JP2002332359A - Particulate additive composition for polyolefin, its preparation process, polyolefin resin composition containing the additive composition and its molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an easily handleable additive composition for dibenzylidene sorbitol-containing polyolefins (DBSs) showing excellent nucleating agent properties and dispersibility. SOLUTION: The particulate additive composition contains (i) from 40 to 60 wt.% DBS having a melting point of >=250 deg.C and (ii) at least two additives for polyolefins selected from antioxidants (B), antacids (C) and lubricants (D). Here, at least one of the additives (ii) has a melting or softening point of <=140 deg.C. A powdery additive composition comprising (i) and (ii) is extruded using an extruder, wherein the temperature of the additive composition on the die plate is adjusted to from Tm to (Tm+30 deg.C) [wherein Tm is the lowest melting or softening point ( deg.C) of the additive having a melting or softening point of <=140 deg.C]. The extruded product is processed into a particulate additive composition, which is compounded with polyolefin resins.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful additive composition for particulate polyolefin, a method for producing the same, and a polyolefin resin composition containing the additive composition for particulate polyolefin.

[0002]

2. Description of the Related Art Dibenzylidene sorbitols (hereinafter abbreviated as "DBSs") are polyolefin resins,
Particularly, it is a compound industrially extremely useful as a nucleating agent for a homopolymer such as polyethylene or polypropylene or a copolymer 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 molding field of various containers and the like that require transparency.

[0003] The commercial forms of DBS so far are usually bulky fine powders. Therefore, when processing a polyolefin, DBSs are liable to be scattered in the air, and there is a problem with workability that handling and continuous automatic weighing are inconvenient.

Further, when these DBSs are used, generally, the powder flowability of the DBSs is poor, so that the DBSs tend to cause bridging in pipes and supply hoppers. There is a problem that supply is not constant.

[0005] Further, there is a problem that a tendency to cause blocking (a phenomenon in which particles are aggregated and aggregated together) during storage is observed.

[0006] Therefore, there is a demand for DBSs in a granular form that do not have these problems. However, DBSs,
In particular, DBSs having a melting point of 250 ° C. or higher generally have high self-aggregation properties and, furthermore, have a high melting point.
It is not industrially easy to uniformly dissolve or disperse in a molten resin.

[0007] DBSs are also used as a clarifying agent for polyolefin resins.
When BSs do not dissolve or disperse uniformly in the molten resin,
There is a problem that white spots are formed on the obtained molded body, and the appearance and transparency are impaired. 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.

[0008] It is expected that the above problems in working and environmental aspects will be solved if such DBSs are made into granules, but it is difficult to uniformly dissolve or disperse the granules in resin. It is thought to be even more difficult.

As a method for solving such a problem, WO
No. 98/33851 discloses that a mixture containing a DBS powder and a binder is stirred at a temperature not lower than the melting point or softening point of the binder and lower than the melting point of the DBS,
A method is disclosed in which the obtained compound is formed into granules or the obtained granules are pulverized. However, in this method, a binder, which is an undesirable heterogeneous component, is added to the polyolefin resin. Therefore, without containing the binder, which is a heterogeneous component, a strong dispersibility of the particulate DBS with good dispersibility in the polyolefin resin is obtained. There is a request.

[0010] Since many of the polyolefin additives added during molding are powders, the working environment can be improved.
As a method for granulating additives such as a flame retardant and an antioxidant for the purpose of improving powder fluidity and the like, a method using a binder (JP-A-9-324071, U.S. Pat.
No. 880), a method of dissolving a part of the additive (Japanese Unexamined Patent Publication No.
79056, JP-A-6-91152, JP-A-8-333
477) have been reported.

However, these reports do not describe granulation using DBSs at all, and whether these techniques can be applied to granulation of DBSs, and if applicable, granulated DBSs. Nothing is taught as to whether the compounds can be highly uniformly dispersed or dissolved in the molten resin.

[0012]

DISCLOSURE OF THE INVENTION The present invention provides a nucleating agent containing DBSs by adding a powdery mixture containing a DBSs powder and an additive powder for polyolefins without granules containing undesired foreign components. Excellent easiness of weighing during molding, safety such as dust proof and explosion proof, excellent transportability in pipes and hoppers, storage stability, etc., without generating dust, without impairing properties and solubility and dispersibility in polyolefin resin An object of the present invention is to provide a novel and useful particulate polyolefin additive composition which is easy to handle.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a component serving as a binder has been added to a polymer additive such as an antioxidant, an antacid and a lubricant. By selecting among them, it has been found that granulation of DBS can be achieved without using a binder which is an undesirable heterogeneous component.

More specifically, at least one selected from the group consisting of (i) an essential component DBS powder and (ii) an antioxidant, an antacid, and a lubricant usually added at the time of molding and processing a polyolefin resin. By extruding and granulating a mixture containing two kinds of polyolefin additive powder at a temperature at which at least one of the polyolefin additives melts or softens, the melted or softened component acts as a binder. It has been found that since the powdery components are mutually bonded, the workability and work environment are improved, and a novel particulate polyolefin additive composition having good storage stability and transportability can be obtained. Moreover, it has been surprisingly found that the particulate additive composition containing no binder has good solubility and dispersibility in a polyolefin resin.

The present invention has been completed based on such findings, and has been further studied.
A novel particulate additive composition comprising a DBS having a melting point of 50 ° C. or more and two or more additives for polyolefin;
It is intended to provide a production method thereof, a polyolefin resin composition obtained by blending the granular additive composition with a polyolefin resin, and a molded article obtained by molding the resin composition.

Item 1 (i) At least one dibenzylidene sorbitol (A) having a melting point of 250 ° C. or more and (ii) an antioxidant (B), an antacid (C) and a lubricant (D)
A particulate polyolefin additive composition comprising at least two types of polyolefin additives selected from the group consisting of: wherein the component (A) is 40 to 60% by weight of the total weight of the additive composition. Wherein at least one of the polyolefin additives (ii) has a melting point or softening point of 140 ° C. or lower, and (i) a component powder (A);
A powdery additive composition obtained by mixing at least two kinds of polyolefin additive powders selected from the group consisting of the component (B), the component (C) and the component (D), and subjecting the mixture to an extruder. The temperature of the additive composition in a die plate of an extruder is set in a temperature range of Tm to (Tm + 30) ° C (where,
Tm is the lowest melting point or softening point (° C) of the polyolefin additive having a melting point or softening point of 140 ° C or lower.
), And extruded (particularly, extruded in a string shape or plate shape (strip shape)), and obtained by processing the extruded product into granules.

Item 2. The particulate polyolefin according to Item 1, wherein the amount of the polyolefin additive having a melting point or softening point of 140 ° C. or lower is 5 to 30% by weight based on the total weight of the additive composition. Additive composition.

