JP3156349B2 - Polyolefin resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition containing an inorganic filler, and more particularly to a polyolefin resin having excellent stability against thermal oxidation and excellent hue. The present invention relates to a resin composition.

[0002]

2. Description of the Related Art Polyolefin resins such as polyethylene and polypropylene are widely used because of their excellent physical, chemical and electrical properties.
Further, in order to improve mechanical properties such as rigidity, impact resistance, dimensional stability and heat resistance, a method of blending an inorganic filler such as talc has been adopted. On the other hand, polyolefin resins are susceptible to thermal oxidative degradation, and thus, antioxidant formulations such as a combination use of a phenolic antioxidant and a sulfur-based antioxidant have been conventionally used. However, the polyolefin resin blended with an inorganic filler has a drawback in that the antioxidant is adsorbed by the inorganic filler or the stability against thermal oxidation is significantly reduced. I was

[0003] In order to improve the stability of a polyolefin resin containing an inorganic filler to thermal oxidation,
A method of blending an epoxy compound (JP-A-1-88543) and a method of blending an amide or amine compound (JP-A-2-49042) have been proposed.

[0004]

However, these known methods do not always provide sufficient stability against thermal oxidation. Further, when an epoxy compound is used, there is a problem that the resin composition is discolored. The present inventors have made various studies to solve these problems and have developed a polyolefin-based resin composition which exhibits excellent stability against thermal oxidation and also has excellent hue. Was.

[0005]

That is, the present invention provides a polyolefin-based resin composition containing a polyolefin-based synthetic resin (A), an inorganic filler (B), and the following components (C) to (F). Things.

(C) A phenolic antioxidant selected from the following compound group: 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy}-
1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanate Nurate and tetrakis [3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane,

(D) a sulfur-based antioxidant selected from the group of compounds represented by the following general formulas (DI) and (D-II):

[0008]

Embedded image (R ¹ -OCOCH ₂ CH ₂ ) ₂ S (DI) (R ¹ -SCH ₂ CH ₂ COOCH ₂ ) ₄ C (D-II)

(Wherein, R ¹ represents alkyl having 4 to 20 carbon atoms)

(E) a nitrogen-containing compound selected from the group of compounds represented by the following general formulas (EI) to (E-III):

[0011]

Embedded image

(Wherein, R ² represents alkyl having 5 to 21 carbons or alkenyl having 5 to 21 carbons, and n represents 1 to 6)
R ³ represents alkyl having 8 to 18 carbons, alkenyl having 8 to 18 carbons or acyl having 8 to 18 carbons, j and k are each 1 or more, and j + k is 2 Represents a number between 10), and

(F) Bisphenol A type glycidyl ether epoxy compound represented by the following general formula (FI):

[0014]

Embedded image

(Where q represents a number of 0 or more).

The polyolefin synthetic resin (A) used in the present invention is a homopolymer of an α-olefin such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and two or more α-olefins. -Random and block copolymers of olefins, copolymers of α-olefins with other copolymerizable unsaturated compounds, and the like. Each of these can be used alone or in combination of two or more.

Examples of the α-olefin homopolymer include polyethylene, polypropylene, poly-1-butene, polyisobutene, poly-3-methyl-1-butene and poly-4.
-Methyl-1-pentene and the like. Examples of the copolymer of α-olefins include ethylene / propylene copolymer, ethylene / 1-butene copolymer, propylene / 4-methyl-1-pentene copolymer, propylene /
Examples thereof include 1-butene copolymer, 1-decene / 4-methyl-1-pentene copolymer, and ethylene / propylene / 1-butene copolymer. Further, a compound containing a polyunsaturated compound such as a conjugated diene or a non-conjugated diene or a monounsaturated compound such as acrylic acid, methacrylic acid, or vinyl acetate together with the α-olefin is also included. These polymers may be acid-modified, for example, graft-modified with α, β-unsaturated fatty acids, alicyclic carboxylic acids, or derivatives thereof.

