JPH0827323A - Nucleator composition and polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain a nucleator compsn. which greatly improves the transparency of a polyolefin resin by compounding a sorbitol compd. with a specified amt. of a specific compd. CONSTITUTION:The compsn. contains 100 pts.wt. sorbitol compd. of formula I (wherein R<1> and R<2> are each H, 1-4C alkyl, halogen, 1-4C alkoxy, or alkylthio) and 0.1-40 pts.wt. compd. selected from among a metal salt of a phosphorus compd. of formula II or III (wherein R<3> is a direct bond, S, alkylene, or alkylidene; R<4> to R<7> are each H, alkyl, or cycloalkyl; c and d are each 0 or 1; M is a metal atom; and e is the valency of the metal atom), an ammonium salt of a phosphoric acid compd. of formula IV or V (wherein R<8> is the same as R<3>; R<9> to R<3> are each the same as R<4> or R<5>; f and g are each 0 or 1; A is an ammonium ion or an org. ammonium ion; and m and n are each 1-6), and 1,6,11-triaminoundecanetricyclohexanecarboxamide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a nucleating agent composition and a polyolefin resin composition containing the nucleating agent composition.

[0002]

2. Description of the Related Art Dibenzylidene sorbitols (hereinafter abbreviated as "DBS compounds") prepared by acetal condensation of aromatic aldehydes and sorbitol in the presence of an acid catalyst are used for polyolefin resin compositions. It has been widely used as a nucleating agent, and the present inventors have been proposing various DBS compounds under intensive studies in order to provide a nucleating agent having more excellent properties.

Specifically, 1,3: 2,4-bis (O-
Benzylidene) sorbitol (hereinafter abbreviated as "DBS") can greatly improve the optical properties of a molded article obtained from a polyolefin resin, especially its transparency, but is used in fields requiring higher transparency. On the other hand, it does not fully satisfy the demand.

In order to solve such a problem, 1,3: 2,4-bis (O-methylbenzylidene) sorbitol (hereinafter referred to as "Me" is prepared by using methyl-substituted benzaldehyde as a starting material instead of benzaldehyde.
-D "is abbreviated. ) (Japanese Patent Laid-Open No. 53-11704)
4, JP-A-54-28348).

1,3: 2,4-bis (polyalkylbenzylidene) sorbitol (JP-A-56-45934)
And a so-called asymmetric DBS compound having different kinds and numbers of substituents on each aromatic ring (Japanese Patent Laid-Open No. 59-1295).
No. 1) provides a polyolefin resin composition suitable for the production of a molded article having excellent transparency as in the case of using Me-D, and also has a drawback of Me-D, that is, odors at the time of heat molding. The occurrence was greatly suppressed.

[0006] Since the DBS compound is a "dissolving type" nucleating agent whose melting point is equal to or higher than its melting point and is uniformly dissolved in the resin, it is necessary to process the polyolefin resin at the time of molding. It is important to melt mix the nucleating agent at high speed.

The nucleating agent composition (Japanese Patent Application Laid-Open No. 2-206627), which has been proposed by the present inventors and which mainly contains an asymmetric diacetaal having a specific structure, is a compound of the same kind known so far. The melting point of the resin composition is much lower than that of, and the resin composition containing the nucleating agent composition is not only significantly improved in processability but also has transparency and various other properties. It gives a molded article excellent in properties.

As a nucleating agent for polyolefin resins,
In addition to the above-mentioned sorbitol-based compounds, dispersion-type nucleating agents such as organic carboxylic acid metal salts, silica, and metal salts of cyclic aromatic phosphorus compounds (Japanese Patent Laid-Open No. 58-1736) are known.

As described above, although various nucleating agents have been proposed, there are various needs for nucleating agents, and there is still room for improvement in order to be applied to a wide range of applications.

[0010]

DISCLOSURE OF THE INVENTION The present invention provides a novel and useful nucleating agent composition capable of imparting a more excellent transparency improving effect to a polyolefin resin and a polyolefin resin containing the nucleating agent composition. It is intended to provide a composition.

[0011]

Means for Solving the Problems The present inventors have deeply studied the combined effect of a sorbitol-based nucleating agent and various nucleating agents conventionally considered to be dispersion-type nucleating agents. By blending a specified amount of a specific compound, they can act synergistically to dramatically improve the transparency of the molded product, and at the same time provide excellent moldability and rigidity, which is a very specific phenomenon. The present invention has been found, and the present invention has been completed based on such findings.

