JP5543304B2 - Antistatic polyolefin resin composition and molded article using the same - Google Patents

Description

  The present invention relates to a polyolefin-based resin composition having excellent crystallinity and antistatic properties and a molded product using the same, and particularly, a molded product having a short molding cycle and excellent transparency, strength, and antistatic properties. It is related with the polyolefin-type resin composition which can provide.

Polyolefin resins are excellent in molding processability, heat resistance, mechanical properties and the like and have an advantage of low specific gravity, and are widely used in various molded products such as films, sheets, and structural parts. On the other hand, since the polyolefin resin has a slow crystallization speed after molding, the molding cycle is long, and crystallization proceeds after heat molding to produce large crystals inside the molded product, resulting in a decrease in transparency and strength. There was a problem.
Polyolefin resins, while having excellent electrical insulation properties, tend to generate and accumulate static electricity, so that dust and the like adhere to the surface and are often contaminated. There has been a problem of lowering.

In order to improve these problems, conventionally, nucleating agents (crystal nucleating agents, crystallization accelerators, crystallization) for increasing the crystallization temperature of polyolefin resins and generating fine crystals rapidly during molding. Additives, nucleating agents, and nucleating agents) and kneading-type antistatic agents have been added to impart continuous antistatic properties to polyolefin resins (patents) Literatures 1-3).
However, the antistatic performance of these antistatic agents is not satisfactory, and there is a problem that the crystallinity of the resin at the time of molding is lowered by blending the antistatic agent with the polyolefin resin.
Further, fatty acid amides of aminoethylethanolamine have been proposed as antistatic agents for synthetic resins (Patent Documents 4 and 5). However, these documents do not describe crystallinity, and the antistatic property depends on the carbon number of the fatty acid. There is no description suggesting that the performance is different.

JP-A-6-67357 JP-A-8-183889 JP 2009-256474 A Japanese Patent Laid-Open No. 62-132946 Japanese Patent Laid-Open No. 11-302446

Accordingly, a first object of the present invention is to provide a polyolefin resin composition having excellent antistatic properties and crystallinity and having a short molding cycle during molding.
The second object of the present invention is to provide a polyolefin resin molded article having excellent antistatic properties as well as transparency and strength.

但し、式（１）中のＲ^１は炭素原子数１１〜１３のアルキル基、Ｒ^２は、水素原子又は−ＣＨ_２ＣＨ_２ＯＨである。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have added a specific amide compound and a nucleating agent to the polyolefin-based resin and have excellent antistatic properties, and are excellent. The inventors have found that a resin composition having crystallinity can be obtained, and have completed the present invention.
That is, in the present invention, 0.01 to 20 parts by mass of the compound (A) represented by the following general formula (1) and 0.001 to 0.001 of the nucleating agent (B) with respect to 100 parts by mass of the polyolefin resin. A polyolefin resin composition characterized by containing 10 parts by mass, and a molded article comprising the polyolefin resin composition.

However, ^{R 1} is an alkyl group having a carbon number of 11 to 13 in the formula (1), ^{R 2} is a hydrogen atom or _-CH 2 _CH 2 OH.

但し、式（２）中のＲ^３〜Ｒ^６は各々独立に、水素原子又は炭素原子数１〜９のアルキル基であり、Ｒ^７は炭素原子数１〜４のアルキリデンである。
Ｍ^１はアルカリ金属原子、アルカリ土類金属原子、ベリリウム原子、マグネシウム原子又はアルミニウム原子である。Ｍ^１がアルカリ金属原子である場合、ｓは１、且つｔは０であり、Ｍ^１がアルカリ土類金属原子、ベリリウム原子又はマグネシウム原子である場合、ｓは２、且つｔは０であり、Ｍ^１がアルミニウム原子である場合、ｓは１又は２、且つｔは３−ｓである。 The nucleating agent (B) is preferably a compound represented by any one of the following general formulas (2) to (4).

However, R < ³ > -R < ⁶ > in Formula (2) is respectively independently a hydrogen atom or a C1-C9 alkyl group, and R < ⁷ > is a C1-C4 alkylidene.
M ¹ is an alkali metal atom, an alkaline earth metal atom, a beryllium atom, a magnesium atom or an aluminum atom. When M ¹ is an alkali metal atom, s is 1 and t is 0; when M ¹ is an alkaline earth metal atom, beryllium atom or magnesium atom, s is 2 and t is 0; When M ¹ is an aluminum atom, s is 1 or 2, and t is 3-s.

但し、式（３）中のＲ^８は水素原子又は炭素原子数１〜９のアルキル基、Ｍ^２はアルカリ金属原子、アルカリ土類金属原子、ベリリウム原子、マグネシウム原子又はアルミニウム原子である。Ｍ^２がアルカリ金属原子である場合、ｙは１、且つｕは０であり、Ｍ^２がアルカリ土類金属原子、ベリリウム原子又はマグネシウム原子である場合、ｙは２、且つｕは０であり、Ｍ^２がアルミニウム原子である場合、ｙは１又は２、且つｕは３−ｙである。

However, R ⁸ in the formula (3) is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, M ² is an alkali metal atom, an alkaline earth metal atom, beryllium atom, a magnesium atom or an aluminum atom. When M ² is an alkali metal atom, y is 1 and u is 0; when M ² is an alkaline earth metal atom, beryllium atom or magnesium atom, y is 2 and u is 0; When M ² is an aluminum atom, y is 1 or 2, and u is 3-y.

