JP6137788B2 - Process for producing olefin-based resin composition - Google Patents

Description

  The present invention relates to a method for producing an olefin resin composition. In detail, it is related with the manufacturing method of the olefin resin composition from which crystallization temperature is excellent and the olefin resin composition with favorable transparency is obtained.

  Olefin resins have the advantage of being excellent in molding processability, heat resistance, mechanical properties, low specific gravity and the like, and are widely used for films, sheets and various molded products (structural parts, etc.). However, the olefin resin has a low crystallization speed at the time of molding, so that the molding cycleability is low, and a large crystal is formed depending on the progress of crystallization after thermoforming, and the transparency and strength are insufficient. It was.

  These drawbacks are all derived from the crystallinity of the olefin resin, and it is known that the defects can be eliminated if the crystallization temperature of the olefin resin can be increased and fine crystals can be rapidly generated. .

Patent 3044259

  For this purpose, it is known to add a crystal nucleating agent or a crystallization accelerator. Conventionally, sodium benzoate, 4-tert-butylaluminum benzoate, sodium adipate and disodium bicyclo [2 2.1] Metal salt of carboxylic acid such as heptane-2,3-dicarboxylate, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis (4,6-ditert-butyl) Phosphoric acid ester metal salts such as phenyl) phosphate and lithium-2,2′-methylenebis (4,6-ditert-butylphenyl) phosphate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (dimethylbenzylidene) sorbitol, etc. A compound having an acetal skeleton has been used.

  Methods for adding these crystal nucleating agents are widely known. Using an Henschel mixer, mill roll, V blender, ribbon blender, kneader blender, Banbury mixer, super mixer, etc., an additive containing an olefin resin and a crystal nucleating agent is added. Mixing, feeding into an extruder and granulating is performed.

  Patent Document 1 proposes a method of adding aluminum-bis (pt-butylbenzoic acid) hydroxy or sodium benzoate as a crystal nucleating agent during propylene polymerization.

  However, in the method of blending the crystal nucleating agent at the time of granulating the polymer, there may be a variation in product properties due to poor dispersion of the crystal nucleating agent. In addition, since the crystal nucleating agent is powder, there are adverse effects on the work environment such as powder flying up during work, and contamination problems. On the other hand, when a crystal nucleating agent is blended at the time of olefin polymerization, there is a problem that the crystal nucleating agent inhibits polymerization activity.

  The method described in Patent Document 1 is aimed at uniform dispersion of the nucleating agent and thereby improving the rigidity of the polymer, and is a polymerization method by two-stage polymerization, wherein the crystal nucleating agent is obtained after one-stage polymerization of propylene. It is a method of adding. Patent Document 1 discloses that a crystal nucleating agent can affect polymerization activity, masking the crystal nucleating agent, preventing an adverse effect on catalytic activity by masking the crystal nucleating agent, and aliphatic carboxylic acid None of the effects of improving the nucleating agent effect by using a metal salt or an alkali metal-containing hydrotalcite in combination is disclosed. Further, the method described in Patent Document 1 cannot provide an effect in the one-stage polymerization method in which the nucleating agent is brought into direct contact with the polymerization catalyst. Moreover, the nucleating agent described in Patent Document 1 does not dissolve in the organoaluminum compound and the organic solvent, and impairs the polymerization activity.

  Then, the objective of this invention is providing the manufacturing method of the olefin resin composition which can manufacture the olefin resin composition which is excellent in crystallization temperature, and is excellent in transparency, without impairing the polymerization activity of olefin. .

  As a result of intensive studies to solve the above problems, the present inventors have added a polymer in which a crystal nucleating agent component is dissolved using an organoaluminum compound during polymerization of an olefin monomer. The above-mentioned problem can be solved by a production method comprising a step and a second step of blending and kneading the aliphatic carboxylic acid metal salt or alkali metal-containing hydrotalcite with the polymer obtained by the polymerization in the first step. As a result, the present invention has been completed.

（式中、Ｒ^１〜Ｒ^４は各々独立して、水素原子又は分岐を有してもよい炭素原子数１〜９のアルキル基を表し、Ｒ^５は水素原子又はメチル基を表し、ｍは１又は２を表し、ｍが１の場合、Ｍ^１は水素原子を表し、ｍが２の場合、Ｍ^１は、二族元素、Ａｌ（ＯＨ）又はＺｎを表す。）