In the present invention, a blend of a synthetic rubber and a polyolefin-based synthetic resin may be used according to the intended use. Examples of a synthetic rubber suitable for blending include an ethylene / α-olefin copolymer rubber. Examples of the ethylene / α-olefin copolymer rubber include copolymer rubbers of ethylene and other α-olefins such as propylene, 1-butene, and 1-hexene;
Tertiary copolymer rubbers obtained by copolymerizing non-conjugated dienes such as ethylidene norbonene and dicyclopentadiene as the third component in the ethylene / propylene system are included.

In the composition containing an inorganic filler as in the present invention, a propylene-based synthetic resin, for example, polypropylene, a copolymer of propylene and another α-olefin, or a synthetic rubber is preferably used. Blends and the like are preferably used as the base resin.

The inorganic filler (B) used in the present invention includes talc, mica, carbon black, titanium oxide,
Zinc oxide, aluminum hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, calcium silicate, magnesium silicate, celite, kaolin, zeolite, silica, asbestos, glass fiber, carbon fiber, barium titanate, lead titanate, etc. No. These can be used alone or in combination of two or more. Among these, as those that improve low-temperature impact resistance, moldability and paintability,
For example, talc, mica or glass fiber is preferably used.

In the present invention, such a polyolefin-based synthetic resin (A) and an inorganic filler (B) are further added to a specific phenolic antioxidant (C), a specific sulfur-based antioxidant (D), A specific nitrogen-containing compound (E) and a specific epoxy compound (F) are blended.

The phenolic antioxidant of the component (C) is
These compounds are selected from the following compound groups, and these may be used alone or in combination of two or more.

3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,
10-tetraoxaspiro [5.5] undecane, 1,
3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate and tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane .

The sulfur-based antioxidant of the component (D) is represented by the above general formula (DI) or (D-II). In the general formulas (DI) and (D-II), R ¹ is alkyl having 4 to 20 carbon atoms, and the alkyl preferably has 6 to 18 carbon atoms.
Each of these sulfur-based antioxidants may be used alone, or two or more of these may be used in combination. Specific examples of the sulfur-based antioxidant (D) used in the present invention include the following.

Dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate;
Tetrakis (3-laurylthiopropionyloxymethyl) methane.

The nitrogen-containing compound of the component (E) has the general formula
It is represented by any of (EI) to (E-III).

In the general formulas (EI) and (E-II), R ²
Is alkyl or alkenyl, and each has 5 to 21 carbon atoms. Among these, those having a relatively large number of carbon atoms, for example, alkyl having 11 to 21 carbons or alkenyl having 11 to 21 carbons are preferable. The general formula (E
N in -I) is an integer of 1 to 6.

In the general formula (E-III), R ³ is alkyl, alkenyl or acyl, wherein alkyl and alkenyl have 8 to 18 carbon atoms, respectively. Acyl represented by R ³ is R ⁴
Alkanoyl or alkenoyl is preferably represented by CO-, wherein R ⁴ is alkyl or alkenyl having 7 to 17 carbon atoms of 7 to 17 carbon atoms. R ³ is particularly preferably alkyl or alkanoyl. Also, j and k in the general formula (E-III) are each selected to be 1 or more, and j + k is in the range of 2 to 10. A compound in which j and k in the general formula (E-III) are each 1 is usually obtained as a single product, but j + k is 2
Above are generally obtained as a mixture in which j + k is constant.

Specific examples of the compound represented by the general formula (EI) include methylenebisstearylamide, ethylenebisstearylamide, ethylenebisoleylamide, hexamethylenebisstearylamide and the like.
Specific examples of the compound represented by the general formula (E-II) include lauric amide, stearic amide, oleic amide, behenic amide, erucic amide and the like. Further, specific examples of the compound represented by the general formula (E-III) include the following.

[0030]

Embedded image

These general formulas (EI), (E-II) and (EI)
All the nitrogen-containing compounds (E) represented by II) are effective in the present invention, and can be used alone or in combination of two or more. In the present invention, ethylene bisstearylamide, erucamide,
Alternatively, N, N-bis (2-hydroxyethyl) stearylamine is preferably used.

The epoxy compound represented by the general formula (FI) of the component (F) is generally produced by a condensation reaction between bisphenol A and epichlorohydrin. Therefore, the epoxy compound (F) is usually a set of molecules having several repetition numbers (q). Further, a product obtained by once purifying a condensation reaction product of bisphenol A and epichlorohydrin, adjusting q to a narrow range, and further subjecting bisphenol A and epichlorohydrin to a condensation reaction to obtain a higher molecular weight epoxy compound (F) There is also.