但し、式（４）中のＲ^９〜Ｒ^１８は各々独立に、水素原子、炭素原子数１〜９のアルキル基、ヒドロキシル基、炭素原子数１〜９のアルコキシ基、炭素原子数１〜９のアルキレンオキシ基、アミノ基、炭素原子数１〜９のアルキルアミノ基、ハロゲン原子、フェニル基、アルキルフェニル基又は炭素原子数１〜９のシクロアルキル基である。任意の二つの隣接炭素に結合又は同一炭素に結合するアルキル基は、一緒になって炭化水素環を形成してもよい。
また、Ｍ^３はアルカリ金属原子、アルカリ土類金属原子、ベリリウム原子、マグネシウム原子又はアルミニウム原子である。Ｍ^３がアルカリ金属原子である場合、ａは２、且つｂは０であり、Ｍ^３がアルカリ土類金属原子、ベリリウム原子又はマグネシウム原子である場合、ａは１、且つｂは０であり、Ｍ^３がアルミニウム原子である場合、ａは１、且ｂは１である。

However, R ^{9 to} R ¹⁸ in formula (4) are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 9 carbon atoms, or 1 to 9 carbon atoms. An alkyleneoxy group, an amino group, an alkylamino group having 1 to 9 carbon atoms, a halogen atom, a phenyl group, an alkylphenyl group, or a cycloalkyl group having 1 to 9 carbon atoms. Alkyl groups bonded to any two adjacent carbons or bonded to the same carbon may be combined to form a hydrocarbon ring.
M ³ is an alkali metal atom, alkaline earth metal atom, beryllium atom, magnesium atom or aluminum atom. When M ³ is an alkali metal atom, a is 2 and b is 0; when M ³ is an alkaline earth metal atom, beryllium atom or magnesium atom, a is 1 and b is 0; When M ³ is an aluminum atom, a is 1 and b is 1.

  According to the present invention, it is possible to provide a polyolefin-based resin molded article having excellent antistatic properties and crystallinity, a short molding cycle during molding, and excellent transparency and strength.

  Examples of the polyolefin resin used in the polyolefin resin composition of the present invention include low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, Α-olefin polymer such as cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene / propylene block or Examples include α-olefin copolymers such as random copolymers.

  In the present invention, as the polyolefin-based resin, propylene-based polymers such as polypropylene, ethylene / propylene block or random copolymer, α-olefin / propylene block or random copolymer other than ethylene, and other α-olefin polymers. You may use the mixture with these.

但し、式（１）中のＲ^１は炭素原子数の１１〜１３のアルキル基であり、Ｒ^２は、水素原子又は−ＣＨ_２ＣＨ_２ＯＨである。
Ｒ^１の炭素原子数が１１未満であっても、１３を超えても、樹脂組成物に帯電防止性を付与することができない The polyolefin resin composition of the present invention contains a compound (A) represented by the following general formula (1).

However, ^{R 1} in the formula (1) is an alkyl group having 11 to 13 carbon atoms, ^{R 2} is a hydrogen atom or _-CH 2 _CH 2 OH.
Even if the number of carbon atoms in R ¹ is less than 11 or more than 13, the resin composition cannot be provided with antistatic properties.

As specific examples of the compound (A) represented by the general formula (1), the following compound No. Although 1-4 are mentioned, this invention is not limited to these compounds.

The nucleating agent (B) may be one generally used as a nucleating agent for polyolefin resins, and either an inorganic nucleating agent or an organic nucleating agent may be used.
Specific examples of inorganic nucleating agents include kaolinite, synthetic mica, clay, zeolite, silica, graphite, carbon black, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, and oxidation. Examples thereof include metal salts of neodymium and phenylphosphonate.
These inorganic nucleating agents may be modified with an organic substance in order to enhance dispersibility in the composition.

  Specific examples of organic nucleating agents include: alcoholate metal salts such as zinc glycerolate and zinc propanetriolate; lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate, sodium laurate, potassium laurate, Sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, barium stearate, sodium montanate, calcium montanate , Sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, sodium β-naphthalate, sodium cyclohexane Organic carboxylic acid metal salts such as ruboxylate; Organic sulfonates such as sodium p-toluenesulfonate and sodium sulfoisophthalate; Carboxylic acid amides such as trimesic acid tris (t-butylamide); Periods such as calcium pimelate and calcium suberate Table 2. Dicarboxylic acid salts of Group 2 elements; Rosin resin acids such as dehydroabithienic acid, dihydroabietic acid, dihydropimaric acid; Calcium, sodium dihydroabietate, potassium dihydroabietic acid, magnesium dihydroabietic acid, calcium dihydroabietic acid, sodium dihydropimate, potassium dihydropimate, dihydropima In addition to rosin-based resin acid metal salts such as magnesium lurate and calcium dihydropimarate; 2,2-methylbis (4,6-di-t-butylphenyl) sodium and the like, and represented by the following general formulas (2) to (9) Compounds.

上記一般式（２）であらわされる化合物は、芳香族リン酸エステルの金属塩化合物であり、式中のＲ^３〜Ｒ^６は各々独立に、水素原子又は炭素原子数１〜９のアルキル基、Ｒ^７は炭素原子数１〜４のアルキリデン基であり、Ｍ^１はアルカリ金属原子、アルカリ土類金属原子、ベリリウム原子、マグネシウム原子又はアルミニウム原子である。
また、Ｍ^１がアルカリ金属原子である場合、ｓは１、且つｔは０であり、Ｍ^１がアルカリ土類金属原子、ベリリウム原子又はマグネシウム原子である場合、ｓは２、且つｔは０であり、Ｍ^１がアルミニウム原子である場合、ｓは１又は２、且つｔは３−ｓである。 General formula (2):

The compound represented by the general formula (2) is a metal salt compound of an aromatic phosphate ester, and R ^{3 to} R ⁶ in the formula are each independently a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, R ⁷ is an alkylidene group having 1 to 4 carbon atoms, and M ¹ is an alkali metal atom, alkaline earth metal atom, beryllium atom, magnesium atom or aluminum atom.
When M ¹ is an alkali metal atom, s is 1 and t is 0. When M ¹ is an alkaline earth metal atom, beryllium atom or magnesium atom, s is 2 and t is 0. Yes, when M ¹ is an aluminum atom, s is 1 or 2, and t is 3-s.

Examples of the alkyl group having 1 to 9 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, amyl group, tertiary amyl group, A hexyl group, a heptyl group, an octyl group, an isooctyl group, a tertiary octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, and the like can be mentioned. R ^{3 to} R ⁶ are preferably a tertiary butyl group.
Examples of the alkylidene group having 1 to 4 carbon atoms include a methylene group, an ethylidene group, a propylidene group, and a butylidene group.

