JP2003096246A - Manufacturing method of additive composition for granular polyolefin resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an additive composition for a polyolefin resin which contains a dibenzylidene sorbitol (DBS) that is excellent in the characteristics as a nucleating agent and in dispersibility and is easy to handle. SOLUTION: The additive composition for the granular polyolefin resin is obtained by mixing a powdered mixture containing a dibenzylidene sorbitol powder and an additive for the polyolefin resin with 1-45 wt.% (based on the total amount of the above powdered mixture) of at least one kind of solvents selected from alcohols, esters, ethers and water having a boiling point of 150 deg.C or less under the atmospheric pressure, by forming the resultant mixture containing the solvent into granules, and by drying the formed products.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an additive composition for a granular polyolefin resin, a granular product produced by the method, a polyolefin resin composition containing the granular product and a molded article thereof.

[0002]

2. Description of the Related Art Dibenzylidene sorbitols (hereinafter abbreviated as "DBSs") are polyolefin resins,
In particular, it is a very industrially useful compound as a nucleating agent for homopolymers such as polyethylene and polypropylene or copolymers containing ethylene or propylene as a main comonomer. In particular, DBSs are excellent in the effect of improving transparency and are widely used as resin additives in the field of molding various containers and the like that require transparency.

The commercial forms of DBSs so far are usually
It is a bulky fine powder. Therefore, when processing the polyolefin resin, the DBSs are easily scattered in the air, and there is a problem in workability that handling and continuous automatic weighing are inconvenient. In addition, when using these DBSs, the powder flowability of the DBSs is generally poor, so that there is a tendency for bridging to occur in the piping and the supply hopper, and as a result, the supply of the DBSs to the polyolefin resin is not constant. There is a problem. Further, there is a problem that blocking (a phenomenon in which particles agglomerate with each other to form a lump) is likely to occur during storage.

For this reason, there is a demand for a granular form of DBS that does not have these problems. However, since DBSs generally have a high self-aggregating property and a high melting point, it is not industrially easy to uniformly dissolve or disperse them in a molten resin. Although DBSs are also used as a clarifying agent for polyolefin resins, if the DBSs are not uniformly dissolved or dispersed in the molten resin in the intended use, white spots will appear in the obtained molded product, and the appearance and appearance There is a problem of impairing transparency. Therefore, the level of uniform dissolution or dispersion of DBSs in the molten resin is required to be much higher than that of other additives. If the DBSs are made into granules, it is expected that the above-mentioned problems in work and environment will be solved, but it becomes more difficult to uniformly dissolve or disperse the granules in the resin. It is considered to be.

Heretofore, a method using a binder has been used as a method for granulating additives for polyolefin such as flame retardants and antioxidants for the purpose of improving the working environment, improving the fluidity of powders, etc. (JP-A-9- 324071, US45308
800), a method of dissolving a part of the additive (JP-A-5-17
9056, JP-A-6-91152, JP-A-8-3334.
77), a method using a solvent (US6056898) and the like. In the method of granulating the additive for polyolefin using the solvent of the above method, solvents such as methylene chloride, chloroform, toluene, acetone, methyl ethyl ketone, xylene, cyclohexane, styrene, methylcyclohexane, hexane, etc. have been proposed.

However, these reports do not describe any granulation using DBSs, and whether these techniques can be applied to the granulation of DBSs, and if applicable, the granulated DBSs. There is no suggestion of whether the classes can be highly uniformly dispersed or dissolved in the molten resin.

[0007]

DISCLOSURE OF THE INVENTION According to the present invention, the DBS powder and the additive powder for polyolefin resin are granulated by using a solvent to obtain the nucleating agent property of DBS and the solubility and dispersibility in polyolefin resin. A method for producing an additive composition for a granular polyolefin resin which is easy to handle during molding, has excellent safety such as dustproof / explosionproof, is excellent in storage stability, and is easy to handle without generating dust, and is produced by the method. An object of the present invention is to provide a granulated product, a polyolefin resin composition containing the granulated product, and a molded article thereof.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the essential component DBS
And at least one additive powder for polyolefin resin selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, antacids and lubricants, which are usually added during molding and processing of polyolefin resins. The powdery mixture is mixed with at least one solvent selected from the group consisting of alcohols, esters, ethers and water having a boiling point of 150 ° C. or less under normal pressure, and the resulting mixture containing the solvent is granulated. After molding, by drying the molded product, the additive component for polyolefin resin dissolved in the solvent acts as a binder even after the solvent is removed, and the powdered components are bonded to each other, so that workability and workability are improved. It has been found that a working environment is improved and a granular polyolefin resin additive composition having good storage stability is obtained. Moreover, it was also surprisingly found that this binder-free granular additive composition has good solubility and dispersibility in a polyolefin resin.

The present invention has been completed based on such findings. That is, the present invention provides the following method for producing an additive composition for a granular polyolefin resin, a granulated product produced by the method, a polyolefin resin composition containing the granular product, and a molded article thereof.

Item 1 General formula (1) [In the formula, R ¹ and R ² are the same or different;
It represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a chlorine atom. m and n represent the integer of 0-3. ] The powdery mixture containing at least 1 sort (s) of dibenzylidene sorbitols (A) and the additive (B) for polyolefin resins represented by these, and alcohols and esters whose boiling point under normal pressure is 150 degreeC or less. At least one solvent selected from the group consisting of compounds, ethers and water is mixed in an amount of 1 to 45% by weight based on the total weight of the powdery mixture, and the resulting mixture containing the solvent is formed into granules. After that, the molded product is dried, and a method for producing an additive composition for granular polyolefin resin, which is characterized in that:

Item 2 (A) component is 1,3: 2,4-dibenzylidene sorbitol, 1,3: 2,4-di (p-
Methylbenzylidene) sorbitol, 1,3: 2,4-
Di (o-methylbenzylidene) sorbitol, 1,3:
2,4-di (p-ethylbenzylidene) sorbitol,
1,3: 2,4-di (3,4-dimethylbenzylidene)
Item 2. The method for producing a particulate additive for a polyolefin resin according to Item 1, which is at least one selected from the group consisting of sorbitol and 1,3: 2,4-di (2,4,5-trimethylbenzylidene) sorbitol.

