JP3248625B2 - 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, and more particularly, to a stabilized polyolefin resin composition obtained by adding a specific phosphonite compound and a hydrotalcite compound in combination.

[0002]

BACKGROUND OF THE INVENTION Polyolefin resins such as polyethylene and polypropylene are
It is known that it deteriorates due to the action of heat, light, and the like, and is colored or has low mechanical strength, so that it cannot withstand use.

For the purpose of preventing the deterioration of the polyolefin-based resin, various antioxidants such as phenol-based, phosphite-based, and sulfur-based resins, ultraviolet absorbers, hindered amine-based light stabilizers, and the like are added. However, these stabilizers have the disadvantage of decomposing during processing at high temperatures and coloring the product due to their lack of thermal stability.

[0004] Japanese Patent Publication No. 48-40100, Japanese Patent Publication No. Sho 4
JP-A 9-45397 proposes a cyclic phosphonite compound as an organic phosphorus compound having excellent thermal stability.
JP-A-54-16480 proposes a cyclic phosphonite compound having a hindered structure. JP-A-55-11597 and JP-A-57-105456 disclose cyclic phosphonite compounds having other functions. Although proposed, the effect of improving the coloring property of the resin is insufficient.

[0005] It is known that polyolefin-based resins deteriorate in rust resistance and colorability due to a halogen compound derived from a catalyst used during production. Therefore, JP-A-52-49258 proposes adding a hydrotalcite compound to a polyolefin resin produced using a Ziegler-type catalyst. JP-A-61-113631, JP-A-61-1332
No. 51 proposes that a hydrotalcite compound, a phenolic antioxidant and an organic phosphite compound are added to a polyolefin resin in combination, and JP-A-64-20249 discloses that It has been proposed to add a talcite compound, a phenolic antioxidant, an organic phosphite compound, an organic phosphonite compound, and a fatty acid metal salt in combination, but none of them has achieved practically satisfactory effects.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the present situation, and as a result, by adding a cyclic phosphonite compound having a hindered structure and a hydrotalcite compound to a polyolefin resin in combination, The present inventors have found that the coloring property of the system resin is remarkably improved and completed the present invention.

That is, the present invention relates to a method for preparing a phosphonite compound represented by the following general formula (I) in an amount of 0.005 to 100 parts by weight of a polyolefin resin.
To 5 parts by weight and a hydrotalcite compound 0.005
The present invention provides a polyolefin-based resin composition to which about 5 parts by weight is added.

[0008]

Embedded image (Wherein, R ₁ and R ₂ each independently represent a group having 1 to 8 carbon atoms)
Represents a substituted or unsubstituted hydrocarbon group or a halogen atom, x and y each independently represent 0 to 3,
n represents 1 to 3, R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₄ represents a substituted or unsubstituted aliphatic or araliphatic hydrocarbon group. )

Hereinafter, the polyolefin resin composition of the present invention will be described in detail. In the above formula (I), a substituted or unsubstituted hydrocarbon group represented by R ₁ and R _2, methyl, isopropyl, tert-butyl, etc. tertiary octyl and the like, R ₁ and R ₂ Examples of the halogen atom represented include fluorine, chlorine, and bromine. The alkyl group having 1 to 4 carbon atoms represented by R _3, methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, isobutyl and the like, substituted or is represented by R ₄ Unsubstituted aliphatic or araliphatic hydrocarbon groups include methyl, 1- (2-hydroxy-
3,5-di-tert-butylphenyl) ethyl, butane-1,
Examples include 1,3-triyl, butane-1,1-diyl, 2-stearyloxycarbonylethyl, 1,3,5-trimethylbenzene-2,4,6-trimethylene-triyl, and the like.

Accordingly, examples of the phosphonite compound represented by the general formula (I) used in the polyolefin resin composition of the present invention include the following [Chemical Formula 3] to [Chemical Formula 8].
(Compound Nos. 1 to 6).

[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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The amount of the cyclic phosphonite compound added is
0.00 parts by weight of polyolefin resin
It is 5 to 5 parts by weight, preferably 0.01 to 3 parts by weight.

The hydrotalcite compound used in the present invention includes a double salt compound comprising magnesium (and zinc) and aluminum represented by the following general formula (II).