That is, the nucleating agent composition of the present invention contains 100 parts by weight of one or more compounds (component A) selected from the sorbitols represented by the general formula (1).
Metal salts of phosphorus compounds represented by general formula (2) or general formula (3) or ammonium salts of phosphoric acid compounds represented by general formula (4) or general formula (5) and 1,6,6
It is characterized by containing 0.1 to 40 parts by weight of one or more compounds (component B) selected from the group consisting of 11-triaminoundecanetricyclohexanecarboxylic acid amide.

[0013] [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen group, an alkyloxy group having 1 to 4 carbon atoms or an alkylthio group having 1 to 4 carbon atoms. . a and b show the integer of 1-3. In R ¹ and R ² , at least one group occupies 4-position. ]

[0014] [In the formula, R ³ represents a direct bond, a sulfur atom, an alkylene group or an alkylidene group, and R ⁴ and R ⁵ are the same or different,
Each represents a hydrogen atom, an alkyl group or a cycloalkyl group. c and d represent 0 or 1. e represents the valence of the metal, and M represents the metal atom. ]

[0015] [Wherein R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom,
It represents an alkyl group or a cycloalkyl group. M represents a metal atom. ]

[0016] [In the formula, R ⁸ represents a direct bond, a sulfur atom, an alkylene group or an alkylidene group, and R ⁹ and R ¹⁰ are the same or different and each represent a hydrogen atom, an alkyl group or a cycloalkyl group. f and g represent 0 or 1. A represents an ammonium ion or an organic ammonium ion. m represents an integer of 1 to 6. ]

[0017] [In the formula, R ¹¹ , R ¹² and R ¹³ are the same or different and each represents a hydrogen atom, an alkyl group or a cycloalkyl group. A represents an ammonium ion or an organic ammonium ion. n shows the integer of 1-6. ]

The synergistic effect of the components A and B according to the present invention is considered to be due to the following unexpected facts. That is, the component A forms a fibril-like network structure at a temperature below a specific sol-gel transition temperature upon cooling after being molecularly dispersed in a molten resin at a high temperature (the latest technology of polymer additives,
p204, published by CMC, 1988). At this time, the B component is excluded and precipitates outside the mesh. Only when the fibril surface of the component A and the surface of the component B have the same polyolefin crystallization promoting effect, the spherulites become finer and the spherulite size distribution becomes smaller than that of the component A alone. Thus, a high degree of transparency is achieved and at the same time the rigidity of the polyolefin is improved. However, if the blending amount of the B component increases, the scattering of light based on the B component increases, and the intended purpose cannot be achieved.

According to the present invention, the following excellent advantages are achieved. (1) The resin composition of the present invention reaches the highest transparency. (2) The molding cycle time is shortened by improving the crystallization temperature. (3) The resin composition of the present invention does not generate sink marks,
Moreover, even when the pigment is dispersed, molding can be performed without causing volume shrinkage. (4) Stretched films can be produced with improved dimensional stability. (5) The molded product also has improved gloss. (6) The molded product is also excellent in mechanical and thermal properties such as elastic modulus, impact resistance, and heat distortion temperature. (7) Staining of the mold during molding is scarcely observed, and continuous molding is facilitated.

In the sorbitol compound represented by the general formula (1), R ¹ or R ² is a hydrogen atom, an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, or a chlorine atom. Halogen groups such as bromine atom, methyloxy, ethyloxy, n-propyloxy, isopropyloxy, n-butyloxy,
Alkyloxy groups such as isobutyloxy, methylthio,
Ethylthio, n-propylthio, isopropylthio, n
-Butylthio, isobutylthio and other alkylthio groups are exemplified, and the substitution positions thereof are 4-position, 2,4-position,
3,4-position, 2,3,4-position and 2,4,6-position are mentioned.

The recommended component A is 1, 3: 2,
4-bis (O-3,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (O-2,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (O-4-) Methylbenzylidene) sorbitol, 1,
3: 2,4-bis (O-4-ethylbenzylidene) sorbitol, 1,3: 2,4-bis (O-4-chlorobenzylidene) sorbitol and 1,3: 2,4-dibenzylidenesorbitol And one or more sorbitols selected from the following.