Those having q in the general formula (FI) of 0 or more and having an average value of about 35 are commercially available, and there are solid and liquid forms at ordinary temperature, all of which are used in the present invention. be able to. Of course, each of these may be used alone, or two or more of them may be used in combination. In general, such epoxy compounds differ depending on the epoxy equivalent. In the present invention, those having an epoxy equivalent of about 170 to about 5000 are preferably used. Those having an epoxy equivalent of more than about 5000 or those having an average q of more than about 35 in the general formula (FI) can be used in the present invention if they are available.

The mixing ratio of each component in the present invention is not particularly limited, but generally, the polyolefin-based synthetic resin (A) and the inorganic filler (B) are the same as those of the polyolefin-based synthetic resin (A). Agent (B)
Is preferably set to 1 to 50% by weight, and more preferably, the inorganic filler (B) is used at a ratio of 5 to 40% by weight. When the amount of the inorganic filler (B) is less than 1% by weight based on the polyolefin synthetic resin (A),
It is not enough to improve mechanical properties such as rigidity, dimensional stability and heat resistance, and if it exceeds 50% by weight, there may be a problem in moldability and the like.

[0035] (C) ~ Stated for use doses of each component (F), relative to the total 100 parts by weight of polyolefin synthetic resin (A) and the inorganic filler (B), phenolic antioxidants (C ) Is 0.001 to 1 part by weight, the sulfur-based antioxidant (D) is 0.002 to 2 parts by weight, and the nitrogen-containing compound (E) and the epoxy compound (F) are 0.01 to 5 parts by weight, respectively.
Parts by weight. The phenolic antioxidant (C) is less than 0.001 part by weight and the sulfur antioxidant (D) is less than 0.002 part by weight, based on 100 parts by weight of the total of the polyolefin synthetic resin (A) and the inorganic filler (B). When the nitrogen-containing compound (E) is less than 0.01 parts by weight or the epoxy compound (F) is less than 0.01 parts by weight, it is difficult to obtain a desired effect, and 1 part by weight, 2 parts by weight, and 5 parts by weight, respectively. If the amount exceeds 5 parts by weight or 5 parts by weight, the effect corresponding thereto cannot be obtained, which is economically disadvantageous.

The polyolefin resin composition of the present invention comprises:
Other additives, such as processing stabilizers, antioxidants, light stabilizers, metal deactivators, metal soaps, nucleating agents, antistatic agents, lubricants, flame retardants, mold release, as long as their properties are not impaired Agent,
A fungicide, a pigment and the like may be used in combination.

Specific examples of the processing stabilizer that can be used include:
The following can be mentioned.

2-t-butyl-6- (3-t-butyl-
2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-
3,5-di-t-pentylphenyl) ethyl] -4,6
-Di-t-pentylphenyl acrylate.

Examples of the antioxidant include phenolic antioxidants other than the component (C), sulfur-based antioxidants other than the component (D), and phosphorus-based antioxidants. Specific examples of the phosphorus antioxidant include the following.

Tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl)
Pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite, 2,2'-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, 2,2'-methylenebis (4,6-di-
t-butylphenyl) octyl phosphite.

Examples of the light stabilizer include benzotriazole-based, benzophenone-based, hydroxybenzoate-based, and cyanoacrylate-based ultraviolet absorbers, nickel-based quencher, and hindered amine-based light stabilizers.

Specific examples of the ultraviolet absorber include the following.

2- (3-tert-butyl-2-hydroxy-
5- (methylphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-
5-methylphenyl) benzotriazole, 2- (2-
Hydroxy-5-t-octylphenyl) benzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6 -Tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole,
2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-di- t-
Butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, ethyl 2-cyano-3,3-diphenylacrylate.

Specific examples of the hindered amine light stabilizer include the following.

