidative stability, characterized in that it contains 0.01 to 1.0 parts by weight of a compound represented by the following formula. (2) An inorganic filler-containing polyolefin composition with excellent thermal oxidative stability, which is obtained by adding 0.01 to 1.0 parts by weight of a sulfur-based antioxidant to the polyolefin composition according to claim 1. (3) An inorganic filler-containing polyolefin composition with excellent light stability, which is obtained by adding 0.01 to 2.0 parts by weight of a light stabilizer to the polyolefin composition according to claim 1.