Item 3 The granular polyolefin resin according to Item 1 or 2, wherein the component (B) is at least one member selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, antacids and lubricants. Of manufacturing additive composition for use.

Item 4 The phenolic antioxidant is 2,6
-Di-t-butyl-4-methylphenol, 4,4'-
Butylidene-bis- (3-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-methyl-)
6-t-butylphenol), 1,1,3-tris-
(2-Methyl-4-hydroxy-5-t-butylphenol) butane, 3,9-bis- {2- [3- (3-t-
Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4
8,10-tetraoxaspiro [5,5] undecane,
2,2'-methylene-bis- (4-ethyl-6-t-butylphenol), triethylene glycol-bis [3
-(3-t-butyl-4-hydroxy-5-methylphenyl) propionate], tetrakis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, n-octadecyl-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 1,3,5-tris (3,5-
From the group consisting of di-t-butyl-4-hydroxybenzyl) isocyanurate and 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene. 4. The method for producing an additive composition for granular polyolefin resin according to the above item 3, which is at least one selected.

Item 5 The phosphorus-based antioxidant is tris (2,
4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite, bis (2,4) -Di-t-
Butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite and 2,2 -Methylene-bis- (4,6-di-t-
The method for producing an additive composition for granular polyolefin resin according to the above item 3 or 4, which is at least one member selected from the group consisting of butylphenyl) octyl phosphite.

Item 6 The antacid is at least one selected from the group consisting of saturated or unsaturated higher fatty acid metal salts having 8 to 32 carbon atoms and hydrotalcite.
5. A method for producing the additive composition for granular polyolefin resin according to any one of 5 to 6.

Item 7 The antacid is lithium palmitate,
At least one selected from the group consisting of sodium palmitate, potassium palmitate, magnesium palmitate, calcium palmitate, lithium stearate, sodium stearate, potassium stearate, magnesium stearate, calcium stearate, and hydrotalcite. Item 7. A method for producing the additive composition for granular polyolefin resin according to Item 6.

Item 8 The lubricant is at least one selected from the group consisting of saturated or unsaturated higher fatty acid amides having 8 to 22 carbon atoms and glycerin ester of saturated or unsaturated higher fatty acids having 8 to 22 carbon atoms. 3-7
A method for producing the additive composition for granular polyolefin resin according to any one of 1.

Item 9 In the above item 8, the lubricant is at least one selected from the group consisting of stearic acid amide, oleic acid amide, erucic acid amide, glycerin monolauric acid ester, glycerin monostearic acid ester and glycerin distearic acid diester. A method for producing the additive composition for a granular polyolefin resin described.

Item 10 The alcohols are methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, t-butyl alcohol and sec.
-The method for producing granular polyolefin resin additives according to any one of items 1 to 9, which is at least one selected from the group consisting of butyl alcohol.

Item 11 The ester is at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate and ethyl propionate. Item 11. A method for producing the additive composition for granular polyolefin resin according to any one of Items 1 to 10 above.

Item 12 The ethers are selected from the group consisting of isopropyl ether, ethyl butyl ether, methyl cellosolve, diethyl cellosolve, cellosolve, ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, dioxolane and methyldioxolane. 12. The method for producing an additive composition for granular polyolefin resin according to any one of the above items 1 to 11, which is at least one kind.

Item 13 The average diameter of the cross section is 1 to 5 m.
m, a column having an average value of 1 to 10 mm, a spherical shape having an average value of 1 to 5 mm, or an average value of major axis of 1 to 10 mm, and an average value of minor axis of 1 to Items 1 to 1 in the form of a plate having a thickness of 5 mm and an average thickness of 0.1 to 3 mm.
3. The method for producing an additive composition for granular polyolefin resin according to any one of 2 above.

Item 14 A granular polyolefin resin additive composition produced by the method according to any one of Items 1 to 13 above.

Item 15 A polyolefin resin composition comprising the granular polyolefin resin additive composition according to Item 14 above.

Item 16 A polyolefin resin molded product which can be obtained by molding the polyolefin resin composition according to Item 15.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Component: DBSs General formula (1) used in the present invention [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a chlorine atom. m and n represent the integer of 1-3. ] The DBSs (A) represented by the above are various dibenzylidene sorbitol powders currently known as nucleating agents for polyolefin resins, and are not particularly limited.

The substitution position of the substituents R ¹ and R ² of the component (A) may be any of the ortho position, the meta position and the para position and is not particularly limited. Examples of the alkyl group having 1 to 5 carbon atoms include linear or branched ones, for example, methyl group, ethyl group, isopropyl group, n-butyl group, n-pentyl group and the like. Alkyl groups of the numbers 1 to 3 are recommended. Examples of the alkoxy group having 1 to 5 carbon atoms include linear or branched ones, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and the like. ,
Particularly, an alkoxy group having 1 to 3 carbon atoms is recommended. Examples of the halogen atom include chlorine and bromine.

Specific examples of the component (A) include 1,3:
2,4-dibenzylidene sorbitol, 1,3: 2,4
-Di (p-methylbenzylidene) sorbitol, 1,
3: 2,4-di (o-methylbenzylidene) sorbitol, 1,3: 2,4-di (p-ethylbenzylidene) sorbitol, 1,3: 2,4-di (p-chlorobenzylidene) sorbitol, 1 , 3: 2,4-di (p-methoxybenzylidene) sorbitol, 1,3: 2,4-di (2,4-dimethylbenzylidene) sorbitol, 1,
Compounds having the same substituted or unsubstituted benzylidene group such as 3: 2,4-di (3,4-dimethylbenzylidene) sorbitol and 1,3: 2,4-di (2,4,5-trimethylbenzylidene) sorbitol Among these, 1,3: 2,4-dibenzylidene sorbitol, 1,3: 2,4-di (p-methylbenzylidene) sorbitol, 1,3: 2,4-di (o -Methylbenzylidene) sorbitol, 1,3: 2,4-di (p-
Ethylbenzylidene) sorbitol, 1,3: 2,4-
Di (3,4-dimethylbenzylidene) sorbitol and 1,3: 2,4-di (2,4,5-trimethylbenzylidene) sorbitol are recommended.

