JP5920524B2 - Diacetal-containing composition, polyolefin resin composition, and resin molded body - Google Patents

Description

  The present invention relates to a diacetal-containing composition containing a specific dibenzylidene sorbitol, a polyolefin resin composition containing the composition, and a resin molded product obtained by molding the polyolefin resin composition.

  Diacetals typified by dibenzylidene sorbitol and its nucleus-substituted derivatives are compounds useful as nucleating agents for polyolefin resins, particularly ethylene and propylene homopolymers or copolymers based on them. Diacetal is particularly excellent in the effect of improving transparency, and is widely used as a resin additive in the field of molded articles such as various containers that require transparency (for example, Patent Document 1).

  As described above, diacetal has a very excellent effect as a nucleating agent for resin, but on the other hand, it has poor powder flowability, so that it does not adhere to pipes, hoppers, feeders, etc. for transfer. There is a tendency to cause bridging. As a result, there is a problem that the supply of diacetal to the polyolefin resin is not constant.

  Furthermore, diacetal has a problem in that it tends to cause blocking during storage (a phenomenon in which particles aggregate together to form a lump).

  For this reason, it is known that diacetal blended into a polyolefin resin is dispersed in a solution and used as a liquid dispersion (for example, Patent Document 2). However, when used as a liquid dispersion of diacetal as in Patent Document 2, a step of mixing the diacetal and the dispersion medium and a step of recovering the dispersion medium to be used are required. An apparatus used in such a process requires an increase in size in industrial production, and is not preferable from an economic viewpoint.

  Moreover, the technique of improving powder fluidity | liquidity by making a diacetal containing composition into a specific shape and mix | blending a fatty acid metal salt is also known (for example, patent document 3 and patent document 4). However, even if such a method is adopted, sufficient powder fluidity cannot be obtained, and there is still room for improvement from the viewpoint of blocking.

  Furthermore, diacetal generally has a high melting point compared to other nucleating agents, and when blended with a polyolefin resin and melt kneaded and various moldings are performed in a low temperature region (for example, about 190 ° C.), Diacetal is not well dispersed. Therefore, conventionally, melt kneading and various moldings must be performed in a relatively high temperature range, and there is a concern of generating odor due to partial thermal decomposition of diacetal, affecting the mechanical characteristics, and the like.

JP 2007-22924 A JP 2002-524599 A International Publication No. 98/33851 JP 59-129239 A

  An object of this invention is to provide the diacetal containing composition which is excellent in powder fluidity | liquidity and is hard to raise | generate blocking during storage even if it is a granular form or a powder form.

  Moreover, it aims at providing the polyolefin resin composition which can be shape | molded also in a low-temperature area | region by mix | blending the said diacetal containing composition with polyolefin resin.

  In view of the present situation, the present inventors have conducted extensive studies to solve the above-mentioned problems, and as a result, specific diacetal as component (A), polyoxyethylene sorbitan fatty acid ester as component (B), and component It has been found that the diacetal-containing composition containing the specific fatty acid metal salt (C) is excellent in powder flowability and hardly causes blocking during storage. Furthermore, the present inventors have found that molding processing is possible even in a low temperature region by including the diacetal-containing composition in a polyolefin resin as a nucleating agent composition.

  The present invention has been completed on the basis of such knowledge, and has been completed. The following diacetal-containing composition, polyolefin resin composition, resin molded article, diacetal fluidity improving method, polyolefin resin at low temperature A molding method and the like are provided.

  Item 1. Component (A): General formula (1):

[In Formula (1), R ¹ and R ² are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms, or a linear or branched carbon number 1 to 1, respectively. 3 represents an alkoxy group or a halogen atom. m and n each represent an integer of 1 to 3. ]
At least one diacetal represented by:
Component (B): polyoxyethylene sorbitan _C 8 _{-C 22} fatty acid ester, and component _(C): a C 12 _{-C 22} fatty acid, zinc, consisting of at least one metal selected from the group consisting of magnesium and lithium fatty acid Metal salts,
A composition comprising:
The composition ratio in the composition is in the range of 0.05 to 5 parts by weight of component (B) and 0.5 to 15 parts by weight of component (C) with respect to 100 parts by weight of component (A) or Powdered diacetal-containing composition.

  Item 2. Item 2. The granular or powdery diacetal-containing composition according to Item 1, comprising 0.1 to 300 parts by weight of component (C) with respect to 1 part by weight of component (B).

Item 3. Item 3. The granular or powdery diacetal-containing composition according to Item 1 or 2, wherein the component (B) is polyoxyethylene sorbitan C ₈ -C ₂₂ fatty acid triester.

  Item 4. Any one of Items 1 to 3, wherein the fatty acid metal salt in Component (C) is at least one selected from the group consisting of zinc myristate, magnesium myristate, zinc palmitate, magnesium palmitate, zinc stearate, and magnesium stearate. The granular or powdery diacetal-containing composition according to claim 1.

  Item 5. Item 5. The granular or powdery diacetal-containing composition according to any one of Items 1 to 4, substantially consisting of only component (A), component (B), and component (C).

  Item 6. Item 5. The granular or powdery diacetal-containing composition according to any one of Items 1 to 4, which substantially comprises only the component (A), the component (B), the component (C) and the optical brightener.

