Polyolefin resin composition, method for producing same, and use of same

Abstract

The present invention provides: a polyolefin resin composition which has high crystallinity (a high crystallization temperature) and excellent mechanical characteristics (especially impact strength); and a method for producing the same. The present invention also provides: a crystal nucleating agent composition for polyolefin resins, which is used for the production of the polyolefin resin composition; and a method for producing the crystal nucleating agent composition for polyolefin resins. Furthermore, the present invention provides a polyolefin resin molded body which contains the polyolefin resin composition. The present invention relates to: a polyolefin resin composition which contains a compound represented by general formula (1), a surfactant (S) that contains a compound represented by general formula (2), and a polyolefin resin; a crystal nucleating agent composition for polyolefin resins; methods for producing those; and a polyolefin resin molded body. [In the formula, R1 is an alkyl group having 1 to 4 carbon atoms; R1 is bonded to a carbon atom in the 3- or 4-position on the cyclohexane ring; M1 is calcium, zinc, hydroxyaluminum, sodium, or lithium; when M1 is calcium, zinc, or hydroxyaluminum, a is 2 and b is 1; and when M1 is sodium or lithium, a is 1 and b is 2.] [In the formula, A's are the same or different and are each a hydrogen atom or -COR; and R is an aliphatic hydrocarbon group having 7 to 29 carbon atoms. At least one A is -COR. n is an integer of 1 to 100 inclusive.]

Description

Polyolefin resin composition, method for producing the same, and its uses

[0001] This invention relates to polyolefin resin compositions, methods for producing the same, and applications thereof.

[0002] Polyolefin resins, such as polypropylene, are inexpensive and possess well-balanced performance, making them a versatile plastic used in a wide range of applications. It is widely known that improving the crystallinity of polyolefin resins can, for example, improve moldability and enhance the mechanical, thermal, and optical properties of the resulting molded products.

[0003] A common and practical method for improving the crystallinity of resins is to incorporate additives such as nucleating agents. Examples of nucleating agents that have been put into practical use include inorganic compounds such as talc, diacetal compounds, metal salts of phosphate esters, and organic compounds such as metal salts of carboxylic acids and sulfonic acids.

[0004] Among crystal nucleating agents, metal salts of carboxylic acids have long been known to have excellent nucleating effects. Representative examples include sodium benzoic acid and hydroxyaluminum salt of p-tert-butylbenzoic acid. Furthermore, metal salts (calcium salts, sodium salts, etc.) of alicyclic dicarboxylic acids such as hexahydrophthalic acid and hydrogenated nadic acid have been reported to have excellent effects as crystal nucleating agents for thermoplastic resins (Patent Documents 1-5, etc.). In addition, it has been reported that metal salts of cyclohexane-1,2-dicarboxylic acid having alkyl substituents function as α-crystal nucleating agents for polyolefin resins, exhibiting excellent dispersibility in the resin and improving the crystallization rate of the resin (raising the crystallization temperature) (Patent Document 6).

[0005] In recent years, polyolefin resins have attracted attention as the most useful material due to their low cost and light weight. In particular, their use in automotive components has advanced significantly due to the increasing demand for improved fuel efficiency driven by recent environmental concerns. Recently, polyolefin resins are being used not only in small components but also in large components. In such fields, the improvement of crystallinity using known crystal nucleating agents is not always sufficient in terms of improving moldability and mechanical properties, and further improvements in crystallinity are desired.

[0006] International Publication No. 2002 / 078924, International Publication No. 2002 / 079312, International Publication No. 2002 / 094759, International Publication No. 2005 / 040259, Japanese Patent Publication No. 2012-97268, International Publication No. 2020 / 054492

[0007] The present invention aims to provide a polyolefin resin composition with high crystallinity (high crystallization temperature) and excellent mechanical properties (particularly impact strength), and a method for producing the same. Furthermore, the present invention aims to provide a nucleating agent composition for polyolefin resins used in the production of the said polyolefin resin composition, and a method for producing the same. Finally, the present invention aims to provide a polyolefin resin molded article containing the said polyolefin resin composition.

[0008] Conventionally, polyolefin resin compositions obtained by adding a crystal nucleating agent such as a metal salt of cyclohexane-1,2-dicarboxylic acid to a polyolefin resin have the advantage of improved crystallinity (higher crystallization temperature) and a reduction in cycle time during the manufacture of molded products. On the other hand, the mechanical properties (especially impact strength) of the molded products are low, so they are not always satisfactory depending on the application. The present inventors conducted diligent research to solve this problem and found that a polyolefin resin composition obtained by adding a surfactant (S) (hereinafter sometimes referred to as "surfactant (S)") containing a compound represented by general formula (1) and a compound represented by general formula (2) to a polyolefin resin exhibits further improved crystallinity (further higher crystallization temperature) and a dramatic improvement in mechanical properties (especially impact strength, etc.). Based on this finding, further research led to the completion of the present invention. That is, the present invention provides the following aspects.

[0009] [1] A polyolefin resin composition comprising a compound represented by general formula (1), a surfactant (S) containing a compound represented by general formula (2), and a polyolefin resin. [In the formula, R １ R is an alkyl group having 1 to 4 carbon atoms. １ It is bonded to the carbon at position 3 or 4 on the cyclohexane ring, M １ It is calcium, zinc, hydroxyaluminum, sodium, or lithium, M １ If is calcium, zinc, or hydroxyaluminum, then a is 2, b is 1, and M １ If a is sodium or lithium, then a is 1 and b is 2. [In the formula, A is the same or different hydrogen atom or -COR, and R is an aliphatic hydrocarbon group having 7 to 29 carbon atoms. At least one A is -COR. n is an integer from 1 to 100.] [2] The polyolefin resin composition according to [1], wherein R is an aliphatic hydrocarbon group having 7 to 17 carbon atoms in the compound represented by general formula (2). [3] The polyolefin resin composition according to [1] or [2], wherein n is an integer from 1 to 30 in the compound represented by general formula (2). [4] The polyolefin resin composition according to any one of [1] to [3], wherein the esterification rate in the compound represented by general formula (2) is 1 to 100. [5] The polyolefin resin composition according to any one of [1] to [3], wherein R １ A polyolefin resin composition according to any one of [1] to [4], wherein R is bonded to the carbon at position 4 on the cyclohexane ring. [6] In a compound represented by general formula (1), R １ A polyolefin resin composition according to any one of [1] to [5], wherein is a methyl group. [7] In a compound represented by general formula (1), M １A polyolefin resin composition according to any one of [1] to [6], wherein the compound is calcium. [8] A polyolefin resin composition according to any one of [1] to [7], comprising 0.001 to 10 parts by mass of a compound represented by general formula (1) per 100 parts by mass of polyolefin resin. [9] A polyolefin resin composition according to any one of [1] to [8], comprising 0.001 to 80 parts by mass of a surfactant (S) containing a compound represented by general formula (2) per 100 parts by mass of polyolefin resin.