Item 3 The component (A) is 1,3: 2,4-di (p-methylbenzylidene) sorbitol, 1,3:
2,4-di (o-methylbenzylidene) sorbitol,
1,3: 2,4-di (3,4-dimethylbenzylidene)
Item 3. The particulate polyolefin additive composition according to Item 1 or 2, which is at least one member selected from the group consisting of sorbitol and 1,3: 2,4-di (2,4,5-trimethylbenzylidene) sorbitol.

Item 4 The component (B) is 2,6-di-t-butyl-4-methylphenol, triethylene glycol-bis- [3- (3-t-butyl-4-hydroxy-5
-Methylphenyl) propionate], tetrakis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, 1,3,5-tris (3,5-di-
t-butyl-4-hydroxybenzyl) -2,4,6-
Trimethylbenzene, tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, tetrakis (2,4-di-t-butyl)
(Butylphenyl) -4,4'-biphenylene-diphosphite and bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite at least one phenolic antioxidant or phosphorus-based oxidation Item 4. The additive composition for particulate polyolefin according to any one of Items 1 to 3, which is an inhibitor.

Item 5 The above item 1 wherein the component (C) is at least one antacid selected from the group consisting of metal salts of higher fatty acids having 8 to 28 carbon atoms, metal oxides, carbonates and hydrotalcite. 5. The additive composition for particulate polyolefin according to any one of items 1 to 4.

Item 6: The component (D) is a saturated or unsaturated higher fatty acid amide having 8 to 22 carbon atoms and 8 to 22 carbon atoms.
Item 1 is at least one selected from the group consisting of glycerin esters of saturated or unsaturated higher fatty acids of
6. The additive composition for granular polyolefin according to any one of claims 5 to 5.

Item 7. The polyolefin additive having a melting point or softening point of 140 ° C. or less is 2,6-di-t-butyl-4-methylphenol, 2,2′-methylene-bis- (4-methyl- 6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-
Hydroxy-5-methylphenyl) propionate],
Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane,
n-octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, distearylpentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4 , 4'-biphenylene-di-phosphonite, dilauryl-3,3 '
-Thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, calcium ricinoleate, calcium montanate, zinc stearate, zinc laurate, zinc behenate , Zinc ricinoleate, magnesium stearate, magnesium behenate, aluminum di- or tristearate, potassium stearate, sodium stearate, stearamide, oleamide, erucamide, glycerin monolaurate, glycerin monostearate Item 7. The particulate polyolefin additive composition according to any one of Items 1 to 6, which is at least one selected from the group consisting of glycerin distearic acid diester.

Item 8: The particle diameter d _{97 of the} component (A) is 150.
Item 8. The particulate polyolefin additive composition according to any one of Items 1 to 7, which has a size of not more than μm.

Item 9: A column having an average diameter of 1 to 5 mm and an average length of 1 to 5 mm, a spherical shape having an average diameter of 1 to 4 mm, or an average of a long diameter 1
Item 9. The additive composition for a granular polyolefin according to any one of Items 1 to 8, wherein the additive composition has a plate shape having a thickness of 1 to 4 mm, an average value of the minor axis of 1 to 3 mm, and an average value of the thickness of 0.1 to 2 mm.

Item 10. The method for producing a particulate polyolefin additive composition according to Item 1, wherein (i) the component (A) powder, (ii) the components (B), (C) and (D) )) Mixing at least two types of polyolefin additive powders selected from the group consisting of components, and using an extruder to obtain a powdery additive composition of the additive composition in a die plate of the extruder; The temperature is adjusted to a temperature range of Tm to (Tm + 30) ° C. (where Tm represents the lowest melting point or softening point (° C.) of the polyolefin additive having a melting point or softening point of 140 ° C. or less). A method for producing an additive composition for a granular polyolefin, comprising extruding (particularly, extruding into a string or a plate (strip)), and processing the obtained extrudate into a granule.

Item 11. The method for producing a particulate polyolefin additive composition according to Item 10, wherein the powdery additive composition is uniformly mixed before being subjected to an extrusion step using an extruder.

Item 12: A polyolefin additive having a melting point or softening point of 140 ° C. or less is extruded under a condition of melting or softening at least 5 to 20% by weight based on the total weight of the additive composition. Item 1 above
12. The method for producing a particulate polyolefin additive composition according to 0 or 11.

Item 13 Among the additives for polyolefin having a melting point or a softening point of 140 ° C. or less, the temperature of the additive composition on a die plate of an extruder is defined as Tm to (Tm +
30) A component which melts or softens when extruded after being adjusted to a temperature range of ° C. in an amount of 5 to 20% by weight based on the total weight of the obtained additive composition for particulate polyolefin. Item 13. The method for producing a particulate polyolefin additive composition according to Item 12 above.

Item 14. The additive for particulate polyolefin according to any one of Items 10 to 13, wherein the additive composition is extruded by controlling the fluctuation range of the temperature of the additive composition in the die plate within ± 5 ° C. A method for producing the composition.

Item 15. A polyolefin resin composition obtained by blending the particulate polyolefin additive composition according to any one of Items 1 to 9 with a polyolefin resin.

Item 16 A polyolefin resin molded article obtained by molding the polyolefin resin composition according to Item 15 above.

Item 17: The component (A) of (i) is 1,3:
2,4-di (p-methylbenzylidene) sorbitol, wherein at least one of the polyolefin additives (ii) is tetrakis [3- (3,5-di-t-butyl-4)].
Item 2. The particulate polyolefin additive composition according to Item 1, which is -hydroxyphenyl) propionyloxymethyl] methane, tris (2,4-di-t-butylphenyl) phosphite, and calcium stearate.

[0033]

DETAILED DESCRIPTION OF THE INVENTION Component (A): As the DBS compound DBS compounds used in the present invention (A), a variety of dibenzylidene sorbitols now known as a nucleating agent for polyolefin resins, 250 ° C. There is no particular limitation as long as it has the above melting point.

Among them, 1,3: 2,4-di (p-methylbenzylidene) sorbitol and 1,3: 2,4-di (o
-Methylbenzylidene) sorbitol, 1,3: 2,4
-Di (3,4-dimethylbenzylidene) sorbitol,
1,3: 2,4-di (2,4,5-trimethylbenzylidene) sorbitol and the like are exemplified, preferably 1,3:
2,4-di (p-methylbenzylidene) sorbitol and 1,3: 2,4-di (3,4-dimethylbenzylidene) sorbitol. These are used alone or in appropriate combination of two or more.

These DBSs are known and easily available, or are disclosed in JP-B-48-43748, JP-A-53-5156, JP-A-57-185287,
It can be produced according to a known method such as JP-A-2-231488. The crystal form is not particularly limited as long as the effects of the present invention can be obtained, and any crystal form such as hexagonal, monoclinic, and cubic can be used.