（式中、Ｒ^６は、分岐鎖を有してもよく、ヒドロキシル基およびシクロアルキル基から選ばれる１種以上の置換基を有してもよい炭素原子数１〜３０の脂肪族基を表し、Ｍ^２は、金属原子を表し、ｎは、１〜４の整数であって、Ｍ^２の金属原子の価数を表す。）
That is, in the method for producing an olefin resin of the present invention, a crystal nucleating agent component composed of one or more compounds represented by the following general formula (1) is dissolved in an organic aluminum compound or an organic aluminum compound and an organic solvent. First step of blending before or during polymerization of the olefin monomer so that the crystal nucleating agent component is 0.001 to 10 parts by mass with respect to 100 parts by mass of the polymer obtained by polymerization,
An aliphatic carboxylic acid metal salt composed of one or more aliphatic carboxylic acid metal salts represented by the following general formula (2) is 0.001 per 100 parts by mass of a polymer obtained by polymerizing an olefin monomer. A second step of adding 10 parts by mass and melt-kneading;
Including
In the step of polymerizing the olefin monomer, a Ziegler catalyst, a Ziegler-Natta catalyst composed of a titanium-containing solid transition metal component and an organic metal component, a group 4 to 6 of the periodic table having at least one cyclopentadienyl skeleton. It is characterized in that at least one of metallocene catalysts comprising a transition metal compound and a promoter component is used.

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms which may have a branch, R ⁵ represents a hydrogen atom or a methyl group, and m represents 1 or 2; when m is 1, M ¹ represents a hydrogen atom; when m is 2, M ¹ represents a group II element, Al (OH) or Zn.)

(In the formula, R ⁶ represents an aliphatic group having 1 to 30 carbon atoms which may have a branched chain and may have one or more substituents selected from a hydroxyl group and a cycloalkyl group. , M ² represents a metal atom, and n is an integer of 1 to 4, and represents the valence of the metal atom of M ^2. )

  In the method for producing an olefin resin composition of the present invention, a crystal nucleating agent component composed of one or more compounds represented by the general formula (1) is dissolved in an organic aluminum compound or an organic aluminum compound and an organic solvent. The ratio of the crystal nucleating agent component to the organoaluminum compound is preferably in the range of 1/1000 to 1 / 0.3 in terms of the molar ratio of the aluminum content of the crystal nucleating agent component and the organoaluminum compound.

  In the method for producing an olefin-based resin composition of the present invention, the aliphatic carboxylic acid metal salt is composed of lithium stearate, lithium myristate, sodium stearate, sodium myristate, and hydroxy-substituted compounds thereof. Those selected from the group are preferably used.

  In the method for producing an olefin-based resin composition of the present invention, one in which the organoaluminum compound is a trialkylaluminum is preferably used.

  According to the present invention, an olefin resin composition having excellent transparency and a high crystallization temperature can be produced.

（式中、Ｒ^１〜Ｒ^４は各々独立して、水素原子又は炭素原子数１〜９のアルキル基を表し、Ｒ^５は水素原子又はメチル基を表し、ｍは１又は２を表し、ｍが１の場合、Ｍ^１は水素原子を表し、ｍが２の場合、Ｍ^１は、二族元素、Ａｌ（ＯＨ）又はＺｎを表す。）で表される１種類又は２種類以上を含むものである。 The crystal nucleating agent component according to the present invention includes the following general formula (1),

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group, m represents 1 or 2, m M ¹ represents a hydrogen atom when m is 1, and when m is 2, M ¹ represents a group II element, Al (OH) or Zn). .

Examples of the alkyl group having 1 to 9 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (1) include, for example, a methyl group, an ethyl group, a propyl group, and an isopropyl group. Butyl group, secondary butyl group, tertiary butyl group, isobutyl group, amyl group, isoamyl group, tertiary amyl group, hexyl group, cyclohexyl group, heptyl group, isoheptyl group, tertiary heptyl group, Of these, those having a tertiary butyl group are particularly preferred.

Examples of the second group element represented by M ¹ in the general formula (1) include beryllium, magnesium, calcium, strontium, barium, and radium. Among these, those that are magnesium and calcium are crystals. Since the nucleating agent effect of the nucleating agent component is remarkable, it is preferable.

As a crystal nucleating agent component used by this invention, the compound shown below is mentioned, for example. However, the present invention is not limited by the following compounds.

  The range of the use amount of the crystal nucleating agent component is a range in which the improvement of the addition effect is not observed from the amount where the effect is manifested. The amount used with respect to 100 parts by mass of the polymer obtained by the production method of the present invention (hereinafter also simply referred to as “polymer”) is preferably in the range of 0.001 to 10 parts by mass, and in the range of 0.005 to 1 part by mass. Is more preferable, and the range of 0.01 to 0.5 parts by mass is particularly preferable.

  In the production method of the present invention, the above-described crystal nucleating agent component is added to an organoaluminum compound or an organic aluminum and an organic solvent dissolved before or during the polymerization of the olefin monomer. For example, it can be added to any of a polymerization system, a catalyst system, and a compounding tube.