[10] A polyolefin resin composition according to any one of [1] to [9], wherein the mass ratio of the compound represented by general formula (1) to the surfactant (S) containing the compound represented by general formula (2) is 1 / 80000 to 1 / 0.0001.

[11] A method for producing the polyolefin resin composition according to [1], comprising the step of mixing a compound represented by general formula (1), a surfactant (S) containing a compound represented by general formula (2), and a polyolefin resin.

[12] A nucleating agent composition (nucleating agent masterbatch) for polyolefin resins comprising a surfactant (S) containing a compound represented by general formula (1) and a compound represented by general formula (2).

[13] A method for producing the nucleating agent composition for polyolefin resins according to

[12] , comprising the step of mixing a surfactant (S) containing a compound represented by general formula (1) and a compound represented by general formula (2).

[14] A method for producing the polyolefin resin composition according to [1], comprising the step of mixing the nucleating agent composition for polyolefin resins according to

[12] and a polyolefin resin.

[15] A polyolefin resin molded article comprising the polyolefin resin composition according to any one of [1] to

[10] .

[0010] The polyolefin resin composition of the present invention contains a surfactant (S) containing a compound represented by general formula (1) and a compound represented by general formula (2) in the polyolefin resin, and therefore exhibits excellent crystallinity (fast crystallization rate and high crystallization temperature), as well as excellent mechanical properties (especially impact strength). Because of its excellent crystallinity, the polyolefin resin composition of the present invention significantly shortens the molding cycle, leading to cost reduction and prevention of processing problems. Furthermore, because the resulting molded product has excellent mechanical properties, it can be made thinner and lighter. It is particularly suitable for use in large components. Therefore, the polyolefin resin composition of the present invention can be used in a variety of applications, and its molded products are particularly useful in the fields of automotive materials and industrial materials.

[0011] 1. Polyolefin Resin Composition The polyolefin resin composition of the present invention is characterized by comprising a compound represented by general formula (1), a surfactant (S) containing a compound represented by general formula (2), and a polyolefin resin. Furthermore, other additives may be contained as needed.

[0012] [Polyolefin Resin] The polyolefin resin composition of the present invention contains a polyolefin resin. The polyolefin resin is not particularly limited as long as it achieves the effects of the present invention, and conventionally known polyolefin resins can be used. Examples include polyethylene resins, polypropylene resins, polybutene resins, polymethylpentene resins, and polybutadiene resins. Specifically, examples include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear polyethylene, ethylene copolymer with an ethylene content of 50% by mass or more (preferably 70% by mass or more), propylene homopolymer, propylene copolymer with an ethylene content of 50% by mass or more (preferably 70% by mass or more), butene homopolymer, butene copolymer with a butene content of 50% by mass or more (preferably 70% by mass or more), methylpentene homopolymer, methylpentene copolymer with a methylpentene content of 50% by mass or more (preferably 70% by mass or more), and polybutadiene. Furthermore, the copolymer may be a random copolymer or a block copolymer. Furthermore, if these resins exhibit stereoregularity, they may be isotactic or syndiotactic. Specific examples of comonomers that can constitute the above copolymer include α-olefins having 2 to 12 carbon atoms such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, and dodecene; bicyclo-type monomers such as 1,4-endomethylenecyclohexene; (meth)acrylic acid esters such as methyl (meth)acrylate and ethyl (meth)acrylate; and vinyl acetate.

[0013] Catalysts that can be used to produce such polymers include not only commonly used Ziegler-Natta type catalysts, but also catalyst systems that combine a transition metal compound (e.g., titanium halides such as titanium trichloride and titanium tetrachloride) supported on a carrier mainly composed of magnesium halides such as magnesium chloride with an alkylaluminum compound (e.g., triethylaluminum, diethylaluminum chloride), metallocene catalysts, and the like.

[0014] The melt flow rate (hereinafter abbreviated as "MFR") of the polyolefin resin according to the present invention is appropriately selected depending on the molding method to be applied, but is generally about 0.01 to 200 g / 10 minutes, preferably about 0.05 to 100 g / 10 minutes is recommended. MFR is a value measured in accordance with JIS K 7210 (2014).

[0015] [Compound represented by general formula (1)] The polyolefin resin composition of the present invention contains a compound represented by general formula (1) (metal salt of alicyclic dicarboxylic acid). The compound represented by general formula (1) functions as a crystal nucleating agent for polyolefin resins. [wherein, R １ is an alkyl group having 1 to 4 carbon atoms, R １ is bonded to the carbon at the 3-position or 4-position on the cyclohexane ring, M １ is calcium, zinc, hydroxyaluminum, sodium or lithium, M １ when is calcium, zinc or hydroxyaluminum, a is 2 and b is 1, M １ when is sodium or lithium, a is 1 and b is 2.]]

[0016] The compound represented by the above general formula (1) can be easily produced by reacting an alicyclic dicarboxylic acid represented by the following general formula (3) or an anhydride thereof with a corresponding metal oxide, metal hydroxide, or metal chloride, or the like. For example, it can be produced according to or in accordance with the descriptions in Patent Documents 1 to 5, etc. [wherein, R １ is the same as defined above.]]