Examples of the alkali metal include lithium, sodium, and potassium, and examples of the alkaline earth metal include calcium and barium.
In particular, M ¹ is preferably an alkali metal atom because an excellent effect as a nucleating agent can be obtained.

  As the method for producing the compound, for example, a cyclic phosphoric acid having a corresponding structure and a metal compound such as a metal hydroxide, metal oxide, metal halide, metal sulfate, metal nitrate, or metal alkoxide compound are required. A method of reacting with a reactive agent such as a basic compound used according to the conditions, an alkali metal salt of a cyclic phosphate of the corresponding structure, a metal hydroxide, a metal oxide, a metal halide, a metal sulfate , A method of subjecting a metal compound such as a metal nitrate and a metal alkoxide compound to a salt exchange reaction using a reagent used as necessary, and cyclic phosphoric acid by hydrolysis using cyclic phosphorus oxychloride as a starting material. Examples thereof include a method of generating and reacting with a metal compound.

Specific examples of the compound represented by the general formula (2) include the following compounds Nos. 5 to 22. However, the present invention is not limited to these compounds.

上記一般式（３）で表わされる化合物は、安息香酸誘導体の金属塩化合物であり、式中のＲ^８は水素原子又は炭素原子数１〜９のアルキル基であり、Ｍ^２はアルカリ金属原子、アルカリ土類金属原子、ベリリウム原子、マグネシウム原子又はアルミニウム原子である。
また、Ｍ^２がアルカリ金属原子である場合、ｙは１、且つｕは０であり、Ｍ^２がアルカリ土類金属原子、ベリリウム原子又はマグネシウム原子である場合、ｙは２、且つｕは０であり、Ｍ^２がアルミニウム原子である場合、ｙは１又は２、且つｕは３−ｙである。 General formula (3):

The compound represented by the general formula (3) is a metal salt compound of a benzoic acid derivative, in which R ⁸ is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, M ² is an alkali metal atom, An alkaline earth metal atom, a beryllium atom, a magnesium atom or an aluminum atom.
When M ² is an alkali metal atom, y is 1 and u is 0, and when M ² is an alkaline earth metal atom, beryllium atom or magnesium atom, y is 2 and u is 0. Yes, when M ² is an aluminum atom, y is 1 or 2, and u is 3-y.

Examples of the alkyl group having 1 to 9 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, amyl notation, tertiary amyl group, Examples include a hexyl group, a heptyl group, an octyl group, an isooctyl group, a tertiary octyl group, a 2-ethylhexyl group, a nonyl group, and an isononyl group.
In particular, R ⁸ is preferably a hydrogen atom or a tertiary butyl group because of its excellent effect as a nucleating agent.

Examples of the alkali metal include lithium, sodium, and potassium, and examples of the alkaline earth metal include calcium and barium.
In particular, M ² is preferably an alkali metal atom because an excellent effect as a nucleating agent can be obtained.

  Specific examples of the compound represented by the general formula (3) include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, aluminum benzoate, 4-tert-butylbenzoate. An acid aluminum salt etc. are mentioned. However, the present invention is not limited to these compounds.

一般式（４）で表される化合物は、飽和二環式ジカルボン酸塩であり、式中のＲ^９〜Ｒ^１８は各々独立に、水素原子、炭素原子数１〜９のアルキル基、ヒドロキシル基、炭素原子数１〜９のアルコキシ基、炭素原子数１〜９のアルキレンオキシ基、アミノ基、炭素原子数１〜９のアルキルアミノ基、ハロゲン原子、フェニル基、アルキルフェニル基、又は炭素原子数１〜９のシクロアルキル基である。
また、任意の二つの隣接炭素に結合又は同一炭素に結合するアルキル基は、一緒になって炭化水素環を形成してもよい。 General formula (4):

The compound represented by the general formula (4) is a saturated bicyclic dicarboxylate, and R ^{9 to} R ¹⁸ in the formula are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, or a hydroxyl group. , An alkoxy group having 1 to 9 carbon atoms, an alkyleneoxy group having 1 to 9 carbon atoms, an amino group, an alkylamino group having 1 to 9 carbon atoms, a halogen atom, a phenyl group, an alkylphenyl group, or the number of carbon atoms 1 to 9 cycloalkyl groups.
Moreover, the alkyl group couple | bonded with arbitrary two adjacent carbons, or couple | bonded with the same carbon may form a hydrocarbon ring together.

In the formula, M ³ is an alkali metal atom, an alkaline earth metal atom, a beryllium atom, a magnesium atom or an aluminum atom, and when M ³ is an alkali metal atom, a is 2, and b is 0. ^{When 3} is an alkaline earth metal atom, beryllium atom or magnesium atom, a is 1 and b is 0. When M ³ is an aluminum atom, a is 1 and b is 1.

Examples of the alkyl group having 1 to 9 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, amyl notation, tertiary amyl group, A hexyl group, a heptyl group, an octyl group, an isooctyl group, a tertiary octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, etc. are mentioned, and an alkoxy group having 1 to 9 carbon atoms, an alkyleneoxy group, and an alkylamino group are And groups corresponding to the alkyl groups having 1 to 9 carbon atoms described above.
In particular, R ^{9 to} R ¹⁸ are preferably hydrogen atoms because of excellent effects as a nucleating agent.

Examples of the alkali metal include lithium, sodium, and potassium, and examples of the alkaline earth metal include calcium and barium.
In particular, M ³ is preferably an alkali metal atom because an excellent effect as a nucleating agent can be obtained.