  Item 7. Component (A ′): Formula (2):

[In Formula (2), R ³ and R ⁴ are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms. q and r are each 1 or 2. ]
At least one diacetal represented by:
Component (B ′): selected from the group consisting of polyoxyethylene (ethylene oxide average addition moles: 2 to 30) sorbitan C ₈ -C ₂₂ fatty acid triester and component (C ′): myristic acid, palmitic acid and stearic acid A fatty acid metal salt comprising at least one fatty acid and at least one metal selected from the group consisting of zinc, magnesium and lithium,
A composition comprising:
The composition ratio in the composition is in the range of 0.05 to 5 parts by weight of component (B ′) and 0.5 to 15 parts by weight of component (C ′) with respect to 100 parts by weight of component (A ′). A granular or powdery diacetal-containing composition.

  Item 8. Item 8. The granular or powdered diacetal-containing composition according to Item 7, comprising 0.1 to 300 parts by weight of component (C ′) with respect to 1 part by weight of component (B ′).

  Item 9. Component (A): General formula (1):

[In Formula (1), R ¹ and R ² are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms, or a linear or branched carbon number 1 to 1, respectively. 3 represents an alkoxy group or a halogen atom. m and n each represent an integer of 1 to 3. ]
At least one diacetal represented by:
Component (B): polyoxyethylene sorbitan _C 8 _{-C 22} fatty acid ester, and component _(C): a C 12 _{-C 22} fatty acid, zinc, consisting of at least one metal selected from the group consisting of magnesium and lithium fatty acid Metal salts,
A step of mixing
A granular or powdered diacetal-containing composition in the range of 0.05 to 5 parts by weight of component (B) and 0.5 to 15 parts by weight of component (C) is produced with respect to 100 parts by weight of component (A). how to.

  Item 10. Component (A ′): Formula (2):

[In Formula (2), R ³ and R ⁴ are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms. q and r are each 1 or 2. ]
At least one diacetal represented by:
Component (B ′): selected from the group consisting of polyoxyethylene (ethylene oxide average addition moles: 2 to 30) sorbitan C ₈ -C ₂₂ fatty acid triester and component (C ′): myristic acid, palmitic acid and stearic acid A fatty acid metal salt comprising at least one fatty acid and at least one metal selected from the group consisting of zinc, magnesium and lithium,
A step of mixing
A granular or powdered diacetal-containing composition in the range of 0.05 to 5 parts by weight of component (B) and 0.5 to 15 parts by weight of component (C) is produced with respect to 100 parts by weight of component (A). how to.

  Item 11. Item 9. A granular or powdery diacetal-containing composition according to any one of Items 1 to 8, and a polyolefin resin composition containing a polyolefin resin.

  Item 12. Item 11. The component (A) in the granular or powdered diacetal-containing composition according to any one of Items 1 to 6, relative to 100 parts by weight of the polyolefin resin, is 0.05 to 0.4 parts by weight. Polyolefin resin composition.

  Item 13. Item 11. The polyolefin according to Item 11, wherein the component (A ′) in the granular or powdered diacetal-containing composition according to Item 7 or 8 is 0.05 to 0.4 parts by weight relative to 100 parts by weight of the polyolefin resin. Resin composition.

Item 14. Item 14. A method for producing a polyolefin resin composition according to any one of Items 11 to 13, comprising a step of mixing the granular or powdered diacetal-containing composition according to any one of Items 1 to 8 and a polyolefin resin.

  Item 15. Item 14. A resin molded article obtained by molding the polyolefin resin composition according to any one of Items 11 to 13.

  Item 16. Component (A): General formula (1):

[In Formula (1), R ¹ and R ² are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms, or a linear or branched carbon number 1 to 1, respectively. 3 represents an alkoxy group or a halogen atom. m and n each represent an integer of 1 to 3. ]
In at least one diacetal represented by
Component (B): polyoxyethylene sorbitan _C 8 _{-C 22} fatty acid ester, and component _(C): a C 12 _{-C 22} fatty acid, zinc, consisting of at least one metal selected from the group consisting of magnesium and lithium fatty acid Metal salts,
Is a method for improving the fluidity of diacetal by blending,
The composition ratio in the diacetal-containing composition is in the range of 0.05 to 5 parts by weight of component (B) and 0.5 to 15 parts by weight of component (C) with respect to 100 parts by weight of component (A). A method for improving the fluidity of diacetal.

  Item 17. Item 17. The method for improving the fluidity of the diacetal according to Item 16, comprising 0.1 to 300 parts by weight of the component (C) with respect to 1 part by weight of the component (B).

Item 18. Item 18. The method for improving the fluidity of the diacetal according to Item 16 or 17, wherein the component (B) is polyoxyethylene sorbitan C ₈ -C ₂₂ fatty acid triester.

  Item 19. Any of paragraphs 16 to 18, wherein the fatty acid metal salt in component (C) is at least one selected from the group consisting of zinc myristate, magnesium myristate, zinc palmitate, magnesium palmitate, zinc stearate, and magnesium stearate. A method for improving the fluidity of diacetal according to claim 1.

  Item 20. Item 9. A polyolefin resin, characterized by mixing the granular or powdered diacetal-containing composition according to any one of Items 1 to 8 and a polyolefin resin, and molding the obtained polyolefin resin composition at 190 to 240 ° C. Molding method.