[0017] R in general formulas (1) and (3) １ is a linear or branched alkyl group having 1 to 4 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among them, a methyl group and a tert-butyl group are particularly recommended from the viewpoint of the effect of improving crystallinity and the like.

[0018] R in general formulas (1) and (3) １The substitution position is either the 3rd or 4th position on the cyclohexane ring, and substitution may occur at either position, but a particularly preferred substitution position is a metal species (M) that forms a metal salt with the substituted alkyl group. １ The appropriate selection is made depending on the type of metal (M １ ) If calcium, zinc, or sodium, R １ The substitution position is preferably at the 4th position on the cyclohexane ring.

[0019] The metal species (M) that form the compound represented by general formula (1) １ The element is selected from the group consisting of calcium, hydroxyaluminum, sodium, and lithium, and among these, calcium, zinc, or sodium is preferred from the viewpoint of improving crystallinity, and calcium is more preferred.

[0020] A preferred compound represented by general formula (1) is R １ is an alkyl group having 1 to 4 carbon atoms (especially a methyl group or a tert-butyl group), and R １ It is bonded to the carbon at position 4 on the cyclohexane ring, M １ It is calcium, zinc, or sodium, M １ If it is calcium or zinc, then a is 2, b is 1, and M １ Examples of compounds where a is 1 and b is 2 are given, in the case of sodium.

[0021] Specific embodiments of the compound represented by general formula (1) include, for example, the disodium salt of 3-methylcyclohexane-1,2-dicarboxylic acid, the calcium salt of 3-methylcyclohexane-1,2-dicarboxylic acid, the zinc salt of 3-methylcyclohexane-1,2-dicarboxylic acid, the hydroxyaluminum salt of 3-methylcyclohexane-1,2-dicarboxylic acid, the dilithium salt of 3-methylcyclohexane-1,2-dicarboxylic acid, the disodium salt of 3-ethylcyclohexane-1,2-dicarboxylic acid, and the calcium salt of 3-ethylcyclohexane-1,2-dicarboxylic acid. 3-ethylcyclohexane-1,2-dicarboxylic acid zinc salt, 3-ethylcyclohexane-1,2-dicarboxylic acid hydroxyaluminum salt, 3-ethylcyclohexane-1,2-dicarboxylic acid dilithium salt, 3-n-propylcyclohexane-1,2-dicarboxylic acid disodium salt, 3-n-propylcyclohexane-1,2-dicarboxylic acid calcium salt, 3-n-propylcyclohexane-1,2-dicarboxylic acid zinc salt, 3-n-propylcyclohexane-1,2-dicarboxylic acid hydroxyaluminum salt, 3-n-propyl Dilithium salt of cyclohexane-1,2-dicarboxylic acid, disodium salt of 3-isopropylcyclohexane-1,2-dicarboxylic acid, calcium salt of 3-isopropylcyclohexane-1,2-dicarboxylic acid, zinc salt of 3-isopropylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 3-isopropylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 3-isopropylcyclohexane-1,2-dicarboxylic acid, disodium salt of 3-n-butylcyclohexane-1,2-dicarboxylic acid, 3-n-butylcyclohexane Calcium salt of 3-1,2-dicarboxylic acid, zinc salt of 3-n-butylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 3-n-butylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 3-n-butylcyclohexane-1,2-dicarboxylic acid, disodium salt of 3-tert-butylcyclohexane-1,2-dicarboxylic acid, calcium salt of 3-tert-butylcyclohexane-1,2-dicarboxylic acid, zinc salt of 3-tert-butylcyclohexane-1,2-dicarboxylic acid, 3-tert-butylcyclohexane-1,Hydroxyaluminum salt of 2-dicarboxylic acid, dilithium salt of 3-tert-butylcyclohexane-1,2-dicarboxylic acid, disodium salt of 3-isobutylcyclohexane-1,2-dicarboxylic acid, calcium salt of 3-isobutylcyclohexane-1,2-dicarboxylic acid, zinc salt of 3-isobutylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 3-isobutylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 3-isobutylcyclohexane-1,2-dicarboxylic acid, 4-methylcyclohexane-1,2- Disodium salt of dicarboxylic acid, calcium salt of 4-methylcyclohexane-1,2-dicarboxylic acid, zinc salt of 4-methylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 4-methylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 4-methylcyclohexane-1,2-dicarboxylic acid, disodium salt of 4-ethylcyclohexane-1,2-dicarboxylic acid, calcium salt of 4-ethylcyclohexane-1,2-dicarboxylic acid, zinc salt of 4-ethylcyclohexa Hydroxyaluminum salt of n-1,2-dicarboxylic acid, dilithium salt of 4-ethylcyclohexane-1,2-dicarboxylic acid, disodium salt of 4-n-propylcyclohexane-1,2-dicarboxylic acid, calcium salt of 4-n-propylcyclohexane-1,2-dicarboxylic acid, zinc salt of 4-n-propylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 4-n-propylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 4-n-propylcyclohexane-1,2-dicarboxylic acid, 4-isopropylcyclohex Disodium salt of san-1,2-dicarboxylic acid, calcium salt of 4-isopropylcyclohexane-1,2-dicarboxylic acid, zinc salt of 4-isopropylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 4-isopropylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 4-isopropylcyclohexane-1,2-dicarboxylic acid, disodium salt of 4-n-butylcyclohexane-1,2-dicarboxylic acid, calcium salt of 4-n-butylcyclohexane-1,2-dicarboxylic acid, 4-n-butylcyclohexane-1,Zinc salt of 2-dicarboxylic acid, hydroxyaluminum salt of 4-n-butylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 4-n-butylcyclohexane-1,2-dicarboxylic acid, disodium salt of 4-tert-butylcyclohexane-1,2-dicarboxylic acid, calcium salt of 4-tert-butylcyclohexane-1,2-dicarboxylic acid, zinc salt of 4-tert-butylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salt of 4-tert-butylcyclohexane-1,2-dicarboxylic acid, dilithium salt of 4-tert-butylcyclohexane-1,2-dicarboxylic acid, disodium salt of 4-isobutylcyclohexane-1,2-dicarboxylic acid, 4-isobutylcyclohexane-1,2-dicarboxylic acid Examples include calcium salts of rubonate, zinc salts of 4-isobutylcyclohexane-1,2-dicarboxylic acid, hydroxyaluminum salts of 4-isobutylcyclohexane-1,2-dicarboxylic acid, and dilithium salts of 4-isobutylcyclohexane-1,2-dicarboxylic acid. Among these, preferred embodiments include disodium salt of 3-methylcyclohexane-1,2-dicarboxylic acid, disodium salt of 4-methylcyclohexane-1,2-dicarboxylic acid, calcium salt of 4-methylcyclohexane-1,2-dicarboxylic acid, calcium salt of 3-methylcyclohexane-1,2-dicarboxylic acid, zinc salt of 4-methylcyclohexane-1,2-dicarboxylic acid, and zinc salt of 3-methylcyclohexane-1,2-dicarboxylic acid. A more preferred embodiment is the calcium salt of 4-methylcyclohexane-1,2-dicarboxylic acid.