Further, as the usable component (A), 1,
3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4
-Benzylidene sorbitol, 1,3-benzylidene-
2,4-p-ethylbenzylidene sorbitol, 1,3
-P-Ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-benzylidene-2,4- (3,4-
Dimethylbenzylidene) sorbitol, 1,3- (3,3
4-dimethylbenzylidene) -2,4-benzylidene sorbitol, 1,3-benzylidene-2,4- (2,4)
-Dimethylbenzylidene) sorbitol, 1,3-
Examples thereof include compounds having different kinds of unsubstituted or substituted benzylidene groups such as (2,4-dimethylbenzylidene) -2,4-benzylidenesorbitol. In the present invention,
The DBSs represented by the general formula (1) include one kind or two kinds.
They may be used in combination of at least one species.

Further, within the scope of the present invention, Japanese Patent No. 21
The dibenzylidene sorbitol compositions described in JP 11253 and JP 2826152 are included.

The above DBSs are publicly known and easily available, or JP-B-48-43748 and JP-A-53.
-5156, JP-A-57-185287, JP-A-2
It can be produced according to a known method such as No. 231488. These crystal forms are not particularly limited as long as the effects of the present invention can be obtained, and any crystal form such as hexagonal crystal, monoclinic crystal and cubic crystal can be used.

The amount of the component (A) is preferably 20 to 80% by weight based on the total weight of the powdery mixture. If it is out of this range, the solubility or dispersibility in the polyolefin resin tends to deteriorate.

The particle size of the component (A) to be used can be selected from a wide range, but in general, the d ₉₇ particle size is 150 μm.
The following is preferably 100 μm or less. d ₉₇ is 15
If it exceeds 0 μm, it tends to be difficult to obtain granules having good dispersibility in the polyolefin resin.

Component (B): Additive for Polyolefin Resin Additive for Polyolefin Resin (B) Used in the Present Invention
Is at least one selected from phenolic antioxidants, phosphorus antioxidants, antacids and lubricants, all of which are known, and are commercially available alone or in various mixtures, and are easily available. is there. As the component (B), for example, various additives described in "Positive List Additives Manual Revised 2nd Edition" (January 1995) edited by the Hygiene Council for Polyolefins are recommended.

These additives are used in the form of powder that is usually obtained, and have a median diameter of 5 to 500 μm.
It is particularly preferably 5 to 300 μm.

Phenolic Antioxidant As the phenolic antioxidant according to the present invention, those widely used in the field of polyolefin resins can be widely used and are not limited as long as the effects of the present invention are not impaired. Specifically, 2,6-di-t-butyl-4-methylphenol, 4,4′-butylidene-bis- (3-methyl-6-t-butylphenol), 2,2′-methylene-bis- (4-methyl-6-t-butylphenol),
1,1,3-tris- (2-methyl-4-hydroxy-
5-t-butylphenol) butane, 3,9-bis-
{2- [3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2′-methylene-bis-
(4-ethyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], tetrakis [3- (3,5-di-). t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, n
-Octadecyl-3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl) propionate, 1,3
5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate and 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Examples include 2,2,4,6-trimethylbenzene and the like.
Of these, tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane is particularly preferable.

Phosphoric Acid-Based Antioxidant As the phosphorus-based antioxidant according to the present invention, those widely used in the field of polyolefin resins can be widely used and are not limited as long as the effects of the present invention are not impaired. Specifically, tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene- Di-phosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,2
6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite and 2,2-methylene-bis-
Examples include (4,6-di-t-butylphenyl) octyl phosphite. Especially, especially Tris (2,4
-Di-t-butylphenyl) phosphite is preferred.

Antacids As the antacid according to the present invention, those widely used in the field of polyolefin resins such as saturated or unsaturated higher fatty acid metal salts having 8 to 32 carbon atoms and hydrotalcite can be widely used. Examples of the saturated or unsaturated higher fatty acid metal salt include octanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, 12-hydroxystearic acid, eicosanoic acid, behenic acid, Examples thereof include aluminum salts such as linoleic acid, linolenic acid, ricinoleic acid and montanic acid, calcium salts, magnesium salts, zinc salts, barium salts, potassium salts, sodium salts and lithium salts.

As the hydrotalcite, 6M
gO ・ Al_TwoO_Three・ CO_Two・ 12H _TwoO, 4MgO · A
l_TwoO_Three・ CO_Two・ 12H_TwoO, 6MgO ・ Al_TwoO_Three
・ CO_Two・ 12H_TwoO, or ZnO ・ 6MgO ・ Al_Two
O_Three・ CO_Two・ 8-9H_TwoNatural or synthetic hide such as O
Rotalsite is exemplified. Commercially available hydrota
As Lucite, for example, product name D manufactured by Kyowa Chemical Industry Co., Ltd.
HT-4A is mentioned.

Among these antacids, especially lithium palmitate, sodium palmitate, potassium palmitate, magnesium palmitate, calcium palmitate, lithium stearate, sodium stearate, potassium stearate, magnesium stearate, stearate. Calcium phosphate and hydrotalcite are preferred. The above antacids are used alone or in appropriate combination of two or more kinds.

Lubricants Lubricants according to the present invention include polyolefin resin fields such as saturated or unsaturated higher fatty acid amides having 8 to 22 carbon atoms, saturated or unsaturated higher fatty acid glycerin mono-, di- or triesters having 8 to 22 carbon atoms. The ones used in can be widely used. Specific examples of the saturated or unsaturated higher fatty acid amide having 8 to 22 carbon atoms include myristic acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, erucic acid amide, and eicosanoic acid amide. . Among them, stearic acid amide, oleic acid amide, and erucic acid amide are particularly exemplified.