Bis (2,2,6,6-tetramethyl-4
-Piperidyl) sebacate, bis (1,2,2,6)
6-pentamethyl-4-piperidyl) sebacate, 2
-Methyl-2- (2,2,6,6-tetramethyl-4-
Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) 2
-(3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, tetrakis (2
2,6,6-tetramethyl-4-piperidyl) 1,2,
3,4-butanetetracarboxylate, poly [@ 6-
(1,1,3,3-tetramethylbutyl) imino-1,
3,5-triazine-2,4-diyl {(2,2,
6,6-tetramethyl-4-piperidyl) imino {hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,
3,5-triazine-2,4-diyl) {(2,2,
6,6-tetramethyl-4-piperidyl) imino {hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2
-Hydroxyethyl) -4-hydroxy-2,2,6
Polycondensate with 6-tetramethylpiperidine, N, N'-
Bis (3-aminopropyl) ethylenediamine and
2,4-bis [N-butyl-N- (1,2,2,6,6
-Pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine, 1,2,2
6,6-pentamethyl-4-piperidinol and 3,
9-bis (2-hydroxy-1,1-dimethylethyl)
-Condensate of 2,4,8,10-tetraoxaspiro [5.5] undecane with 1,2,3,4-butanetetracarboxylic acid.

The following are specific examples of the metal deactivator.

N, N'-diphenyloxalic acid diamide, N-
Salicylidene-N'-salicyloylhydrazine, N,
N'-bis (salicyloyl) hydrazine, N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 3-salicyloylamino-1,2,4 -Triazole, bis (benzylidene) oxalic acid dihydrazide.

Specific examples of the nucleating agent include the following.

Alkali metal salts or alkaline earth metal salts such as sodium salts and calcium salts of aromatic monocarboxylic acids such as benzoic acid, toluic acid and pt-butylbenzoic acid; 1,3,2,4-di (benzylidene) ) Sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, dibenzylidene sorbitols such as 1,3,2,4-di (p-ethylbenzylidene) sorbitol; sodium bis (4-t-) Butylphenyl) phosphate, sodium 6,6'-methylenebis (2,
Metal salts of aromatic phosphoric acid compounds such as 4-di-t-butylphenyl) phosphate.

Specific examples of the flame retardant include the following.

Phosphates such as tricresyl phosphate, triphenyl phosphate, diphenyloctyl phosphate and tributyl phosphate; tris (2-chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate and the like Halogen-containing phosphoric acid esters of vinyl chloride; Halogen-containing vinyl compounds such as vinyl chloroacetate, bromostyrene, bromophenyl allyl ether; chlorinated paraffin, brominated polyphenyl, perchloropentacyclodecane, tetrabromoethane, hexabromocyclododecane Halogen compounds such as tetrachlorophthalic anhydride, tetrabromophthalic anhydride, tetrabromobisphenol A, decabromodiphenyl oxide; antimony trioxide;
Metal-containing inorganic compounds such as aluminum hydroxide.

Specific examples of the pigment include the following.

Inorganic pigments such as carbon black, titanium white, titanium yellow, iron oxide, and cadmium red; phthalocyanine, quinacridone, perylene,
Polycyclic organic pigments such as anthraquinone and isoindolinone.

[0054]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, parts and% represent parts by weight and% by weight, respectively, unless otherwise specified.

The test compounds used in the examples are as shown in the following table, and are indicated by the respective symbols.

[0056]

[Table 1] Inorganic filler B-1: talc [micron white 5000S (trade name):
Hayashi Kasei Co., Ltd.] B-2: Mica [S-150 (trade name): Repco Co., Ltd.]

[0057]

Table 2 Phenolic antioxidant C-1: 3,9-bis [2- {3- (3-t-butyl-)
4-hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] -2,4,8,10
-Tetraoxaspiro [5.5] undecane C-2: 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate C-3: tetrakis [3- (3, 5-di-t-butyl-4
-Hydroxyphenyl) propionyloxymethyl] methane C-4: 2,2'-thiodiethylenebis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] C-5: triethylene glycol bis [3- (3-t
-Butyl-4-hydroxy-5-methylphenyl) propionate]

[0058]

TABLE 3 Sulfur antioxidant D-1: distearyl 3,3'-thiodipropionate D-2: tetrakis (3-laurylthiopropionyloxymethyl) methane

[0059]

Table 4 Nitrogen-containing compounds E-1: ethylenebisstearylamide E-2: erucamide E-3: N, N-bis (2-hydroxyethyl) stearylamine