[0022] The compounds represented by general formula (1) may be used individually, or two or more may be used in combination.

[0023] Compounds represented by general formula (1) include R on the cyclohexane ring. １Furthermore, there exist cis isomers (isomers where all are in a cis configuration) in which both oxycarbonyl groups are oriented in the same direction relative to the plane of the paper, and other stereoisomers. In the present invention, as long as the effects of the present invention are achieved, it is not dependent on the structure of the isomer, but from the viewpoint of improving crystallinity, it is desirable that the cis isomer is rich, and for example, it is recommended that the ratio (mol%) of cis isomers among the above stereoisomers be 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly 97 mol% or more.

[0024] Compounds represented by general formula (1) are usually solids, and are preferably particulate. The shape of the particles is not particularly limited as long as the effects of the present invention are achieved. Since the metal salt of the above alicyclic dicarboxylic acid is a dispersion type, the smaller the particle size to the extent that dispersibility in the resin does not deteriorate due to secondary aggregation, the wider the contact surface with the resin, and the greater the possibility of exhibiting better performance as a crystal nucleating agent with a smaller amount. Therefore, from the viewpoint of promoting crystallization, it is recommended that the average value of the particle size determined by laser diffraction particle size distribution measurement be 100 μm or less, preferably 50 μm or less, more preferably 20 μm or less, and particularly preferably 10 μm or less. Furthermore, from the viewpoint of dispersibility, as described above, it is recommended that the average value of the particle size determined by laser diffraction particle size distribution measurement be 0.01 μm or more, preferably 0.1 μm or more, and more preferably 0.5 μm or more.

[0025] The content of the compound represented by general formula (1) in the polyolefin resin composition of the present invention is not particularly limited as long as the effects of the present invention are achieved. The content of the compound represented by general formula (1) is usually 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the polyolefin resin.

[0026] [Surfactant (S) containing the compound represented by general formula (2)] The polyolefin resin composition of the present invention contains a surfactant (S) containing the compound represented by general formula (2) (hereinafter sometimes referred to as "surfactant (S)"). [wherein, A are the same or different and each represent a hydrogen atom or -COR, R is an aliphatic hydrocarbon group having 7 to 29 carbon atoms. At least one A is -COR. n is an integer of 1 to 100.]

[0027] The compound represented by general formula (2) includes a single compound selected from the compounds represented by general formula (2) and a mixture of two or more compounds selected therefrom. In addition, the compound represented by general formula (2) may be described as a (poly)glycerin fatty acid ester represented by general formula (2). Here, the (poly)glycerin fatty acid ester means a glycerin fatty acid ester or a polyglycerin fatty acid ester.

[0028] In general formula (2), R in -COR represented by A is preferably an aliphatic hydrocarbon group having 7 to 25 carbon atoms, more preferably 7 to 18 carbon atoms, still more preferably 7 to 17 carbon atoms, and particularly preferably 7 to 10 carbon atoms. The aliphatic hydrocarbon group may be either saturated or unsaturated, and may be linear, branched or cyclic. A saturated and linear aliphatic hydrocarbon group is preferred. Typical examples of saturated aliphatic hydrocarbon groups include linear or branched heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and the like, and linear heptyl, octyl or nonyl groups are preferred. Typical examples of unsaturated aliphatic hydrocarbon groups include groups having one or more unsaturated bonds (carbon-carbon double bonds or carbon-carbon triple bonds) in the carbon chain of the above-mentioned saturated aliphatic hydrocarbon groups. When the unsaturated aliphatic hydrocarbon group has a carbon-carbon double bond, the double bond can be in the cis (Z) or trans (E) form. R is more preferably a linear heptyl group or a linear octyl group (n-heptyl group or n-octyl group), and particularly preferably an n-heptyl group.

[0029] In general formula (2), n represents the degree of polymerization of (poly)glycerin, and is preferably an integer of 1 to 50, more preferably an integer of 1 to 30, still more preferably an integer of 1 to 15, and particularly preferably an integer of 1 to 10.

[0030] In general formula (2), the esterification rate (%) is usually 1 to 100%, preferably 5 to 85%, more preferably 5 to 70%, and particularly preferably 5 to 66%. Here, the esterification rate is expressed as a percentage of the number (Y) of esterified hydroxyl groups (-OCOR) relative to the total number of hydroxyl groups (X) of (poly)glycerin constituting the (poly)glycerin fatty acid ester, that is, it can be expressed by Y / X×100 (%). This esterification rate can be calculated for the compound represented by general formula (2) using the following formula from the saponification value and hydroxyl value obtained, for example, in accordance with the standard fat and oil analysis test method. Esterification rate (%) = saponification value / (hydroxyl value + saponification value) × 100

[0031] Among the compounds represented by general formula (2), a preferred embodiment includes compounds in which R is an aliphatic hydrocarbon group having 7 to 15 carbon atoms, and n is an integer of 1 to 100 (preferably an integer of 1 to 50, more preferably an integer of 1 to 30, still more preferably an integer of 1 to 15, particularly preferably an integer of 1 to 10). Further, another compound includes those in which R is an aliphatic hydrocarbon group having 17 carbon atoms, and n is an integer of 1 to 100 (preferably an integer of 1 to 50, more preferably an integer of 2 to 30, still more preferably an integer of 2 to 15, particularly preferably an integer of 2 to 10).