  When the nucleating agent component is added before or during the polymerization of the olefin monomer, it may be a mixture of the nucleating agent component and organic aluminum, and the nucleating agent component is dispersed in an organic solvent. In addition, an organic aluminum compound may be added to dissolve the crystal nucleating agent component. Thereby, it is considered that the crystal nucleating agent component is masked by the organic aluminum.

As the organoaluminum compound, for example, alkylaluminum, alkylaluminum hydride and the like can be used, but alkylaluminum is preferable, and trialkylaluminum is particularly preferable, and specifically, trimethylaluminum, triethylaluminum, tri-n. -Propyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum and the like. Any of the organoaluminum compounds can be used as a mixture. Moreover, the aluminoxane obtained by reaction of alkylaluminum or alkylaluminum hydride and water can be used similarly.
In the method for producing a polyolefin-based resin composition of the present invention, an organoaluminum compound that can be regenerated by treating a masking treatment with an organoaluminum compound with a hydrogen-based donor compound such as water, alcohol, or acid. Is preferably used.

  As the mixing ratio of the crystal nucleating agent component and the organoaluminum compound, the molar ratio of the aluminum content of the crystal nucleating agent component and the organoaluminum compound is preferably 1/1000 to 1 / 0.3. If the crystal nucleating agent component is more than 1 / 0.3, there is a problem that the excess crystal nucleating agent component adversely affects the polymerization activity of the olefin. If the crystal nucleating agent component is less than 1/1000, the organoaluminum compound is present after polymerization. It may remain in the polymer and physical properties of the polymer may decrease, or the desired metal may not be polymerized due to the influence of the catalyst metal component.

Examples of the organic solvent include aliphatic and aromatic hydrocarbon compounds. Examples of the aliphatic hydrocarbon compound include saturated hydrocarbon compounds such as n-pentane, n-hexane, n-heptane, n-octane, isooctane and purified kerosene, and cyclic saturated hydrocarbons such as cyclopentane, cyclohexane and cycloheptane. Examples of the aromatic hydrocarbon compound include compounds such as benzene, toluene, ethylbenzene, and xylene. These organic solvents may be used individually by 1 type, and may use 2 or more types together.
Of the above organic solvents, n-hexane or n-heptane is preferably used. The concentration of the organoaluminum compound in the organic solvent is preferably in the range of 0.001 to 0.5 mol / L, particularly preferably 0.01 to 0.1 mol / L.

  Examples of the olefin monomer used in the present invention include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. Examples include alkane, styrene, and derivatives thereof.

  The polymer in the present invention is obtained by homopolymerization of the olefin monomer or copolymerization containing the olefin monomer, for example, propylene homopolymer, ethylene-propylene copolymer, ethylene-propylene-butene copolymer. Examples thereof include polypropylene such as a copolymer of propylene such as coalescence and α-olefin other than propylene, polyethylene such as high-density polyethylene, and cycloolefin.

  The polymerization of the olefin monomer needs to be performed in an inert gas atmosphere such as nitrogen in the presence of a polymerization catalyst, but may be performed in the above inert solvent. In addition, an active hydrogen compound, a particulate carrier, an organoaluminum compound, an ion exchange layered compound, and an inorganic silicate may be added as long as polymerization is not inhibited.

  In the present invention, the polymerization catalyst is not particularly limited, and a known polymerization catalyst can be used. For example, a transition metal of Groups 3 to 11 of the periodic table (for example, titanium, zirconium, hafnium, vanadium) , Iron, nickel, lead, platinum, yttrium, samarium, etc.), typical examples being Ziegler catalysts, Ziegler-Natta catalysts consisting of a titanium-containing solid transition metal component and an organometallic component, at least one A metallocene catalyst, a chromium-based catalyst, or the like comprising a transition metal compound of Group 4 to Group 6 of the periodic table having a cyclopentadienyl skeleton and a promoter component can be used.

  In the present invention, the polymerization method of the olefin monomer is not particularly limited, and any known method can be used. For example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, isooctane, cyclopentane, cyclohexane , Slurry polymerization method that polymerizes in an inert solvent such as alicyclic hydrocarbon such as methylcyclohexane, aromatic hydrocarbon such as toluene, xylene, ethylbenzene, gasoline fraction, hydrogenated diesel fraction, etc., in the gas phase Gas phase polymerization method carried out in, bulk polymerization method using olefin monomer itself as a solvent, solution polymerization method in which a polymer is formed in liquid form, or a polymerization method combining these, one-stage polymerization method or multi-stage polymerization method, propylene, At least one selected from the group consisting of olefin units having 2 to 12 carbon atoms Olefin (excluding propylene) polymerization process of a method for producing a copolymer to copolymer can be mentioned a unit, also a batch, can be employed interchangeably production method continuously.

  As a polymerization tank used in the polymerization method, a continuous reaction tank in an existing polymerization facility may be used as it is, and conventional polymerization facilities such as size, shape and material can be used without any particular limitation.