As the alkylene group represented by R ³ in the general formula (2) or R ⁸ in the general formula (4),
Examples thereof include methylene, ethylene, propylene and butylene, and examples of the alkylidene group include methylidene, ethylidene, butylidene, hexylidene, octylidene, nonylidene, cyclopentylidene, cyclohexylidene, cyclooctylidene and the like.

R ⁴ and R ^{5 in} the general formula (2), R ⁶ and R ^{7 in} the general formula (3), R ⁹ in the general formula (4),
R ^10, R ¹¹ in the general formula (5), R ¹² and R ¹³ are each methyl, ethyl, isopropyl, n-butyl,
Isobutyl, secondary butyl, tertiary butyl, n-amyl, tertiary amyl, hexyl, heptyl, n-octyl, 2-ethylhexyl, tertiary octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Examples thereof include alkyl groups such as heptayl and octadecyl, and cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

M in the general formulas (2) and (3)
Are Li, Na, K, Be, Mg, Ca, Sr,
Ba, Zn, Cd, Al, Ge, Sn, Pb, Ti, Z
r, Sb, Cr, Bi, Mo, Mn, Fe, Co, Ni
And the like, and alkali metals such as Li, Na, and K, and alkaline earth metals such as Mg, Ca, Sr, and Ba are particularly preferable.

The organic amine compound constituting the organic ammonium salt represented by the general formulas (4) and (5) is a saturated or unsaturated aliphatic amine having 1 to 18 carbon atoms, an alicyclic amine, Heterocyclic amines and monovalent and polyvalent amines such as aromatic amines are exemplified, and specifically, various amines disclosed in JP-A-5-9390, for example, methylamine, ethylamine, diethylamine,
Triethylamine, propylamine, 2-aminopropane, dipropylamine, butylamine, isobutylamine, tert-butylamine, dipropylamine, diisobutylamine, ditert-butylamine, pentylamine, 2-
Aminopentane, hexylamine, octylamine, 2
-Ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, coconutamine,
Benzylamine, dibenzylamine, phenylethylamine, 3-methoxypropylamine, piperidine, pipecoline, N-aminopropylpipecoline, morpholine,
Monovalent amine compounds such as lupetidine, aniline, toluidine, xylidine, ethylaniline, pyridine, picoline, ethylpyridine, lutidine, methylethylpyridine, 3-aminotriazine, aminotetrazole, ethylenediamine, propylenediamine, butylenediamine,
Hexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine, phenyldiamine, piperazine, pyrazine, aminoethylpyridine, N, N'-bisaminoethyl-ethylenediamine, N , N'-bisaminoethyl-hexamethylenediamine, N, N'-bisaminopropyl-ethylenediamine, N, N'-bisaminopropyl-hexamethylenediamine, tris (2-aminoethyl) amine, tris (3-amino) Propyl) amine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine,
Octamethylenediamine, decamethylenediamine, undecamethylenediamine, 3,9-bis (aminopropyl) -2,4,8,10-tetraoxaspiro [5.
5] undecane, 4-oxa-1,7-diaminopentane, 4,7-dioxa-1,10-diaminodecane,
4,8-Dioxa-6,6-dimethyl-1,11-diaminoundecane, m-xylylenediamine, 1,6,1
1-triaminoundecane, 4-aminomethyl-1,8
-Polyamines such as diaminooctane are mentioned.

As the recommended component B, undecane-1,6,11-triammonium salt of 2,2'-methylenebis (4,6-tert-butylphenyl) phosphoric acid ester, 2,2-methylenebisphosphoric acid is recommended. Examples include one or more compounds selected from the group consisting of (4,6-tert-butylphenyl) sodium and 1,6,11-triaminoundecanetricyclohexanecarboxylic acid amide.

In the nucleating agent composition according to the present invention, the combined amount of component B with respect to 100 parts by weight of component A is 0.1-40.
By weight, more preferably 0.2 to 5 parts by weight. When the component B is blended in an amount of less than 0.1 part by weight or more than 40 parts by weight, the predetermined combined effect of the present invention, specifically, the specific effect of improving transparency cannot be obtained.

The components A and B are both known compounds and can be easily produced according to known methods. Therefore,
The nucleating agent composition according to the present invention can be prepared by mixing the A component and the B component in a predetermined ratio.

