JP3058487B2 - Crystalline 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 crystalline polyolefin resin composition, and more particularly, to the addition of an alkali metal salt of an organic phosphate, a hydrotalcite compound and an alkaline earth metal salt of an aliphatic carboxylic acid. The present invention relates to a crystalline polyolefin resin composition having improved transparency.

[0002]

2. Description of the Related Art Polyolefin resins such as polyethylene, polypropylene and polybutene-1 have a low crystallization rate after heat molding, and therefore have low molding cycleability and must be used to lower the mold temperature. Must. In addition, there is a disadvantage that the molded product shrinks due to crystallization after heat molding. In addition, these crystalline polyolefin resins have a disadvantage that transparency is inferior because large crystals are generated.

[0003] These disadvantages are all caused by the crystallinity of the polyolefin resin, and are known to be eliminated if the crystallization temperature of the polyolefin resin can be increased and fine crystals can be rapidly formed. I have.

It is known to add a nucleating agent or a crystallization accelerator for this purpose.
A metal salt of a carboxylic acid such as aluminum tertiary butyl benzoate, sodium adipate, sodium bis (4-
Tert-butylphenyl) phosphate, sodium-2,
2'-methylenebis (4,6-di-tert-butylphenyl)
Organic phosphate metal salts such as phosphates and polyhydric alcohol derivatives such as dibenzylidene sorbitol and bis (methylbenzylidene) sorbitol have been used.

[0005] Among these compounds, JP-A-58-1
The metal salts of organic phosphoric esters described in JP-A-736-736 and JP-A-59-184252 have relatively large effects and are widely used.

However, the effect of the metal salt of the above-mentioned organic phosphoric acid ester may still be insufficient, and a method using a combination of an aluminum salt of p-tert-butylbenzoic acid and an alkali metal or zinc of a higher aliphatic carboxylic acid ( JP 6
JP-A-2-263244, JP-A-63-125551) or a method of reducing the average particle size of the alkali metal salt of the above-mentioned cyclic phosphoric acid ester of alkylidene bisphenols (JP-A-2-73837). A method using a metal salt nucleating agent, a hydrotalcite, and a metal salt of Group I of the periodic table of higher fatty acids in combination (Japanese Unexamined Patent Publication No.
No. 3-69853) has been proposed, but is not yet sufficient, and practical improvement has been demanded.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to eliminate the insufficient effect of the alkali metal salt of an organic phosphate, and as a result, have found that an alkali metal It has been found that by adding a hydrotalcite compound and an alkaline earth metal salt of an aliphatic carboxylic acid to the salt, an excellent effect that has not been seen so far appears, and the present invention has been completed.

That is, the present invention relates to (a) an organic phosphate ester represented by the general formula (I) or (II) represented by the following chemical formula 2 (same as chemical formula 1) in 100 parts by weight of a polyolefin resin. 0.005 to 5 parts by weight of an alkali metal salt, (b)
Transparency is improved by adding 0.005 to 5 parts by weight of a hydrotalcite compound and (c) 0.005 to 5 parts by weight of an alkaline earth metal salt of an aliphatic carboxylic acid having 8 to 30 carbon atoms. And a crystalline polyolefin resin composition.

Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, R ₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
M represents an alkali metal. )

Hereinafter, the crystalline polyolefin resin composition according to the present invention will be described in detail.

In the alkali metal salt of the organic phosphate represented by the general formula (I) or (II) of the component (a) of the present invention, the alkyl having 1 to 9 carbon atoms represented by R _{1 to} R ₄ is used. Examples of groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,
Isobutyl, amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl, tertiary octyl, nonyl and the like;
_As an alkyl group having 1 to 4 carbon atoms represented by ₅ ,
Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl and the like.

As the alkali metal salt of the organic phosphoric ester represented by the general formula (I) or (II) used in the present invention, a compound represented by the following chemical formulas 3 to 12 (No. 1)
-No. 10 compounds) are particularly preferred.

[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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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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The amount of the alkali metal salt of the organic phosphoric acid ester is 0.005 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the polyolefin resin.

The hydrotalcite compound as the component (b) of the present invention includes, for example, an anhydrous or hydrous double salt compound of magnesium and aluminum represented by the following general formula (III).

Mg _1-x Al _x (OH) ₂ A _{X / 2} · mH ₂ O (III) (where x is a real number in the range of 0 <x ≦ 0.5, and A
Represents CO ₃ or SO ₄ , and m represents 0 or a real number. )

The hydrotalcite compound may be a natural product or a synthetic product. As the synthesis method, JP-B-46-2280, JP-B-50-280
Known methods described in JP-A-30039 and JP-B-51-29129 can be exemplified. Further, in the present invention, it can be used without being limited by its crystal structure, crystal particle diameter and the like.

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.

Further, a compound in which a part of the metal in the hydrotalcite compound represented by the above general formula (III) is substituted with another metal such as zinc can also be used.