（式中、Ｒ^６は、分岐鎖を有してもよく、ヒドロキシル基およびシクロアルキル基から選ばれる１種以上の置換基を有してもよい炭素原子数１〜３０の脂肪族基を表し、Ｍ^２は、金属原子を表し、ｎは、１〜４の整数であって、Ｍ^２の金属原子の価数を表す）で表される１種類又は２種類以上のものである。 The aliphatic carboxylic acid metal salt used in the second step of the production method of the present invention is the following general formula (2),

(In the formula, R ⁶ represents an aliphatic group having 1 to 30 carbon atoms which may have a branched chain and may have one or more substituents selected from a hydroxyl group and a cycloalkyl group. , M ² represents a metal atom, and n is an integer of 1 to 4 and represents the valence of the metal atom of M ² ).

In the general formula (2), the R ⁶ group is an aliphatic group having 1 to 30 carbon atoms, may have a hydroxyl group, may have a cycloalkyl group, or may have a branch. . Examples of the aliphatic group include an alkyl group, an alkenyl group, and a hydrocarbon group such as an alkyl group into which two or more unsaturated bonds are introduced. Specific examples of the aliphatic carboxylic acid represented by the general formula (2) include acetic acid, propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, 2-ethylhexanoic acid, enanthic acid, pelargonic acid, caprylic acid, Neodecylic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, succinic acid , Lindelic acid, Tuzuic acid, Palmitoleic acid, Myristoleic acid, Petrothelic acid, Oleic acid, Elaidic acid, Vaccenoic acid, Linoleic acid, Linoleic acid, γ-Linolenic acid, Linolenic acid, Ricinoleic acid, Naphthenic acid, Abietic acid , Hydroxyacetic acid, lactic acid, β-hydroxypropionic acid, 2-methyl -Β-hydroxypropionic acid, α-hydroxybutyric acid, β-hydroxybutyric acid, γ-hydroxybutyric acid, monomethylolpropionic acid, dimethylolpropionic acid, 12-hydroxystearic acid and the like. Among these, those having an aliphatic group having 12 to 22 carbon atoms are preferable because the effect of improving the physical properties of the olefin resin is enhanced, and myristic acid, stearic acid, 12-hydroxystearic acid, and the like are particularly preferable.

In the general formula (2), examples of the metal atom represented by M ² include alkali metal, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, barium, and hafnium. It is done. Among these, alkali metals such as sodium, lithium, and potassium are preferable, and sodium and lithium are particularly preferably used because the crystallization temperature of the olefin resin is good.

  The range of the use amount of the aliphatic carboxylic acid metal salt is a range in which the improvement of the addition effect is not observed from the amount where the effect is exhibited. The amount of the aliphatic carboxylic acid metal salt used with respect to 100 parts by mass of the polymer is preferably in the range of 0.001 to 10 parts by mass, more preferably in the range of 0.005 to 1 part by mass, and 0.01 to 0.5 parts by mass. Part ranges are particularly preferred.

（式中、ｘ１およびｘ２は各々下記式で表される条件を満たす数を表し、ｐは０または正の数を表す。０≦ｘ２／ｘ１＜１０，２≦ｘ１＋ｘ２≦２０である。）

（式中、Ａ^ｑ−は、ｑ価のアニオンを表し、ｐは０または正の数を表す。）
また、上記ハイドロタルサイトにおける炭酸アニオンは、一部を他のアニオンで置換したものでもよい。 The alkali metal-containing hydrotalcite is a complex salt compound composed of magnesium, aluminum, a hydroxyl group, a carbonate group and any crystal water known as a natural product or a synthetic product. And those obtained by substituting a hydroxyl group or carbonate group with another anion group. Specifically, for example, the hydrotalcite metal represented by the following formula (3) is an alkali metal. Is substituted. As the Al—Li hydrotalcite, a compound represented by the formula (4) can also be used.

(Wherein, x1 and x2 each represent a number satisfying the condition represented by the following formula, and p represents 0 or a positive number. 0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 ≦ 20)

(In the formula, A ^q- represents a q-valent anion, and p represents 0 or a positive number.)
The carbonate anion in the hydrotalcite may be partially substituted with another anion.

  The hydrotalcite may be obtained by dehydrating crystal water, higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal such as alkali metal dodecylbenzenesulfonate. It may be coated with a salt, higher fatty acid amide, higher fatty acid ester or wax.

  The hydrotalcite may be a natural product or a synthetic product. As methods for synthesizing the compounds, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-174270, Known methods described in, for example, Kaihei No. 5-179052. Moreover, the said hydrotalcite can be used without being restrict | limited to the crystal structure, crystal grain, etc.