Specific examples of the saturated or unsaturated higher fatty acid glycerin ester having 8 to 22 carbon atoms include fatty acids such as myristic acid, palmitic acid, stearic acid, oleic acid, erucic acid and eicosanoic acid, and glycerin. And mono-, di- or triesters and mixtures thereof.

Among these lubricants, stearic acid amide, oleic acid amide, erucic acid amide, glycerin monolauric acid ester, glycerin monostearic acid ester and glycerin distearic acid diester are particularly preferable. The above lubricants are used alone or in combination of two or more kinds.

Solvent The solvent according to the present invention is at least one solvent selected from the group consisting of alcohols, esters, ethers and water having a boiling point of 150 ° C. or less under normal pressure, and selected from the component (B). It is important that it has a solubility in at least one additive for polyolefins. Examples of such a solvent include (B) based on 100 parts by weight of the above solvent.
The amount of the components in the temperature range from room temperature to the boiling point of the solvent or less,
The solvent may be 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more. When the amount of the component (B) is less than 1% by weight, a solvent that dissolves less than 1% by weight tends to be difficult to be granulated.

The following alcohols, esters, ethers and water are exemplified as the solvent in which the component (B) dissolves in an amount of 1% by weight or more and has a boiling point of 150 ° C. or less under normal pressure.
Specific examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, t-butyl alcohol and sec-.
Butyl alcohol and the like are exemplified. Of these, methanol and ethanol are particularly preferable.

Specific examples of the esters include dimethyl carbonate, diethyl carbonate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate and ethyl propionate. Particularly, methyl acetate, ethyl acetate and dimethyl carbonate are preferable.

Specific examples of ethers include isopropyl ether, ethyl butyl ether, methyl cellosolve, diethyl cellosolve, cellosolve, ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, dioxolane and methyldioxolane. It is illustrated. The solvent selected from the alcohols, esters, ethers and water may be used alone or in combination of two or more.

The amount of the solvent used is 1 to 45% by weight, preferably 2 to 45% by weight, based on the total weight of the powdery mixture containing the components (A) and (B) in the temperature range from room temperature to the boiling point or lower. It is 30% by weight. If it is out of this range, it tends to be difficult to granulate in the granulation step.

In the case of alicyclic hydrocarbons such as cyclohexane and methylcyclohexane and aromatic hydrocarbons such as toluene and xylene, which are disclosed in US Pat. No. 5,068,988, although they are soluble in the component (B),
It is recognized that the obtained granular additive composition tends to have poor solubility and dispersibility in the polyolefin resin.

Granular Additive Composition The granular additive composition according to the present invention is an essential component DB
It is composed of at least one selected from the group S and the component (B), and at least one of the component (B) acts as a binder and bonds particles other than the binder to each other, so that it maintains a granular form. In selecting the component (B), it is not particularly limited as long as the effect of the present invention can be obtained, but at least one of the additives for polyolefin resin is an alcohol having a boiling point of 150 ° C. or less under normal pressure, an ester, It is important to dissolve at least 1% by weight based on 100 parts by weight of the solvent in at least one solvent selected from the group consisting of ethers and water.

The component (B) that dissolves in the solvent in an amount of 1% by weight or more is not particularly limited as long as the effects of the present invention can be obtained, and the above-mentioned phenolic antioxidant and phosphorus antioxidant are used. It can be selected from agents, antacids and lubricants. Among these,
Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane,
n-octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, tris (2,4-di-t-butylphenyl) phosphite, stearic acid amide, oleic acid amide , Erucic acid amide, glycerin monostearic acid ester, glycerin distearic acid diester, and mixtures thereof are preferable, and tetrakis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, n-octadecyl-3- (3 ′,
5'-di-t-butyl-4'-hydroxyphenyl) propionate. These (B) components may be used alone or in combination of two or more.

The total amount of at least one additive selected from the component (B) is preferably about 20 to 80% by weight based on the total weight of the additive composition of the present invention. The use ratio of the additive for polyolefin resin may be appropriately determined according to the required performance of the resin composition used, the final use of the resin molded product, the required performance, and the like.

The form of the additive composition for granular polyolefin resin according to the present invention is not limited as long as the effects of the present invention can be obtained, and it may have a cylindrical, spherical, plate-like or similar form. Granules can be exemplified.
As a specific example of the recommended form, in the case of a columnar shape, the average value of the diameter of its cross section is 1 to 5 mm, particularly 1.5 to 4 mm.
The average length is preferably 1 to 10 mm, and more preferably 1.5 to 5 mm. Average diameter 5
When the average value of mm or length exceeds 10 mm, the solubility and dispersibility deteriorate, and it becomes difficult to uniformly disperse in the resin, and when the average value of diameter or length is less than 1 mm, dust is easily generated. There is a tendency. In the case of a spherical shape, the average diameter is preferably 1 to 5 mm, and particularly preferably 1.5 to 3 mm. In the case of a plate, the average value of the major axis is 1 to 10 m
m, especially 1.5 to 5 mm, the average value of the minor axis is 1 to 5 mm,
Especially 1.5 to 3 mm, the average thickness is 0.1 to 3 mm,
It is particularly preferably 0.2 to 2 mm.

The hardness of the granular additive composition of the present invention is not particularly limited as long as the effects of the present invention can be obtained, but it is preferably 15 to 100 kg / cm ² , more preferably 20 to 80 kg / cm ² . is there. Within this range, it is less likely to be broken during transportation, the solubility and dispersibility in the molten polyolefin resin are good, and the number of white spots in the molded product is suppressed. In addition, if necessary, the additive composition for a granular polyolefin resin according to the present invention may include a conventionally known modifier for a polyolefin resin other than the component (B), depending on the purpose of use and the use thereof. It can be used in combination as long as the effects of the invention are not impaired. Specific examples include modifiers such as pigments, dyes, ultraviolet absorbers, antistatic agents, fillers, and antibacterial agents.