一般式（５）で表される化合物は、飽和二環式ジカルボン酸塩であり、式中のＲ^１９〜Ｒ^２６は各々独立に、水素原子、炭素原子数１〜９のアルキル基、ヒドロキシル基、炭素原子数１〜９のアルコキシ基、炭素原子数１〜９のアルキレンオキシ基、アミノ基、炭素原子数１〜９のアルキルアミノ基、ハロゲン原子、フェニル基、アルキルフェニル基、又は炭素原子数１〜９のシクロアルキル基である。
また、任意の二つの隣接炭素に結合又は同一炭素に結合するアルキル基は、一緒になって炭化水素環を形成してもよい。 General formula (5):

The compound represented by the general formula (5) is a saturated bicyclic dicarboxylate, and R ^{19 to} R ²⁶ in the formula are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, or a hydroxyl group. , An alkoxy group having 1 to 9 carbon atoms, an alkyleneoxy group having 1 to 9 carbon atoms, an amino group, an alkylamino group having 1 to 9 carbon atoms, a halogen atom, a phenyl group, an alkylphenyl group, or the number of carbon atoms 1 to 9 cycloalkyl groups.
Moreover, the alkyl group couple | bonded with arbitrary two adjacent carbons, or couple | bonded with the same carbon may form a hydrocarbon ring together.

M ⁴ is an alkali metal atom, an alkaline earth metal atom, a beryllium atom, a magnesium atom, or an aluminum atom, and when M ⁴ is an alkali metal atom, a is 2 and b is 0, and M ⁴ Is an alkaline earth metal atom, beryllium atom or magnesium atom, a is 1 and b is 0; when M ⁴ is an aluminum atom, a is 1 and b is 1.

Examples of the alkyl group having 1 to 9 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, amyl notation, tertiary amyl group, Examples include a hexyl group, a heptyl group, an octyl group, an isooctyl group, a tertiary octyl group, a 2-ethylhexyl group, a nonyl group, and an isononyl group.
Examples of the alkoxy group having 1 to 9 carbon atoms, the alkyleneoxy group, and the alkylamino group include groups corresponding to the alkyl groups having 1 to 9 carbon atoms.

Examples of the alkali metal include lithium, sodium, and potassium, and examples of the alkaline earth metal include calcium and barium.
In particular, M ⁴ is preferably an alkali metal atom because an excellent effect as a nucleating agent can be obtained.

上記一般式（６）で表される化合物はジカルボン酸塩であり、式中のＲ^２７〜Ｒ^３６は各々独立に、水素原子、炭素原子数１〜９のアルキル基、ヒドロキシル基、炭素原子数１〜９のアルコキシ基、炭素原子数１〜９のアルキレンオキシ基、アミノ基、炭素原子数１〜９のアルキルアミノ基、ハロゲン原子、フェニル基、アルキルフェニル基、又は炭素原子数１〜９のシクロアルキル基である。
また、任意の二つの隣接炭素に結合又は同一炭素に結合するアルキル基は、一緒になって炭化水素環を形成してもよい。 General formula (6):

The compound represented by the general formula (6) is a dicarboxylic acid salt, and R ^{27 to} R ³⁶ in the formula are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a hydroxyl group, or the number of carbon atoms. An alkoxy group having 1 to 9 carbon atoms, an alkyleneoxy group having 1 to 9 carbon atoms, an amino group, an alkylamino group having 1 to 9 carbon atoms, a halogen atom, a phenyl group, an alkylphenyl group, or an alkyl group having 1 to 9 carbon atoms A cycloalkyl group;
Moreover, the alkyl group couple | bonded with arbitrary two adjacent carbons, or couple | bonded with the same carbon may form a hydrocarbon ring together.

M ⁵ is an alkali metal atom, alkaline earth metal atom, beryllium atom, magnesium atom or aluminum atom, and when M ⁵ is an alkali metal atom, v is 2 and w is 0, and M ⁵ is an alkali When it is an earth metal atom, beryllium atom or magnesium atom, v is 1 and w is 0. When M ⁵ is an aluminum atom, v is 1 and w is 1.

Examples of the alkyl group having 1 to 9 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, amyl notation, tertiary amyl group, A hexyl group, a heptyl group, an octyl group, an isooctyl group, a tertiary octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, etc. are mentioned, and an alkoxy group having 1 to 9 carbon atoms, an alkyleneoxy group, and an alkylamino group are And those corresponding to the aforementioned alkyl group having 1 to 9 carbon atoms.
In particular, R ^{27 to} R ³⁶ are preferably hydrogen atoms because of excellent effects as a nucleating agent.

Examples of the alkali metal include lithium, sodium, and potassium, and examples of the alkaline earth metal include calcium and barium.
In particular, M ⁵ is preferably an alkali metal atom or a calcium atom because an excellent effect as a nucleating agent can be obtained.

一般式（７）で表される化合物は、ジベンジリデンソルビトール化合物であり、式中のｎは０、１又は２であり、Ｒ^３７〜Ｒ^４１は、各々独立に、水素原子、ハロゲン原子、炭素原子数１〜４のアルキル基、炭素原子数２〜４のアルコキシ基、炭素原子数２〜４のアルケニル基、炭素原子数１〜４のヒドロキシアルキル基、炭素原子数１〜４のハロゲン化アルキル基又は炭素原子数１〜４のヒドロキシハロゲン化アルキル基である。 General formula (7):

The compound represented by the general formula (7) is a dibenzylidene sorbitol compound, in which n is 0, 1 or 2, and R ^{37 to} R ⁴¹ each independently represent a hydrogen atom, a halogen atom, a carbon An alkyl group having 1 to 4 atoms, an alkoxy group having 2 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, and an alkyl halide having 1 to 4 carbon atoms Or a hydroxyhalogenated alkyl group having 1 to 4 carbon atoms.

  Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group, and an isobutyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the alkenyl group having 2 to 4 carbon atoms include allyl group and 3-methylallyl group. Examples of the hydroxyalkyl group having 1 to 4 carbon atoms include 1-hydroxypropyl group and 1,2,3-trihydroxypropyl group. Examples of the halogenated alkyl group having 1 to 4 carbon atoms include a 1,2-dibromopropyl group. Examples of the hydroxyhalogenated alkyl group having 1 to 4 carbon atoms include a 1-hydroxy-2-bromopropyl group.

Specific examples of the compound represented by the general formula (7) include the following compound Nos. 23-No. However, the present invention is not limited to these compounds.