  According to the diacetal-containing composition of the present invention, since the powder fluidity is excellent, bridging can be suppressed, for example, in the piping for transfer, in the supply hopper, in the feeder and the like when supplying the raw material. Moreover, since it is hard to raise | generate blocking during the storage of a diacetal containing composition, it is excellent in storage stability.

  Furthermore, the polyolefin composition of the present invention can be molded even in a low temperature region by using the diacetal-containing composition.

In an Example, it is the figure which represented typically the biaxial screw type feeder used by "5. Adhesion evaluation to a metal (feeder test)." In “5. Evaluation of adhesion to metal (feeder test)”, a photograph showing the state of adhesion to a biaxial screw (feeder screw) seen after feeding the diacetal-containing composition of Example 2 using a feeder. is there. In "5. Evaluation of adhesion to metal (feeder test)", it is a photograph showing the state of adhesion to a biaxial screw (feeder screw) seen after feeding the diacetal of Comparative Example 1 using a feeder. FIG. 5 is a graph in which vertical stress is plotted on the horizontal axis and shear stress is plotted on the vertical axis according to “6. Shear test (evaluation of internal friction angle)” for Example 2 and Comparative Example 1. FIG. FIG. 5 is a graph in which vertical stress is plotted on the horizontal axis and shear stress is plotted on the vertical axis according to “6. Shear test (evaluation of internal friction angle)” for Example 1. FIG. FIG. 5 is a graph in which vertical stress is plotted on the horizontal axis and shear stress is plotted on the vertical axis in Example 3, according to “6. Shear test (evaluation of internal friction angle)”. FIG. 5 is a graph in which vertical stress is plotted on the horizontal axis and shear stress is plotted on the vertical axis in Example 4 according to “6. Shear test (evaluation of internal friction angle)”. FIG. 5 is a graph in which vertical stress is plotted on the horizontal axis and shear stress is plotted on the vertical axis according to “6. Shear test (evaluation of internal friction angle)” for Example 5. FIG. FIG. 6 is a graph in which vertical stress is plotted on the horizontal axis and shear stress is plotted on the vertical axis according to “6. Shear test (evaluation of internal friction angle)” for Example 6. FIG. FIG. 7 is a graph in which vertical stress is plotted on the horizontal axis and shear stress is plotted on the vertical axis according to “6. Shear test (evaluation of internal friction angle)” for Example 7. FIG. In Example 8, according to “6. Shear Test (Evaluation of Internal Friction Angle)”, the vertical axis represents the vertical stress and the vertical axis represents the shear stress. In Example 17, according to “6. Shear Test (Evaluation of Internal Friction Angle)”, the horizontal axis represents vertical stress and the vertical axis represents shear stress. 19 is a graph in which vertical stress is plotted on the horizontal axis and shear stress is plotted on the vertical axis according to “6. Shear test (evaluation of internal friction angle)” for Example 18. FIG. In Example 19, according to “6. Shear Test (Evaluation of Internal Friction Angle)”, a vertical stress is plotted on the horizontal axis and a shear stress is plotted on the vertical axis. In Example 20, according to “6. Shear Test (Evaluation of Internal Friction Angle)”, a vertical stress is plotted on the horizontal axis and a shear stress is plotted on the vertical axis. 24 is a graph in which vertical stress is plotted on the horizontal axis and shear stress is plotted on the vertical axis according to “6. Shear test (evaluation of internal friction angle)” for Example 28. FIG. 40 is a graph in which vertical stress is plotted on the horizontal axis and shear stress is plotted on the vertical axis according to “6. Shear test (evaluation of internal friction angle)” for Example 29. FIG. In Comparative Example 5, according to “6. Shear Test (Evaluation of Internal Friction Angle)”, it is a graph in which vertical stress is plotted on the horizontal axis and shear stress is plotted on the vertical axis. In Comparative Example 16, according to “6. Shear Test (Evaluation of Internal Friction Angle)”, the horizontal axis represents vertical stress and the vertical axis represents shear stress. In Comparative Example 24, according to “6. Shear Test (Evaluation of Internal Friction Angle)”, the horizontal axis represents vertical stress and the vertical axis represents shear stress. In Comparative Example 25, according to “6. Shear Test (Evaluation of Internal Friction Angle)”, the horizontal axis represents vertical stress and the vertical axis represents shear stress.

  In this specification, the expression “comprising” includes the concepts of “comprising”, “consisting essentially of”, and “consisting solely”.

1. Diacetal-containing composition The diacetal-containing composition according to the present invention comprises component (A): general formula (1):

At least one diacetal, components in represented by (B): polyoxyethylene sorbitan _C 8 _{-C 22} fatty acid ester, and component _(C): a C 14 _{-C 22} fatty acid, zinc, magnesium, and the group consisting of lithium A granular or powder composition containing a fatty acid metal salt composed of at least one metal selected from the group consisting of: Hereinafter, each component will be described in detail.

1-1. Component (A): Diacetal The diacetal is represented by the following general formula (A):

[In Formula (A), R ¹ and R ² are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched carbon. It represents an alkoxy group having 1 to 4 carbon atoms, a linear or branched alkoxycarbonyl group having 1 to 4 carbon atoms, or a halogen atom. R ³ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkenyl group having 2 to 4 carbon atoms. m and n each represent an integer of 1 to 5. p represents 0 or 1; Two R ¹ may be bonded to each other to form a tetralin ring with a benzene ring to which they are bonded, and two R ² groups may be bonded to each other to form a tetralin ring with a benzene ring to which they are bonded. It may be. ]
At least one diacetal represented by the formula can be used.