[0060]

Table 5 Epoxy compound F-1: bisphenol A type glycidyl ether epoxy compound [Epicoat 1002 (trade name): manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 600 to 700] F-2: bisphenol A type glycidyl ether Epoxy compound [Epicoat 1007 (trade name): Yuka Shell Epoxy Co., Ltd., epoxy equivalent 1750-2200] F-3: o-cresol novolak type epoxy compound [Epicoat 180S65 (trade name): Yuka Shell Epoxy ( Co., Ltd., epoxy equivalent 205-220]

Using unstabilized propylene / ethylene block copolymer (ethylene content: 7.3%), compositions were prepared according to the formulations shown in Tables 6 to 9. In the table, the amounts of the propylene / ethylene block copolymer and the inorganic filler are the respective percentages (%) based on the total weight of the two, and the amounts of the other components are the total of the block copolymer and the inorganic filler. It is shown by the ratio (part) of each component to 100 parts. After mixing each composition with a Henschel mixer,
30mmφ twin screw extruder (Nakatani Machinery Co., Ltd., NAS30
(Cylinder temperature, 230 to 240 ° C.) and pelletized. From this pellet, 1 oz. Injection molding machine (SAV-30A type, manufactured by Yamashiro Seiki Co., Ltd., cylinder temperature 22
0 to 240 ° C.) to form a sheet of 40 × 60 × 1 mm.

A test piece of 40 × 40 × 1 mm was prepared from the obtained sheet, and the thermal oxidation stability and the hue of the test piece were evaluated. Stability against thermal oxidation was determined by placing a test piece in a gear oven at 150 ° C. and measuring the time until the test piece became brittle (brittle life). The longer the embrittlement life, the better the stability against thermal oxidation. The hue is the yellowness index (yellownes index) of the surface of the test piece after molding.
s index: YI). The smaller the YI, the better the hue. The results are shown in Tables 6 to 9.

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

[Table 9]

[0067]

Industrial Applicability According to the present invention, a composition in which a specific compound is blended with a polyolefin-based synthetic resin containing an inorganic filler, exhibits excellent stability against thermal oxidation, has little coloring, and has a stable hue. give.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification code FI C08K 5/20 C08K 5/3477 5/3477 5/15 (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 23 / 00 C08K 3/00 C08K 5/13-5/20 C08K 5/3477 CA, REGISTRY (STN)

Claims (1)

(57) [Claims] (A) a polyolefin-based synthetic resin, (B) an inorganic filler, (C) 3,9-bis [2- {3- (3-t-butyl-4)
-Hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] -2,4,8,10-
Tetraoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, and tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionyloxymethyl] methane, a phenolic antioxidant selected from the group consisting of: (D) the following general formulas (DI) and (D-II): (R ¹ -OCOCH ₂ CH ₂ ) ₂ S (DI) (R ¹ -SCH ₂ CH ₂ COOCH ₂ ) ₄ C (D-II) (wherein R ¹ represents alkyl having 4 to 20 carbon atoms) (E) the following general formulas (EI) to (E-III): (Wherein, R ² represents alkyl having 5 to 21 carbons or alkenyl having 5 to 21 carbons, n represents an integer of 1 to 6, R ³ represents alkyl having 8 to 18 carbons, 18
Represents alkenyl or acyl having 8 to 18 carbon atoms,
j and k are each 1 or more, and j + k is 2
And (F) a nitrogen-containing compound selected from the group consisting of compounds represented by the following general formula (FI): (Wherein, q represents a number of 0 or higher) Ri greens contain bisphenol A type glycidyl ether-based epoxy compound represented by, based on the weight of the polyolefin-based synthetic resin (A)
Containing 1 to 50% by weight of inorganic filler (B)
Total of fin-based synthetic resin (A) and inorganic filler (B)
100 parts by weight of phenolic antioxidant (C)
0.001 to 1 part by weight, sulfur-based antioxidant (D) 0.002
To 2 parts by weight, and 0.01 to 5 parts by weight of the nitrogen-containing compound (E).
And 0.01 to 5 parts by weight of the epoxy compound (F), respectively.
Polyolefin resin composition characterized Rukoto to Yusuke.