The amount of DBS is preferably 40 to 60% by weight based on the total weight of the particulate additive composition. Outside this range, the solubility and dispersibility in the polyolefin resin tend to be poor.

The particle size of the DBS to be used can be appropriately selected from a wide range, but it is generally preferable that the d ₉₇ particle size is 150 μm or less, preferably 100 μm or less. If d ₉₇ exceeds 150 μm, it tends to be difficult to obtain a granular material having good dispersibility.

In the present specification, d ₉₇ is measured by the method described in the section “d ₉₇ Particle Size of Dibenzylidene Sorbitol Powder” in the Examples section described later.

Polyolefin Additives The polyolefin additives used in the present invention are all known and commercially available either alone or as various mixtures.
It is easily available.

Component (B): Antioxidant As the antioxidant (B) according to the present invention, those used in the field of polyolefin resins can be widely used.
There is no particular limitation as long as the effects of the present invention are not impaired, but phenol-based antioxidants, phosphorus-based antioxidants and sulfur-based antioxidants are preferred. These are used alone or in appropriate combination of two or more. In particular, it is more preferable to use a combination of a phenolic antioxidant and a phosphorus-based antioxidant from the viewpoint of preventing oxidative deterioration during molding of a polyolefin resin.

As phenolic antioxidants, 2,6
-Di-t-butyl-4-methylphenol, 2,2'-
Methylene-bis- (4-methyl-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, octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 1,3,5-tris (3,5- Di-t-butyl-
4-hydroxybenzyl) isocyanurate, 1,3
5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene and the like are exemplified.

As the phosphorus antioxidant, tris (2,
4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-diphosphite, and bis (2,4- Di-t
-Butylphenyl) pentaerythritol diphosphite and the like.

Examples of the sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-
3,3′-thiodipropionate and distearyl-
3,3′-thiodipropionate and the like are exemplified.

These antioxidants are used in the form of powders which are generally available and have an average particle size of 10 to 500.
It is preferably about μm, especially about 20 to 300 μm.

Component (C): Antacid An antacid (C) includes saturated higher fatty acid metal salts,
Those used in the field of polyolefin resins such as metal oxides can be widely used.

Examples of the above-mentioned metal salts of saturated higher fatty acids include metal salts of saturated higher fatty acids having 8 to 28 carbon atoms, for example, octanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, eicosanoic acid. , Behenic acid, ricinoleic acid, montanic acid and the like, calcium salt, magnesium salt, zinc salt, barium salt, potassium salt, sodium salt, lithium salt and the like.

Examples of the metal oxide include oxides such as zinc oxide, magnesium oxide and titanium oxide, carbonates such as magnesium carbonate and calcium carbonate, particularly alkaline earth metal carbonates, and 6MgO.Al ₂ O _3.・ CO ₂・
12H ₂ O, 4MgO.Al ₂ O ₃ .CO ₂ .9H ₂ O, 4
_{MgO · Al 2 O 3 · CO} 2 · 6H 2 O, or ZnO · 3M
natural or synthetic hydrotalcites such _{gO · Al 2 O 3 · CO} 2 · 8-9H 2 O is exemplified. As commercially available hydrotalcite, for example, manufactured by Kyowa Chemical Industry Co., Ltd.
The trade name is DHT-4A.

The above-mentioned antacids are used alone or in combination of two or more. These antacids are usually used in the form of powder, and the average particle size is preferably about 5 to 500 μm, particularly preferably about 10 to 200 μm.

Component (D): Lubricant As the lubricant (D) component, a saturated or unsaturated higher fatty acid amide having 8 to 22 carbon atoms, a saturated or unsaturated higher fatty acid glycerin mono or di or triester having 8 to 22 carbon atoms is used. And those used in the field of polyolefin resins can be widely used.

Specific examples of the saturated or unsaturated higher fatty acid amide having 8 to 22 carbon atoms include myristic amide, palmitic amide, stearic amide, oleic amide, erucic amide, eicosamide, and the like. No. In particular, stearamide,
Oleic acid amide and erucic acid amide are preferred.

The saturated or unsaturated higher fatty acid glycerol esters having 8 to 22 carbon atoms include, specifically, fatty acids such as myristic acid, palmitic acid, stearic acid, oleic acid, erucic acid, eicosanoic acid and glycerin. And mono- or di- or triesters and mixtures thereof.

The above lubricants may be used alone or in combination of two or more. These lubricants are usually used in the form of powder, and the average particle size is 10 to 5
It is preferably about 00 μm, especially about 20 to 300 μm.

Granular Additive Composition The granular additive composition of the present invention is obtained by granulating DBSs using a component not desired in a polyolefin resin such as a binder used in the composition of WO98 / 33851. Rather, the component (B), which is a component originally used as an additive for polyolefin resins,
Of two or more components of component (C) and component (D), 1
Using at least one of components having a melting point or softening point of 40 ° C. or lower as a binder, DB as component (A)
Since it is intended to granulate S and contains no undesired components, it is more suitable for the needs of the polyolefin resin field.

In the granular additive composition of the present invention, the component acting as the binder melts or softens during the production thereof,
Particles of components other than the binder component are mutually bonded.

In the present invention, the component (B)
At least two of the component (C) and the component (D) are used. By using two or more kinds, 1) a compounding composition matching the physical properties of the required polyolefin is possible, and 2) the selection range of additives for the polyolefin having a melting point or softening point of 140 ° C. or less is widened. As a result, DBS can be granulated at a lower temperature. 3) There is no need to add each component individually, and there are advantages such as remarkable power saving and energy saving as compared with the related art.

In selecting at least two kinds of polyolefin additives selected from the above-mentioned components (B), (C) and (D), there is no particular limitation as long as the effects of the present invention can be obtained. It is important that at least one of the polyolefin additives has a melting point or softening point of 140 ° C. or less.

The amount of the polyolefin additive having a melting point or softening point of 140 ° C. or less is 5 to 30% by weight, based on the total weight of the granular additive composition of the present invention.
Particularly, 10 to 25% by weight is preferable. 5% by weight
If the amount is less than the above, the processing temperature becomes high because granulation is difficult unless other additives for polyolefin having a melting point or softening point exceeding 140 ° C. are melted or softened. For this reason, the obtained granulated material is yellow, which is undesirable because it causes coloring of the polyolefin resin. 140 ° C
Even if an additive for polyolefin having the following melting point or softening point is used in an amount exceeding 30% by weight based on the total weight of the granular additive composition of the present invention, no further advantage tends to be recognized.