[0019]

Embedded image Mg _X1 Zn _X2 Al ₂ (OH) _{2 (X1 + X2) + 4} · CO ₃ · mH ₂ O (II) (where x1 and x2 satisfy the conditions represented by the following formulas, respectively) And m represents a real number: 0 ≦ x2 / x1 <10,2
≦ x1 + x2 <20)

The hydrotalcite compound may be a natural product or a synthetic product. As the synthesis method, JP-B-46-2280, JP-B-50-3
Known methods described in JP-A-0039, JP-B-51-29129, JP-A-61-174270 and the like can be exemplified. Further, in the present invention, it can be used without being limited by the crystal structure, the crystal particle diameter, the presence or absence of crystallization water and the amount thereof.

The surface of the above hydrotalcite compound may be made of a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate, or a higher fatty acid amide. And those coated with higher fatty acid esters or waxes.

The amount of the hydrotalcite compound to be added is 0.1 to 100 parts by weight of the polyolefin resin.
005 to 5 parts by weight, preferably 0.01 to 3 parts by weight.

As the polyolefin resin in the present invention, ethylene, propylene, butene, pentene, 3-
Homo- or copolymers of α-olefins such as methylbutene, hexene, 4-methylpentene, heptene and octene; a majority of these α-olefins and vinyl esters such as vinyl acetate, acrylic acid, maleic anhydride and methyl methacrylate Unsaturated organic acids (esters,
Salts, amides and amines), random, block or graft copolymers such as vinylsilanes such as vinyltrimethoxysilane; or modified polymers such as chlorination, sulfonation and oxidation of these polymers. Can be mentioned.

Specifically, low, medium or high density polyethylene, polypropylene, polybutene, ethylene-propylene random or block copolymer, ethylene-
Examples thereof include a propylene-butene copolymer, an ethylene-butene copolymer, an ethylene-4-methylpentene copolymer, a propylene-hexene copolymer, and a propylene-hexene-butene copolymer.

Among the above-mentioned polyolefin resins, those having a large stabilizing effect particularly by the polyolefin resin composition of the present invention include polypropylene, propylene-ethylene random or block copolymer,
Propylene-ethylene-butene copolymer, propylene-
A propylene-based copolymer such as a hexene-butene copolymer is exemplified.

In the polyolefin resin composition of the present invention, other general-purpose additives such as antioxidants, ultraviolet absorbers and stabilizers can be used together with the phosphonite compound and the hydrotalcite compound.

Particularly preferred examples of the additives include phenol-based, sulfur-based, phosphite-based antioxidants, ultraviolet absorbers, hindered amine-based light stabilizers, and the like.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresol.
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-
4-hydroxyphenyl) propionate], 1,6-
Hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butyl) Tributylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid]
Glycol ester, 4,4'-butylidenebis (6-
Tert-butyl-m-cresol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2′-
Ethylidenebis (4-sec-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-di-tert-butyl-4-
Hydroxylbenzyl) isocyanurate, 1,3,5-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-
Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tetrakis [methylene-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate] methane, 2
-Tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-} (3-tert-butyl Butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy) −5-
Methylphenyl) propionate].

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Β-alkyl mercaptopropionates.

Examples of the phosphite antioxidants include trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and tris [2-tert-butyl-4- (3 -Tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, di (tridecyl) pentaerythritoldi Phosphite, distearylpentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertbutyl) -4-methylphenyl) pentaerythritol diphos Aito, tetra (tridecyl)
Isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-
Tert-butyl-5-methylphenol) diphosphite,
Hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 2 , 2'-methylenebis (4,6-di-tert-butylphenyl) (octyl) phosphite.

As the above-mentioned ultraviolet absorber, for example,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2-hydroxybenzophenones such as hydroxy-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'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3'5.5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-
2- (2′-) such as 6-benzotriazolyl) phenol
Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,
4-di-tert-butylphenyl-3 ′, 5′-di-tert-butyl-4′-hydroxybenzoate, hexadecyl-3,
Benzoates such as 5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano And cyanoacrylates such as -β, β-diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the hindered amine light stabilizer include, for example, 2,2,6,6-tetramethyl-4-
Piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6
-Tetramethyl-4-piperidylbenzoate, N-
(2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6 6-tetramethyl-4-piperidyl- (3,5-di-tert-butyl-4-hydroxyphenyl)
Propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4
-Hydroxybenzyl) malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butane Tetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4
-Piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl).
Di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2 -{Tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.
5] undecane, 3,9-bis [1,1-dimethyl-2
-Tris (1,2,2,6,6-pentamethyl-4-
Piperidyloxycarbonyloxy) butylcarbonyloxy {ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4,6-bis} N- (2 , 2,6,6-tetramethyl-4-piperidyl) butylamino {-1,3,5-
Triazin-2-yl] -1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,
6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine / N, N'-bis (2,2
6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-
(Tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate.