Additive composition for granular polyolefin resin
Production Method The granular additive composition for polyolefin resin according to the present invention can be produced, for example, as follows. (A) component powder, phenol-based antioxidant, phosphorus-based antioxidant,
At least one additive powder for polyolefin selected from an antacid and a lubricant, and, if necessary, an additive for polyolefin resin other than the above-mentioned components are mixed in advance before the granulation step, preferably uniformly mixed. A powdery mixture is prepared. For example, Nauta mixer, Henschel mixer,
It can be uniformly mixed using a V blender, a ribbon blender, or the like.

Next, the powdery mixture uniformly mixed and at least one solvent selected from the group consisting of alcohols, esters, ethers and water having a boiling point of 150 ° C. or less under normal pressure are mixed with the powder. 1 to 45% by weight, based on the total weight of the mixture, is mixed using a conventionally known mixing device such as a universal stirrer. The mixing conditions are not particularly limited as long as the effects of the present invention can be obtained, but the mixing temperature is usually from room temperature to the boiling point of the solvent or less, preferably room temperature to
50 ° C., mixing time is 1 to 60 minutes, preferably 1
10 minutes.

Next, the uniformly mixed solvent-containing mixture is mixed with a single-screw or twin-screw extruder at a temperature in the range of room temperature to the boiling point of the solvent or less, for example, a diameter of the mixture. Extrude in strands through holes of 1-5 mm. The temperature of the solvent-containing mixture in the extruder (cylinder portion) up to the die plate is not particularly limited and may be room temperature to a temperature not higher than the boiling point of the solvent, preferably room temperature to 50 ° C. It may be adjusted so that it falls within the temperature range.

To process the extrudate obtained through such an extrusion process into granules, for example, the following method can be adopted.
For example, the extruded string-shaped strand can be cooled to room temperature if necessary, and cut into a length of about 1 to 10 mm to form a cylindrical solvent-containing pellet. In addition, the solvent-containing mixture that has been uniformly mixed is treated with a compression granulator such as a disk pelleter or a gear pelletizer to about 1
It can also be a cylindrical pellet of 10 mm.

The method for drying the solvent-containing pellets thus produced is not particularly limited, and a conventionally known method generally known in the art can be adopted. For example,
Dry pellets can be obtained by using a box-type tray dryer, a vibration dryer, a fluidized bed dryer, a double rotary drum dryer and the like. In order to prevent fusion of pellets, the drying temperature needs to be set below the melting point or softening point of the compound having the lowest melting point or softening point among the additives for polyolefin resin. Usually room temperature to 100
C., preferably in the range of room temperature to 80.degree. C., and the degree of reduced pressure is atmospheric pressure to 0.5 kPa, preferably 0.5 to 50 kP.
The range is a. Further, the drying time can be appropriately set depending on the drying temperature, the degree of reduced pressure, the solvent used (type, amount), the pellet shape, and the like.

In order to produce spherical pellets, the cylindrical pellets containing the solvent produced by the above method may be rolled into a spherical pellet using a sizing machine. In addition, in order to obtain a plate-shaped pellet, a plate having a thickness of 0.1 to 3 mm is extruded from a die and cut into a plate having a predetermined size, or the solvent-containing mixture is heated to room temperature or heated. The compressed plate-shaped molded product may be crushed and dried. Alternatively, the plate-shaped molded product may be dried and crushed in advance.

The extruded strands, extrudates from a die or a solvent-containing mixture at room temperature or under heating can be immediately dried by the above-mentioned drying method without cooling. As a method of cooling the pellet after drying, a known method which is usually used industrially can be applied. For example,
A method of using a gas such as air, nitrogen, or argon cooled to room temperature or below room temperature is preferable, and a method using air is preferably recommended.

By the above, the component (B) dissolved in at least one solvent selected from the group consisting of alcohols, esters, ethers and water having a boiling point of 150 ° C. or lower under normal pressure is It works as a binder and binds particles of other components that are in powder form, which suppresses the generation of dust, improves transportability through pipes and hoppers, enables automatic continuous weighing, and is easy to handle. In addition, it is possible to obtain a good granular additive composition having no variation in solubility and dispersibility during molding.

Polyolefin Resin Composition The polyolefin resin composition can be obtained by blending the particulate polyolefin resin additive composition produced by the method of the present invention with a polyolefin resin according to a conventional method. For example, a polyolefin resin (powder or flake), an additive composition for a granular polyolefin resin, and optionally a modifier for a polyolefin resin are mixed with a conventional kneading machine such as a uniaxial or biaxial extruder. A method of forming a pellet type by melt-kneading at a desired temperature, cooling the extruded strand, and cutting the obtained strand can be exemplified. Also, a granular additive composition master-batch containing the above-mentioned modifier for polyolefin resin in the granular additive composition in advance can be used.

The blending amount of the additive composition for granular polyolefin resin is not particularly limited as long as the desired nucleating effect of DBS can be obtained, and can be appropriately selected. Usually, with respect to 100 parts by weight of the polyolefin resin,
0.01-5 parts by weight in terms of DBS, preferably 0.0
5 to 3 parts by weight are blended. By blending within these ranges, the desired nucleating agent effect of DBS can be obtained.

Examples of the polyolefin resin include polyethylene resin, polypropylene resin and polybutene resin, and more specifically, high density polyethylene, medium density polyethylene, linear polyethylene, and ethylene content of 50% by weight or more. Ethylene copolymer, propylene homopolymer, propylene 50% by weight or more propylene copolymer, butene homopolymer, butene content 50% by weight or more butene copolymer, methylpentene homopolymer, methylpentene 50% by weight or more methylpentene copolymer, polybutadiene, etc. It is illustrated. The copolymer may be a random copolymer or a block copolymer. The stereoregularity of these resins may be isotactic or syndiotactic.

Specific examples of the copolymer that can form the above copolymer include α-olefins such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene and dodecene, 1,4
Examples thereof include bicyclo-type monomers such as endomethylenecyclohexene, methyl (meth) acrylate, (meth) acrylates such as ethyl (meth) acrylate, vinyl acetate and the like.