A conventionally known dispersion type nucleating agent (component C) can be appropriately added to the nucleating agent composition according to the present invention.

Examples of the dispersion type nucleating agent include mono- or polyvalent aromatic carboxylic acid salts such as sodium p-tert-butylbenzoate, and carbon atoms such as sodium myristate having 10 to 2 carbon atoms.
The aliphatic carboxylic acid metal salt and the alicyclic carboxylic acid metal salt of 4 are exemplified.

The present invention also provides a useful polyolefin resin composition containing the nucleating agent composition.

The blending amount of the nucleating agent composition according to the present invention with respect to the polyolefin resin is not particularly limited as long as a predetermined effect can be obtained, and can be appropriately selected. Usually, it is usually per 100 parts by weight of the resin. 0.01 to 1 part by weight,
Preferably about 0.1 to 0.5 part by weight is compounded. By blending within these ranges, the effects prescribed by the present invention can be sufficiently obtained.

As a method of adding the nucleating agent composition, a one-step addition method is preferable, but for example, a two-step method by addition in the form of a high-concentration masterbatch of about 2 to 15% by weight may be adopted. Alternatively, the A component and the B component may be separately blended with the resin and molded.

Examples of the polyolefin resin to which the nucleating agent according to the present invention is applied include polyethylene resins and polypropylene resins, and more specifically, high density polyethylene, medium density polyethylene, linear polyethylene,
Ethylene copolymer having an ethylene content of 50% by weight or more, propylene homopolymer, propylene copolymer having a propylene content of 50% by weight or more, butene homopolymer, butene copolymer having a butene content of 50% by weight or more, methylpentene homopolymer, methylpentene content of 50% by weight or more The methyl pentene copolymer, crystalline polybutadiene, crystalline polyisoprene, etc.

The above copolymer may be a random copolymer or a block copolymer. The stereoregularity of these resins may be isotactic or syndiotactic.

Specific examples of the comonomer capable of forming the above copolymer include α-olefins such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene and dodecene, 1,4
Examples thereof include bicyclo-type monomers such as endomethylenecyclohexene, methyl (meth) acrylate, (meth) acrylates such as ethyl (meth) acrylate, vinyl acetate and the like. Any molecular weight and molecular weight distribution of these polymers can be applied.

To the polyolefin resin composition according to the present invention, conventionally known modifiers for polyolefin can be added as appropriate depending on the purpose of use and the use thereof within a range that does not impair the effects of the present invention.

As such a modifier for polyolefin,
Examples thereof include various additives described in "Positive List of Additives" (October 1990) edited by the Council for Hygiene of Polyolefins, and more specifically, stabilizers (metal compounds, epoxy compounds, nitrogen). Compounds, phosphorus compounds, sulfur compounds, etc., ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), antioxidants (phenolic compounds, phosphite compounds, sulfur compounds, etc.), surfactants, Lubricants (aliphatic hydrocarbons such as paraffin and wax, higher fatty acids having 8 to 22 carbon atoms, higher fatty acid metals having 8 to 22 carbon atoms (Al, Ca, M
g, Zn) salt, fatty acid having 8 to 18 carbon atoms, 8 to 2 carbon atoms
2 aliphatic alcohols, polyglycols, 4 to 2 carbon atoms
Esters of 2 higher fatty acids and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher fatty acid amides having 8 to 22 carbon atoms, silicone oil, rosin derivatives, etc., fillers (talc, hydrotalcite, mica, zeolite) , Perlite, diatomaceous earth, calcium carbonate, glass fiber, etc.), foaming agent, foaming aid, polymer additive, plasticizer (dialkyl phthalate, dialkyl hexahydrophthalate, etc.), cross-linking agent, cross-linking accelerator, antistatic agent, Examples include flame retardants, dispersants, organic-inorganic pigments, and processing aids.

In producing the resin composition, any conventionally known method can be applied. For example, the nucleating agent composition according to the present invention is directly blended with a polyolefin resin and finally molded. Alternatively, the nucleating agent composition may be blended in advance with the resin and pelletized,
After that, final molding may be performed. The nucleating agent and the organic amine may be blended in advance and then molded by the above method.

In molding the resin composition according to the present invention, any conventionally known molding method such as injection molding, extrusion molding, blow molding, pressure molding, rotational molding, film molding, etc. can be adopted.