一般式（８）で表される化合物はアミド系化合物であり、式中のＲ^４２は、炭素原子数２〜３０の飽和若しくは不飽和脂肪族又は芳香族の２〜６価のポリカルボン酸残基であり、ｚは２〜６の整数である。
また、Ｘは各々独立に、Ｒ^４３−（Ｒ^４４）_ｄで表される基であって、Ｒ^４３は炭素原子数５〜１２のシクロアルキル基、Ｒ^４４は炭素原子数１〜１０の直鎖状又は分岐状のアルキル基であり、ｄは１〜３の整数である。 General formula (8):

The compound represented by the general formula (8) is an amide compound, and R ^{42 in} the formula is a residue of a saturated or unsaturated aliphatic or aromatic 2-6 valent polycarboxylic acid having 2 to 30 carbon atoms. And z is an integer of 2-6.
Also, X is ^{independently, R} 43 ^{- (R} ₄₄₎ a group represented by ^{_d, R 43} is a cycloalkyl group having 5 to 12 carbon ^{atoms, R 44} is a straight C10 carbon atoms It is a chain or branched alkyl group, and d is an integer of 1 to 3.

Wherein the polycarboxylic acid residue, R ^{42 -} (COOH) is a residue obtained by removing all the carboxyl groups from an aliphatic or aromatic polycarboxylic acid represented by _z, z the same valence and, That is, it is a 2-6 valent group, and C2-C30 is carbon number which the polycarboxylic acid residue obtained by remove | excluding all the carboxyl groups of the said aliphatic or aromatic polycarboxylic acid has.
As the aliphatic polycarboxylic acid, a saturated or unsaturated polycarboxylic acid having 2 to 6 carboxyl groups is preferable, and an aliphatic polycarboxylic acid having 3 or 4 carboxyl groups is particularly preferable.

  Examples of the aromatic polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Examples of the aliphatic polycarboxylic acid include diphenylmalonic acid, succinic acid, phenylsuccinic acid, diphenylsuccinic acid, and glutar. Acid, 3,3-dimethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, citric acid Acid, methanetricarboxylic acid, ethanetricarboxylic acid, propanetricarboxylic acid, propenetricarboxylic acid, camphoronic acid, butanetricarboxylic acid, pentanetricarboxylic acid, hexanetricarboxylic acid, heptanetricarboxylic acid, octanetricarboxylic acid, nonanetricarboxylic acid, decanetricarboxylic acid Acetoxypropanetricarboxylic acid, acetoxypentanetricarboxylic acid, acetoxyheptanetricarboxylic acid, ethanetetracarboxylic acid, propanetetracarboxylic acid, butanetetracarboxylic acid, pentanetetracarboxylic acid, dodecanetetracarboxylic acid, pentanepentacarboxylic acid, acetoxypentanepentacarboxylic acid , Pentane hexacarboxylic acid, tetradecan hexacarboxylic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylene glycol bis (β-aminoethyl ether) N, N, N ′, N′-tetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethyl Ethylenediamine-N, N ′, N′-triacetic acid, 1,3-diaminopropan-2-ol-N, N, N ′, N′-tetraacetic acid, 1,2-diaminopropane-N, N, N ′ , N′− Examples include tetraacetic acid, triethylenetetramine hexaacetic acid, nitrilotripropionic acid, 1,6-hexamethylenediaminetetraacetic acid, N- (2-carboxyethyl) iminodiacetic acid, and the like.

The group R ⁴³ — (R ⁴⁴ ) _d corresponding to X is a residue obtained by removing the amino group of the monoamine represented by H ₂ N—R ⁴³ — (R ⁴⁴ ) _d , and specific examples of monoamines As cyclopentylamine, cyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, cycloheptylamine, cyclooctylamine, cyclododecylamine, 2,3-dimethylcyclohexylamine, 2,4-dimethylcyclohexylamine, 2 , 5-dimethylcyclohexylamine, 2,6-dimethylcyclohexylamine, 2,4,6-trimethylcyclohexylamine and other cycloalkylamines.

  Among these, 2-alkylcyclohexylamine is particularly preferable, for example, 2-methylcyclohexylamine, 2-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 2-iso-propylcyclohexylamine, 2-n-butyl. Cyclohexylamine, 2-iso-butylcyclohexylamine, 2-sec-butylcyclohexylamine, 2-tert-butylcyclohexylamine, 2-n-pentylcyclohexylamine, 2-n-hexylcyclohexylamine, 2-n-heptylcyclohexylamine , 2-n-octylcyclohexylamine, 2-ethylhexylcyclohexylamine, 2-n-nonylcyclohexylamine, 2-n-decylcyclohexylamine, etc. Jo or a branched alkyl group of 2-alkyl-cyclohexylamine cis form of include trans-form or a mixture thereof.

The amide compound represented by the general formula (8) can be obtained by reacting the monoamine with the polycarboxylic acid, polycarboxylic anhydride, or polycarboxylic acid chloride.
Specific examples of the compound represented by the general formula (8) include the following compound Nos. 31-No. 35, but the present invention is not limited to these compounds.

一般式（９）で表される化合物は、ジアミド系化合物であり、式中のＲ^４５は、炭素数１〜２４の脂肪族ジアミン残基又は脂環族ジアミン残基又は芳香族ジアミン残基である。
また、Ｒ^４６、Ｒ^４７はそれぞれ独立に、炭素数３〜１４のシクロアルキル基、シクロアルケニル基、フェニル基、炭素原子数１〜４の直鎖状若しくは分岐状のアルキル基を有するフェニル基、炭素原子数２〜４の直鎖状若しくは分岐状のアルケニル基を有するフェニル基、炭素原子数１〜４の直鎖状若しくは分岐状のアルキル基を有するシクロヘキシル基、炭素原子数２〜４の直鎖状若しくは分岐状のアルケニル基を有するシクロヘキシル基、又は、フェニルメチレン基、フェニルエチレン基、フェニルプロピレン基、シクロヘキシルメチレン基、シクロヘキシルエチレン基又はシクロヘキシルプロピレン基である。 General formula (9):

The compound represented by the general formula (9) is a diamide compound, and R ^{45 in} the formula is an aliphatic diamine residue, an alicyclic diamine residue or an aromatic diamine residue having 1 to 24 carbon atoms. is there.
R ⁴⁶ and R ⁴⁷ are each independently a cycloalkyl group having 3 to 14 carbon atoms, a cycloalkenyl group, a phenyl group, a phenyl group having a linear or branched alkyl group having 1 to 4 carbon atoms, A phenyl group having a linear or branched alkenyl group having 2 to 4 carbon atoms, a cyclohexyl group having a linear or branched alkyl group having 1 to 4 carbon atoms, a straight chain having 2 to 4 carbon atoms A cyclohexyl group having a chain or branched alkenyl group, or a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a cyclohexylmethylene group, a cyclohexylethylene group, or a cyclohexylpropylene group.