  As the alkali metal of the alkali metal-containing hydrotalcite, lithium and sodium are preferably used since a product with good transparency and crystallization temperature can be obtained.

  In the present invention, as long as it does not adversely affect the polymerization, other additives usually used for the olefin resin can be further added during the polymerization of the olefin monomer as necessary. When adding at the time of superposition | polymerization of an olefin monomer, you may use what mixed and stirred the other additive, the crystal nucleating agent component, and the organoaluminum compound. In the reaction by this method, when the by-product compound does not affect the polymer, it can be used as it is. However, when the by-product compound has an adverse effect on the polymer, the compound is removed by distillation under reduced pressure or the like. It is preferable to use it.

  Moreover, even if other additives have a negative effect on polymerization when added directly, if the influence on the polymerization can be suppressed by masking with an organoaluminum compound, the production of the polyolefin-based resin composition of the present invention Can be used in the method.

  In addition to the aliphatic carboxylic acid metal salt represented by the general formula (2) or the alkali metal-containing hydrotalcite, other additives are added to the polymer obtained in the first step, and an extruder. It can be granulated and molded by melt-kneading with a molding machine such as the above.

  Examples of the other additives include phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet absorbers, heavy metal deactivators, flame retardants, metal soaps, hydrotalcite, and fillers. , Lubricants, antistatic agents, pigments, dyes, plasticizers and the like.

  Examples of the phenolic antioxidant include 2,6-di-t-butyl-4-ethylphenol, 2-t-butyl-4,6-dimethylphenol, styrenated phenol, 2,2′-methylenebis ( 4-ethyl-6-tert-butylphenol), 2,2′-thiobis- (6-tert-butyl-4-methylphenol), 2,2′-thiodiethylenebis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4 Hydroxyphenyl) propionamide, 2,2′-oxamido-bis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-ethylhexyl-3- (3 ′, 5 ′ -Di-t-butyl-4'-hydroxyphenyl) propionate, 2,2'-ethylenebis (4,6-di-t-butylphenol), 3,5-bis (1,1-dimethylethyl) -4- Hydroxy-benzenepropanoic acid and ester of C13-15 alkyl, 2,5-di-t-amylhydroquinone, hindered phenol polymer (trade name AO.OH998, manufactured by Adeka Palmalol), 2,2′-methylenebis [ 6- (1-methylcyclohexyl) -p-cresol], 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methyl) Benzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 6- [3- (3-t-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-t-butylbenz [d, f] [1,3,2] -dioxaphosphobin, Hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate calcium salt, 5,7 -Bis (1,1-dimethylethyl) -3-hydroxy-2 (3H) -benzofuranone and the reaction product of o-xylene, 2,6-di-t-butyl-4- (4,6-bis (Ok Tilthio) -1,3,5-triazin-2-ylamino) phenol, DL-a-tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3 -Bis- (4′-hydroxy-3′-t-butyl-phenyl) butanoic acid] glycol ester, 2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol Stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-t- Butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], , 4′-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (2, 6-di-t-butylphenol), 4,4'-butylidenebis (6-t-butyl-3-methylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 1,1 , 3-Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-methyl) Benzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-t- Butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate ] Methane, 2-t-butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis [2- ( -T-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β -(3-t-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide, palmityl-3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, myristyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-ditert 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as tributyl-4-hydroxyphenyl) propionic acid amide I can get lost.

  Examples of the phosphorus antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctyloctylphenyl phosphite, diphenyltridecyl Phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (tridecyl) ) Phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenyl bis (nonyl fe) Phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropyl glycol diphosphite, trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2, 4-di-tert-butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos Phyto, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, Di (Tori Syl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-) 4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetraphenyl Tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4 , 4'-n-Butylidenebis (2-t-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, tetrakis (2, 4-di-t-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propanyl-3-ylidene) tris (2-1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecyl phosphite, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-di-t-butylphenyl) -octadecyl phosphite, 2,2'-ethylidenebis 4,6-di-tert-butylphenyl) fluorophosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8, 10-tetrakis-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2, 4,8,10-tetraoxa-3,9-diphosphasspiro [5,5] undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2ethyl-1,3-propanediolphos Phyto, poly 4,4'-isopropylidenediphenol C12-15 alcohol phosphite, 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-t-butylphenol Sufaito, and the like.

  Examples of the thioether-based antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-t-butyl. Phenyl) sulfide, ditridecyl-3,3′-thiodipropionate, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipro Pionate, lauryl / stearyl thiodipropionate, 4,4'-thiobis (6-t-butyl-m-cresol), 2,2'-thiobis (6-t-butyl-p-cresol), distearyl- Disulfide is mentioned.