The additives for the polyolefin having a melting point or softening point of 140 ° C. or less are not particularly limited as long as the effects of the present invention can be obtained. Antioxidants (B), antacids (C) and It can be selected from among the lubricants (D). As typical examples, specifically, 2,
6-di-t-butyl-4-methylphenol, 2,2 ′
-Methylene-bis- (4-methyl-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, distearylpentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite, dilauryl- 3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, calcium ricinoleate, calcium montanate, zinc stearate, zinc laurate , Zinc behenate, zinc ricinoleate, magnesium stearate, magnesium behenate, aluminum di- or tristearate, potassium stearate, sodium stearate, stearamide, oleamide, erucamide, glycerin monolaurate, glycerin Nosutearin ester, glycerin distearate phosphodiester like. These may be used alone or in combination of two or more.

The proportions of the components (B), (C) and (D) other than the polyolefin additive having a melting point or softening point of 140 ° C. or lower are determined by the ratio of the resin composition used. What is necessary is just to determine suitably according to required performance, the final use of a resin molded product, required performance, etc.

Generally, the total amount of at least two additives selected from the group consisting of the components (B), (C) and (D) is 40% of the total weight of the additive composition of the present invention. It is preferably about 60% by weight. In general, the component (B) is preferably appropriately selected and used from a usage range of about 0 to 50% by weight based on the total weight of the additive composition of the present invention. The components (C) and (D) are
Each is generally from 0 to 3 of the total weight of the additive composition of the present invention.
It is preferable to select and use appropriately from the usage amount range of about 0% by weight.

The polyolefin additive composition according to the present invention has a granular form. In the present specification, “granular” refers to a sphere, a column, a plate, or a shape similar thereto.

When the granular additive composition of the present invention is cylindrical, the average value of the diameter of the cross section thereof is 1 to 5 mm, especially 1.
It is preferably 5 to 4 mm, and the average value of the length is 1 to
It is preferably 5 mm, especially 1.5-4 mm. If the average value of the diameter and length exceeds 5 mm, the solubility and dispersibility deteriorate, and it is difficult to uniformly disperse in the resin, and if the average value of the diameter or length is less than 1 mm, it is blended with the polyolefin resin. At this time, a tendency is observed that the resin is fused to the lower part of the hopper or the inside of the pipe and becomes difficult to be uniformly dispersed in the resin.

In the case of a spherical shape, the average value of the diameter is 1 to
It is preferably 4 mm, especially 1.5 to 2 mm. In the case of a plate, the average value of the major axis is 1 to 4 mm, particularly 1.5 to 3 mm.
mm, average value of minor axis is 1 to 3 mm, especially 1.5 to 2 m
m, average thickness is 0.1 to 2 mm, especially 0.2 to 1 m
m is preferred. Average value of diameter, length and major axis is 4
If it exceeds mm, the solubility and dispersibility deteriorate, it becomes difficult to uniformly disperse in the resin, and, when the average value of the diameter or length is less than 1 mm, when blended with the polyolefin resin,
There is a tendency that the resin is fused to the lower part of the hopper or the inside of the pipe and becomes difficult to be uniformly dispersed in the resin.

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 is preferably 15 to 80 kg / cm ² , more preferably 20 to 70 kg / cm ² . is there. Within this range, it is difficult to break during transfer, has good solubility and dispersibility in the molten polyolefin resin, and suppresses the number of white spots.

In the present specification, the “hardness” is measured by the method described in the “hardness” section in the Examples section described later.

The additive composition for a granular polyolefin resin according to the present invention may optionally contain the components (B), (C) and (D) according to the purpose of use and its use. Other known modifiers for polyolefin resins other than the above can be used in combination as long as the effects of the present invention are not impaired. Specifically, examples thereof include modifying agents such as pigments, dyes, ultraviolet absorbers, antistatic agents, reinforcing agents, and antibacterial agents.

Production of Additive Composition for Granular Polyolefin
The granular additive composition for polyolefin according to the present invention is:
For example, it can be manufactured as follows.

The DBS powder as the component (A) and the additive powder for at least two kinds of the polyolefin resin of the components (B), (C) and (D), and if necessary the components (B), The additives for the polyolefin resin other than the components (C) and (D) are mixed in advance before the granulation step, and preferably uniformly mixed to prepare a powdery additive composition.
The method of mixing uniformly is not particularly limited as long as the effects of the present invention can be obtained, and for example, uniform mixing can be performed using a Nauta mixer, a Henschel mixer, a V blender, a ribbon blender, or the like.

Next, the uniformly mixed powdery additive composition is mixed with a single-screw or twin-screw extruder, and the temperature of the additive composition on a die plate is not less than Tm.
At a temperature of (Tm + 30) ° C. or less, for example, a diameter of 1
Extrude into a strand through a ~ 5 mm hole. Here, Tm (° C.) is 140 ° C. in the powdery additive composition.
It shows the melting point or softening point of the additive for polyolefin resin having the lowest melting point or softening point among the components having the following melting point or softening point.

In this specification, an extruder is used, and the temperature of the additive composition on the die plate of the extruder is set to T.
A component that melts or softens when extruded after being adjusted to a temperature of m to (Tm + 30) ° C. may be referred to as a “Tm component”.

The temperature of the powdery additive composition in the extruder (cylinder portion) up to the die plate is not particularly limited, and is adjusted, if necessary, to a temperature range from room temperature to (Tm + 30) ° C. do it.

In order to process the extrudate obtained through such an extrusion step into granules, for example, the following method can be adopted. For example, the extruded string strand can be cooled to room temperature and cut into a length of about 1 to 5 mm to obtain a cylindrical pellet. In addition, by cutting while the strand is extruded immediately after being extruded, pellets having a more uniform shape can be obtained. To produce spherical pellets, the cylindrical pellets produced by the above method, while soft, immediately round the corner using a sizing machine,
The shape may be spherical. Further, in order to obtain a plate-shaped pellet, it may be extruded from a die into a plate having a thickness of 0.1 to 2 mm and cut into a plate having the predetermined size. Further, in order to obtain plate-like pellets, a method of roughly pulverizing a plate-like molded product obtained by heating and compressing the powdery additive composition can be employed.

The method of cooling the extruded material from the extruded strand or die is not particularly limited.
A known method generally used in industry can be applied.
For example, a method using an inert gas, air, or the like cooled to room temperature or lower than room temperature may be mentioned, and cooling with air is preferably applied.

The powdery additive composition comprising the components (A) to (D) and, if necessary, the additive for polyolefin, can be obtained by heating at a temperature as low as possible to obtain a granular material having good dispersibility. Specifically, in order to melt or soften an additive for a polyolefin resin having a melting point of 140 ° C. or less, the powdery additive composition is heated to a temperature in the range of Tm to (Tm + 30) ° C. Is preferred.