  Examples of the cycloalkyl group having 3 to 14 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a cyclodecyl group.

Examples of the alkyl group of a cyclohexyl group having a linear or branched alkyl group having 1 to 4 carbon atoms and a phenyl group having a linear or branched alkyl group having 1 to 4 carbon atoms include, for example, Methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group and the like.

  Examples of the alkenyl group of a phenyl group having a linear or branched alkenyl group having 2 to 4 carbon atoms and a cyclohexyl group having a linear or branched alkenyl group having 2 to 4 carbon atoms include: , Allyl group, 3-methylallyl group and the like.

  In the present invention, particularly from the viewpoint of crystallization and antistatic properties, the nucleating agent (B) is at least one compound selected from the compounds represented by the general formulas (2) to (4). Is preferably used.

The compounding quantity of the compound (A) in the polyolefin resin composition of this invention is 0.01-20 mass parts with respect to 100 mass parts of polyolefin resin, and it is preferable that it is 0.05-15 mass parts. It is more preferable that it is 1-10 mass parts.
Moreover, the compounding quantity of a nucleating agent (B) is 0.001-10 mass parts with respect to 100 mass parts of polyolefin resin, and it is preferable that it is 0.005-5 mass parts, 0.01- More preferably, it is 3 parts by mass. When the blending amount of the nucleating agent (B) is less than 0.001 part by mass, the effect as a nucleating agent does not appear, and when it exceeds 5 parts by mass, the physical properties of the resin are lowered.

  The compounding method of the compound (A) and the nucleating agent (B) is not particularly limited, and any commonly used method can be arbitrarily used. For example, roll kneading, bumper kneading, an extruder, a kneader, etc. What is necessary is just to mix and knead and mix | blend.

In the present invention, the compound (A) may be added to the polyolefin resin as it is, but if necessary, the compound (A) may be added after impregnating the carrier.
As a method for impregnating the carrier, a method of heating and mixing the compound (A) and the carrier as they are, or if necessary, diluting the compound (A) with an organic solvent and impregnating the carrier, and then removing the solvent. There is a way to do it.

As the carrier, those known as synthetic resin fillers and fillers, or solid flame retardants and light stabilizers at room temperature can be used. For example, calcium silicate powder, silica powder, talc powder, alumina powder, oxidation powder Examples thereof include titanium powder, those obtained by chemically modifying the surface of these carriers, and solid materials among the flame retardants and antioxidants listed below.
Among these carriers, those obtained by chemically modifying the surface of the carrier are preferably used, and those obtained by chemically modifying the surface of the silica powder with a silane coupling agent are more preferred. The average particle diameter of these carriers is preferably 0.1 to 100 μm, and more preferably 0.5 to 50 μm.

  The polyolefin resin composition of the present invention may be further added with a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, an ultraviolet absorber, a hindered amine-based light stabilizer, and the like as necessary. Well, by doing so, the polyolefin resin composition of the present invention can be stabilized.

Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) ) Isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) ) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-ditert Tributyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bis [ 3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl ] Terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3 -Tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane , Triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.
The amount of these phenolic antioxidants added is preferably 0.001 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

Examples of the phosphorus antioxidant include trisnonylphenyl phosphite and tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl]. Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1 , 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Tributylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6- Tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) Oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, and the like.
The addition amount of these phosphorus antioxidants is preferably 0.001 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-alkylmercaptopropionate). Kind.
The amount of these thioether-based antioxidants added is preferably 0.001 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyolefin resin.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert. Octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis ( 2- (2′-hydroxyphenyl) such as tert-octyl-6- (benzotriazolyl) phenol) and 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole Benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-di Benzoates such as tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxy Substituted oxanilides such as zanylide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3 Cyanoacrylates such as methyl-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s- Triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2, And triaryltriazines such as 4-ditertiarybutylphenyl) -s-triazine.
The addition amount of these ultraviolet absorbers is preferably 0.001 to 30 parts by mass, particularly preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-4-piperidyl) Sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 -Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2, 6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (Tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditertiary Butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2, 2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl- 4-piperidylamino) Xanthane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6 , 6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2 6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] hindered amine compounds such as aminoundecanoic the like.
The amount of these hindered amine light stabilizers added is preferably 0.001 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the polyolefin resin.

  The polyolefin resin composition of the present invention is further added with at least one selected from the group consisting of an alkali metal or alkaline earth metal salt, a surfactant and a polymer antistatic agent, if necessary. Thus, the antistatic property of the polyolefin resin composition can be further improved.

Examples of the alkali metal or alkaline earth metal salt include monocarboxylic acid or dicarboxylic acid having 1 to 20 carbon atoms (for example, formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, etc.), and sulfonic acid having 1 to 20 carbon atoms (for example, Methanesulfonic acid, p-toluenesulfonic acid, etc.), alkali metals, alkaline earth metals and salts of organic acids such as thiocyanic acid, hydrohalic acids (eg hydrochloric acid, hydrobromic acid, etc.), hydrobromic acid, peroxy Preferred examples include salts of inorganic acids such as chloric acid, sulfuric acid and phosphoric acid. Among these, halides such as lithium chloride, sodium chloride and potassium chloride, acetates such as potassium acetate, and perchlorates such as potassium perchlorate are preferable.
The addition amount of the alkali metal or alkaline earth metal salt in the polyolefin-based resin composition of the present invention is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It is preferably 01 to 2 parts by mass.

