JP2007092020A - Polypropylene resin composition for blow molding, blow molded product using the composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition giving blow molded products excellent in transparency, whitening resistance, heat resistance, low migration properties and odor characteristics and having little unevenness in thickness of the molded product and provide the blow molded products using the resin composition and provide a method for producing the same. <P>SOLUTION: The polypropylene resin composition comprises 100 pts.wt. propylene resin, 0.005-5 pts.wt. amide-based compound having a specific structure expressed by general formula (1) and, if necessary, a fatty acid metal salt. In the formula (1), R<SP>1</SP>expresses a residue prepared by removing all carboxylic acid groups from 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid; R<SP>2</SP>s in number k are mutually the same or different and express each H or a 1-10C straight or branched alkyl; k expresses 3 or 4 integer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polypropylene resin composition for blow molding, a blow molded article using the composition, and a method for producing the same. Specifically, a polypropylene resin composition that is excellent in transparency, heat resistance, migration / odor characteristics, and whitening resistance, and can provide a blow molded product with less thickness unevenness of the molded product, and a blow molded product using the composition And a method for producing the molded product.

Polypropylene resin is used in a wide range of applications as one of the plastic materials with the widest application fields in terms of physical properties, molding processability, and price. Furthermore, the polypropylene resin exhibits various excellent characteristics by modification, and the blow molded product of the resin is excellent in heat resistance, transparency, impact resistance, rigidity, gas barrier property, and the like. In particular, it is used in the food packaging / container field, medical field, and scientific equipment field.
However, depending on the field of use, there are cases where further improvement in physical properties is required by consumers. For example, when the blow-molded product is used for medical containers such as medical solution injections in the medical field, food containers, physics and chemistry laboratory equipment, etc., in addition to transparency, the container may be deformed by a sterilization process by heating. High rigidity and heat resistance that do not occur, and whitening resistance are required. In addition, from the viewpoint of safety, low elution, odorlessness, etc., in which components such as additives in the resin do not elute into the content liquid are required.

Known methods for improving the transparency of polypropylene resins include random copolymerization with ethylene and a method of blending a nucleating agent (crystallization accelerator) (see Patent Documents 1 to 3). However, random copolymerization alone is not sufficient in improving the transparency, and has a drawback that rigidity and heat resistance are lowered. Further, the method of blending the nucleating agent is useful because it is effective in improving rigidity, heat resistance and the like in addition to improving transparency.
As such practical nucleating agents, sorbitol compounds such as dibenzylidene sorbitol and bis (methylbenzylidene) sorbitol, nucleating agents such as sodium benzoate, organic phosphate salts and talc are widely known. The sorbitol-based compound is a soluble nucleating agent, and the shell nucleating agent and talc are dispersive nucleating agents.

Unlike the dissolution type nucleating agent, the use of the dispersion type nucleating agent is insoluble in the polypropylene resin and thus needs to be uniformly dispersed. However, a dispersion type nucleating agent dispersion failure may occur, and an undispersed material may remain in the resin. If such an undispersed material is generated, stretching unevenness and breakage are likely to occur during blow molding. For this reason, quality stability and a molding yield fall. Therefore, the use of the dispersion-type nucleating agent may be limited in that the application range of the molding process conditions is narrow.

On the other hand, the dissolution type nucleating agent has an advantage that it dissolves uniformly in the polypropylene resin and hardly causes problems such as uneven stretching and breakage at the time of blow molding due to the undispersed matter generated when the dispersion type nucleating agent is used. Sorbitol-based compounds such as dibenzylidene sorbitol and bis (methylbenzylidene) sorbitol known as a soluble nucleating agent are known as useful nucleating agents (see Patent Document 4). However, sorbitol-based compounds may be thermally decomposed to generate decomposition components depending on molding processing conditions. This is the main cause, which may impair odor characteristics and low migration, and may not be preferred by consumers depending on the application.

JP-A-9-77925 Japanese Patent Laid-Open No. 9-176393 Japanese Patent Laid-Open No. 11-116745 International Publication No. 99/24496 Pamphlet

  An object of the present invention is to provide a resin composition that is excellent in transparency, whitening resistance, heat resistance, low migration, odor characteristics, and can provide a blow molded product with less thickness unevenness of the molded product, It is to provide a blow molded article using the resin composition and to provide a method for producing them.

As a result of intensive studies in view of the present situation, the present inventors have found that a polypropylene resin composition containing a specific amount of an amide compound having a specific structure in a polypropylene resin has transparency, whitening resistance, heat resistance, and low migration. As a result, it was found that a blow molded product made of polypropylene resin having excellent properties and odor characteristics and small thickness unevenness of the molded product can be formed.

That is, the present invention provides the following items of the invention.

［式中、Ｒ^１は、１，２，３−プロパントリカルボン酸又は１，２，３，４−ブタンテトラカルボン酸から全てのカルボキシル基を除いて得られる残基を表す。ｋ個のＲ^２は、互いに同一又は異なって、それぞれ水素原子又は炭素数１〜１０の直鎖状若しくは分岐鎖状のアルキル基を表す。ｋは、３又は４の整数を表す。］
で表される少なくとも一種のアミド系化合物（Ｂ）０．００５〜５重量部を含有することを特徴とするブロー成形用ポリプロピレン樹脂組成物。 Item 1 General formula (1) with respect to 100 parts by weight of polypropylene resin (A)

[Wherein, R ¹ represents a residue obtained by removing all carboxyl groups from 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid. k R ^{2 s} are the same as or different from each other and each represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. k represents an integer of 3 or 4. ]
A polypropylene resin composition for blow molding, comprising 0.005 to 5 parts by weight of at least one amide compound (B) represented by the formula:

Item 2 The polypropylene resin composition for blow molding according to claim 1, wherein the polypropylene resin (A) has a melt flow rate (MFR) at 230 ° C of 0.1 to 80 g / 10 min.

Item 3. The polypropylene resin composition for blow molding according to claim 1 or 2, wherein the polypropylene resin (A) is a homopropylene polymer.

Item 4. The blown polypropylene resin composition according to claim 1 or 2, wherein the polypropylene resin (A) is a copolymer of propylene and ethylene and / or an α-olefin having 4 to 40 carbon atoms.