  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 such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-th Octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzene Zotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxy) Ethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2- Methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) 2- (2-hydroxypheny) such as phenyl] benzotriazole B) benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6 -Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 2-hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as 5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5- Di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5- Ditert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-ditert-butyl-4-hydroxy) benzoate, octadecyl (3,5-ditert Benzoates such as butyl-4-hydroxy) benzoate, behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxy Substituted oxanilides such as zanilides; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts Or metal chelates, especially nickel, chromium salts, or chelates.

  Examples of the flame retardant include aromatic phosphoric acid such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, and resorcinol bis (diphenyl phosphate). Phosphonates such as esters, divinyl phenylphosphonate, diallyl phenylphosphonate and phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phospha Phosphonic acid esters such as phenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, Melamine phosphate, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, bromine Phenol novolac epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclo Octane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl Reimido, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, and include brominated flame retardants such as brominated styrene and the like.

  Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, Dolomite, mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate and the like are preferable. Among these fillers, those having an average particle diameter (spherical or flat) or an average fiber diameter (needle or fiber) of 5 μm or less are preferable.

  The above-mentioned lubricant is added for the purpose of imparting lubricity to the surface of the molded body and enhancing the effect of preventing damage. Examples of the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide. These may be used alone or in combination of two or more.

  The antistatic agent is added for the purpose of reducing the chargeability of the molded product and preventing dust from adhering due to charging. Examples of the antistatic agent include cationic, anionic and nonionic. Preferable examples include polyoxyethylene alkylamine and polyoxyethylene alkylamide. These may be used alone or in combination of two or more.

  The range of the preferable usage-amount of the additive used by this invention used for resin is a range from which the improvement of an addition effect is not seen from the quantity by which an effect is expressed. The amount of each additive used with respect to 100 parts by mass of the polymer is 0.1 to 20 parts by mass of the plasticizer, 1 to 50 parts by mass of the filler, 0.001 to 1 part by mass of the surface treatment agent, and phenolic antioxidant. 0.001 to 10 parts by mass of the agent, 0.001 to 10 parts by mass of the phosphorus antioxidant, 0.001 to 10 parts by mass of the thioether antioxidant, 0.001 to 5 parts by mass of the ultraviolet absorber, It is preferable that the hindered amine compound is 0.01 to 1 part by mass, the flame retardant is 1 to 50 parts by mass, the lubricant is 0.03 to 2 parts by mass, and the antistatic agent is 0.03 to 2 parts by mass. In addition, the usage-amount shown above shows the final usage-amount of each additive in the molded article shape | molded using the polymer manufactured with the manufacturing method of this invention.

  The polymer obtained by the production method of the present invention can be molded by a known molding method such as extrusion molding, injection molding, hollow molding, blow molding, compression molding, etc., food containers, cosmetic / clothing containers, Molding of food bottles, beverage bottles, edible oil bottles, seasoning bottles, etc., food packaging materials, wrapping materials, packaging materials for transport, etc., sheets / films, fibers, daily goods, toys, etc. Goods can be easily obtained. Moreover, it is good also as a fiber reinforced plastic by mix | blending glass fiber, carbon fiber, etc.

  Hereinafter, the present invention will be described more specifically with reference to production examples, examples, and comparative examples. However, the present invention is not limited to the following examples.

[Production Example 1]
[Examples 1-2, Comparative Examples 1-5]
(Preparation of solid catalyst component)
Anhydrous magnesium chloride (4.76 g, 50 mmol), decane (25 mL) and 2-ethylhexyl alcohol (23.4 mL, 150 mmol) were added, and the mixture was reacted at 130 ° C. for 2 hours to obtain a homogeneous solution. 11 g (7.5 mmol) was added and stirred for 1 hour while maintaining 130 ° C. to dissolve phthalic anhydride in the homogeneous solution. Next, the homogeneous solution was cooled to room temperature and charged dropwise into 200 mL (1.8 mol) of titanium tetrachloride maintained at −20 ° C. over 1 hour. After completion of charging, the temperature was raised to 110 ° C. over 4 hours. After reaching 110 ° C., 2.68 mL (12.5 mmol) of diisobutyl phthalate was added, and the mixture was reacted by stirring for 2 hours while maintaining 110 ° C. After completion of the reaction, the residue was collected by hot filtration, and the residue was resuspended in 200 ml of titanium tetrachloride, and then heated to 110 ° C. and reacted for 2 hours. After completion of the reaction, the residue was again collected by hot filtration, and thoroughly washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution to obtain a solid catalyst component. A part of the solid titanium catalyst component was sampled and dried, and the catalyst composition was analyzed. As a result, 3.1% by weight of titanium, 56.0% by weight of chlorine, 17.0% by weight of magnesium and 20.9% by weight of isobutyl phthalate Met.