When the lowest melting point or softening point of the binder component among the components (B) to (D) exceeds 140 ° C., the obtained granulated product tends to have poor solubility and dispersibility in polyolefin resin. The obtained granulated product exhibits a yellowish color, which is not preferable because it causes coloring of the polyolefin resin.

The polyolefin additive having a melting point or softening point of 140 ° C. or less is preferably melted or softened by 5 to 20% by weight, based on the total weight of the additive composition. If the ratio is out of this range, the resin tends to be broken at the time of transfer, and the solubility and dispersibility in the resin tend to be poor.

In order to melt or soften the polyolefin additive having a melting point or softening point of 140 ° C. or less based on the total weight of the additive composition, for example, the melting point or softening point of 140 ° C. or less A polyolefin additive having a melting point or softening point is used in an amount of 5 to 20% by weight, based on the total weight of the additive composition, and Tm to
It may be carried out by a method of extruding at a temperature of (Tm + 30) ° C., a method of melting or softening 5 to 20% by weight by controlling the temperature at the time of extrusion.

During the heat treatment, the fluctuation range of the temperature of the additive composition on the die plate is preferably smaller, and more preferably, the temperature can be controlled within a range of ± 5 ° C. By doing as described above, at least one of the components having a melting point or softening point of 140 ° C. or lower serves as a binder, and binds particles of other components that maintain a powder state, so that dust is not generated. Suppressed, improved transferability through pipes and hoppers, automatic continuous weighing is possible, easy to handle, and a good granular additive composition with no variation in solubility and dispersibility during molding is obtained. Can be

Polyolefin Resin Composition of the Present Invention The polyolefin resin composition of the present invention is obtained by blending the particulate polyolefin resin additive composition of the present invention with a polyolefin resin in a conventional manner.

For example, a polyolefin resin (powder or flake), the particulate polyolefin additive composition of the present invention,
And, if necessary, the polyolefin resin modifier is melt-kneaded at a desired temperature using a conventional kneading machine, for example, a single-screw or twin-screw extruder, and the extruded strand is cooled. And a method in which the obtained strand is cut into a pellet type by cutting. Further, a master batch of a granular additive composition containing the above-mentioned modifier for polyolefin resin in the granular additive composition of the present invention in advance can also be used.

The amount of the additive composition for a granular polyolefin resin according to the present invention is not particularly limited as long as a desired nucleating agent effect of DBS is obtained, and can be appropriately selected. Usually, the amount is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight in terms of DBS, based on 100 parts by weight of the polyolefin resin. By blending within these ranges, a desired DBS nucleating agent effect can be obtained.

Examples of the polyolefin resin according to the present invention include polyethylene resins, polypropylene resins and polybutene resins. More specifically, high-density polyethylene, medium-density polyethylene, linear polyethylene, ethylene content of 50 wt. % Ethylene copolymer, propylene homopolymer, propylene 50% or more propylene copolymer, butene homopolymer, butene content 50% or more butene copolymer, methylpentene homopolymer, methylpentene content 50% or more methylpentene copolymer, Examples thereof include polybutadiene.

The above 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 which can constitute the above copolymer include α-olefins such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene and dodecene;
-Bicyclo-type monomers such as endmethylenecyclohexene; (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate; and vinyl acetate.

Examples of the catalyst used for producing such a polymer include generally used Ziegler-Natta type catalysts and transition metal compounds (for example, titanium halides such as titanium trichloride and titanium tetrachloride). ) Is supported on a carrier containing magnesium halide such as magnesium chloride as a main component, and a catalyst system or a metallocene catalyst obtained by combining an alkylaluminum compound (eg, triethylaluminum, diethylaluminum chloride).

The recommended melt flow rate (hereinafter abbreviated as “MFR”; JIS K 7210-1976) of the polyolefin resin according to the present invention is appropriately selected depending on the molding method to be applied. 01 ~
200 g / 10 min, preferably 0.05 to 100 g / 1
0 minutes.

If necessary, the polyolefin resin composition according to the present invention may be appropriately added to conventionally known components other than the components (B), (C) and (D) according to the purpose of use and its use. The modifier for polyolefin resin may be used in combination as long as the effects of the present invention are not impaired.

Examples of such polyolefin resin modifiers include, for example, “Polylist Additives Handbook Revised Second Edition” edited by the Polyolefin Sanitation Council (1995, January).
), More specifically, ultraviolet absorbers (benzophenone-based compounds, benzotriazole-based compounds, etc.), surfactants, fillers (talc, mica, zeolite, perlite, Diatomaceous earth,
Calcium carbonate, glass fiber, etc.), foaming agents, foaming assistants, polymer additives, plasticizers, cross-linking agents, cross-linking accelerators, antistatic agents, anti-blocking agents, anti-fogging agents, polymer alloy components (block SBR or Random SB
R and rubbers such as hydrides thereof and polystyrene, etc.), flame retardants, dispersants, organic or inorganic pigments or dyes,
Various additives such as processing aids are exemplified.

Molded Article of the Present Invention When molding the resin composition according to the present invention, injection molding, extrusion molding, blow molding, air pressure molding, rotational molding,
Any of conventionally known forming methods such as film forming can be adopted. As the molding conditions, any conventionally used conditions can be used.

The molded article obtained by molding the polyolefin resin composition according to the present invention is applicable to the same fields as those in which a polyolefin resin molded article containing a DBS as a nucleating agent has been used. And more specifically, medical instruments such as disposable syringes, infusion / transfusion sets, and blood collection instruments that are sterilized by heat, radiation, or the like;
Packaging of foods and plants sterilized by radiation, etc .; various cases such as clothing cases and clothing storage containers; cups for hot-filling food; packaging containers for retort food; microwave containers; juices and teas For beverages, cosmetics, etc.
Containers for cans and bottles for pharmaceuticals, shampoos, etc .; Miso,
Containers and caps for seasonings such as soy sauce; food cases and containers such as water, rice, bread, and pickles; miscellaneous goods such as refrigerator cases; stationery; electric and mechanical parts;

In the molded article of the present invention, since the additive composition of the present invention has excellent dispersibility in a molten polyolefin resin, generation of white spots is suppressed.