Item 5. The copolymer of propylene and ethylene and / or an α-olefin having 4 to 40 carbon atoms is a copolymer of propylene and ethylene, or a copolymer of propylene, ethylene and 1-butene. The polypropylene resin composition for blow molding described in 1.

Item 6 A copolymer of propylene and ethylene and / or an α-olefin having 4 to 40 carbon atoms is a random copolymer, and the content of propylene constituting the copolymer is 95.0% by weight or more and 100 The polypropylene resin composition for blow molding according to claim 4 or 5, which is less than 0.0% by weight.

Item 7 A copolymer of propylene and ethylene and / or an α-olefin having 4 to 40 carbon atoms is a block copolymer, and the content of propylene constituting the copolymer is 70.0% by weight or more and 100 The polypropylene resin composition for blow molding according to claim 4 or 5, which is less than 0.0% by weight.

［式中、Ｒ³は、分子内に１個以上の水酸基を有していてもよい炭素数８〜３２の飽和若しくは不飽和の脂肪族モノカルボン酸からカルボキシル基を除いて得られる残基を表す。ｎは、１又は２の整数を表し、ｎ＝２の場合、２個のＲ³は同一又は異なっていてもよい。Ｍは１価又は２価の金属を表す。］
で表される少なくとも一種の脂肪酸金属塩（Ｃ）を含有することを特徴とする請求項１〜請求項７のいずれかに記載のブロー成形用ポリプロピレン樹脂組成物。 Item 8 Furthermore, the general formula (2)

[Wherein R ³ represents a residue obtained by removing a carboxyl group from a saturated or unsaturated aliphatic monocarboxylic acid having 8 to 32 carbon atoms which may have one or more hydroxyl groups in the molecule. To express. n represents an integer of 1 or 2, and when n = 2, two R ^{3 s} may be the same or different. M represents a monovalent or divalent metal. ]
The blow molding polypropylene resin composition according to claim 1, comprising at least one fatty acid metal salt (C) represented by the formula:

Item 9 The polypropylene resin composition for blow molding according to claim 8, wherein M in the general formula (2) is at least one selected from the group consisting of alkali metals, alkaline earth metals, magnesium and zinc.

Item 10 The aliphatic carboxylic acid in the general formula (2) is at least one selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and 12-hydroxystearic acid. The polypropylene resin composition for blow molding according to claim 8 or 9.

Item 11. A molded product obtained by blow molding the polypropylene resin composition for blow molding according to any one of claims 1 to 10.

Item 12 The film thickness uniformity of a molded product obtained by blow molding the polypropylene resin composition for blow molding according to any one of claims 1 to 10 is 0.1 or less. 12. The molded article according to 12.

Item 13 The molded product according to claim 11, wherein the molded product is a food container, a toiletry solution container, a household detergent container, a liquid cosmetic container, an industrial chemical container, a medical container, an article for a motor vehicle, or a special pipe. Goods.

Item 14. When blow-molding the polypropylene resin composition for blow molding according to any one of claims 1 to 10, the amide compound (B) represented by the general formula (1) is dissolved in a molten propylene resin. A process for producing a blow molded product, comprising blow molding the polypropylene resin.

According to the present invention, by adding a specific amount of an amide compound having a specific structure to a polypropylene resin, a blow molded product having excellent transparency, whitening resistance, heat resistance, low migration, and odor characteristics can be provided. It is possible to provide a polypropylene resin composition for blow molding excellent in thickness uniformity of a molded product.

Hereinafter, embodiments of the present invention will be described in detail.

<Polypropylene resin (A)>
The polypropylene resin (A) according to the present invention is a polymer mainly composed of propylene, and specifically includes a homopropylene polymer, a copolymer of propylene and ethylene, and a copolymer of propylene and α-olefin. Examples thereof include copolymers, copolymers with propylene, ethylene and α-olefin. The α-olefin is preferably one having 4 to 20 carbon atoms, particularly 4 to 10 carbon atoms. Specifically, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1 -Nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4-dimethyl-1-pentene, etc. are mentioned.

The polypropylene copolymer may be either a random copolymer or a block copolymer. When the polypropylene resin (A) is a random copolymer of propylene and ethylene and / or an α-olefin having 4 to 40 carbon atoms, the content of propylene constituting the copolymer is 95.0% by weight. The content is preferably less than 100.0% by weight. Moreover, when it is a block copolymer of propylene and ethylene and / or an α-olefin having 4 to 40 carbon atoms, the content of propylene constituting the copolymer is 70.0% by weight or more and 100.0% by weight. It is preferable that it is less than. As the polypropylene resin (A), a homopropylene polymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, a propylene-1- A butene-ethylene copolymer is preferred. Among these, a homopropylene polymer and a propylene-ethylene copolymer are particularly preferable.

As a catalyst applied for producing such a polymer, not only a Ziegler-Natta type catalyst generally used but also a transition metal compound (for example, a titanium halide such as titanium trichloride and titanium tetrachloride) is chlorinated. A catalyst system or metallocene catalyst obtained by combining a catalyst formed on a carrier mainly composed of magnesium halide such as magnesium and an alkylaluminum compound (tetraethylaluminum, diethylaluminum chloride, etc.) can also be used.

The polypropylene resin (A) has a melt flow rate at 230 ° C. (hereinafter referred to as MFR, according to JIS K7210 (1999)), preferably 0.1 to 80 g / 10 minutes, more preferably 0.3 to 20 g / 10. Minutes. If it is less than 0.1 g / 10 min, blow molding tends to be difficult, and if it exceeds 80 g / 10 min, the parison hangs down, the moldability deteriorates, and the uneven thickness becomes remarkable, so it is stable and good. It may not be possible to obtain a simple molded product.

<Amide compound (B)>
The amide compound (B) according to the present invention is at least one compound represented by the above general formula (1), and is a compound having a nucleating action on a polypropylene resin. The amide compound is easily prepared by amidating a predetermined aliphatic polycarboxylic acid component and a predetermined alicyclic monoamine component according to a conventionally known method, for example, the method described in JP-A-7-242610. be able to.