The amount of the hydrotalcite compound is 0.0 to 100 parts by weight of the polyolefin resin.
It is 0.5 to 5 parts by weight, preferably 0.01 to 3 parts by weight.

Further, examples of the metal constituting the alkaline earth metal salt of the aliphatic carboxylic acid having 8 to 30 carbon atoms as the component (c) of the present invention include magnesium, calcium, strontium, and barium. The use of magnesium and calcium is preferred.

The aliphatic carboxylic acid constituting the alkaline earth metal salt of the aliphatic carboxylic acid of the component (c) of the present invention includes octylic acid, 2-ethylhexylic acid, nonanoic acid, isononanoic acid and decanoic acid. , Undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, hexadecanoic acid, stearic acid, oleic acid, 12-hydroxystearic acid, phenylstearic acid, behenic acid, montanic acid, soricic acid and the like.

The amount of the alkaline earth metal salt of the aliphatic carboxylic acid to be added is 0.005 to 5 parts by weight, preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the polyolefin resin.

The polyolefin resins to be stabilized in the present invention include, for example, ethylene, propylene, butene-1, pentene, hexene, 4-methylpentene,
Α-olefin homo- or copolymers such as heptene and octene; a majority weight of these α-olefins and a vinyl ester such as vinyl acetate, an unsaturated organic acid such as acrylic acid, maleic anhydride or methyl methacrylate (ester, (Including salts, amides and amines), random, block or graft copolymers with vinyl silanes such as vinyl trisethoxy silane; or modified polymers such as chlorination, sulfonation and oxidation of these polymers. I can give it.

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

In the composition of the present invention, among the above-mentioned polyolefin resins, those having an effect of improving transparency include polypropylene, propylene-ethylene random or block copolymer, propylene-ethylene-butene copolymer, propylene And propylene-based polymers and copolymers such as hexene-butene copolymer.

The polyolefin resin composition of the present invention may contain, if necessary, a phenolic antioxidant, an organic phosphoric acid-containing antioxidant such as organic phosphite, a thioether antioxidant, an ultraviolet absorber or a hindered amine compound. Such oxidative stability and light stability can be further improved by adding a light stabilizer such as.

Examples of the phenolic antioxidants that can be used in the composition of the present invention include, for example, 2,6-di-tert-butyl-p-cresol, 2,6-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-di-tert-butyl-4 -Hydroxyphenyl)
Propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy)
-S-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4 , 4'-butylidenebis (6-tert-butyl-m-cresol), 2,2 '
-Ethylidenebis (4,6-di-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-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
-2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-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-hydroxyethyl) -2,4 , 8,10-Tetraoxaspiro [5,5] undecane-bis [β- (3-tert-butyl-
4-hydroxy-5-butylphenyl) propionate] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

The amount of the phenolic antioxidant 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 polyolefin resin.
Parts by weight.

The organic phosphorylation inhibitor usable in the composition of the present invention includes, for example, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, (Tridecyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertbutyl-4-)
Methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4 ′ -N-butylidenebis (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) octyl phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octadecyl phosphite, 2,2 ' -Methylenebis (4,6-di-tert-butylphenyl) fluorophosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite and the like.

The amount of the organic phosphorylation inhibitor is preferably 0.1 to 100 parts by weight of the polyolefin resin.
001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight.

Examples of the thioether-based antioxidants which can be used in the composition of the present invention include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, distearyl ester of thiodipropionic acid, and pentaerythritol tetra ( β-
Β-alkylmercaptopropionates of polyols such as dodecylmercaptopropionate).

The amount of the thioether-based antioxidant added is preferably 0.001 to 5 parts by weight, more preferably 0.05 to 5 parts by weight, per 100 parts by weight of the polyolefin resin.
3 parts by weight.

Examples of the ultraviolet absorber which can be used in the composition of the present invention include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone,
2-hydroxybenzophenones such as 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-tert-octylphenyl) benzotriazole, 2
-(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-
(Hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis ( 2- such as 4-tert-octyl-6-benzotriazolyl) phenol
(2′-hydroxyphenyl) benzotriazoles;
Phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. 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.

The amount of the ultraviolet absorber added is preferably 0.01 to 5 parts by weight per 100 parts by weight of the polyolefin resin.
Parts by weight, more preferably 0.05 to 3 parts by weight.

The light stabilizer such as the above hindered amine compound which can be used in the composition of the present invention includes, 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-piperidyl benzoate, bis (2,2,6,6-
Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate , Tetrates (1,2,2,6,6-pentamethyl-
4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2-
(3 ′, 5′-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,
2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6
-Tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6
-Tetramethyl-4-piperidylamino) hexane /
2,4-chloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-
4-piperidylamino) hexane / 2,4-chloro-6
Hindered amine compounds such as tertiary octylamino-s-triazine polycondensates.

The light stabilizer is added in an amount of preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the polyolefin resin.