[0032] Among the compounds represented by general formula (2), another preferred embodiment includes compounds in which R is a saturated aliphatic hydrocarbon group having 7 to 17 carbon atoms, and the esterification rate is 1 to 100% (preferably 5 to 85%, more preferably 5 to 70%, particularly preferably 5 to 66%).

[0033] Among the compounds represented by general formula (2), other preferred embodiments include compounds in which R is a saturated aliphatic hydrocarbon group having 7 to 17 carbon atoms, n is an integer from 1 to 100 (preferably an integer from 1 to 50, more preferably an integer from 1 to 30, even more preferably an integer from 1 to 15, and particularly preferably an integer from 1 to 10), and the esterification rate is 1 to 100 (preferably 5 to 85%, more preferably 5 to 70%, and particularly preferably 5 to 66%). Also, there are compounds in which R is a saturated aliphatic hydrocarbon group having 17 carbon atoms, n is an integer from 1 to 100 (preferably an integer from 1 to 50, more preferably an integer from 2 to 30, even more preferably an integer from 2 to 15, and particularly preferably an integer from 2 to 10), and the esterification rate is 1 to 100 (preferably 5 to 85%, more preferably 5 to 70%, and particularly preferably 5 to 66%).

[0034] Among the compounds represented by general formula (2), other preferred embodiments include compounds in which R is an unsaturated aliphatic hydrocarbon group having 7 to 17 carbon atoms, n is an integer from 1 to 100 (preferably an integer from 1 to 50, more preferably an integer from 1 to 30, even more preferably an integer from 1 to 15, and particularly preferably an integer from 1 to 10), and the esterification rate is 1 to 100 (preferably 5 to 85%, more preferably 5 to 70%, and particularly preferably 5 to 66%). Also, there are compounds in which R is an unsaturated aliphatic hydrocarbon group having 17 carbon atoms, n is an integer from 1 to 100 (preferably an integer from 1 to 50, more preferably an integer from 1 to 30, even more preferably an integer from 1 to 15, and particularly preferably an integer from 1 to 10), and the esterification rate is 1 to 100 (preferably 5 to 85%, more preferably 5 to 70%, and particularly preferably 5 to 66%).

[0035] Compounds represented by general formula (2) are commercially available or can be produced by known methods. For example, they can be produced by esterifying the corresponding (poly)glycerin with RCOOH or a derivative thereof.

[0036] The compound represented by general formula (2) can generally be used as a surfactant. In the present invention, by blending a surfactant (S) containing the compound represented by general formula (2) and the compound represented by general formula (1) with a polyolefin resin, the crystallinity of the resin can be increased and its mechanical properties can be improved.

[0037] The surfactant (S) comprises a compound represented by general formula (2) and may also contain other surfactant components to the extent that they do not affect the effects of the present invention. The surfactant (S) preferably consists substantially of a compound represented by general formula (2), and more preferably consists solely of a compound represented by general formula (2).

[0038] The content of the surfactant (S) containing the compound represented by general formula (2) in the polyolefin resin composition of the present invention is not particularly limited as long as the effects of the present invention are achieved. The content of the surfactant (S) containing the compound represented by general formula (2) is usually 0.001 to 80 parts by mass, preferably 0.005 to 40 parts by mass, and more preferably 0.01 to 30 parts by mass, per 100 parts by mass of the polyolefin resin.

[0039] [Other Additives] Depending on the intended use and application, the polyolefin resin composition of the present invention may contain additives for polyolefin resins other than the components described above, to the extent that they do not impair the effects of the present invention.

[0040] Examples of additives for polyolefin resins include the various additives listed in the "Positive List Additive Handbook" (September 2004) compiled by the Polyolefin Hygiene Council. Specifically, these include fluorescent whitening agents (2,5-thiophenediyl(5-tert-butyl-1,3-benzoxazole), 4,4'-bis(benzoxazole-2-yl)stilbene, etc.), antioxidants, stabilizers (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), surfactants (excluding the aforementioned "surfactants (S) containing compounds represented by general formula (2)"), lubricants (aliphatic hydrocarbons such as paraffin and wax, higher fatty acids with 8 to 22 carbon atoms, metal (Al, Ca, etc.) salts of higher fatty acids with 8 to 22 carbon atoms, higher aliphatic alcohols with 8 to 22 carbon atoms, polyglycols, etc.) Examples of additives include esters of higher fatty acids having 4 to 22 carbon atoms and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher fatty acid amides having 8 to 22 carbon atoms, silicone oils, rosin derivatives, etc.), fillers (talc, hydrotalcite, mica, zeolite, perlite, diatomaceous earth, calcium carbonate, glass fiber, etc.), blowing agents, blowing aids, polymer additives, plasticizers (dialkyl phthalates, dialkyl hexahydrophthalates, etc.), crosslinking agents, crosslinking accelerators, antistatic agents, flame retardants, dispersants, organic and inorganic pigments (indigo compounds, phthalocyanine compounds, anthraquinone compounds, ultramarine compounds, cobalt aluminate compounds, etc.), processing aids, and other nucleating agents.

[0041] Examples of the above-mentioned antioxidants include phenolic antioxidants, phosphite ester antioxidants, and sulfur-based antioxidants. Specific examples of antioxidants include phenolic antioxidants such as 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, and 2-hydroxy-4-methoxybenzophenone; sulfur-based antioxidants such as alkyl disulfides, thiodipropionates, and benzothiazoles; and phosphite ester antioxidants such as trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane. Among these, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, a phenolic antioxidant, tris(2,4-di-tert-butylphenyl)phosphite, and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane are particularly recommended.

[0042] If the polyolefin resin composition of the present invention contains the above-mentioned other additives, the content of the additives is not particularly limited as long as the effects of the present invention are achieved, and can be within the range of commonly used additives. The content of the additives is usually 0.0001 to 100 parts by mass, preferably 0.001 to 50 parts by mass, per 100 parts by mass of the polyolefin resin.