(Preparation of solution of crystal nucleating agent component)
To a flask purged with nitrogen, 10 mg of heptane, 22 mg of triethylaluminum and the compound shown in Table 1 were added, and the mixture was stirred to prepare a solution of the crystal nucleating agent component containing 16 mg / ml of the compound shown in Table 1. P-2 is one of the specific examples of the crystal nucleating agent component exemplified above.
When no compound was described in the column of additives added during polymerization in Table 1, a mixed solution of 10 mg of heptane and 22 mg of triethylaluminum was used.

(polymerization)
To a nitrogen-substituted autoclave, 600 mL of heptane, 303 mg of triethylaluminum, and the crystal nucleating agent solution are added to 100 parts by mass of the polymer so as to have the blending amounts shown in Table 1, 0.26 mmol of dicyclopentyldimethoxysilane and solids A heptane slurry of catalyst components (0.013 mmol in terms of Ti) was sequentially added and stirred. The inside of the autoclave was replaced with a propylene atmosphere, a pressure of 1 kgf / cm ² G was applied with propylene, and prepolymerization was performed at 50 ° C. for 5 minutes. After purging propylene, 340 ml (23 ° C.) of hydrogen was blown, the temperature was raised to 70 ° C., a pressure of 6 kgf / cm ² G was applied with propylene in the autoclave, and a polymerization reaction was performed at 70 ° C. for 1 hour. After replacing the system with nitrogen gas, 5 ml of ethanol was added at 40 ° C. to stop the polymerization reaction, and then the solvent was removed under reduced pressure at 50 ° C. Then, the polymer was dried at 40 ° C. in vacuum for 5 hours. A polymer was obtained.

[Production Example 2]
Example 3
(Preparation of solution of crystal nucleating agent component)
A solution having a crystal nucleating agent component of P-2 was prepared in the same procedure as in Production Example 1.

(Preparation of phenoxide solution)
A flask purged with nitrogen was mixed and stirred with 10 ml of heptane, 54 mg of triethylaluminum, and 161 mg of phenolic antioxidant stearyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide. Antioxidant was masked to prepare a stabilizer solution having a phenolic antioxidant concentration of 16 mg / ml.

(Preparation of phosphite solution)
To a flask purged with nitrogen, 144 mg of phosphorous antioxidant tris (2,4-di-t-butylphenyl) phosphite was added, 6 mL of heptane was added, mixed and stirred, and 24 mg / day of phosphorous antioxidant was added. Prepared mL phosphite solution

(polymerization)
To a nitrogen-substituted autoclave, 600 ml of heptane, 303 mg of triethylaluminum, the crystal nucleating agent solution, the phenoxide solution, and the phosphite solution were added to 100 parts by mass of the polymer so as to have the blending amounts shown in Table 1. Then, 0.26 mmol of dicyclopentyldimethoxysilane and a heptane slurry (0.013 mmol in terms of Ti) of the solid catalyst component were sequentially added and stirred. The same solid catalyst component as that prepared in Example 1 was used. The inside of the autoclave was replaced with a propylene atmosphere, a pressure of 1 kgf / cm ² G was applied with propylene, and prepolymerization was performed at 50 ° C. for 5 minutes. After purging propylene, 340 ml (23 ° C.) of hydrogen was blown, the temperature was raised to 70 ° C., a pressure of 6 kgf / cm ² G was applied with propylene in the autoclave, and a polymerization reaction was performed at 70 ° C. for 1 hour. After replacing the system with nitrogen gas, 5 ml of ethanol was added at 40 ° C. to stop the polymerization reaction, and then the solvent was removed under reduced pressure at 50 ° C. Then, the polymer was dried at 40 ° C. in vacuum for 5 hours. A polymer was obtained.

(Molding)
Each additive was added and mixed in the blending amount shown in Table 1 with respect to 100 parts by mass of each of the polymers produced in Production Examples 1 and 2, and a small laboratory injection molding machine (Compounder 15, manufactured by DSM Xplore, A strand was obtained by melt-kneading at 230 ° C. in an injection molder 12). Further, using the small laboratory injection molding machine, injection molding was performed under the conditions of an injection temperature of 230 ° C. and a mold temperature of 40 ° C. to obtain a 50 mm × 90 mm × 2 mm flat test piece.

(Evaluation)
The following evaluation was performed using the strand and flat plate-shaped test piece obtained by said manufacturing method. These results are shown in Table 1.

(Crystallization temperature)
A small amount of the obtained strand was cut, and the crystallization temperature was measured using a differential scanning calorimeter (Diamond; manufactured by Perkin Elmer). In the chart obtained by increasing the temperature from room temperature to 230 ° C. at a rate of 50 ° C./min, holding for 10 minutes and then cooling to 50 ° C. at a rate of −10 ° C./min, the endothermic reaction has a peak top. This temperature was defined as the crystallization temperature. These results are shown in Table 1 below.