As the surfactant, nonionic, anionic, cationic or amphoteric surfactants can be used.
Nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyethylene oxide, fatty acid esters of glycerin And polyvalent alcohol type nonionic surfactants such as fatty acid esters of pentaerythritol, fatty acid esters of sorbit or sorbitan, alkyl ethers of polyhydric alcohols, aliphatic amides of alkanolamines, and the like.

  Examples of the anionic surfactant include carboxylates such as alkali metal salts of higher fatty acids; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates, alkyl sulfonates, Examples include sulfonates such as paraffin sulfonates; phosphate ester salts such as higher alcohol phosphates.

Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as higher alkylaminopropionate, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine.
These surfactants may be used alone or in combination of two or more.

As the surfactant, an anionic surfactant is preferably used, and in particular, a sulfonate such as an alkylbenzene sulfonate, an alkyl sulfonate, or a paraffin sulfonate is preferably used.
The addition amount of the surfactant in the polyolefin resin composition of the present invention is preferably 0.001 to 5 parts by mass, particularly 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin. Preferably there is.

Examples of the polymer antistatic agent include polyether ester amides composed of polyoxyalkylene adducts of bisphenol A described in JP-A No. 7-10998, or polyolefin blocks and hydrophilic polymers described in US Pat. No. 6,552,131. Examples thereof include a block polymer block polymer having a repeating structure having 2 to 50 block bonding units.
The addition amount of the polymer antistatic agent in the polyolefin resin composition of the present invention is preferably 0 to 40 parts by mass, particularly 5 to 20 parts by mass with respect to 100 parts by mass of the polyolefin resin. Is preferred.

In addition, in the polyolefin-based fat composition of the present invention, a compatibilizer may be added as necessary in order to improve the compatibility between the component of the present invention and other components and polyolefin-based resin. Good.
As the compatibilizer, for example, at least one polar group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and a polyoxyalkylene group described in JP-A-3-258850 is used. A modified vinyl polymer having a sulfonyl group or a resin composition containing a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, as described in JP-A-6-345927 Is mentioned.
0.1-15 mass parts is preferable with respect to 100 mass parts of polyolefin resin, and, as for the addition amount of the compatibilizing agent in the said polyolefin resin, 1-10 mass parts is preferable.

  The polyolefin-based resin composition of the present invention may further include an aromatic carboxylic acid metal salt, an alicyclic alkyl carboxylic acid metal salt, an aluminum p-tert-butylbenzoate, an aromatic phosphate metal salt, dibenzylidene as required. Nucleating agents such as sorbitol, metal soap, hydrotalcite, triazine ring-containing compound, metal hydroxide, phosphate ester flame retardant, condensed phosphate ester flame retardant, phosphate flame retardant, inorganic phosphorus flame retardant , (Poly) phosphate flame retardants, halogen flame retardants, silicon flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardant aids, other organic flame retardant aids, fillers, Pigments, lubricants, foaming agents and the like may be added.

  Examples of the triazine ring-containing compound include melamine, ammelin, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene Dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimeramine and the like can be mentioned.

  Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.) and the like.

  Examples of the phosphate ester flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, Trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t-butyl Phenyl) phosphate, isopropylphenyldiphenylphosphate, bis- (isopropylphenyl) Phenyl phosphate, tris - (isopropylphenyl) phosphate, and the like.

Examples of the condensed phosphate ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like.
Examples of the (poly) phosphate flame retardant include ammonium salts and amine salts of (poly) phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrophosphate, and piperazine pyrophosphate.

Examples of other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, montmorillonite, and surface-treated products thereof. For example, TIPAQUE R-680 ( Titanium oxide: manufactured by Ishihara Sangyo Co., Ltd.), Kyowa Mag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), Alkamizer 4 (zinc modified hydro Various commercial products such as talcite (manufactured by Kyowa Chemical Industry Co., Ltd.) can be used.
Examples of other organic flame retardant aids include pentaerythritol.

  In addition, the polyolefin resin composition of the present invention includes, for example, a crosslinking agent, an antifogging agent, a plate-out preventing agent, a surface treatment agent, a plasticizer, a lubricant, a flame retardant, a fluorescent agent, an antifungal agent, a bactericidal agent, and a foam. Additives usually used in polyolefin resins, such as additives, metal deactivators, mold release agents, pigments, processing aids, antioxidants, light stabilizers, etc., if necessary, antistatic properties and crystallization properties You may mix | blend in the range which does not impair.

By molding the polyolefin resin composition of the present invention, the molded article of the present invention is obtained. Since the molded article of the present invention is excellent in antistatic properties and has a high crystallization temperature, it has high strength and transparency. The molding method is not particularly limited, and various shapes such as a resin plate, a sheet, a film, a fiber, and an irregular shape can be formed by a known method such as extrusion, calendaring, injection molding, roll, compression molding, blow molding, and the like. The molded product is manufactured.
In particular, the polyolefin resin composition of the present invention is suitable for a film-like or sheet-like molded product.

The polyolefin-based resin composition of the present invention and the molded product thereof are electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood, It can be used in a wide range of industrial fields such as building materials, civil engineering, furniture, printing, and musical instruments.
More specifically, the polyolefin resin composition of the present invention and the molded product thereof are printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers). ), Calculators, electronic notebooks, cards, holders, office supplies such as stationery, OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, kotatsu and other household appliances, TVs, VTRs, video cameras , Radio-cassettes, tape recorders, mini-discs, CD players, speakers, liquid crystal displays and other AV equipment, connectors, relays, capacitors, switches, printed boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers, Electrical and electronic parts such as deflection yokes, distribution boards, watches, and communication equipment, fills for plate making , Adhesive film, bottles, food containers, food packaging film, wrap film for pharmaceutical and pharmaceutical, product packaging film, agricultural film, agricultural sheeting, used for greenhouse films and the like.