[0043] [Preparation of Polyolefin Resin Composition] The polyolefin resin composition of the present invention can be prepared by mixing a compound represented by general formula (1), a surfactant (S) containing a compound represented by general formula (2), and a polyolefin resin. Other additives as described above may be added as needed. As a preparation method, for example, these components can be mixed and then melt-mixed. For example, they can be mixed at room temperature using a general-purpose rotary or agitator-type dry powder mixer such as a Henschel mixer, and then melt-mixed using a twin-screw extruder at a barrel temperature of 160 to 260°C.

[0044] The polyolefin resin composition of the present invention contains a surfactant (S) containing the compound represented by general formula (1) and the compound represented by general formula (2), thereby providing excellent crystallization promotion and improved mechanical properties of molded articles. In particular, the crystallization promotion effect and the improvement of mechanical properties of molded articles are significantly greater compared to cases where the surfactant (S) containing the compound represented by general formula (1) or the compound represented by general formula (2) is used alone in a polyolefin resin.

[0045] The ratio (mass ratio) of the compound represented by general formula (1) to the surfactant (S) containing the compound represented by general formula (2) in the polyolefin resin composition is not particularly limited as long as the effects of the present invention are achieved, and is usually 1 / 80000 to 1 / 0.0001, preferably 1 / 4000 to 1 / 0.001, and more preferably 1 / 3000 to 1 / 0.005. Setting the ratio (mass ratio) of the compound represented by general formula (1) to the surfactant (S) containing the compound represented by general formula (2) within the above range provides a better crystallization promotion effect and an improvement in the mechanical properties of the molded product.

[0046] Since the compound represented by general formula (1) is a solid, considering its dispersibility and handling in the polyolefin resin composition, it is also possible to prepare the polyolefin resin composition of the present invention by first preparing a nucleating agent masterbatch containing the compound represented by general formula (1). The nucleating agent masterbatch can also be described as a crystal nucleating agent composition for polyolefin resins.

[0047] Specifically, the polyolefin resin composition of the present invention can be prepared by mixing the compound represented by general formula (1) with a polyolefin resin and / or surfactant (S) to make a masterbatch, mixing this masterbatch with the remaining components (surfactant (S) and / or polyolefin resin) to a predetermined proportion, and then melt-kneading it. If necessary, other additives may be added at one or both of these steps.

[0048] The above mixing can be performed, for example, at room temperature using a general-purpose rotary or agitator-type dry powder mixer such as a Henschel mixer. Melt kneading can be performed, for example, using a twin-screw extruder at a barrel temperature of 160 to 260°C.

[0049] Typically, the polyolefin resin composition of the present invention can be prepared by stepwise mixing a surfactant (S) containing the compound represented by general formula (1) and the compound represented by general formula (2), and optionally a polyolefin resin to prepare a masterbatch, mixing this with the polyolefin resin, and then melt-kneading it.

[0050] The ratio (mass ratio) of the compound represented by general formula (1) to the surfactant (S) containing the compound represented by general formula (2) in the masterbatch is not particularly limited, and is usually 1 / 8000 to 1 / 0.01, preferably 1 / 6000 to 1 / 0.1, and more preferably 1 / 5000 to 1 / 0.5.

[0051] When the masterbatch contains a polyolefin resin, the content of the compound represented by general formula (1) in the masterbatch is usually 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the polyolefin resin.

[0052] When the masterbatch contains a polyolefin resin, the content of the surfactant (S) containing the compound represented by general formula (2) in the masterbatch is usually 0.1 to 80 parts by mass, preferably 0.5 to 60 parts by mass, and more preferably 1 to 50 parts by mass, per 100 parts by mass of the polyolefin resin.

[0053] If the masterbatch further contains the other additives mentioned above, the additive content is usually 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, when the entire masterbatch is considered to be 100% by mass.

[0054] 2. Polyolefin Resin Molded Article The polyolefin resin molded article of the present invention is obtained by molding the above-mentioned polyolefin resin composition according to a conventional molding method. As long as the effects of the present invention are achieved, there are no particular restrictions on the molding method, and any conventionally known molding method such as injection molding, extrusion molding, blow molding, pressure molding, rotational molding, and film molding can be used.

[0055] The resulting polyolefin resin molded articles have a high crystallization temperature and a fast crystallization rate. As a result, the molding cycle of the polyolefin resin molded articles is significantly shortened. In particular, the molding cycle of molded articles such as large components is significantly shortened, which can lead to cost reduction and prevention of problems during processing, making the polyolefin resin molded articles of the present invention extremely useful.

[0056] Furthermore, the resulting polyolefin resin molded articles exhibit significantly improved mechanical properties (particularly impact strength). This is because the polyolefin resin composition of the present invention, by including a surfactant containing the compound represented by general formula (1) and the compound represented by general formula (2), greatly improved crystallinity. Conventionally, the compound represented by general formula (1) has been used as an α-crystal nucleating agent for polyolefin resins, but by using the compound represented by general formula (1) and a surfactant containing the compound represented by general formula (2) in combination, the β-crystals of the polyolefin resin unexpectedly increased, and it is believed that the mechanical properties of the molded article improved dramatically. This increase in β-crystals can be confirmed by the increase in the K value. Thus, because the crystallinity of the polyolefin resin molded articles of the present invention is improved, weight reduction can be achieved by thinning the wall while maintaining rigidity. Therefore, it can be suitably used in the fields of automotive materials and industrial materials.

[0057] In this specification, the expressions “contain,” “include,” or “possess” encompass not only their literal meanings but also the meanings of “substantially consisting of” and “consisting of only.”

[0058] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto. In the table, "parts" refers to "parts by mass" unless otherwise specified. 1. Compounds Used

[0059] <Crystal Nucleating Agent> The following metal salts of cyclohexanedicarboxylic acid were used as the crystal nucleating agent.