The polyolefin resin composition according to the present invention is applied in various fields similar to those in which a polyolefin resin composition prepared by blending a DBS compound as a nucleating agent composition has hitherto been used, and more specifically, , Disposable syringes that are sterilized by heat, radiation, etc.
Medical instruments such as blood transfusion sets and blood collection instruments; packages of foods and plants that are sterilized by radiation etc .; various cases such as clothing cases and clothing storage containers; cups for heat-filling food, retort foods Packaging containers for microwave ovens; containers for beverages such as juice and tea, cosmetics, pharmaceuticals, shampoo, cans, bottles, etc .; containers and caps for seasonings such as miso, soy sauce; water, rice, It is suitable as a material for cases and containers for food such as bread and pickles; miscellaneous goods such as cases for refrigerators; stationery; electrical and mechanical parts; parts for automobiles.

[0042]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples. The evaluation in each of the following examples was performed by the following method.

Haze (%) and gloss were measured using a transparency haze meter of the polyolefin resin composition (JIS K 6714, JIS K 6717). The smaller the haze, the better the optical properties. (As a result of the measurement, the resin compositions containing the nucleating agent of the examples all showed good gloss.)

Rigidity of Polyolefin Resin Composition Calculated from the results of bending test of test pieces (JIS
K 7203).

Preparation of Nucleating Agent Composition Predetermined A and B components, and optionally C component, are mixed in a 1 liter universal stirrer for 15 minutes to prepare a nucleating agent composition having the composition shown in Table 1. To do. Component A A1: 1,3: 2,4-bis (O-3,4-dimethylbenzylidene) sorbitol (powder) A2: 1,3: 2,4-bis (O-benzylidene) sorbitol (powder) A3: 1 , 3: 2,4-bis (O-4-ethylbenzylidene) sorbitol (powder)

Component B B1: 2,2'-methylenebis (4,6-tert-butylphenyl) phosphoric acid ester undecane-1,6,11
-Triammonium salt (powder) B2: 2,2'-methylenebis (4,6-di-te phosphate)
rt-Butylphenyl) sodium B3: tricyclohexylcarboxylic acid amide of 1,6,11-undecaneamine

Component C C1: sodium myristate C2: sodium p-tert-butylbenzoate

Example 1 For an isotactic random polypropylene resin having an ethylene content of 3.0% by weight (hereinafter abbreviated as "polypropylene A"), a prescribed nucleating agent composition, tetrakis [methylene-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (trade name, Irganox 1010, manufactured by Ciba Geigy) and calcium stearate are added in the following composition and mixed by a Henschel mixer for 5 minutes, Then, the mixture was kneaded at 245 ° C. with a Labo Plastomill extruder and extruded, and pellets were obtained by a water cooling method. The pellets were injection-molded at 230 ° C. to obtain a sheet having a thickness of 1.0 mm, which was used as a sample, and its transparency and rigidity were evaluated. The results obtained are shown in Table 1.

Polypropylene A 100 parts by weight Nucleating agent composition 0.25 parts by weight Irganox 1010 0.05 parts by weight Calcium stearate 0.03 parts by weight

Examples 2 to 18 Samples were prepared in the same manner as in Example 1 except that the nucleating agent composition shown in Table 1 was applied, and their transparency and rigidity were evaluated. The results obtained are shown in Table 1.

Comparative Examples 1 to 6 "Polypropylene A" resin compositions prepared by blending the nucleating agents shown in Table 1 in predetermined amounts were prepared and evaluated for transparency and rigidity in the same manner as in Example 1. . The results obtained are shown in Table 1.

Comparative Example 7 A "polypropylene A" resin composition prepared in the same manner as in Example 1 except that no nucleating agent was added was evaluated for transparency and rigidity. The results obtained are shown in Table 1.

Example 19 A resin composition prepared by mixing 2 parts by weight of the nucleating agent composition shown in Table 2 with 100 parts by weight of linear low-density polyethylene was mixed with a Henschel mixer for 5 minutes, and then 240 A master batch pellet (hereinafter referred to as "pellet A") was prepared by extrusion molding at ℃. At the same time, the same linear low-density polyethylene pellet as described above (hereinafter referred to as "pellet B") was prepared from the powder. Pellet A for both
After mixing at a ratio of / pellet B = 1/9, the mixture was extruded at 200 ° C. to form a 1.0 mm thick sheet, and its transparency was evaluated. The results obtained are shown in Table 2.