As the catalyst applied for producing such a polymer, not only the commonly used Ziegler-Natta type catalyst but also transition metal compounds (for example, titanium halides such as titanium trichloride and titanium tetrachloride) can be used. It is also possible to use a catalyst system or a metallocene catalyst in which a catalyst in which (1) is supported on a carrier containing magnesium halide as a main component such as magnesium chloride is combined with an alkylaluminum compound (triethylaluminum, diethylaluminum chloride, etc.).

The recommended melt flow rate of such a polyolefin resin (hereinafter abbreviated as "MFR". JIS.
K 7210-1976) is appropriately selected depending on the molding method applied, but is usually 0.01 to 200 g /
It is 10 minutes, preferably 0.05 to 100 g / 10 minutes.

If necessary, the polyolefin resin composition may be appropriately added depending on the purpose of use and its application.
Conventionally known modifiers for polyolefin resins can be used together within a range that does not impair the effects of the present invention.

As such a modifier for polyolefin resin, for example, “Positive List Additives Handbook, Revised 2nd Edition” edited by the Hygiene Council for Polyolefins, etc. (1995 1
Monthly) various additives, more specifically, ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), surfactants, fillers (talc, mica, zeolite, perlite, Diatomaceous earth,
Calcium carbonate, glass fiber, etc.), foaming agent, foaming aid, polymer additive, plasticizer, crosslinking agent, crosslinking accelerator, antistatic agent, antiblocking agent, antifog agent, polymer alloy component (block SBR or Random SB
R and rubbers such as hydrides thereof, polystyrene, etc.), flame retardants, dispersants, organic or inorganic pigments or dyes,
Various additives such as processing aids are exemplified.

[0071] When forming a molded body thus obtained polyolefin resin composition, injection molding, extrusion molding, blow molding, pressure forming, rotational molding, can be employed any of conventionally known molding methods film molding or the like. As the molding conditions, any of the conventionally used conditions can be used.

The above-mentioned polyolefin resin composition has hitherto been known.
It is applied in the same fields where polyolefin resin compositions prepared by blending DBS as a nucleating agent have been used, and more specifically, disposable syringes, infusion / transfusion sets, blood collection devices that are sterilized by heat or radiation. Medical instruments such as; packaging of foods and plants sterilized by radiation; various cases such as clothing cases and clothing storage containers; cups for heat-filling food; packaging containers for retort food; electronic Containers for microwave ovens; containers for beverages such as juice and tea, cosmetics, pharmaceuticals, shampoos, cans, bottles, etc .; containers and caps for seasonings such as miso and soy sauce;
It is suitable as a material for food and food cases such as water, rice, bread, and pickles; miscellaneous goods such as refrigerator cases; stationery; electrical / mechanical parts; automotive parts.

[0073]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples. The following compounds are used in the following Examples and Comparative Examples. (1) DBSs 1,3: 2,4-dibenzylidene sorbitol: trade name “Gelol D”, Shin Nippon Rika Co., Ltd. 1,3: 2,4-di (p-methylbenzylidene) sorbitol: trade name "Gel All MD", New Japan Rika Co., Ltd.
1,3: 2,4-di (3,4-dimethylbenzylidene)
Sorbitol: Trade name "Millad 3988", Mi
(2) phenolic antioxidant tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane manufactured by liken:
Trade name "Irganox 1010", Ciba Specialty Chemicals (3) Phosphorus antioxidant tris (2,4-di-t-butylphenyl) phosphite: Trade name "Irgafos 168", Ciba Specialty Chemicals (4 ) Antacid calcium stearate: trade name "calcium stearate CP-S", Nitto Kasei Co., Ltd. hydrotalcite: trade name "DHT-4A", Kyowa Chemical Industry (5) lubricant glycerine monostearate and distearate mixture : Product name "Rikemar S-100", manufactured by Riken Vitamin Co., Ltd.

The degree of dust generation, hardness, diameter and length, dispersibility of the particulate additive composition for polyolefin of the present invention,
Fluidity, storage stability and particle size d ₉₇ of DBS powder,
Was measured as follows.

Dust generation rate : 50 g of the additive composition for granular polyolefin resin was used to obtain an inner diameter of 1
The sample was placed on a 5 cm mesh with 50 mesh openings and shaken for 30 minutes with a shaking sieving machine. The weight of the powder under the sieve was weighed to determine the degree of dust generation. The smaller the value, the more difficult it is for dust to stand.

Hardness After measuring the hardness of the additive composition for granular polyolefin resin using a Kiya type hardness meter KHT-20 (manufactured by Kiya Seisakusho), it is converted to a value per unit area and the average value of 10 times ( kg / cm ² ) was calculated.

Diameter and Length The diameter and length of ten obtained cylindrical additive compositions for polyolefin resin were measured, and the average value of each was determined.

The number of white spots based on undispersed dibenzylidene sorbitols in 10 sheets of polyolefin resin moldings having a dispersibility of 40 mm × 70 mm × 2 mm was visually counted and determined as an average value per sheet. The smaller the value, the better the dispersibility.

Fluidity (angle of repose) A 4 g sample was placed flat on one end of a clean surface stainless steel bat having a length of 17 cm (Lcm), a width of 13 cm and a depth of 1 cm. One end of the bat on which the sample is placed is lifted in steps of 1 cm and then rested for 30 seconds. By repeating this operation, the height from the horizontal surface of one end of the bat is measured when almost all of the sample falls. The same operation is repeated 3 times, and the average value (Hcm) is calculated. The angle of repose θ was calculated according to the following formula. The smaller the angle of repose θ, the better the fluidity. θ = sin ⁻¹ (H / L)

Storage stability test Immediately after production, 100 g of the additive composition for granular polyolefin resin was put into a plastic bag, and 1 kg / cm ² was added to the whole.
The sample was placed under a load of 2 and left in a thermostat bath at 80 ° C. for 2 weeks.
Then, it was taken out from the oven, cooled to room temperature, and visually checked for blocking. The case where blocking was not recognized was marked with ◯, and the case where blocking was recognized was marked with x.