[0060] <Surfactants> The surfactant used was the (poly)glycerol fatty acid ester listed below. (*1): The number of carbon atoms in the aliphatic hydrocarbon chain obtained by removing the carbonyl group (CO) from the ester constituting the (poly)glycerol fatty acid ester (corresponding to the number of carbon atoms in R in general formula (2)). The aliphatic hydrocarbon chains of the (poly)glycerol fatty acid esters of surfactants G and H are unsaturated (containing carbon-carbon double bonds), while those of the other surfactants A to F and I are saturated. (*2): Corresponding to n in general formula (2) (*3): The number of hydroxyl groups (Y) esterified with fatty acids relative to the total number of hydroxyl groups (X) of (poly)glycerol constituting the (poly)glycerol fatty acid ester, expressed as a percentage (= Y / X × 100 (%))

[0061] <Polyolefin Resins> The following compounds were used for the polyolefin resins.

[0062] 2. Preparation of Polypropylene Resin Compositions [Examples 1-5 and 9-27, Comparative Examples 1-3 and 7-23] Polypropylene resin, surfactant, and nucleating agent were mixed in a Henschel mixer in the amounts shown in Tables 1-8. Then, the mixture was melt-kneaded at 200°C using a single-screw or twin-screw extruder, cooled, and cut to obtain resin pellets.

[0063] Using the resin pellets obtained above, injection molding was performed using an injection molding machine (NS40-5A, manufactured by Nissei Plastic Industrial Co., Ltd.) under the conditions of an injection molding temperature (heating temperature) of 200°C and a mold temperature (cooling temperature) of 40°C to obtain molded bodies (test specimens) for Examples 1-5 and 9-27, and Comparative Examples 1-3 and 7-23. The test specimens used for measuring each physical property were as follows: • For bending test and Charpy impact strength measurement: 4 mm × 10 mm × 90 mm test specimens • For crystallization temperature and K value measurement: 1 mm thick test specimens (sheets)

[0064] [Examples 6-8, Comparative Examples 4-6] In Examples 6-8, homo-PP, a surfactant, and a nucleating agent were mixed in a Henschel mixer, then melt-kneaded at 200°C using a twin-screw extruder, followed by cooling and cutting to obtain resin pellets (masterbatch). In Comparative Examples 4-6, homo-PP and a surfactant were mixed in a Henschel mixer, then melt-kneaded at 200°C using a twin-screw extruder, followed by cooling and cutting to obtain resin pellets (masterbatch).

[0065] The resin pellets obtained above and the polypropylene resin were mixed in a Henschel mixer in the proportions shown in Tables 4 and 5. Then, the mixture was injection molded in an injection molding machine (NS40-5A, manufactured by Nissei Plastic Industrial Co., Ltd.) under the conditions of an injection molding temperature (heating temperature) of 200°C and a mold temperature (cooling temperature) of 40°C to obtain molded bodies (test pieces) of Examples 6 to 8 and Comparative Examples 4 to 6. The test pieces used for measuring each physical property were the same as above.

[0066] [Examples 28 and 29, Comparative Examples 24 and 25] Homo PP and a nucleating agent (compound 1) were pre-kneaded and then mixed in a Henschel mixer to obtain pellets. The mass ratio of homo PP to nucleating agent (compound 1) was 95 / 5. The obtained resin pellets (polypropylene masterbatch) were used as masterbatch 1.

[0067] Low-density PE and a nucleating agent (compound 1) were pre-kneaded and then mixed in a Henschel mixer to obtain pellets. The mass ratio of low-density PE to nucleating agent (compound 1) was 95 / 5. The obtained resin pellets (polyethylene-based masterbatch) were used as masterbatch 2.

[0068] In Examples 28 and 29, homo PP, surfactant A, and masterbatch 1 or 2 were mixed in a Henschel mixer in the amounts shown in Table 9. Then, the mixture was melt-kneaded at 200°C using a twin-screw extruder, cooled, and cut to obtain resin pellets. In Comparative Examples 24 and 25, homo PP and masterbatch 1 or 2 were mixed in a Henschel mixer in the amounts shown in Table 9. Then, the mixture was melt-kneaded at 200°C using a twin-screw extruder, cooled, and cut to obtain resin pellets.

[0069] The resin pellets obtained above were injection molded using an injection molding machine (NS40-5A, manufactured by Nissei Plastic Industrial Co., Ltd.) under the conditions of an injection molding temperature (heating temperature) of 200°C and a mold temperature (cooling temperature) of 40°C to obtain molded bodies (test pieces) for Examples 28 and 29 and Comparative Examples 24 and 25. The test pieces used for measuring each physical property were the same as those described above.

[0070] 3. Measurement and Evaluation of Physical Properties The following physical properties were measured and evaluated using the obtained test specimens. (1) Crystallization Temperature A differential scanning calorimetry analyzer (PerkinElmer, product name DSC8500) was used to measure the crystallization temperature in accordance with JIS K7121:2012 "Method for Measuring Transition Temperature of Plastics". The test specimen was set in the apparatus, held at 200°C for 3 minutes, then cooled at a cooling rate of 10°C / min, and the peak of the endothermic peak was taken as the crystallization temperature (°C). The evaluation criteria for crystallization temperature are as follows: ◎: 130°C or higher ○: 125°C or higher and less than 130°C ×: Less than 125°C

[0071] (2) The flexural modulus (MPa) was measured using a universal material testing machine (Instron, product name 68™) in accordance with JIS 7171:2016. The evaluation criteria for flexural modulus are as follows: (When using homopolypropylene) ◎: 1550 or more ○: 1450 or more and less than 1550 ×: Less than 1450 (When using block polypropylene) ◎: 1200 or more ○: 1100 or more and less than 1200 ×: Less than 1100

[0072] (3) The bending strength (MPa) was measured in accordance with JIS 7171:2016 using a universal bending strength tester (Instron, product name 68™). The evaluation criteria for bending strength are as follows: (When using homopolypropylene) ◎: 49 or higher ○: 46 or higher and less than 49 ×: less than 46 (When using block polypropylene) ○: 35 or higher ×: less than 35