As the aliphatic polycarboxylic acid component, 1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, acid chlorides thereof, the polycarboxylic acid and a lower alcohol having 1 to 4 carbon atoms An ester compound can be used. In particular, 1,2,3-propanetricarboxylic acid is recommended. In addition, there is no limitation in particular in the manufacturing method of the said polycarboxylic acid, its acid chloride, and ester compound, It can manufacture using a conventionally well-known method.

The alicyclic monoamine component is a cyclohexylamine optionally substituted with a linear or branched alkyl group having 1 to 10 carbon atoms, specifically, cyclohexylamine, 2-methylcyclohexylamine. 2-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 2-iso-propylcyclohexylamine, 2-n-butylcyclohexylamine, 2-iso-butylcyclohexylamine, 2-sec-butylcyclohexylamine, 2-tert -Butylcyclohexylamine, 2-n-pentylcyclohexylamine, 2-n-hexylcyclohexylamine, 2-n-heptylcyclohexylamine, 2-n-octylamine, 2- (2-ethylhexyl) cyclohexylamine, 2-n- Nonirushi Cyclohexylamine, 2-n-decylcyclohexylamine, 3-methylcyclohexylamine, 3-ethylcyclohexylamine, 3-n-propylcyclohexylamine, 3-iso-propylcyclohexylamine, 3-n-butylcyclohexylamine, 3- iso-butylcyclohexylamine, 3-sec-butylcyclohexylamine, 3-tert-butylcyclohexylamine, 3-n-pentylcyclohexylamine, 3-n-hexylcyclohexylamine, 3-n-heptylcyclohexylamine, 3-n- Octylamine, 3- (2-ethylhexyl) cyclohexylamine, 3-n-nonylcyclohexylamine, 3-n-decylcyclohexylamine, 4-methylcyclohexylamine, 4-ethylcyclohexyl Silamine, 4-n-propylcyclohexylamine, 4-iso-propylcyclohexylamine, 4-n-butylcyclohexylamine, 4-iso-butylcyclohexylamine, 4-sec-butylcyclohexylamine, 4-tert-butylcyclohexylamine, 4-n-pentylcyclohexylamine, 4-n-hexylcyclohexylamine, 4-n-heptylcyclohexylamine, 4-n-octylamine, 4- (2-ethylhexyl) cyclohexylamine, 4-n-nonylcyclohexylamine, 4 Examples include -n-decylcyclohexylamine. These can be used alone or in appropriate combination of two or more.

Among these, cyclohexylamine and a cyclohexylamine having a linear or branched alkyl group having 1 to 4 carbon atoms as a substituent are preferable, and a cyclohexylamine having a methyl group is particularly preferable. Further, when the substituent is a linear or branched alkyl group having 2 to 4 carbon atoms, the substitution position is preferably the 2-position. Specific examples of these preferable alicyclic monoamine components include cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 2 -Iso-propylcyclohexylamine, 2-n-butylcyclohexylamine, 2-iso-butylcyclohexylamine, 2-sec-butylcyclohexylamine, 2-tert-butylcyclohexylamine. These can be used alone or in appropriate combination of two or more.

The cyclohexylamine having an alkyl group may be any of a cis isomer, a trans isomer, and a mixture of these stereoisomers, but a preferred cis isomer: trans isomer ratio is 50:50 to 0: 100, particularly 35:65 to 65. A range of 0: 100 is recommended.

These alicyclic monoamine components can be used alone or in combination of two or more for amidation.

<Preferred amide compound (B)>
Among the amide compounds according to the present invention, an amide in which R ² in the general formula (1) is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms because of its high nucleating action Series compounds are recommended.

Specific examples of preferred amide compounds include 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid. Tri (3-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-ethylcyclohexylamide) 1,2,3- Propanetricarboxylic acid tri (3-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3- -Propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-iso-propylcyclohexylamide), 1,2, 3-propanetricarboxylic acid tri (3-iso-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-iso-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-n -Butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-n-butylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri (4-n-butylcyclohexylamide), 1,2,3 -Propanetricarboxylic acid tri (2-iso-butylcyclohexane) Xylamide), 1,2,3-propanetricarboxylic acid tri (3-iso-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-iso-butylcyclohexylamide), 1,2,3-propane Tricarboxylic acid tri (2-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-sec-butylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri (4-sec-butylcyclohexylamide) ), 1,2,3-propanetricarboxylic acid tri (2-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid Tri (4-tert-butylcyclohexyl) acid Bromide),

1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-butanetetracarboxylic acid tetra (2-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-ethylcyclohexylamide) 1 , 2,3,4-Butanetetracarboxylic acid tetra (3-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-ethylcyclohexylamide), 1,2,3,4-butane Tetracarboxylic acid tetra (2-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic Tetra (3-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2- iso-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-iso-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-iso-propylcyclohexyl) Amide), 1,2,3,4-butanetetracarboxylic acid tetra (2-n-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-n-butylcyclohexylamide) 1, 2,3,4-butanetetracarboxylic acid tetra (4-n-butylcyclohexylamide), 1,2,3 4-Butanetetracarboxylic acid tetra (2-iso-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-iso-butylcyclohexylamide) 1,2,3,4-butanetetracarboxylic Acid tetra (4-iso-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3 -Sec-butylcyclohexylamide) 1,2,3,4-butanetetracarboxylic acid tetra (4-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-tert-butylcyclohexyl) Amide), 1,2,3,4-butanetetracarboxylic acid tetra (3-tert-butyl) (Lucyclohexylamide) 1,2,3,4-butanetetracarboxylic acid tetra (4-tert-butylcyclohexylamide) and the like. These can be used alone or in appropriate combination of two or more.

Among the amide compounds, an amide compound in which R ² in the general formula (1) is a hydrogen atom or a methyl group is particularly preferable because of its high nucleating action and easy availability of raw materials. Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methyl) Cyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-butanetetracarboxylic acid Tetra (2-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-methylcyclohexylamide) And in particular, 1,2,3-propanetricarboxylic acid tricyclo Xylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4 -Methylcyclohexylamide) is preferred.

The crystal system of the amide compound (B) according to the present invention is not particularly limited as long as the effects of the present invention can be obtained, and any crystal system such as hexagonal crystal, monoclinic crystal, cubic crystal and the like can be used. These crystals are also known or can be produced according to known methods.