In addition, the synthetic resin composition of the present invention may contain other nucleating agents, metal soaps, pigments, dyes, fillers, foaming agents, flame retardants, antistatic agents, lubricants, processing aids, if necessary. Agents and the like may be added.

Further, the crystalline polyolefin resin composition of the present invention can be used for various molded articles, fibers, biaxially stretched films, sheets and the like.

[0048]

Next, the present invention will be described specifically with reference to examples. However, the invention is not limited by these examples.

[Example 1] <Blending> Polypropylene homopolymer 100 tetrakis [methylene-β- (3,5-ditert-butyl0.1tyl-4-hydroxyphenyl) propionate] methane tris (2,4-di) Tertiary butylphenyl) phosphite 0.1 ight) Metal salt of organophosphate (Table 1) 0.2 Hydrotalcite (DHT-4A *) 0.05 Calcium stearate 0.05 * Synthetic hydrotal made by Kyowa Chemical Industry site

After pre-blend the above-mentioned composition with a Henschel mixer at 1100 rpm × 3 minutes,
Extrusion was performed under the conditions of × 20 rpm to produce pellets. Next, using the pellets, injection molding was performed at 250 ° C., and then rapidly cooled to 60 ° C. to prepare a test piece having a thickness of 1 mm.

Using this test piece, ASTM D-100
Haze Value was measured based on 3-61.
The pellets were placed in a differential calorimeter, heated to 230 ° C., melted for 5 minutes, and then cooled at a rate of 3 ° C./minute to measure the crystallization temperature. The results are shown in Table 1 below.

[0052]

Example 2 The ethylene copolymerization ratio was 0.1%.
For 100 parts by weight of a 3% by weight crystalline ethylene / propylene random copolymer, 0.2 parts by weight of 2,6-ditert-butyl-4-methylphenol, stearyl-β- (3,
0.1 part by weight of 5-di-tert-butyl-4-hydroxyphenyl) propionate, an organic phosphate metal salt (No.
7 compounds) 0.1 part by weight, calcium stearate 0.1 part by weight.
05 parts by weight and hydrotalcite compound (Table 3)
0.05 parts by weight of the formulation was mixed using a Henschel mixer. Using this mixture, a test piece having a thickness of 1 mm was prepared in the same manner as in Example 1.

Using this test piece, ASTM D-100
The haze value (HazeValue) was measured based on 3-61. Table 2 shows the results.

[0055] * 1, * 2: Synthetic hydrotalcite manufactured by Kyowa Chemical Industry * 3: Zinc-modified synthetic hydrotalcite manufactured by Kyowa Chemical Industry

Example 3 1,3,5-Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate 0 based on 100 parts by weight of ethylene-propylene block copolymer 0.2 parts by weight, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite 0.1 part by weight, organophosphate metal salt (No. 7 compound) 0.2 part by weight, Alcamizer 2
And 0.05 parts by weight of an aliphatic carboxylic acid metal salt (Table-
3) 0.05 parts by weight of the formulation was mixed well with a Henschel mixer. Using this mixture, a test piece having a thickness of 1 mm was prepared in the same manner as in Example 1, and the haze was measured. The results are shown in Table 3 below.

[0057]

Polyethylene (Mirason Neo23H) 1
4,4-thiobis (3-methyl-
6-tert-butylphenol) 0.1 part by weight, metal salt of an organic phosphate (Table-4) 0.2 part by weight, DHT-4A
A pellet was prepared by uniaxial extrusion of 0.1 part by weight and 0.05 part by weight of calcium stearate, followed by injection molding to prepare a 1 mm thick test piece. The haze of this test piece was measured in the same manner as in Example 1, and the results are shown in Table-4.

[0059]

As is clear from the above examples, the specific alkali metal salt of the organic phosphoric acid ester used in the present invention can be obtained by using a hydrotalcite compound and an alkaline earth metal salt of an aliphatic carboxylic acid in combination. It can be seen that, since the crystallization temperature of the crystalline polyolefin resin is increased, the molding cycle can be improved, and the transparency of the polyolefin resin is significantly improved.

[0061]

The crystalline polyolefin resin composition of the present invention has improved transparency.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-9390 (JP, A) JP-A-1-1299051 (JP, A) JP-A-64-9251 (JP, A) JP-A-63-9 210152 (JP, A) JP-A-63-69853 (JP, A) JP-A-59-96145 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/00 C08K 3 / 26 C08K 5/098 C08K 5/521

Claims (1)

(57) [Claims] 1. A polyolefin resin having 100 parts by weight,
(A) 0.001 alkali metal salt of an organic phosphate represented by the following general formula (I) or (II):
5 to 5 parts by weight, (b) hydrotalcite compound 0.0
A crystalline polyolefin resin composition comprising 0.55 to 5 parts by weight and (c) 0.005 to 5 parts by weight of an alkaline earth metal salt of an aliphatic carboxylic acid having 8 to 30 carbon atoms. Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, R ₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
M represents an alkali metal. )