In the general formula (A), examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Examples thereof include tert-butyl groups, and examples of linear or branched alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, and butoxy groups. . Examples of the linear or branched alkoxycarbonyl group having 1 to 4 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, and an isopropoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

In the diacetal represented by the general formula (1) used in the present invention, the linear or branched alkyl group having 1 to 3 carbon atoms represented by R ¹ and R ² is a methyl group. , Ethyl group, propyl group, isopropyl group and the like, and linear or branched alkoxy groups having 1 to 3 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group and the like. Is done. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

In the general formula (A), m and n are each an integer of 1 to 5, and in the general formula (1), an integer of 1 to 3. Further, p in the general formula (A) is more preferably 1. In the general formula (A) and the general formula (1), the substitution positions of the substituents represented by R ¹ and R ² are not particularly limited, but when m and n are 1, o-, In the case of m- or p-position and m and n are 2, examples are 2,3-position, 2,4-position, 2,5-position, 3,4-position, 3,5-position, etc. And when m and n are 3, examples thereof include 2,4,5-position, 3,4,5-position, and the like.

  These diacetals represented by the general formula (A) and the general formula (1) are both known, or Japanese Patent Publication No. 48-43748, Japanese Patent Publication No. 53-5165, Japanese Patent Publication No. 57. It can be easily produced according to known methods such as JP-A-185287 and JP-A-2-231488.

  The following can be illustrated as a representative example of the diacetal represented by the general formula (A).

1,3: 2,4-bis-O-benzylidene-D-sorbitol,
1,3: 2,4-bis-O- (o-methylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-methylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-ethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-ethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-isopropylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-isopropylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-isopropylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (on-propylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (mn-propylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (pn-propylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (on-butylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (mn-butylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (pn-butylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-tert-butylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-tert-butylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-tert-butylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 3′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 5′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 5′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 3′-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 4′-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 5′-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 5′-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 4 ′, 5′-trimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 4 ′, 5′-trimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 4 ′, 5′-triethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 4 ′, 5′-triethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-methoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-methoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-methoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-ethoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-ethoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-ethoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-isopropoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-isopropoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-isopropoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (on-propoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (mn-propoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (pn-propoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-methoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-methoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-methoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-ethoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-ethoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-ethoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-isopropoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-isopropoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-isopropoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (on-propoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (mn-propoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (pn-propoxycarbonylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-fluorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-fluorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-fluorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-chlorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-chlorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-chlorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-bromobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-bromobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-bromobenzylidene) -D-sorbitol,
1,3-O-benzylidene-2,4-O- (p-methylbenzylidene) -D-sorbitol,
1,3-O- (p-methylbenzylidene) -2,4-O-benzylidene-D-sorbitol,
1,3-O-benzylidene-2,4-O- (p-ethylbenzylidene) -D-sorbitol,
1,3-O- (p-ethylbenzylidene) -2,4-O-benzylidene-D-sorbitol,
1,3-O-benzylidene-2,4-O- (p-chlorobenzylidene) -D-sorbitol,
1,3-O- (p-chlorobenzylidene) -2,4-O-benzylidene-D-sorbitol,
1,3-O-benzylidene-2,4-O- (2 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3-O- (2 ′, 4′-dimethylbenzylidene) -2,4-O-benzylidene-D-sorbitol,
1,3-O-benzylidene-2,4-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3-O- (3 ′, 4′-dimethylbenzylidene) -2,4-O-benzylidene-D-sorbitol,
1,3-O- (p-methylbenzylidene) -2,4-O- (p-ethylbenzylidene) -D-sorbitol,
1,3-O- (p-ethylbenzylidene) -2,4-O- (p-methylbenzylidene) -D-sorbitol,
1,3-O- (p-methylbenzylidene) -2,4-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3-O- (3 ′, 4′-dimethylbenzylidene) -2,4-Op-methylbenzylidene-D-sorbitol,
1,3-O- (p-ethylbenzylidene) -2,4-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3-O- (3 ′, 4′-dimethylbenzylidene) -2,4-Op-ethylbenzylidene-D-sorbitol,
1,3-O- (p-methylbenzylidene) -2,4-O- (p-chlorobenzylidene) -D-sorbitol,
1,3-O- (p-chlorobenzylidene) -2,4-O- (p-methylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O-benzylidene-1-methylsorbitol,
1,3: 2,4-bis-O- (p-methylbenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (p-ethylbenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (2 ′, 3′-dimethylbenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (2 ′, 4′-dimethylbenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (2 ′, 5′-dimethylbenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (3 ′, 5′-dimethylbenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (3′-methyl-4′-methoxybenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dichlorobenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (p-methoxycarbonylbenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (3′-methyl-4′-fluorobenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O- (3′-bromo-4′-ethylbenzylidene) -1-methylsorbitol,
1,3: 2,4-bis-O-benzylidene-1-ethylsorbitol,
1,3: 2,4-bis-O- (p-methylbenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (p-ethylbenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (2 ′, 3′-dimethylbenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (2 ′, 4′-dimethylbenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (2 ′, 5′-dimethylbenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (3 ′, 5′-dimethylbenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (3′-methyl-4′-methoxybenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dichlorobenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (p-methoxycarbonylbenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (3′-methyl-4′-fluorobenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O- (3′-bromo-4′-ethylbenzylidene) -1-ethylsorbitol,
1,3: 2,4-bis-O-benzylidene-1-n-propylsorbitol,
1,3: 2,4-bis-O- (p-methylbenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (p-ethylbenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (2 ′, 3′-dimethylbenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (2 ′, 4′-dimethylbenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (2 ′, 5′-dimethylbenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (3 ′, 5′-dimethylbenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (3′-methyl-4′-methoxybenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dichlorobenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (p-methoxycarbonylbenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (3′-methyl-4′-fluorobenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O- (3′-bromo-4′-ethylbenzylidene) -1-n-propylsorbitol,
1,3: 2,4-bis-O-benzylidene-1-allylsorbitol,
1,3: 2,4-bis-O- (p-methylbenzylidene) -1-allylsorbitol,
1,3: 2,4-bis-O- (p-ethylbenzylidene) -1-allylsorbitol,
1,3: 2,4-bis-O- (pn-propylbenzylidene) -1-allylsorbitol,
1,3: 2,4-bis-O- (2 ′, 3′-dimethylbenzylidene) -1-allylsorbitol,
1,3: 2,4-bis-O- (2 ′, 4′-dimethylbenzylidene) -1-allylsorbitol,
1,3: 2,4-bis-O- (2 ′, 5′-dimethylbenzylidene) -1-allylsorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -1-allylsorbitol,
1,3: 2,4-bis-O- (3 ′, 5′-dimethylbenzylidene) -1-allylsorbitol,
1,3: 2,4-bis-O- (3′-methyl-4′-methoxybenzylidene) -1-allylsorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dichlorobenzylidene) -1-allylsorbitol,
1,3: 2,4-bis-O- (p-methoxycarbonylbenzylidene) -1-allylsorbitol,
1,3: 2,4-bis-O- (3′-methyl-4′-fluorobenzylidene) -1-allylsorbitol,
Examples include 1,3: 2,4-bis-O- (3′-bromo-4′-ethylbenzylidene) -1-allyl sorbitol.