(Haze)
The test piece obtained on the flat plate was allowed to stand for 48 hours or more in a thermostatic bath at 23 ° C. after injection molding, and then the haze of the test piece was obtained with Hayes Guard II (manufactured by Toyo Seiki Seisakusho Co., Ltd.). It was. These results are shown in Table 1 below.

１）Ｎａ−Ｓｔ：ステアリン酸ナトリウム塩
２）Ｌｉ−Ｓｔ：ステアリン酸リチウム塩
３）ＡＯ−１： テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン
４）ＡＯ−２：トリス（２，４−ジ第三ブチルフェニル）ホスファイト
５）ＡＯ−３： ステアリル−３−（３，５−ジ第三ブチル−４−ヒドロキシフェニル）プロピオン酸アミド
６）ＤＨＴ−４Ａ：ハイドタルサイト（協和化学工業社製）

1) Na-St: sodium stearate 2) Li-St: lithium stearate 3) AO-1: tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) ) Propionate] methane 4) AO-2: tris (2,4-ditert-butylphenyl) phosphite 5) AO-3: stearyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propion Acid amide 6) DHT-4A: Hydtalsite (manufactured by Kyowa Chemical Industry Co., Ltd.)

From Comparative Example 2, when the aliphatic carboxylic acid metal salt was not blended in the second step, it was confirmed that the effect of promoting crystallization was small.
Moreover, from Comparative Example 3 and Comparative Example 4, when the crystal nucleating agent component was not added at the time of polymerization in the first step, the crystallization promoting effect was not satisfactory.
On the other hand, from Examples 1 and 2, it was confirmed that the polymer produced by the method of the present invention was excellent in crystallization promoting effect and excellent in transparency improving effect. From the above, by molding the polymer obtained by the production method of the present invention, it is possible to obtain a molded product excellent in crystallization promoting effect and transparency.
Moreover, even if it was a case where the crystal nucleating agent component represented with General formula (1) and another additive were added to a polymerization system from Example 3, it has confirmed that the influence with respect to the physical property of a molded article was small. .

  Moreover, in the manufacturing method of the polyolefin-type resin composition of this invention, when using the polymer obtained at a 1st process as a masterbatch, the crystal | crystallization represented by General formula (1) with respect to 100 mass parts of polymers. A masterbatch can also be produced by blending 10 parts by mass or more of the nucleating agent component.

Claims (4)

What dissolve | melted the crystal nucleating agent component which consists of 1 or more types of the compound represented by following General formula (1) in the organic aluminum compound or the organic aluminum compound, and the organic solvent with respect to 100 mass parts of polymers obtained by superposition | polymerization A first step of blending before or during the polymerization of the olefin monomer so that the crystal nucleating agent component is 0.001 to 10 parts by mass;
An aliphatic carboxylic acid metal salt composed of one or more aliphatic carboxylic acid metal salts represented by the following general formula (2) is 0.001 per 100 parts by mass of a polymer obtained by polymerizing an olefin monomer. A second step of adding 10 parts by mass and melt-kneading;
Including
In the step of polymerizing the olefin monomer, a Ziegler catalyst, a Ziegler-Natta catalyst composed of a titanium-containing solid transition metal component and an organic metal component, a group 4 to 6 of the periodic table having at least one cyclopentadienyl skeleton. process for producing an olefin-based resin composition which comprises using at least one kind of metallocene catalysts comprising a transition metal compound and a cocatalyst component.

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms which may have a branch, R ⁵ represents a hydrogen atom or a methyl group, and m represents 1 or 2; when m is 1, M ¹ represents a hydrogen atom; when m is 2, M ¹ represents a group II element, Al (OH) or Zn.)

(In the formula, R ⁶ represents an aliphatic group having 1 to 30 carbon atoms which may have a branched chain and may have one or more substituents selected from a hydroxyl group and a cycloalkyl group. , M ² represents a metal atom, and n is an integer of 1 to 4, and represents the valence of the metal atom of M ^2. )   In the case where a crystal nucleating agent component composed of one or more compounds represented by the general formula (1) is dissolved in an organoaluminum compound or an organoaluminum compound and an organic solvent, the ratio of the crystal nucleating agent component to the organoaluminum compound is The method for producing an olefin-based resin composition according to claim 1, wherein the molar ratio of the crystal nucleating agent component to the aluminum content of the organoaluminum compound is within a range of 1/1000 to 1 / 0.3.   The aliphatic carboxylic acid metal salt represented by the general formula (2) is selected from the group consisting of lithium stearate, lithium myristic acid, sodium stearate, sodium myristic acid, and hydroxy-substituted compounds thereof. The method for producing an olefin-based resin composition according to claim 1 or 2.   The method for producing an olefin-based resin composition according to any one of claims 1 to 3, wherein the organoaluminum compound is trialkylaluminum.