[0092]

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. (A) DBSs ・ 1,3: 2,4-di (p-methylbenzylidene) sorbitol: trade name “Gelol MD”, manufactured by Shin Nippon Rika Co., Ltd. ・ 1,3: 2,4-di (3,3) 4-dimethylbenzylidene) sorbitol: trade name “Millad3988”,
1/3: 2,4-di (2,4,5-trimethylbenzylidene) sorbitol: a laboratory synthetic product (B) Antioxidant tetrakis [3- (3,5-di-t-butyl) -4-Hydroxyphenyl) propionyloxymethyl] methane: trade name “Irganox1010”, manufactured by Ciba Specialty Chemicals, melting point 110 to 125 ° C. n-octadecyl-3- (3 ′, 5′-di-t-butyl- 4′-hydroxyphenyl) propionate: trade name “Irgafos 1076”, manufactured by Ciba Specialty Chemicals, melting point 50-55 ° C. tris (2,4-di-t-butylphenyl) phosphite: trade name “Irgafos 168”, Ciba Specialty Chemicals, melting point 181-186 ° C (C) antacids Umm: trade name "calcium stearate CP", Nitto Kasei Kogyo Co., Ltd., melting point of 145 to 160
° C Hydrotalcite: trade name “DHT-4A”, manufactured by Kyowa Chemical Industry, melting point 200 ° C or higher (D) Lubricant • Glycerin monostearate and distearate mixture: trade name “Likemar S-100”, manufactured by Riken Vitamin Co. Melting point 66 ° C ・ Stearic acid amide: trade name “fatty acid amide S”,
Made by Kao, melting point 100-105 ° C ・ Oleic acid amide: trade name “fatty acid amide O-
N ", manufactured by Kao, melting point 70-78 ° C. Erucamide: trade name" fatty acid amide E ", manufactured by Kao, melting point 76-85 ° C. Also, the degree of dust generation of the particulate additive composition for polyolefin of the present invention, hardness, diameter and length, dispersibility, fluidity, storage stability, and dibenzylidene sorbitol powder particle diameter d ₉₇ of was measured as follows.

Dust generation degree A sample of 10 g was dropped from a height of 50 cm at a time, and the degree of dust generation after 5 seconds was visually judged and evaluated in the following three steps.

：: Dust was hardly generated. Δ: A small amount of dust was generated. X: Hardness of dust was extremely generated. Additive composition for granular polyolefin using Kiya type hardness tester KHT-20 (manufactured by Kiya Seisakusho). Hardness (breaking strength, k
g / cm ² ), converted to a value per unit area, and the average value of 10 measurements was calculated.

Additive composition 1 for columnar granular polyolefin obtained in diameter and length
About 0 pieces, the diameter and length were measured, and the average value of each was obtained.

The number of white spots based on undispersed dibenzylidene sorbitol in 10 polyolefin resin molded articles 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 is placed flat on one end of a stainless steel bat having a clean surface of 17 cm (Lcm ) in length, 13 cm in width and 1 cm in depth. One end of the bat where the sample is placed is raised in 1 cm increments, and then allowed to stand for 30 seconds. This operation is repeated, and the height of one end of the bat from the horizontal plane when almost the entire amount of the sample falls is measured. The same operation is repeated three times, and the average value (Hcm) is calculated. The angle of repose θ was calculated according to the following equation. The smaller the angle of repose θ, the better the fluidity.

Θ = sin ⁻¹ (H / L) Storage stability test The additive composition for granular polyolefin was prepared as follows:
It was put in a paper bag in an amount of 0 g, applied with a load of 1 kg / cm ² as a whole, and left in a constant temperature bath at 80 ° C. for 2 weeks. afterwards,
It was taken out of the oven, cooled to room temperature, and the presence or absence of blocking was visually determined. The case where blocking was not recognized was evaluated as ○, and the case where blocking was recognized was evaluated as ×.

[0099] dibenzylidene sorbitol powder having a particle diameter d ₉₇ laser diffraction / scattering particle size distribution analyzer ( "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 and the method for preparing and molding the polyolefin resin composition according to the present invention.

Method for Preparing Additive Composition for Granular Polyolefin A predetermined amount of DBS powder and a predetermined amount of additive powder for polyolefin were put into a 2 L Henschel mixer, and stirred and mixed at a rotation speed of 750 rpm for 3 minutes without heating. As a result of analyzing 1 g of the obtained powdery additive composition by HPLC,
It was confirmed that they were mixed uniformly.

Next, the powdery additive composition was set to a length of 255 m.
screw rotation speed 4 with a twin-screw extruder (S1 KRC kneader manufactured by Kurimoto Iron Works) having a diameter of 25 mm and a diameter of 25 mm.
The mixture was fed at 0 rpm at a rate of 100 g / min, and extruded from a die having nine holes with a diameter of 2 mm at an extrusion temperature of 120 ± 5 ° C. to obtain a cord-like strand. This was cooled to room temperature and cut into a length of about 2 mm to obtain a granular additive composition in the form of a cylindrical pellet.

[0103] The "extrusion temperature" refers to the temperature of the additive composition in the die plate.

Preparation of Polyolefin Resin Composition and Molding 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"). On the other hand, the pellet-shaped resin additive was blended so that the added amount of DBS was 0.2 parts by weight, and mixed for 3 minutes. Resin temperature 240 ° C
The mixture was melt-kneaded with a single screw extruder having a diameter of 25 mm set as described above and pelletized. Further, the pellets were repeatedly melt-kneaded twice under the same conditions.

The obtained pellets were injection-molded under the conditions of a resin temperature of 240 ° C. and a mold temperature of 40 ° C.
An mx 2 mm polyolefin resin molded product was obtained.

Example 1 180 g of 1,3: 2,4-di (p-methylbenzylidene) sorbitol having a particle diameter d ₉₇ of 100 μm, tetrakis
[3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (melting point 110
45 g of tris (2,4-di-t-butylphenyl) phosphite and 45 g of calcium stearate were added to 45 g of tris (2,4-di-t-butylphenyl) phosphite and 45 g of calcium stearate according to the above-mentioned "Preparation method of granular polyolefin additive composition", and the average value of diameter and length was used. Each obtained a columnar pellet of about 2 mm. The hardness of the obtained cylindrical pellet is 60 kg / cm ² and the angle of repose θ is 2
4 degrees. Further, Table 1 shows the degree of dust generation of the obtained granulated product and the evaluation results of the storage stability test.

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

In Tables 1 and 2, each abbreviation has the following meaning: "Me-DBS": 1,3: 2,4-bis-O- (p-
Methylbenzylidene) -D-sorbitol "3,4-DMDBS": 1,3: 2,4-bis-O-
(3,4-dimethylbenzylidene) -D-sorbitol “2,4,5-TDDMBS”: 1,3: 2,4-bis-O- (2,4,5-trimethylbenzylidene) -D-
Sorbitol Example 2 Example 1 except that the amount of tris (2,4-di-t-butylphenyl) phosphite was changed to 90 g instead of 45 g.
The same operation as described above was performed. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

Example 3 160 g of 1,3: 2,4-di (p-methylbenzylidene) sorbitol and tetrakis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane 40 g, tris (2,4-di-t-butylphenyl) phosphite 80
g and 80 g of calcium stearate, except that the same operation as in Example 1 was performed. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