As a representative example of the diacetal represented by the general formula (1) according to the constitutional requirements of the present invention, 1,3: 2,4-bis-O- (o-methylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-methylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-ethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-ethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-isopropylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-isopropylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-isopropylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (on-propylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (mn-propylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (pn-propylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 3′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 5′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 5′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 3′-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 4′-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 5′-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 5′-diethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 4 ′, 5′-trimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 4 ′, 5′-trimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 4 ′, 5′-triethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 4 ′, 5′-triethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-methoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-methoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-methoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-ethoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-ethoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-ethoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-isopropoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-isopropoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-isopropoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (on-propoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (mn-propoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (pn-propoxybenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-fluorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-fluorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-fluorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-chlorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-chlorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-chlorobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (o-bromobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (m-bromobenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-bromobenzylidene) -D-sorbitol,
1,3-O- (p-methylbenzylidene) -2,4-O- (p-ethylbenzylidene) -D-sorbitol,
1,3-O- (p-ethylbenzylidene) -2,4-O- (p-methylbenzylidene) -D-sorbitol,
1,3-O- (p-methylbenzylidene) -2,4-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3-O- (3 ′, 4′-dimethylbenzylidene) -2,4-Op-methylbenzylidene-D-sorbitol,
1,3-O- (p-ethylbenzylidene) -2,4-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3-O- (3 ′, 4′-dimethylbenzylidene) -2,4-Op-ethylbenzylidene-D-sorbitol,
1,3-O- (p-methylbenzylidene) -2,4-O- (p-chlorobenzylidene) -D-sorbitol,
Examples include 1,3-O- (p-chlorobenzylidene) -2,4-O- (p-methylbenzylidene) -D-sorbitol.

Among these, more effective diacetals represented by the general formula (1) include 1,3: 2,4-bis-O- (o-methylbenzylidene) sorbitol,
1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-isopropylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (pn-propylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (2 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 5′-dimethylbenzylidene) -D-sorbitol,
1,3-O- (p-methylbenzylidene) -2,4-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol,
1,3-O- (3 ′, 4′-dimethylbenzylidene) -2,4-Op-methylbenzylidene-D-sorbitol,
1,3-O- (p-ethylbenzylidene) -2,4-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol and 1,3-O- (3 ′, 4′-dimethylbenzylidene) ) -2,4-Op-ethylbenzylidene-D-sorbitol is preferred.

1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol,
1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol is particularly preferred.

  These diacetals are used singly or in appropriate combination of two or more.

  The crystal form of the diacetal is not particularly limited as long as the effects of the present invention can be obtained, and any crystal form such as hexagonal, monoclinic, cubic, trigonal or orthorhombic can be used. These crystals are also known or can be produced according to known methods.

  The diacetal used in the present invention preferably has a purity of the 1,3: 2,4-isomer represented by the general formula (1) of 100%, but may contain some impurities.

1-2. Ingredient (B)
Component (B) according to the present invention is polyoxyethylene sorbitan C ₈ -C ₂₂ fatty acid ester.

Polyoxyethylene sorbitan C ₈ -C ₂₂ fatty acid ester, a sorbitan polyoxyethylene is substituted, an ester having a fatty acid ester-linked carbon number C ₈ -C _22.