The amide compound (B) according to the present invention may contain some impurities. It is recommended that the purity of the amide compound represented by the general formula (1) is 90% by weight or more, preferably 95% by weight or more, particularly preferably 97% by weight or more. Examples of impurities include monoamide dicarboxylic acid or ester derived from a reaction intermediate or unreacted substance, diamide monocarboxylic acid or ester thereof, and a compound having an imide skeleton such as an amide-imide structure or a bisimide structure.

The particle size of the amide compound (B) according to the present invention is not particularly limited as long as the effects of the present invention are obtained, but those having a particle size as small as possible are preferable from the viewpoint of the dissolution rate (dissolution time) in the molten polypropylene resin. . Specifically, the maximum particle size obtained by measurement by a laser diffraction light scattering method is usually 200 μm or less, preferably 100 μm or less, more preferably 50 μm, and particularly preferably 10 μm or less.

Examples of a method for preparing the maximum particle size of the amide compound within the above range include a method of finely pulverizing using a conventional apparatus known in this field, and classifying it. Specifically, a method of pulverizing and classifying using a fluidized bed type counter jet mill 100AFG (trade name, manufactured by Hosokawa Micron Corporation), a supersonic jet mill PJM-200 (trade name, manufactured by Nippon Pneumatic Co., Ltd.), etc. is exemplified. Is done.

In the polypropylene resin composition of the present invention, the content of the amide compound (B) is 0.005 to 5 parts by weight, and 0.02 to 2.5 parts by weight with respect to 100 parts by weight of the polypropylene resin (A). Part is preferred. If the amount is less than 0.005 parts by weight, a sufficient nucleating agent effect may not be exhibited. Even if the amount exceeds 5 parts by weight, not only the nucleating agent effect corresponding to the content is not obtained, but the cost is increased, The physical properties of the resulting blow molded product may be affected.

<Fatty acid metal salt (C)>
The fatty acid metal salt (C) according to the present invention is represented by the general formula (2), and may have 8 to 32 carbon atoms (preferably 10 to 10 carbon atoms) which may have one or more hydroxyl groups in the molecule. 22) a fatty acid metal salt comprising a saturated or unsaturated aliphatic monocarboxylic acid and a monovalent or divalent metal. By containing the fatty acid metal salt together with the amide compound (B) in the polypropylene resin (A), a blow molding resin composition having even more excellent physical properties can be obtained.

  Specific examples of the aliphatic monocarboxylic acid in the general formula (2) include caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecane. Acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, mellicic acid, succinic acid, lindelic acid, tuzuic acid, palmitoleic acid, petraseric acid, oleic acid , Elaidic acid, vaccenic acid, linoleic acid, linoleic acid, γ-linolenic acid, linolenic acid, ricinoleic acid, 12-hydroxystearic acid, naphthenic acid, abietic acid and the like. Preferably, at least one selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and 12-hydroxystearic acid is recommended.

Examples of the monovalent or divalent metal in the general formula (2) include alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, strontium, barium, etc.), magnesium, zinc, etc. Preferably, at least one selected from the group consisting of lithium, sodium, potassium, magnesium, calcium and zinc is recommended.

Preferred fatty acid metal salts (C) include at least one aliphatic monocarboxylic acid selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and 12-hydroxystearic acid, A fatty acid metal salt composed of at least one metal selected from the group consisting of lithium, sodium, potassium, magnesium, calcium and zinc is recommended.
Specifically, magnesium stearate, calcium stearate, zinc stearate, sodium stearate, potassium stearate, lithium stearate, 12-hydroxy magnesium stearate, 12-hydroxy calcium stearate, 12-hydroxy zinc stearate, 12- Examples include sodium hydroxystearate, potassium 12-hydroxystearate, lithium 12-hydroxystearate and the like. These can be used alone or in appropriate combination of two or more.

When the fatty acid metal salt (C) is used, the content thereof is preferably 0.001 to 10 parts by weight, particularly 0.01 to 5 parts by weight with respect to 100 parts by weight of the polypropylene resin (A). If the amount is less than 0.001 part by weight, the combined effect with the amide compound (B) may not be obtained. If the amount exceeds 10 parts by weight, the combined effect corresponding to the content cannot be obtained. Cost increases. Further, the content ratio of the fatty acid metal salt (C) to the amide compound (B) is preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 2 parts by weight with respect to 1 part by weight of the amide compound. Is recommended.

<Other additives (D)>
As needed, the following modifier for polypropylene etc. can be mix | blended with the resin composition for blow molding as another additive (D) in the range which does not impair the effect of this invention.

Examples of the polyolefin modifiers include various additives described in “Polylist Additives Manual” (January 2002) edited by the Sanitation Council for Polyolefins, and more specifically, Agents (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), hindered amine light stabilizers (HALS), ultraviolet absorbers (benzophenone compounds, benzotetraazole compounds, etc.), antioxidants (phenolic compounds) 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 aliphatic alcohols having 8 to 22 carbon atoms) , Polyglycol, ester of higher fatty acid having 4 to 22 carbon atoms and aliphatic monohydric alcohol having 4 to 18 carbon atoms, carbon number 8 22 higher fatty acid amides, silicone oils, rosin derivatives, etc.), fillers (talc, hydrotalcite, mica, zeolite, perlite, diatomaceous earth, calcium carbonate, glass fibers, etc.), foaming agents, foaming aids, polymer additives Other additives such as plasticizers (dialkyl phthalates, dialkyl hexahydrophthalates, etc.), crosslinking agents, crosslinking accelerators, antistatic agents, flame retardants, dispersants, organic and inorganic pigments, processing aids, and other nucleating agents Is exemplified. The amount of addition is not particularly limited as long as the predetermined effect of the present invention is not adversely affected.

Examples of the other nucleating agents include lithium benzoate, sodium benzoate, aluminum benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate and other carboxylic acid metal salts; sodium bis (4-tert-butylphenyl) ) Phosphate, cyclic organophosphate metal salts; polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis (p-methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, and the like.

Specific examples of the hindered amine light stabilizer (HALS) include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate. Rate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl) -4-piperidyl) sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2 , 6,6-tetramethyl-piperidyl methacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracar Xylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) .Bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .bis (tridecyl) -1,2,3 4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8,1 -Tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy ] Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, etc.