Particles of dibenzylidene sorbitols powder
Diameter d ₉₇ Laser diffraction / scattering type particle size distribution measuring device (“LA-91
0 ”(trade name), manufactured by Horiba, Ltd., using distilled water as a dispersion medium and polyethylene glycol mono-p-isooctylphenyl ether as a dispersant, and a cumulative distribution value of 9
The particle size corresponding to 7% was determined.

The following methods were used for the method for preparing the additive composition for granular polyolefin resin, the method for preparing the polyolefin resin composition and the molding method according to the present invention. Preparation Method of Granular Polyolefin Resin Additive Composition A predetermined amount of DBS powder and a predetermined amount of polyolefin resin additive powder were put in a 2 L Henschel mixer, and stirred and mixed for 3 minutes at a rotation speed of 750 rpm under non-heating conditions. As a result of analyzing 1 g of the obtained powdery additive composition by HPLC, it was confirmed that they were uniformly mixed. Next, the powdered additive composition was placed in a 5 L universal stirrer (manufactured by Dalton), a predetermined amount of solvent was added, and the mixture was mixed at room temperature for 1 minute.

The solvent-containing mixture thus obtained was measured to have a length of 255 m.
m, 25 mm diameter twin-screw extruder (Kurimoto Tekkosho S1 KRC kneader), screw rotation speed 4
It was supplied at 0 rpm at a rate of 100 g / min and extruded from a die having 9 holes of 2 mm in diameter at an extrusion temperature of room temperature to obtain a string-like strand. This was cut into a length of about 2 mm to form a cylindrical pellet form and dried under reduced pressure at a drying temperature of 80 ° C. and a reduced pressure degree of 2 kPa to obtain a granular additive composition.
The “extrusion temperature” refers to the temperature of the additive composition on the die plate.

Preparation and molding of polyolefin resin composition
Method 100 parts by weight of an isotactic random polypropylene resin having an ethylene content of 3.0% by weight (MFR = 20 g / 10 minutes, hereinafter abbreviated as "r-PP") was added with a pelletized resin additive of DBS type. The mixture was blended so that the amount added was 0.2 parts by weight, and mixed by hand for 3 minutes. Resin temperature 24
It was melt-kneaded and pelletized by a uniaxial extruder having a diameter of 25 mm set to 0 ° C. Further, the pellets were melt-kneaded twice under the same conditions. The pellets obtained are heated to a resin temperature of 2
Injection molding under the conditions of 40 ℃, mold temperature 40 ℃, 40m
A polyolefin resin molded body of m × 70 mm × 2 mm was obtained.

Example 1 1,3: 2,4-di (p- having a particle diameter d ₉₇ of 100 μm)
180 g of methylbenzylidene) sorbitol, 45 g of tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, 45 g of tris (2,4-di-t-butylphenyl) phosphite, Then, 45 g of calcium stearate and 105 g of methanol were obtained according to the above-mentioned “Method for preparing additive composition for granular polyolefin resin” to obtain cylindrical pellets each having a diameter and a length of about 2 mm. The obtained cylindrical pellet has a hardness of 75 kg / cm ² and an angle of repose θ of 21.
It was degree. Furthermore, the degree of dust generation of the obtained granules,
The evaluation results of the storage stability test are shown in Table 1.

Next, a polyolefin resin molded body was obtained using the obtained additive composition for a polyolefin resin according to the method for preparing and molding the polyolefin resin composition. Table 1 shows the evaluation results of the dispersibility of the obtained polypropylene resin molded body. As shown in Table 1, it was confirmed that the dispersibility of the nucleating agent was good.

In Table 1, the abbreviations have the following meanings: "DBS": 1,3: 2,4-dibenzylidene sorbitol "Me-DBS": 1,3: 2,4-di (p -Methylbenzylidene) sorbitol "3,4-DMDBS": 1,3: 2,4-di (3,4)
-Dimethylbenzylidene) sorbitol

Examples 2 to 9 The same operation as in Example 1 was carried out except that the solvent and the amount of solvent shown in Table 1 were used instead of methanol. The degree of dust generation and storage stability of the obtained granules, and the dispersibility of polypropylene moldings were evaluated. The evaluation results are shown in Table 1.

Example 10 The same operation as in Example 1 was carried out except that 1,3: 2,4-di (p-methylbenzylidene) sorbitol was replaced by 1,3: 2,4-dibenzylidenesorbitol. The degree of dust generation and storage stability of the obtained granules, and the dispersibility of polypropylene moldings were evaluated.

Example 11 Example 1 was repeated except that 1,3: 2,4-di (p-methylbenzylidene) sorbitol was replaced with 1,3: 2,4-di (3,4-dimethylbenzylidene) sorbitol. The same operation was performed. The degree of dust generation and storage stability of the obtained granules, and the dispersibility of polypropylene moldings were evaluated.

Example 12 The same operation as in Example 1 was carried out except that calcium stearate was replaced with hydrotalcite. The degree of dust generation and storage stability of the obtained granules, and the dispersibility of polypropylene moldings were evaluated.

Example 13 160 g of 1,3: 2,4-di (p-methylbenzylidene) sorbitol, tetrakis [3- (3,5-di-t-]
Butyl-4-hydroxyphenyl) propionyloxymethyl] methane 40 g, tris (2,4-di-t-butylphenyl) phosphite 40 g, and calcium stearate 40 g, glycerin monostearate and distearate mixture 40 g, methanol 107 g
In the same manner as in Example 1, a granular product was obtained. The degree of dust generation and storage stability of the obtained granules, and the dispersibility of polypropylene moldings were evaluated.

Comparative Example 1 Example 1 except that cyclohexane was used instead of methanol.
The same operation was performed. The degree of dust generation and storage stability of the obtained granules, and the dispersibility of polypropylene moldings were evaluated. The evaluation results are shown in Table 1.

Comparative Example 2 The same operation as in Example 4 was carried out except that toluene was used instead of ethyl acetate. The degree of dust generation and storage stability of the obtained granules, and the dispersibility of polypropylene moldings were evaluated. The evaluation results are shown in Table 1.