  The carbon number of the fatty acid is 8 to 22, and 12 to 22 is particularly preferable. When the carbon number is less than 8, there is a tendency to bleed out from the resin molded body. On the other hand, when the number of carbon atoms exceeds 22, the transparency of the molded product tends to be impaired.

  The fatty acid is preferably a saturated or unsaturated carboxylic acid, and particularly preferably lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, or oleic acid.

  The average added mole number of ethylene oxide in polyoxyethylene is preferably 1 to 40, more preferably 2 to 30, further preferably 5 to 30, and particularly preferably 5 to 20.

Specific examples of the component (B) include, for example, polyoxyethylene (average number of moles of added ethylene oxide: 2 to 30) sorbitan monolaurate,
Polyoxyethylene (ethylene oxide average addition mole number: 2 to 30) sorbitan monomyristate,
Polyoxyethylene (ethylene oxide average addition mole number: 2 to 30) sorbitan monopalmitate,
Polyoxyethylene (ethylene oxide average addition mole number: 2 to 30) sorbitan monostearate,
Polyoxyethylene (ethylene oxide average addition mole number: 2 to 30) sorbitan monoisostearate,
Polyoxyethylene (ethylene oxide average addition mole number: 2 to 30) sorbitan monooleate,
Polyoxyethylene (ethylene oxide average addition mole number: 2 to 30) sorbitan trilaurate,
Polyoxyethylene (ethylene oxide average addition mole number: 2 to 30) sorbitan trimyristate,
Polyoxyethylene (ethylene oxide average addition mole number: 2 to 30) sorbitan tripalmitate,
Polyoxyethylene (ethylene oxide average addition mole number: 2 to 30) sorbitan tristearate,
Polyoxyethylene (ethylene oxide average addition mole number: 2 to 30) sorbitan triisostearate,
Examples include polyoxyethylene (ethylene oxide average addition mole number: 2 to 30) sorbitan trioleate.

More preferably, polyoxyethylene (average added mole number of ethylene oxide: 5 to 20) sorbitan monomyristate,
Polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan monopalmitate,
Polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan monostearate,
Polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan monoisostearate,
Polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan monooleate,
Polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan trimyristate,
Polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan tripalmitate,
Polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan tristearate,
Polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan triisostearate, and polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan trioleate are mentioned.

More preferably, polyoxyethylene (average added mole number of ethylene oxide: 5 to 20) sorbitan trimyristate,
Polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan tripalmitate,
Polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan tristearate,
Polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan triisostearate, and polyoxyethylene (ethylene oxide average addition mole number: 5-20) sorbitan trioleate are mentioned.

Among the esters of the component (B), polyoxyethylene sorbitan C ₈ -C ₂₂ fatty acid monoester, polyoxyethylene sorbitan C ₈ -C ₂₂ fatty acid diester, and polyoxyethylene sorbitan C ₈ -C ₂₂ fatty acid triester It is preferably at least one selected from the group, and polyoxyethylene sorbitan C ₈ -C ₂₂ fatty acid triester is more preferable from the viewpoint of suppressing bleed out from the molded product.

These polyoxyethylene sorbitan C ₈ -C ₂₂ fatty acid esters may be used alone or in combination.

As the polyoxyethylene sorbitan C ₈ -C ₂₂ fatty acid ester as the component (B), those obtained by a conventionally known production method can be used as long as the effects of the present invention are not impaired. For example, it can be generally obtained by heating and synthesizing sorbitol and a fatty acid in the presence of an alkali catalyst, and further adding ethylene oxide to the sorbitan fatty acid ester.

  The resulting polyoxyethylene sorbitan fatty acid esters are generally mono-, di-, tri-, tetra-fatty acid esters of various polyoxyethylene sorbitans, and mono- and di-products of 1,4,3,6-sorbide. -It is a mixture of fatty acid esters and the like, and these mixtures can be used in the present invention as they are. Alternatively, a single component can be isolated from the mixture and used alone or in appropriate combination of two or more.

  What is marketed can also be used for the polyoxyethylene sorbitan fatty acid ester which concerns on this invention, unless the effect of this invention is impaired. For example, the commercial item etc. which are described in "Chemical goods of 16112" (Chemical Industry Daily Co., Ltd., February 21, 2012 issue) are illustrated.

  The content of the component (B) is preferably about 0.05 to 5 parts by weight, more preferably about 0.1 to 3 parts by weight, with respect to 100 parts by weight of the component (A), and 0.3 to 1.5 More preferred are parts by weight. By setting the content of the component (B) to 0.05 parts by weight or more, an effect that the chargeability of the acetal composition of the present invention is suppressed can be obtained. Moreover, the effect that the bleed out from a molded object can be suppressed is acquired by setting content of a component (B) to 5 weight part or less.

1-3. Ingredient (C)
The fatty acid metal salt according to the present invention comprises a C ₁₂ -C ₂₂ fatty acid and at least one metal selected from the group consisting of zinc, magnesium, and lithium.

  As carbon number of a fatty acid, it is 12-22, and 14-18 are especially preferable. Other than this recommended number of carbons, it is difficult to obtain transparency in the low temperature processing region, and a special advantage cannot be obtained.

  Specific examples of the fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like. Among these, stearic acid is preferable from the viewpoint of odor of the diacetal-containing composition of the present invention.

  Moreover, as a metal which forms a fatty-acid metal salt, they are zinc, magnesium, and lithium, and zinc is especially preferable from a viewpoint of the expression of transparency in a low temperature processing area | region.