1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2 , 6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5 , 8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1, 5,8,12-tetraazadodecane, 1,6,11-tri [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane, 1,6,11-tris [ 2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane cyanuric chloride condensed HALS,

1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- And high molecular weight type HALS such as piperidylamino) hexane / dibromoethane polycondensate.

These hindered amine light stabilizers (HALS) can be used alone or in combination of two or more. As for those compounding quantities, 0.001-10 weight part is preferable with respect to 100 weight part of polypropylene resins (A).

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 Alternatively, metal chelates, particularly nickel or chromium salts or chelates may be mentioned. These may be used alone or in combination of two or more. Each compounding amount is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the polypropylene resin (A).

Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (2,5-ditert-butylphenyl) phosphite, and tris (nonylphenyl). ) Phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-ditert-butylphenyl) octyl phosphite , Diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite Ite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentylglycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol Diphosphite, bis (2,5-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4- Dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenylphosphite, bis [2,2'-methylenebis (4,6 -Diamylphenyl)] Isopropylidene diphenyl phosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5 Tert-butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis tert-butyldibenzo) [D, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, Examples include 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite, and the like. These may be used alone or in combination of two or more. Each compounding amount is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the polypropylene resin (A).

Examples of the phenol-based antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-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-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl- 3-methylphenol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy -4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-to Lis (3,5-ditertiarybutyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditertiarybutyl-4-hydroxyphenyl) propionyl Oxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acrolate) Yloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl ] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) Ropioneto], and the like. These may be used alone or in combination of two or more. Each compounding amount is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the polypropylene resin (A).

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecyl mercaptopropionate). Β-alkyl mercaptopropionic acid esters of the above polyols. These may be used alone or in combination of two or more. Each compounding amount is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the polypropylene resin (A).

<Preparation method of polypropylene resin composition for blow molding>
The method for preparing the polypropylene resin composition for blow molding of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and a preparation method applied to the preparation of a resin composition mainly composed of a conventionally known polypropylene resin is used. be able to. Specifically, (i) polypropylene resin (A) (in the form of powder, granules or pellets), an amide compound (B) and, if necessary, a fatty acid metal salt (C), and further if necessary And (ii) a dry-blend type resin composition obtained by melt-kneading a dry-blend type resin composition. The pellet type is recommended.
Examples of the mixing apparatus used when mixing in advance include mixing apparatuses commonly used in the blow molding field, such as a mixer with a high-speed stirrer such as a tumbler mixer, a Henschel mixer, and a super mixer, a ribbon blender, and a tumbler mixer.
Examples of the apparatus used for melt kneading include apparatuses used in the blow molding field, such as a conventionally known single-screw or twin-screw extruder, tandem kneading extruder, and the like. The resin temperature at the time of melt-kneading is usually 180 to 300 ° C, preferably 200 to 280 ° C. It is preferable to dissolve the amide compound (B) in the molten polypropylene resin (A) at the time of melt-kneading because the effects of the present invention are easily exhibited.

As a method for adding the amide compound (B) and, if necessary, the fatty acid metal salt (C) and / or other additives (D) to the polypropylene resin (A), for example, (i) amide compound (B) and a method of adding the fatty acid metal salt (C) and / or other additives (D) separately to the polypropylene resin (A), if necessary,
(Ii) The amide compound (B) and, if necessary, the fatty acid metal salt (C) and / or other additives (D) are mixed to form a dry blend type mixture, and the mixture is converted into a polypropylene resin (A )
(Iii) Amide compound (B), if necessary, fatty acid metal salt (C) and / or other additives (D), and if necessary, as a binder, granulation aids such as wax, solvent, silica, etc. After dry blending together with the agent in a desired ratio, it is heated or wet granulated to form a one-pack composite additive (in the form of granules, granules, pellets, etc.), and the composite additive is made of polypropylene resin (A) And the like.

The blow molded article of the present invention is produced by blow molding the polypropylene resin composition for blow molding of the present invention. As a method for molding the resin composition for blow molding of the present invention, a parison is melt-extruded using an extruder, or a bottomed parison is molded by injection molding, and then blow molding maintained at 50 ° C. or lower. For example, a molding method may be used in which a parison is brought into a metal mold, air having a gas pressure of 0.5 to 1 MPa is blown from an air blowing port, and air pressure is applied until the shape is fixed.

The uniformity of the film thickness of the blow molded product is an important characteristic in maintaining the uniformity of the content of the blow molded product bottle. The uniformity of the thickness of the bottle barrel portion of the blow molded product of the present invention is preferably 0.1 or less, more preferably 0.04 to 0.1, and particularly preferably 0.04 to 0.07.
In the present invention, “thickness uniformity” is a value evaluated by a test method described later. The smaller the value, the higher the thickness uniformity.

When blow-molding the polypropylene resin composition of the present invention, a blow-molded product may be produced by using a plurality of types of the polypropylene resin composition of the present invention and combining them in multiple layers as necessary. Alternatively, the polypropylene resin composition of the present invention and other types of blow molding resin compositions may be combined and combined into a multilayer shape to produce a blow molded product.

According to the present invention, it is possible to obtain a blow-molded product having excellent transparency, heat resistance, whitening resistance, low migration, and odor characteristics, and having a small thickness unevenness of the molded product. Moreover, it was confirmed that the blow molded product made of polypropylene resin of the present invention has good gloss and dimensional stability. The polypropylene resin blow-molded product of the present invention is suitable when heat treatment is performed after blow molding because it has low devitrification and excellent whitening resistance even in heat treatment processes such as heat sterilization, particularly in autoclave sterilization. is there.