  Further, the polyolefin-based resin composition of the present invention and the molded product thereof are a seat (filling, outer material, etc.), belt, ceiling, compatible top, armrest, door trim, rear package tray, carpet, mat, sun visor, foil cover, Mattress cover, airbag, insulation material, suspension hand, suspension band, electric wire coating material, electrical insulation material, paint, coating material, upholstery material, flooring material, corner wall, carpet, wallpaper, wall covering material, exterior material, Interior materials, roofing materials, deck materials, wall materials, pillar materials, flooring materials, fence materials, frames and repetitive shapes, windows and door shapes, slabs, glazing, terraces, balconies, soundproofing plates, heat insulating plates, window materials Automobiles, vehicles, ships, aircraft, buildings, housing and building materials and civil engineering materials, clothing, curtains, sheets, nonwoven fabrics, plywood, synthetic fiber boards, carpets, doormats, sheets, buckets, ho Vinegar, container, glasses, bags, cases, goggles, skis, rackets, tents, household goods of musical instruments, etc., there is a variety of applications such as sporting goods.

Hereinafter, the present invention will be specifically described by way of examples. In the following examples and the like,% and ppm are based on mass unless otherwise specified.
[Examples 1 to 10, Comparative Examples 1 to 18]
In Examples and Comparative Examples, the following Compound No. 1-No. 4 was used, and glycerin monostearate and the following comparative compounds-1 to 5 were used as comparative compounds.
As the nucleating agent (B), the following compound No. 13, sodium benzoate, compound no. 36 was used.

<Pellet creation>
A polypropylene resin composition obtained by blending based on the blending amounts shown in Tables 1 to 4 using a twin screw extruder manufactured by Ikegai Co., Ltd. (with PCM30, 60 mesh) is 230 ° C., 6 kg / hour. Granulation was performed under conditions to obtain pellets.
About the obtained pellet, the crystallization temperature was measured.
<Measurement of crystallization temperature>
The obtained pellet was heated to 230 ° C. at a rate of 10 ° C./min with a differential scanning calorimeter (Diamond; manufactured by Perkin Elmer), held for 5 minutes, and then 50 at a rate of −10 ° C./min. In the chart obtained by cooling to ° C., the peak top of the endotherm was taken as the crystallization temperature.

The obtained pellets were molded using a horizontal injection molding machine (NEX80: Nissei Plastics Industries) under processing conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C., and a test piece of 100 mm × 100 mm × 3 mm Got.
About each obtained test piece, surface specific resistance value (SR value) was measured on condition of the following, and antistatic property was evaluated.
<Measurement of surface resistivity (SR value)>
After molding, the obtained test piece was immediately stored at 25 ° C. under a humidity of 50%. After storage for 1 day after molding, the surface resistivity (Ω / □) was measured under the same atmosphere using an R8340 resistance meter manufactured by Advantest Corporation under the conditions of an applied voltage of 100 V and an applied time of 1 minute. The measurement was performed for 5 points, and the average value was obtained.

The compositions and evaluation results of the examples and comparative examples are shown in Tables 1 to 4 below.

  As is clear from the results shown in Tables 1 to 4, since the polyolefin resin composition of the present invention has a high crystallization temperature, the molding cycle can be shortened and the surface specific resistance value is low. It was confirmed that the antistatic property was excellent.

  The polyolefin-based resin composition of the present invention and the molded product thereof are electric / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood, It can be used in a wide range of industrial fields such as building materials, civil engineering, furniture, printing, and musical instruments.

Claims (5)

0.01 to 20 parts by mass of the compound (A) represented by the following general formula (1) and 0.001 to 10 parts by mass of the nucleating agent (B) are contained with respect to 100 parts by mass of the polyolefin resin. A polyolefin-based resin composition characterized by:

However, ^{R 1} in the formula (1) is an alkyl group having a carbon number of 11 to 13, ^{R 2} is a hydrogen atom or _-CH 2 _CH 2 OH. The polyolefin resin composition according to claim 1, wherein the nucleating agent (B) contains a compound represented by the following general formula (2);

However, each independently ^R 3 to R ⁶ in the formula (2) is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, ^{R 7} is an alkylidene group having 1 to 4 carbon atoms, ^{M 1} is an alkali A metal atom, an alkaline earth metal atom, a beryllium atom, a magnesium atom or an aluminum atom; when M ¹ is an alkali metal atom, s is 1 and t is 0, and M ¹ is an alkaline earth metal atom; When it is a beryllium atom or a magnesium atom, s is 2, and t is 0. When M ¹ is an aluminum atom, s is 1 or 2, and t is 3-s. The polyolefin resin composition according to claim 1, wherein the nucleating agent (B) contains a compound represented by the following general formula (3);

However, R < ⁸ > in Formula (3) is a hydrogen atom or a C1-C9 alkyl group, M < ² > is an alkali metal atom, an alkaline-earth metal atom, a beryllium atom, a magnesium atom, or an aluminum atom; When M ² is an alkali metal atom, y is 1 and u is 0. When M ² is an alkaline earth metal atom, beryllium atom or magnesium atom, y is 2 and u is 0. And when M ² is an aluminum atom, y is 1 or 2, and u is 3-y. The polyolefin resin composition according to claim 1, wherein the nucleating agent (B) contains a compound represented by the following general formula (4);

However, R ^{9 to} R ¹⁸ in formula (4) are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 9 carbon atoms, or 1 to 9 carbon atoms. An alkyleneoxy group, an amino group, an alkylamino group having 1 to 9 carbon atoms, a halogen atom, a phenyl group, an alkylphenyl group, or a cycloalkyl group having 1 to 9 carbon atoms; on any two adjacent carbons The bonds or alkyl groups attached to the same carbon may combine to form a hydrocarbon ring;
M ³ is an alkali metal atom, alkaline earth metal atom, beryllium atom, magnesium atom or aluminum atom; when M ³ is an alkali metal atom, a is 2 and b is 0, and M ³ is alkaline earth In the case of a similar metal atom, beryllium atom or magnesium atom, a is 1, and b is 0. When M ³ is an aluminum atom, a is 1 and b is 1.   The molded object formed by shape | molding the polyolefin resin composition in any one of Claims 1-4.