If necessary, the polyolefin resin composition of the present invention may contain a heavy metal deactivator, a nucleating agent, a metal soap, an organotin compound, a plasticizer, an epoxy compound, a foaming agent, an antistatic agent, Flame retardants, lubricants, processing aids and the like can be included.

The polyolefin resin composition of the present invention can be used for applications requiring high weather resistance over a long period of time, such as agricultural materials, automotive paints and interior / exterior materials, food packaging applications, medical applications, etc. It can also be suitably used for applications irradiated with radiation of, for example, films, fibers, tapes, sheets, various molding materials, paints, lacquer binders, adhesives, putty and base materials in photographic materials and the like. be able to.

[0035]

EXAMPLES Next, the polyolefin-based resin composition of the present invention will be specifically described with reference to examples. However, the invention is not limited by these examples.

Example 1 The following formulation was blended at 280 ° C. and 25 rpm
The change in the melt flow rate (MFR) (g / 10 minutes) at the first and fifth extrusions was measured. Further, the first and fifth pellets were extruded at 250 ° C.
To prepare a test piece having a thickness of 1 mm, and its yellowness was measured with a Hunter colorimeter to observe the change. In addition, it was placed in a gear oven at 150 ° C., and the degree of yellowness was measured in the same manner for thermal coloring after 72 hours.

The results are shown in Table 1 below. In the table, Compound No. 1 to Compound No. 6 correspond to the above [Chemical Formula 3], respectively.
To [Formula 8]. In addition, comparative compounds 1 to
Comparative compound 3 is a compound represented by the following [Chemical Formula 10] to [Chemical Formula 12], respectively.

[Blending] parts by weight ethylene-propylene block polymer 100 tetrakis [methylene-3- (3,5-di-tert-butyl 0.1-4-hydroxyphenyl) propionate] methane DHT-4A [Kyowa Chemical Co., Ltd.] Hydrotalcite) ^{* 1} 0.1 Test compound (see [Table 1]) 0.1 * 1: Composition formula Mg _4.5 Al ₂ (OH) ₁₃ · CO ₃ · 3.5 H ₂ O

[0039]

[Table 1]

[0040]

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[0041]

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[0042]

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Example 2 The same test as in Example 1 was conducted for the following formulation.

The results are shown in the following [Table 2].

[Blending] Parts by weight Ethylene-propylene block polymer 100 Tetrakis [methylene-3- (3,5-di-tert-butyl 0.1-4-hydroxyphenyl) propionate] methane Calcium stearate 0.05 Compound No. 3 (compound of the above formula [5]) 0.1 Test compound (see [Table 2])

[0046]

[Table 2]

As is evident from the above Examples, by adding a specific phosphonite compound and a hydrotalcite compound to a polyolefin resin in combination, the processing stability is remarkably unpredictable when used alone. Show the effect.

[0048]

The polyolefin resin composition of the present invention is obtained by remarkably improving the coloring property of the polyolefin resin.

Continuation of front page (56) References JP-A-2-75641 (JP, A) JP-A-54-16480 (JP, A) JP-A-57-105456 (JP, A) JP-A-62-81436 (JP, A) , A) (58) Fields studied (Int. Cl. ⁷ , DB name) C08L 23/00-23/36 CA (STN)

Claims (1)

(57) [Claims] 1. 100 parts by weight of a polyolefin resin,
A polyolefin-based resin composition comprising 0.005 to 5 parts by weight of a phosphonite compound represented by the following general formula (I) and 0.005 to 5 parts by weight of a hydrotalcite compound. Embedded image (Wherein, R ₁ and R ₂ each independently represent a group having 1 to 8 carbon atoms)
Represents a substituted or unsubstituted hydrocarbon group or a halogen atom, x and y each independently represent 0 to 3,
n represents 1 to 3, R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₄ represents a substituted or unsubstituted aliphatic or araliphatic hydrocarbon group. )