[0095]

Note) In Table 1, a to e indicate the following additives. a: tetrakis [3- (3,5-di-t-butyl-4-]
Hydroxyphenyl) propionyloxymethyl] methane b: tris (2,4-di-t-butylphenyl) phosphite c: calcium stearate d: hydrotalcite e: glycerin monostearate and distearate mixture Also, in Table 1, D And L respectively show the average value of the diameter and the length of the obtained cylindrical pellet. The amount of the solvent added is% by weight based on the total weight of the powdery additive composition.

[0097]

According to the present invention, it becomes possible to granulate a powdery additive composition containing DBSs and an additive powder for polyolefin. As a result, without sacrificing the nucleating agent properties of DBS and the solubility and dispersibility in polyolefin resin, easy weighing during molding, safety such as dust and explosion proof, transportability in piping and hopper, storage stability It is possible to obtain an additive composition for a granular polyolefin resin which is excellent in, for example, dust, and is easy to handle.

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Claims (16)

[Claims] 1. The general formula (1) [In the formula, R ¹ and R ² are the same or different;
It represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a chlorine atom. m and n represent the integer of 0-3. ] The powdery mixture containing at least 1 sort (s) of dibenzylidene sorbitols (A) and the additive (B) for polyolefin resins represented by these, and alcohols and esters whose boiling point under normal pressure is 150 degreeC or less. At least one solvent selected from the group consisting of compounds, ethers and water is mixed in an amount of 1 to 45% by weight based on the total weight of the powdery mixture, and the resulting mixture containing the solvent is formed into granules. After that, the molded product is dried, and a method for producing an additive composition for granular polyolefin resin, which is characterized in that: 2. The component (A) comprises 1,3: 2,4-dibenzylidene sorbitol, 1,3: 2,4-di (p-methylbenzylidene) sorbitol and 1,3: 2,4-di ( o-Methylbenzylidene) sorbitol, 1,3:
2,4-di (p-ethylbenzylidene) sorbitol,
1,3: 2,4-di (3,4-dimethylbenzylidene)
The method for producing a particulate additive for a polyolefin resin according to claim 1, which is at least one selected from the group consisting of sorbitol and 1,3: 2,4-di (2,4,5-trimethylbenzylidene) sorbitol. 3. The granular polyolefin resin according to claim 1, wherein the component (B) is at least one selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, antacids and lubricants. Of manufacturing additive composition for use. 4. The phenolic antioxidant is 2,6-di-t-butyl-4-methylphenol, 4,4′-butylidene-bis- (3-methyl-6-t-butylphenol), 2, 2'-methylene-bis- (4-methyl-6-
t-butylphenol), 1,1,3-tris- (2-
Methyl-4-hydroxy-5-t-butylphenol)
Butane, 3,9-bis- {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,1
0-tetraoxaspiro [5,5] undecane, 2,
2'-methylene-bis- (4-ethyl-6-t-butylphenol), triethylene glycol-bis [3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionate], tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, n-octadecyl-3 −
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 1,3,5-tris (3,5-
From the group consisting of di-t-butyl-4-hydroxybenzyl) isocyanurate and 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene. The method for producing an additive composition for granular polyolefin resin according to claim 3, wherein the additive composition is at least one selected. 5. The phosphorus-based antioxidant is tris (2,4-
Di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite, bis (2,4-di) -T-
Butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite and 2,2 -Methylene-bis- (4,6-di-t-
The method for producing an additive composition for granular polyolefin resin according to claim 3 or 4, which is at least one selected from the group consisting of butylphenyl) octylphosphite. 6. The antacid is at least one selected from the group consisting of saturated or unsaturated higher fatty acid metal salts having 8 to 32 carbon atoms and hydrotalcite.
A method for producing the additive composition for granular polyolefin resin according to any one of 1. 7. The antacid is lithium palmitate, sodium palmitate, potassium palmitate, magnesium palmitate, calcium palmitate, lithium stearate, sodium stearate, potassium stearate, magnesium stearate, calcium stearate and hydro. The method for producing an additive composition for granular polyolefin resin according to claim 6, which is at least one selected from the group consisting of talcite. 8. The lubricant is at least one selected from the group consisting of saturated or unsaturated higher fatty acid amides having 8 to 22 carbon atoms and glycerin esters of saturated or unsaturated higher fatty acids having 8 to 22 carbon atoms. A method for producing the additive composition for granular polyolefin resin according to any one of 3 to 7. 9. The lubricant according to claim 8, wherein the lubricant is at least one selected from the group consisting of stearic acid amide, oleic acid amide, erucic acid amide, glycerin monolauric acid ester, glycerin monostearic acid ester and glycerin distearic acid diester. A method for producing the additive composition for a granular polyolefin resin described. 10. The alcohol is methyl alcohol,
The additive particulate material for a polyolefin resin according to any one of claims 1 to 9, which is at least one selected from the group consisting of ethyl alcohol, n-propyl alcohol, isopropyl alcohol, t-butyl alcohol and sec-butyl alcohol. Production method. 11. The ester is at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate and ethyl propionate. A method for producing the additive composition for granular polyolefin resin according to any one of claims 1 to 10. 12. The ethers are selected from the group consisting of isopropyl ether, ethyl butyl ether, methyl cellosolve, diethyl cellosolve, cellosolve, ethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran, tetrahydropyran, dioxolane and methyldioxolane. It is at least 1 sort (s), The manufacturing method of the additive composition for granular polyolefin resins in any one of Claims 1-11. 13. A column having an average diameter of the cross section of 1 to 5 mm and an average length of 1 to 10 mm, a spherical shape having an average diameter of 1 to 5 mm, or an average of the long diameters. The additive composition for a granular polyolefin resin according to any one of claims 1 to 12, which is a plate having a value of 1 to 10 mm, an average value of minor axis of 1 to 5 mm, and an average value of thickness of 0.1 to 3 mm. Method of manufacturing things. 14. A granular polyolefin resin additive composition produced by the method according to any one of claims 1 to 13. 15. A polyolefin resin composition comprising the additive composition for granular polyolefin resin according to claim 14. 16. A polyolefin resin molded product obtainable by molding the polyolefin resin composition according to claim 15.