Example 4 180 g of 1,3: 2,4-di (p-methylbenzylidene) sorbitol and tetrakis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane 36 g, tris (2,4-di-t-butylphenyl) phosphite 5
The same operation as in Example 1 was performed except that the preparation was performed from 2.2 g, 55.8 g of calcium stearate and 36 g of stearamide. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

Example 5 180 g of 1,3: 2,4-di (p-methylbenzylidene) sorbitol was added to a powdery additive composition, and tetrakis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane 18 g, tris (2,4-di-t-butylphenyl) phosphite 10
The same operation as in Example 1 was performed, except that 6.2 g and 55.8 g of calcium stearate were prepared. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

Comparative Example 1 A powdery additive composition was obtained in the same manner as in Example 1. Next, the powdery additive composition and the polypropylene resin were mixed in a Henschel mixer under non-heating conditions at a rotation speed of 750.
After stirring and mixing at 5 rpm for 5 minutes, the same operation as in Example 1 was performed. The angle of repose θ of the obtained granulated product was 70 degrees. Table 2 shows the evaluation results of the dispersibility of the obtained polypropylene molded articles. The abbreviations in Table 2 are the same as in Table 1.

Comparative Example 2 The extrusion temperature at the time of extruding the powdery additive composition was 160 ±
The same operation as in Example 1 was performed except that the temperature was changed to 5 ° C. Table 2 shows the evaluation results of the dispersibility of the obtained polypropylene molded articles.

Comparative Example 3 The same operation as in Example 1 was carried out except that the diameter of the hole in the die was 6 mm, and the additive composition for granular polyolefin in the form of cylindrical pellets having a diameter of about 6 mm and a length of about 6 mm was prepared. Was done. Table 2 shows the evaluation results of the dispersibility of the obtained polypropylene molded articles.

Comparative Example 4 The same operation as in Example 1 was performed except that the particle diameter d ₉₇ of 1,3: 2,4-di (p-methylbenzylidene) sorbitol was changed to 200 μm. Table 2 shows the evaluation results of the dispersibility of the obtained polypropylene molded articles.

Comparative Example 5 The extrusion temperature at the time of extruding the powdery additive composition was 125 ±
The same operation as in Example 1 was performed except that the temperature was changed to 15 ° C (110 to 140) ° C. Table 2 shows the results of evaluating the dispersibility of the obtained molded product of polypropylene.

Comparative Example 6 In the preparation of the powdery additive composition, 1,3: 2,4-
180 g of di (p-methylbenzylidene) sorbitol,
Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane 3
The same operation as in Example 1 was performed, except that 0 g, 30 g of tris (2,4-di-t-butylphenyl) phosphite, and 30 g of calcium stearate were used. Table 2 shows the evaluation results of the dispersibility of the obtained polypropylene molded articles.

Example 6 160 g of 1,3: 2,4-di (p-methylbenzylidene) sorbitol and tetrakis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane 40 g, tris (2,4-di-t-butylphenyl) phosphite 40
g, calcium stearate 40 g, and a mixture of glycerin monostearate and distearate (mp 66
° C) using 40 g and extruding at an extrusion temperature of 9
The same operation as in Example 1 was performed except that the temperature was set to 0 ± 5 ° C. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

Comparative Example 7 The extrusion temperature for extruding the powdery additive composition was 130 ±
The same operation as in Example 6 was performed except that the temperature was changed to 5 ° C. Table 2 shows the evaluation results of the dispersibility of the obtained polypropylene molded articles.

Example 7 1,3: 2,4-Di (3,4-di (p-methylbenzylidene) sorbitol)
The same operation as in Example 1 was performed except that 180 g of (dimethylbenzylidene) sorbitol was used. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

Example 8 1,3: 2,4-di (2,4,4-di (p-methylbenzylidene) sorbitol)
The same operation as in Example 1 was performed, except that 180 g of 5-trimethylbenzylidene) sorbitol was used. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

Example 9 Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane 4
Using 45 g of n-octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate instead of 5 g, the extrusion temperature at the time of extruding the powdery additive mixture was 65 ± 5 ° C. Other than that described above, the same operation as in Example 1 was performed. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated.
The evaluation results are shown in Table 1.

Example 10 In place of 40 g of a mixture of glycerin monostearate and distearate, stearic acid amide (melting point: 100 to 100 g) was used.
105 ° C.), and the same operation as in Example 6 was performed except that the extrusion temperature at the time of extruding the powdery additive mixture was 115 ± 5 ° C. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

Example 11 Oleic acid amide (melting point 70-78) was used in place of 40 g of glycerin monostearate and distearate mixture.
The same operation as in Example 6 was performed except that the extrusion temperature at the time of extruding the powdery additive mixture was set to 100 ± 5 ° C. using 40 g. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

Example 12 Erucic acid amide (melting point: 76-85) was used instead of glycerin monostearate and distearate mixture (40 g).
The same operation as in Example 6 was performed except that the extrusion temperature at the time of extruding the powdery additive mixture was set to 100 ± 5 ° C. using 40 g. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

Example 13 The same operation as in Example 1 was performed except that 45 g of hydrotalcite was used instead of 45 g of calcium stearate. The degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

Example 14 The same operation as in Example 12 was carried out except that the diameter of the hole in the die was 5 mm, and a granular additive composition in the form of a cylindrical pellet having a diameter of about 5 mm and a length of about 5 mm was prepared. Was.
With respect to the obtained granulated product, the degree of dust generation and storage stability of the obtained granulated product and the dispersibility of the polypropylene molded product were evaluated. The evaluation results are shown in Table 1.

[0128]

[Table 1]

[0129]

[Table 2]

Note: In Tables 1 and 2, a to i indicate the following additives.

A: Tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyloxymethyl] methane b: n-octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate c: tris (2,4-di- t-butylphenyl) phosphite d: calcium stearate e: mixture of glycerin monostearate and distearate f: stearamide g: oleamide h: erucamide i: hydrotalcite In Tables 1 and 2, D And L are
The average value of the diameter and length of the obtained cylindrical pellet is shown.