  Specific examples of the fatty acid metal salt include zinc myristate, magnesium myristate, lithium myristate, zinc stearate, magnesium stearate, and lithium stearate. Among these, zinc stearate is more preferable.

  Content of a component (C) is 0.5-15 weight part with respect to 100 weight part of component (A), About 1.0-8 weight part is more preferable, About 3-6 weight part is further preferable. By setting the content of the component (C) to 0.5 parts by weight or more, high transparency in the low temperature processing region can be obtained. Further, even if the content of the component (C) exceeds 15 parts by weight, the advantage of the present invention cannot be obtained and it is not economical.

  The content of the component (C) relative to 1 part by weight of the component (B) is preferably about 0.1 to 300 parts by weight, more preferably about 0.2 to 160 parts by weight, and 0.6 to 120 parts by weight. Further preferred. By containing the component (B) and the component (C) within this range, the powder flowability of the diacetal-containing composition which is the effect of the present invention can be sufficiently obtained.

1-4. Other components The diacetal-containing composition of the present invention is a composition containing the component (A), the component (B), and the component (C), but the component (A), the component (B), and the component ( In addition to C), an optional component may be included as long as the effects of the present invention are not impaired. Examples of the optional component include various additives described in "Polylist Additives Manual" (January 2002) edited by Sanitation Council for Polyolefins and the like. Specifically, fluorescent whitening agents (2,5-thiophenediyl (5-tert-butyl-1,3-benzoxazole), 4,4′-bis (benzoxazol-2-yl) stilbene, etc.), Antioxidants, stabilizers (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), UV absorbers (benzophenone compounds, benzotriazole compounds, etc.), surfactants, lubricants (paraffin, wax, etc.) Aliphatic hydrocarbon, higher fatty acid having 8 to 22 carbon atoms, higher fatty acid metal (Al, Ca) salt having 8 to 22 carbon atoms, higher aliphatic alcohol having 8 to 22 carbon atoms, polyglycol, 4 to 22 carbon atoms Esters of higher fatty acids and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher fatty acid amides having 8 to 22 carbon atoms, silicone oils, rosin derivatives, etc.), fillers (talc, Hydrotalcite, mica, zeolite, perlite, diatomaceous earth, calcium carbonate, glass fiber, etc.), foaming agent, foaming aid, polymer additive, plasticizer (dialkyl phthalate, dialkyl hexahydrophthalate, etc.), crosslinking agent, crosslinking accelerator Various additives such as antistatic agents, flame retardants, dispersants, organic inorganic pigments (indigo compounds, phthalocyanine compounds, anthraquinone compounds, ultramarine compounds, cobalt aluminate compounds, etc.), processing aids, and other nucleating agents Agents are exemplified.

  When these optional additives are used, the amount used thereof may be used within a range that is usually used as long as the effect of the present invention is not impaired, but is preferably based on 100 parts by weight of component (A). Is used in an amount of about 0.005 to 100 parts by weight, more preferably about 0.01 to 50 parts by weight.

  When these arbitrary additives are blended, the mixing method is not particularly limited as long as it can be uniformly mixed at a practical level. For example, a method of dry blending as described below to produce a uniform mixture is exemplified.

  The antioxidant also has the effect of improving the storage stability of the diacetal-containing composition of the present invention. When the antioxidant is used for the purpose of improving the storage stability, the amount used is preferably 0.01 to 5 parts by weight, more preferably 0.1 parts by weight with respect to 100 parts by weight of the component (A). 03 to 3 parts by weight.

  Examples of such antioxidants include phenol-based antioxidants, phosphite-based compounds, sulfur-based antioxidants, and the like. Specifically, 2,6-di-t-butylphenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3 , 5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), triethylene glycol-bis- [3- (3-t -Butyl-4-hydroxy-5-methylphenyl) propionate] and the like. Among these, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is recommended.

  However, these optional components are preferably blended at an arbitrary ratio when the polyolefin composition described later is produced, and as a specific example of the form of the diacetal-containing composition of the present invention, the effects of the present invention can be obtained. Demonstrate enough. Specifically, from the viewpoint of appearance, color, etc. of the molded article, a composition consisting essentially of only component (A), component (B), component (C), and fluorescent brightener, or substantially It is recommended that the composition be composed of only component (A), component (B), and component (C).

1-5. Preferred Combination of Diacetal-Containing Composition As a combination of component (A), component (B), and component (C) contained in the diacetal-containing composition of the present invention, the following component (A ' ), Component (B ′), and component (C ′).

  Component (A ′): Formula (2):

[In Formula (2), R ³ and R ⁴ are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms. q and r are each 1 or 2.
At least one diacetal represented by:
Component (B ′): selected from the group consisting of polyoxyethylene (ethylene oxide average addition moles: 2 to 30) sorbitan C ₈ -C ₂₂ fatty acid triester and component (C ′): myristic acid, palmitic acid and stearic acid A fatty acid metal salt comprising at least one fatty acid and at least one metal selected from the group consisting of zinc, magnesium and lithium,
A granular or powdery diacetal-containing composition comprising:

As a more preferable combination of the component (A ′), the component (B ′), and the component (C ′),
Component (A ′): 1,3: 2,4-bis-O- (3,4-dimethylbenzylidene) -D-sorbitol,
Component (B ′): polyoxyethylene (average number of moles of added ethylene oxide: 5 to 20) sorbitan C ₈ -C ₂₂ fatty acid triester,
And component (C ′): a fatty acid metal salt comprising at least one metal selected from the group consisting of myristic acid or stearic acid, zinc, and magnesium,
It is.