Examples 20 to 36 Samples were prepared in the same manner as in Example 19 except that the nucleating agent composition shown in Table 2 was applied, and their transparency and rigidity were evaluated. The results obtained are shown in Table 2.

Comparative Examples 7 to 14 Samples of linear low-density polyethylene resin compositions prepared by blending the nucleating agents shown in Table 2 in predetermined amounts were prepared in the same manner as in Example 19, and their transparency was evaluated. did. Second result obtained
Shown in the table.

Comparative Example 15 A sample of a linear low-density polyethylene resin composition was prepared in the same manner as in Example 19 except that no nucleating agent was added, and its transparency was evaluated. The results obtained are shown in Table 2.

[0057]

The polyolefin resin composition containing the nucleating agent composition according to the present invention has the highest degree of transparency that cannot be obtained with a single nucleating agent, and at the same time, has improved rigidity and high molding. Satisfies workability.

Claims (5)

[Claims] 1. One or more compounds (A component) selected from sorbitols represented by the general formula (1).
With respect to 100 parts by weight, the metal salt of the phosphorus compound represented by the general formula (2) or (3) or the ammonium salt of the phosphoric acid compound represented by the general formula (4) or (5). And a nucleating agent containing 0.1 to 40 parts by weight of one or more compounds (component B) selected from the group consisting of 1,6,11-triaminoundecanetricyclohexanecarboxylic acid amide. Composition. [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen group, an alkyloxy group having 1 to 4 carbon atoms or an alkylthio group having 1 to 4 carbon atoms. . a and b show the integer of 1-3. In R ¹ and R ² , at least one group occupies 4-position. ] [In the formula, R ³ represents a direct bond, a sulfur atom, an alkylene group or an alkylidene group, and R ⁴ and R ⁵ are the same or different,
Each represents a hydrogen atom, an alkyl group or a cycloalkyl group. c and d represent 0 or 1. e represents the valence of the metal, and M represents the metal atom. ] [Wherein R ⁶ and R ⁷ are the same or different and each represents a hydrogen atom,
It represents an alkyl group or a cycloalkyl group. M represents a metal atom. ] [In the formula, R ⁸ represents a direct bond, a sulfur atom, an alkylene group or an alkylidene group, and R ⁹ and R ¹⁰ are the same or different and each represent a hydrogen atom, an alkyl group or a cycloalkyl group. f and g represent 0 or 1. A represents an ammonium ion or an organic ammonium ion. m represents an integer of 1 to 6. ] [In the formula, R ¹¹ , R ¹² and R ¹³ are the same or different and each represents a hydrogen atom, an alkyl group or a cycloalkyl group. A represents an ammonium ion or an organic ammonium ion. n shows the integer of 1-6. ] 2. The component A comprises 1,3: 2,4-bis (O-
3,4-dimethylbenzylidene) sorbitol, 1,
3: 2,4-bis (O-2,4-dimethylbenzylidene) sorbitol, 1,3: 2,4-bis (O-4-methylbenzylidene) sorbitol, 1,3: 2,4-bis (O- 4-ethylbenzylidene) sorbitol, 1,
One or two or more sorbitols selected from the group consisting of 3: 2,4-bis (O-4-chlorobenzylidene) sorbitol and 1,3: 2,4-dibenzylidene sorbitol, wherein the B component is , 2'-methylenebis (4,6-tert-butylphenyl) phosphate ester undecane-1,6,11-triammonium salt, 2,2'-methylenebis (4,6-tert-butylphenyl phosphate) The nucleating agent composition according to claim 1, which is one or more compounds selected from the group consisting of sodium and 1,6,11-triaminoundecanetricyclohexanecarboxylic acid amide. 3. The nucleating agent composition according to claim 1 or 2, wherein the blending amount of the component B is 0.2 to 5 parts by weight relative to 100 parts by weight of the component A. 4. A polyolefin resin and claims 1 to 3.
A polyolefin-based resin composition comprising the nucleating agent composition according to claim 1. 5. A polyolefin resin composition comprising 0.01 to 1 part by weight of the nucleating agent composition according to any one of claims 1 to 3 relative to 100 parts by weight of the polyolefin resin.