[0073] (4) Using a Charpy impact strength tester (manufactured by Toyo Seiki Co., Ltd., product name ImpactTesterIT), the impact strength (kJ / m²) of a notched test specimen at 23°C was measured in accordance with JIS K7111-1:2012. ２ The Charpy impact strength was measured. The evaluation criteria for Charpy impact strength are as follows: (When using homopolypropylene) ◎: 3.0 or higher ○: 2.0 or higher and less than 3.0 ×: less than 2.0 (When using block polypropylene) ○: 7.0 or higher ×: less than 7.0

[0074] (5) K-value The K-value was determined by performing X-ray diffraction on a test piece (sheet) obtained by injection molding using a fully automatic multi-purpose X-ray diffractometer (manufactured by Rigaku Corporation, product name: SmartLab), and using the following formula: K-value = H(β1) / [H(β1) + H(α1) + H(α2) + H(α3)] H(β1): Diffraction intensity (height) of the β-crystal (300) plane H(α1): Diffraction intensity (height) of the α-crystal (110) plane H(α2): Diffraction intensity (height) of the α-crystal (040) plane H(α3): Diffraction intensity (height) of the α-crystal (130) plane

[0075] (6) Overall evaluation In the evaluation of the physical properties in (1) to (4) above, items with no "×" marks were marked as "○", and items with even one "×" mark were marked as "×".

[0076] The evaluation results of the physical properties of the test specimens obtained in the examples and comparative examples are shown in Tables 4 to 8.

[0077] Comparing Examples 1-29 with Comparative Examples 1-25, it was found that compositions containing a crystal nucleating agent and a surfactant in addition to a polypropylene resin exhibited a superior crystallization-promoting effect compared to compositions containing either a crystal nucleating agent or a surfactant in addition to a polypropylene resin, and that the molded articles possessed superior mechanical properties.

[0078] Examples 1 to 29 show that even when various surfactants and various nucleating agents are used, the crystallization promoting effect is excellent, and the molded articles exhibit superior mechanical properties.

[0079] The polyolefin resin composition of the present invention exhibits excellent crystallinity (high crystallization temperature), and its molded products possess excellent mechanical properties (particularly impact strength). Due to its excellent crystallinity, the molding cycle can be significantly shortened, especially for large components, leading to cost reduction and prevention of processing problems. Due to its excellent impact strength, it can be used to reduce weight through thinning, for example, in the fields of automotive and industrial materials. Taking advantage of the above-mentioned characteristics, the polyolefin resin composition of the present invention can be used in a variety of applications, not limited to automotive and industrial materials, but also including electrical components, machine parts, daily necessities, clothing cases, food containers, and more.

Claims

1. A polyolefin resin composition comprising a compound represented by general formula (1), a surfactant (S) containing a compound represented by general formula (2), and a polyolefin resin. [In the formula, R １ R is an alkyl group having 1 to 4 carbon atoms. １ It is bonded to the carbon at position 3 or 4 on the cyclohexane ring, M １ It is calcium, zinc, hydroxyaluminum, sodium, or lithium, M １ If is calcium, zinc, or hydroxyaluminum, then a is 2, b is 1, and M １ If a is sodium or lithium, then a is 1 and b is 2. [In the formula, A is the same or different hydrogen atom or -COR, and R is an aliphatic hydrocarbon group having 7 to 29 carbon atoms. At least one A is -COR. n is an integer from 1 to 100.] 2. The polyolefin resin composition according to claim 1, wherein in the compound represented by general formula (2), R is an aliphatic hydrocarbon group having 7 to 17 carbon atoms.

3. The polyolefin resin composition according to claim 1, wherein n is an integer from 1 to 30 in the compound represented by general formula (2).

4. The polyolefin resin composition according to claim 1, wherein the compound represented by general formula (2) has an esterification rate of 1 to 100.

5. In a compound represented by general formula (1), R １ The polyolefin resin composition according to claim 1, wherein the carbon atom is bonded to the carbon atom at position 4 on the cyclohexane ring.

6. In a compound represented by general formula (1), R １ The polyolefin resin composition according to claim 1, wherein the group is a methyl group.

7. In a compound represented by general formula (1), M １ The polyolefin resin composition according to claim 1, wherein the compound is calcium.

8. The polyolefin resin composition according to claim 1, comprising 0.001 to 10 parts by mass of a compound represented by general formula (1) per 100 parts by mass of polyolefin resin.

9. The polyolefin resin composition according to claim 1, comprising 0.001 to 80 parts by mass of a surfactant (S) containing a compound represented by general formula (2) per 100 parts by mass of the polyolefin resin.

10. The polyolefin resin composition according to claim 1, wherein the mass ratio of the compound represented by general formula (1) to the surfactant (S) containing the compound represented by general formula (2) is 1 / 80000 to 1 / 0.0001.

11. A method for producing the polyolefin resin composition according to claim 1, comprising the step of mixing a compound represented by general formula (1), a surfactant (S) containing a compound represented by general formula (2), and a polyolefin resin.

12. A crystal nucleating agent composition for polyolefin-based resins, comprising a surfactant (S) containing a compound represented by general formula (1) and a compound represented by general formula (2). [wherein, R １ is an alkyl group having 1 to 4 carbon atoms, R １ is bonded to a carbon at position 3 or position 4 on the cyclohexane ring, M １ is calcium, zinc, hydroxyaluminum, sodium or lithium, M １ when M is calcium, zinc or hydroxyaluminum, a is 2 and b is 1, M １ when M is sodium or lithium, a is 1 and b is 2.]] [wherein, A are the same or different and each represent a hydrogen atom or -COR, R is an aliphatic hydrocarbon group having 7 to 29 carbon atoms. At least one A is -COR. n is an integer from 1 to 100.]] 13. A method for producing a crystal nucleating agent composition for polyolefin resins according to claim 12, comprising the step of mixing a surfactant (S) containing a compound represented by general formula (1) and a compound represented by general formula (2).

14. A method for producing the polyolefin resin composition according to claim 1, comprising the step of mixing the crystal nucleating agent composition for polyolefin resins according to claim 12 and the polyolefin resin.

15. A polyolefin resin molded article comprising the polyolefin resin composition according to any one of claims 1 to 10.

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