The blow molded article thus obtained is a molded article having excellent transparency, heat resistance, whitening resistance, migration and odor characteristics, and little thickness unevenness. Therefore, the blow molded product of the present invention is, for example, a food container such as a beverage container, a fruit juice container, a mineral water container, and a container for toiletries such as shampoo, rinse, liquid soap, acidic, neutral, etc. Or containers for alkaline household detergents, containers for liquid cosmetics, containers for alcohol, industrial chemicals, medical containers such as infusion bottles, seat backs, headrests, knee bolsters, glove box doors, instrument panels, Bumper fascia, bumper beam, center console, intake manifold, spoiler, side molding, pillar, door trim, airbag cover, HVAC duct, spare tire cover, fluid tank, rear window shelf, resonator, trunk board or armrest, etc. Dual-use goods, stationery, toys, sundries, etc. It is preferably used.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples.
Haze value (%), deflection temperature under load (° C.), thickness of test piece cut out from blow molded product bottle obtained from propylene resin composition of present invention shown in Examples 1-8 and Comparative Examples 1-5 The uniformity (degree of uneven thickness), migration, odor characteristics, and whitening resistance were measured and evaluated by the following methods. Moreover, about the test piece cut out from what blow-molded the infusion container in Example 9 and Comparative Example 6, glossiness and dimensional stability were measured and evaluated.

(1) Thickness uniformity For 10 cylindrical bottles having a barrel diameter of 65 mm and an internal volume of 500 ml, thicknesses of 10 barrels / piece at 1 cm intervals were measured with a film thickness meter (“SME-1” manufactured by Sanko Electronics Laboratory). The average thickness (Tave), the maximum thickness (Tmax) and the minimum thickness (Tmin) were determined and calculated from the formula (Tmax−Tmin) / Tave. It shows that it is excellent in the uniformity of thickness, so that this value is small.

(2) Transparency (haze value (%)
Using a haze meter manufactured by Toyo Seiki Seisakusho, the haze value of a test piece (thickness 1 mm) cut out from a blow molded bottle container in accordance with ASTM D1003 was measured. It shows that it is excellent in transparency, so that the obtained numerical value is small.

(3) Deflection temperature under load (℃)
The deflection temperature under load was measured by a method according to ASTM D648 (load 0.45 MPa) using an HDT test apparatus manufactured by Toyo Seiki Seisakusho. The measurement test piece was blow-molded from a square bottle and cut out from its body. The higher the deflection temperature under load, the better the heat resistance.

(4) Migration and odor characteristics
(I) Migrating property: Ten test pieces (3 cm × 3 cm) having a thickness of 1 mm cut out from a blow-molded bottle container and 10 ml of distilled water were sealed in a 225 ml glass bottle and sealed in a fine oven at 60 ° C. 3 Let stand for hours. Next, the molded product was taken out after cooling at room temperature for 2 hours. A sensory test of the sample was performed on six panelists. A blow molded product corresponding to Comparative Example 1, Comparative Example 4, or Comparative Example 5 was used as the blank.
Evaluation was determined by the total score of 6 people based on the blank. The smaller the score, the less the transferability to a water-soluble liquid.
1 point: No difference from the blank.
2 points; slightly different from blank.
3 points: Slight odor is observed.
4 points; I feel a weak odor.
5 points: Strong odor is recognized.
(Ii) Odor characteristics: A blow-molded product (3 cm × 3 cm) was placed in a 225 ml glass bottle, sealed, and allowed to stand in a 90 ° C. phi oven for 3 hours. Next, it was cooled at room temperature for 2 hours. An odor test was conducted on the sample of 6 panelists. A blow molded product corresponding to Comparative Example 1, Comparative Example 4, or Comparative Example 5 was used as the blank.
Evaluation was determined by a total score of 6 people. The smaller the score, the better the odor characteristics.
1 point: No difference from blank.
2 points; slightly different from blank.
3 points: Slight odor is observed.
4 points; I feel a weak odor.
5 points: Strong odor is recognized.

(5) Whitening resistance test
The test piece (thickness 1 mm) used for the transparency measurement was subjected to a steam treatment at 121 ° C. for 30 minutes in a sterilization autoclave, and then a haze of the test piece according to ASTM D1003 using a haze meter manufactured by Toyo Seiki Seisakusho. The value was measured. It shows that it is excellent in whitening resistance, so that the obtained numerical value is small.

(6) Glossiness (60 ° specular gloss (%))
Using a digital gloss meter manufactured by Murakami Color Research Laboratory, the 60 ° specular glossiness of a test piece (thickness 0.3 mm) cut out from a blow-molded infusion container according to ASTM D523 was measured. It shows that it is excellent in glossiness, so that the obtained numerical value is large.

(7) Dimensional stability (Linear expansion coefficient (× 10 ⁵ / K)
For the blow molded infusion bag, cut the middle part of the fuselage along the longitudinal direction of the molded product into a width of 5 mm, a thickness of 0.3 mm, and a length of 15 mm. The sample was heated at a load of 10.0 g and the average expansion coefficient at 50 to 80 ° C. was measured. The smaller the numerical value obtained, the better the dimensional stability.

<Amide compound (B) Production Example 1>
9.7 g (0.055 mol) of 1,2,3-propanetricarboxylic acid (hereinafter abbreviated as “PTC”) in a 500 ml four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a gas inlet. 100 g of N-methylpyrrolidone was weighed and PTC was completely dissolved while stirring at room temperature in a nitrogen atmosphere. Subsequently, 2-methylcyclohexylamine (trans isomer: cis isomer = 74.3: 25.7, GLC area%) 20.4 g (0.18 mol), triphenyl phosphite 55.8 g (0.18 mol) ), 14.2 g (0.18 mol) of pyridine and 50 g of N-methylpyrrolidone were added, and the reaction was performed at 100 ° C. for 4 hours with stirring in a nitrogen atmosphere. After cooling, the reaction solution was slowly poured into a mixed solution of 500 ml of isopropyl alcohol and 500 ml of water and stirred at about 40 ° C. for 1 hour, and then the precipitated white precipitate was filtered off. Further, the obtained white solid was washed twice with 500 ml of isopropyl alcohol at about 40 ° C. and then dried at 100 ° C. and 133 Pa for 6 hours.
The obtained dried product was pulverized in a mortar, passed through a standard sieve having an aperture of 106 μm (JIS Z-8801 standard), and 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide) (hereinafter referred to as “PTC”). 18.8 g (yield 74%).