[0132]

According to the present invention, it has become possible to granulate a powder mixture containing DBS powder and additive powder for polyolefin. As a result, without including undesired heterogeneous components, and without impairing the nucleating agent properties of DBS and the solubility and dispersibility in polyolefin resins, easy weighing during molding, safety such as dust proof and explosion proof,
A novel and useful particulate polyolefin additive composition which is excellent in transportability and storage stability in pipes and hoppers and which is easy to handle without generating dust can be obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) C08K 3/22 C08K 3/22 3/26 3/26 5/053 5/053 5/098 5/098 5/13 5 / 13 5/20 5/20 5/3477 5/3477 5/52 5/52 C08L 23/00 C08L 23/00 // B29K 23:00 B29K 23:00 F term (reference) 4F070 AA13 AA15 AC13 AC14 AC15 AC16 AC36 AC37 AC42 AC43 AC47 AC48 AC55 AD01 AD04 DA11 DC07 FC05 4F071 AA15 AA20 AA84 AA85 AB18 AB21 AC05 AC09 AC10 AC11 AC12 AC15 AD02 AD06 AE11 AE22 AG28 AG29 BA01 BB06 4F201 AA03 AB01 AB06 AB07 AB08 AB19 AH55 BC01 BL43 BM06 4F207 AA03 AB06 AB07 AB08 AB19 AR06 KA01 KA17 KM15 KW26 4J002 BB031 BB121 DE078 DE108 DE138 DE218 DE238 EC056 EG058 EH039 EH049 EJ017 EJ027 EJ037 EP019 EU197 EW067 FD077 FD179 FD179 FD179 206

Claims (16)

[Claims] (I) at least one of dibenzylidene sorbitols (A) having a melting point of 250 ° C. or more, and (i)
i) a particulate polyolefin additive composition containing at least two kinds of polyolefin additives selected from the group consisting of an antioxidant (B), an antacid (C), and a lubricant (D); A) Component is 40 to 6 of the total weight of the additive composition.
0% by weight, wherein at least one of the polyolefin additives of (ii) has a melting point or softening point of 140 ° C. or lower, and (i) the component (A) powder, and (ii) (B) Component, at least two types of polyolefin additive powder selected from the group consisting of component (C) and component (D) are mixed, and the resulting powdery additive composition is extruded using an extruder. The temperature of the additive composition in the die plate is defined as Tm to (Tm + 3
And 0) ° C. (where Tm represents the lowest melting point or softening point (° C.) of the polyolefin additive having a melting point or softening point of 140 ° C. or less) and extruded. An additive composition for a granular polyolefin, which is obtained by processing an extrudate into a granular form. 2. The polyolefin additive having a melting point or softening point of 140 ° C. or less is used in an amount of 5 to 30% by weight based on the total weight of the additive composition.
The additive composition for a particulate polyolefin according to the above. 3. Component (A) is 1,3: 2,4-di (p
-Methylbenzylidene) sorbitol, 1,3: 2,4
-Di (o-methylbenzylidene) sorbitol, 1,
It is at least one selected from the group consisting of 3: 2,4-di (3,4-dimethylbenzylidene) sorbitol and 1,3: 2,4-di (2,4,5-trimethylbenzylidene) sorbitol. 3. The additive composition for granular polyolefin according to 1 or 2. 4. The composition according to claim 1, wherein the component (B) is 2,6-di-t-butyl-4-methylphenol or triethylene glycol-bis- [3- (3-t-butyl-4-hydroxy-5-methylphenyl). ) Propionate], tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxymethyl] methane, octadecyl-3
-(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 1,3,5-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tris ( 2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-diphosphite and bis (2,4 A particulate polyolefin according to any one of claims 1 to 3, which is at least one phenolic antioxidant or phosphorus antioxidant selected from the group consisting of (-di-t-butylphenyl) pentaerythritol diphosphite. Additive composition. 5. The component (C) is at least one antacid selected from the group consisting of metal salts of higher fatty acids having 8 to 28 carbon atoms, metal oxides, carbonates and hydrotalcite. 5. The additive composition for particulate polyolefin according to any one of items 1 to 4. 6. The component (D) is at least one selected from the group consisting of a saturated or unsaturated higher fatty acid amide having 8 to 22 carbon atoms and a glycerin ester of a saturated or unsaturated higher fatty acid having 8 to 22 carbon atoms. Certain claims 1-5
The additive composition for granular polyolefin according to any one of the above. 7. The polyolefin additive having a melting point or softening point of 140 ° C. or lower is 2,6-di-t-butyl-
4-methylphenol, 2,2'-methylene-bis-
(4-methyl-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, distearylpentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite, dilauryl-3,3'-
Thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, calcium ricinoleate, calcium montanate, zinc stearate, zinc laurate, zinc behenate; Zinc ricinoleate, magnesium stearate, magnesium behenate, aluminum or tristearate, potassium stearate, sodium stearate, stearamide, oleamide, erucamide, glycerin monolaurate, glycerin monostearate and The additive composition for a granular polyolefin according to any one of claims 1 to 6, wherein the additive composition is at least one selected from the group consisting of glycerin distearic acid diester. 8. The particulate polyolefin additive composition according to claim 1, wherein the component (A) has a particle diameter d ₉₇ of 150 μm or less. 9. A column having an average diameter of 1 to 5 mm and an average length of 1 to 5 mm or an average diameter of 1 to 5 mm.
4 mm spherical or average of major axis is 1 to 4 m
m, average value of minor axis is 1-3 mm, average value of thickness is 0.1
The granular polyolefin additive composition according to any one of claims 1 to 8, wherein the additive composition has a plate shape of 2 to 2 mm. 10. The method for producing a particulate polyolefin additive composition according to claim 1, wherein (i) the component (A) powder, (ii) the component (B), the component (C) and the component (D). )) Mixing at least two kinds of polyolefin additive powders selected from the group consisting of components, and obtaining a powdery additive composition,
Using an extruder, the temperature of the additive composition in the die plate of the extruder is set in a temperature range of Tm to (Tm + 30) ° C (where Tm is a temperature of the polyolefin having a melting point or softening point of 140 ° C or lower). A process for producing an additive composition for a granular polyolefin, comprising adjusting the material to the lowest melting point or softening point (° C.) of the additive, extruding the resultant, and processing the obtained extrudate into granules. 11. The method for producing a particulate polyolefin additive composition according to claim 10, wherein the powdery additive composition is uniformly mixed before being subjected to an extrusion step using an extruder. 12. The method according to claim 1, wherein the polyolefin additive having a melting point or softening point of 140 ° C. or less is extruded under conditions of melting or softening by 5 to 20% by weight based on the total weight of the additive composition. The method for producing a granular polyolefin additive composition according to claim 10 or 11, wherein 13. Among additives for polyolefin having a melting point or a softening point of 140 ° C. or less, the temperature of the additive composition on a die plate of an extruder is Tm to (Tm + 3).
0) The component which melts or softens when extruded after being adjusted to a temperature range of ° C. is used in an amount of 5 to 20% by weight based on the total weight of the obtained additive composition for particulate polyolefin. A method for producing the granular polyolefin additive composition according to claim 12. 14. The additive for a particulate polyolefin according to claim 10, wherein a temperature fluctuation range of the additive composition in the die plate is controlled and extruded within ± 5 ° C. A method for producing the composition. 15. A polyolefin resin composition obtained by blending the particulate polyolefin additive composition according to claim 1 with a polyolefin resin. 16. A polyolefin resin molded article obtained by molding the polyolefin resin composition according to claim 15.