<Production Example 2 of Amide Compound (B)>
The same procedure as in Production Example 1 was conducted except that 17.9 g (0.18 mol) of cyclohexylamine was used instead of 2-methylcyclohexylamine, and 1,2,3-propanetricarboxylic acid tricyclohexylamide (hereinafter referred to as “PTC-”). Abbreviated as “CHA”.) 17.3 g (75% yield) was obtained.

<Production Example 3 of Amide Compound (B)>
In place of 1,2,3-propanetricarboxylic acid, 12.9 g (0.055 mol) of 1,2,3,4-butanetetracarboxylic acid was used, and 2-methylcyclohexylamine (trans isomer: cis isomer = 54). .6.3: 45.4, GLC area%) 20.4 g (0.18 mol) is used in the same manner as in Production Example 1, and 1,2,3,4-butanetetracarboxylic acid tetrakis ( 2-methylcyclohexylamide) (hereinafter abbreviated as “BTC-2MeCHA”) was obtained in an amount of 21.3 g (yield 63%).

[Example 1]
<Blow molding (bottle))>
Random polypropylene resin (propylene-ethylene random copolymer having an ethylene content of 3.0% by weight, MFR = 20 g / 10 minutes, hereinafter abbreviated as “r-PP”) as an amide compound with respect to 100 parts by weight 0.15 parts by weight of PTC-2MeCHA prepared in Production Example 1 and 0.05 parts by weight of calcium stearate as a fatty acid metal salt were added, and tetrakis [methylene-3- (3,5-di-t-butyl- 4-Hydroxyphenyl) propionate] methane (manufactured by Ciba Specialty Chemicals, trade name “IRGANOX1010”) 0.05 parts by weight and tetras (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals) , Trade name "IRGAFOS168") 0.05 parts by weight, Henschelmi It was dry blended 1000rpm, 5 minutes at Sir.
Next, the mixture was melt-kneaded using a twin screw extruder having a resin temperature of 240 ° C. and a diameter of 15 mm. At this time, it was confirmed that PTC-2MeCHA was dissolved in the molten polypropylene. (In the following Examples and Comparative Examples, it was confirmed that the amide compound (B) was dissolved in the polypropylene resin (A) during the production of the resin composition.) The extruded strands after kneading were water-cooled and then obtained. The obtained strand was cut to obtain a pellet-shaped polypropylene resin composition.
The obtained pellet-shaped polypropylene resin composition was supplied to an injection stretch blow molding machine, and a preform for a container (500 ml capacity) was molded at a resin temperature of 230 ° C. and a mold temperature of 20 ° C. Subsequently, the preform was transferred to a stretch blow molding machine, the preform was heated to 135 ° C. in the mold, and then stretched 2.8 times in the longitudinal direction using a stretching rod. Next, 10 kgf / cm ² of pressurized air was blown into the preform, and the preform was stretched 2.9 times in the lateral direction. The preform was expanded into the shape of a 500 ml capacity bottle container, and held for 10 seconds. Then, 5 degreeC cooling air was inject | poured in the container, the container was cooled, and the bottle container which is blow molding was obtained.

A test piece was cut out from the obtained blow molded product bottle container, and the thickness uniformity, transparency, heat resistance, migration / odor characteristics, and whitening resistance were measured.
The results are shown in Tables 1 and 2.

[Example 2]
Except not using a fatty acid metal salt, it carried out similarly to Example 1, and measured the thickness uniformity, transparency, heat resistance, transferability, odor characteristic, and whitening resistance.

[Example 3]
Except for using PTC-CHA prepared in Production Example 2 as an amide compound, measurement was performed in the same manner as in Example 1 to measure the uniformity of thickness, transparency, heat resistance, migration / odor characteristics, and whitening resistance. did

[Example 4]
Except that BTC-2MeCHA prepared in Production Example 3 was used as an amide compound, measurement was performed in the same manner as in Example 1 to measure thickness uniformity, transparency, heat resistance, migration / odor characteristics, and whitening resistance. did.

[Example 5]
The same as in Example 1 except that a homopolypropylene resin (homopropylene polymer, MFR = 30 g / 10 min, hereinafter referred to as “h-PP”) was used as the polypropylene resin. , Heat resistance, migration / odor characteristics, and whitening resistance were measured.

[Example 6]
Except not using a fatty acid metal salt, it carried out similarly to Example 5, and measured the thickness uniformity, transparency, heat resistance, transferability, odor characteristic, and whitening resistance.

[Example 7]
Example 1 except that a block polypropylene resin (propylene-ethylene block copolymer having an ethylene content of 20% by weight, MFR = 45 g / 10 minutes, hereinafter abbreviated as “b-PP”) was used as the polypropylene resin. In the same manner, the thickness uniformity, transparency, heat resistance, migration / odor characteristics, and whitening resistance were measured.

[Example 8]
Except not using a fatty acid metal salt, it carried out similarly to Example 7, and measured the thickness uniformity, transparency, heat resistance, transferability, odor characteristic, and whitening resistance.

[Example 9]
<Blow molding (infusion pack)>
Random polypropylene resin (propylene-ethylene random copolymer having an ethylene content of 3.0% by weight, MFR = 20 g / 10 minutes, hereinafter abbreviated as “r-PP”) as an amide compound with respect to 100 parts by weight 0.1 part by weight of PTC-2MeCHA prepared in Production Example 1 and 0.05 part by weight of hydrotalcite (trade name “DHT-4A” manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (trade name “IRGANOX1010” manufactured by Ciba Specialty Chemicals) and tetras (2,4-di-t-butyl) Phenyl) phosphite (Ciba Specialty Chemicals, trade name “IRGAFOS168”) 0.05 parts by weight And, were dry-blended 1000rpm, 5 minutes by a Henschel mixer.
Next, the mixture was melt-kneaded using a twin screw extruder having a resin temperature of 240 ° C. and a diameter of 15 mm, the extruded strand was water-cooled, and then the obtained strand was cut to obtain a pellet-shaped polypropylene resin composition. .
The obtained pellet-shaped polypropylene resin composition was supplied to an injection stretch blow molding machine, and a preform for a container (800 ml capacity) was molded at a resin temperature of 240 ° C. and a mold temperature of 20 ° C. Subsequently, the preform was transferred to a stretch blow molding machine, the preform was heated to 135 ° C. in the mold, and then stretched using a stretching rod. Next, 8 kgf / cm ² of pressurized air was blown into the preform and stretched in the transverse direction, and the preform was expanded to the shape of an infusion container having a capacity of 800 ml and held for 10 seconds. Then, 5 degreeC cooling air was inject | poured in the container, the container was cooled, and the infusion container which is blow molding was obtained.

A test piece was cut out from the obtained blow molded product infusion container, and the thickness uniformity, transparency, gloss, and dimensional stability were measured. The results are shown in Table 2.

[Comparative Example 1]
<Blow molding (bottle))>
Except not using an amide type compound, it carried out similarly to Example 1, and measured the uniformity of thickness, transparency, heat resistance, transferability, odor characteristic, and whitening resistance.

[Comparative Example 2]
Instead of the amide compound, 1,3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol is hereinafter abbreviated as “nucleating agent A”. ) Was used in the same manner as in Example 1, and the thickness uniformity, transparency, heat resistance, migration / odor characteristics, and whitening resistance were measured.

[Comparative Example 3]
Instead of the amide compound, methylene bis (2,4-di-tert-butylphenyl) phosphate sodium salt is hereinafter abbreviated as “nucleating agent B”. ) Was used in the same manner as in Example 1, and the thickness uniformity, transparency, heat resistance, migration / odor characteristics, and whitening resistance were measured.

[Comparative Example 4]
Except not using an amide-type compound, it carried out like Example 5 and measured the uniformity of thickness, transparency, heat resistance, transferability, odor characteristic, and whitening resistance.

[Comparative Example 5]
Except not using an amide compound, it carried out similarly to Example 7, and measured the thickness uniformity, transparency, heat resistance, transferability, odor characteristic, and whitening resistance.

[Comparative Example 6]
<Blow molding (infusion pack)>
Except not using an amide-type compound, it carried out similarly to Example 9, and measured the thickness uniformity, transparency, glossiness, and dimensional stability.

The blow molded product obtained from the polypropylene resin composition for blow molding of the present invention is a molded article having excellent transparency, heat resistance, transferability / odor characteristics, glossiness and dimensional stability, and having little thickness unevenness. Therefore, the blow molded product of the present invention is, for example, a food container such as a beverage container, a fruit juice container, a mineral water container, and a container for toiletries such as shampoo, rinse, liquid soap, acidic, neutral, etc. Or containers for alkaline household detergents, containers for liquid cosmetics, containers for alcohol, industrial chemicals, medical containers such as infusion bottles, seat backs, headrests, knee bolsters, glove box doors, instrument panels, Bumper fascia, bumper beam, center console, intake manifold, spoiler, side molding, pillar, door trim, airbag cover, HVAC duct, spare tire cover, fluid tank, rear window shelf, resonator, trunk board or armrest, etc. Dual-use goods, stationery, toys, sundries, etc. It is preferably used.

Claims (14)

General formula (1) with respect to 100 parts by weight of polypropylene resin (A)

[Wherein, R ¹ represents a residue obtained by removing all carboxyl groups from 1,2,3-propanetricarboxylic acid or 1,2,3,4-butanetetracarboxylic acid. k R ^{2 s} are the same as or different from each other and each represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. k represents an integer of 3 or 4. ]
A polypropylene resin composition for blow molding, comprising 0.005 to 5 parts by weight of at least one amide compound (B) represented by the formula: The polypropylene resin composition for blow molding according to claim 1, wherein the polypropylene resin (A) has a melt flow rate (MFR) at 230 ° C of 0.1 to 80 g / 10 min.   The polypropylene resin composition for blow molding according to claim 1 or 2, wherein the polypropylene resin (A) is a homopropylene polymer.   The polypropylene resin composition for blow molding according to claim 1 or 2, wherein the polypropylene resin (A) is a copolymer of propylene and ethylene and / or an α-olefin having 4 to 40 carbon atoms.   The copolymer of propylene and ethylene and / or an α-olefin having 4 to 40 carbon atoms is a copolymer of propylene and ethylene or a copolymer of propylene, ethylene and 1-butene. Polypropylene resin composition for blow molding.   A copolymer of propylene and ethylene and / or an α-olefin having 4 to 40 carbon atoms is a random copolymer, and the content of propylene constituting the copolymer is 95.0% by weight or more and 100.0%. The polypropylene resin composition for blow molding according to claim 4 or 5, which is less than% by weight.   A copolymer of propylene and ethylene and / or an α-olefin having 4 to 40 carbon atoms is a block copolymer, and the content of propylene constituting the copolymer is 70.0% by weight or more and 100.0%. The polypropylene resin composition for blow molding according to claim 4 or 5, which is less than% by weight. Furthermore, the general formula (2)

[Wherein R ³ represents a residue obtained by removing a carboxyl group from a saturated or unsaturated aliphatic monocarboxylic acid having 8 to 32 carbon atoms which may have one or more hydroxyl groups in the molecule. To express. n represents an integer of 1 or 2, and when n = 2, two R ^{3 s} may be the same or different. M represents a monovalent or divalent metal. ]
The blow molding polypropylene resin composition according to claim 1, comprising at least one fatty acid metal salt (C) represented by the formula: 9. The polypropylene resin composition for blow molding according to claim 8, wherein M in the general formula (2) is at least one selected from the group consisting of alkali metals, alkaline earth metals, magnesium and zinc. The aliphatic monocarboxylic acid in the general formula (2) is at least one selected from the group consisting of lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and 12-hydroxystearic acid. Or the polypropylene resin composition for blow molding of Claim 9. The molded article formed by blow-molding the polypropylene resin composition for blow molding of any one of Claims 1-10.   The uniformity of the film thickness of a molded product obtained by blow molding the polypropylene resin composition for blow molding according to any one of claims 1 to 10 is 0.1 or less. The molded product described.   The molded article is a food container, a container for toiletry solution, a container for household detergent, a container for liquid cosmetics, a container for industrial chemicals, a medical container, an article for a motor vehicle, or special piping. The molded product described. In blow-molding the polypropylene resin composition for blow molding according to any one of claims 1 to 10, the amide compound (B) represented by the general formula (1) is dissolved in a molten propylene resin, A method for producing a blow-molded product, comprising blow-molding the polypropylene resin composition.