As a particularly preferred combination of the component (A ′), the component (B ′), and the component (C ′), the component (A ′): 1,3: 2,4-bis-O- (3,4-dimethylbenzylidene) ) -D-sorbitol,
(B ′): Polyoxyethylene (ethylene oxide average addition mole number: 5 to 20) sorbitan C ₂₀ fatty acid tristearate, and component (C ′): a granular or powdered diastereous composition containing zinc stearate is recommended. The

  As content of component (B ') and component (C') with respect to 100 parts by weight of component (A '), component (B') is about 0.05 to 5.0 parts by weight, and component (C ') is The amount is preferably about 0.5 to 15 parts by weight, the component (B ′) is about 0.1 to 3.0 parts by weight, and the component (C ′) is about 1.0 to 8.0 parts by weight. Is more preferable.

  The content of the component (C ′) with respect to 1 part by weight of the component (B ′) in the diacetal-containing composition is preferably about 0.1 to 300 parts by weight, more preferably about 0.2 to 160 parts by weight.

1-6. Shape of Diacetal-Containing Composition The form of the diacetal-containing composition of the present invention is granular or powder. As a granular form, various forms, such as a granular form, a spherical form, a cylindrical form, and a pellet form, can be taken.

  When the diacetal containing composition concerning this invention is granular, the average value of the particle diameter is 500 micrometers-10 mm, Preferably it is 600 micrometers-5 mm.

  When the diacetal-containing composition according to the present invention is in a powder form, the average value of the particle diameter is 1 μm to 1 mm, preferably 5 μm to 600 μm.

  The average particle diameter (average particle diameter) and particle size distribution of the granular or powdery material are measured using, for example, a laser diffraction / scattering particle size distribution measuring apparatus (trade name “LA-910” manufactured by Horiba, Ltd.). can do.

  For granular materials with a large particle size of 1 mm, 10 mm, etc., the measurement using the LA-910 causes precipitation in the cell and an accurate value cannot be obtained, so the openings are 1000 μm, 500 μm, 150 μm, 106 μm, 90 μm. , 75μm, 63μm, 45μm, 25μm sieve (JIS-Z8801) and saucer in this order, put about 10g of granular material on the uppermost sieve, shake well, weigh the granular material remaining on each sieve The particle size distribution can be determined from the weight fraction, assuming that the total weight is 100%. The average particle size can be determined from the 50% particle size based on weight.

  The particle size distribution of the diacetal-containing composition according to the present invention may be distributed over a wide range, and is not particularly required to be monodispersed. That is, the particle size distribution obtained with a normal industrial pulverizer is sufficient.

  In order to obtain the shape of the diacetal-containing composition, pulverization / disintegration, granulation, molding, classification, or the like can be performed as necessary.

  The diacetal-containing composition of the above form can be produced using a known granulator, pulverizer / pulverizer, classifier or the like. For example, for granulators, dry or wet extrusion granulators, mixed agitation granulators, tablet machines, dry compression roll granulators, spherical granulators, pin mills, jet mills, pulverizers, cutter mills Examples of hammer mills, planar crushers, flake crushers, nibblers, and classifiers include vibrating sieve machines and wind classifiers.

2. Manufacturing method of diacetal containing composition The manufacturing method of the diacetal containing composition of this invention comprises the process of mixing the said component (A), component (B), and component (C). Such a mixing method is not particularly limited as long as a desired diacetal-containing composition is obtained.

For example, the following method is exemplified:
(I) In the process of producing the diacetal according to the conventionally known diacetal production method represented by the general formula (1) (for example, the method described in JP-A-2-231488), the component (B) and the component ( A method of mixing C),
(Ii) A method of mixing (dry blending) the component (A), the component (B), and the component (C) using a known mixing device such as a Henschel mixer, a V blender, or a ribbon blender,
(Iii) Component (A), component (B), and component (C) are placed in a dispersion medium such as C1-C3 lower alcohols such as methanol and ethanol and water, and stirred at room temperature or under heating. And mixing to make a slurry or swollen state, and then distilling off the dispersion medium,
(Iv) After the component (A) is put into a dispersion medium such as C1-C3 lower alcohols such as methanol and ethanol, water, etc., and stirred at room temperature or under heating to form a slurry or swollen state , Component (B), and component (C) as they are or in the form of a solution such as water or a lower alcohol having 1 to 3 carbon atoms such as methanol and ethanol, and then the dispersion medium is distilled off. .

  In addition, the addition time of the component (B) in the mixing method (i) is preferably when the reaction system is in a neutral state after completion of the diacetalization reaction between sorbitol and the benzaldehyde. The amount of the dispersion medium used in the mixing method (iii) and (iv) is preferably about 5 to 200 parts by weight, more preferably about 10 to 100 parts by weight, with respect to 10 parts by weight of the component (A). is there. The mixing temperature in the presence of the dispersion medium is usually about 20 to 100 ° C, preferably about 50 to 80 ° C.

  As a preferable method for producing a diacetal-containing composition, the above methods (i), (iii) and (iv) are recommended.

3. Method for improving fluidity of diacetal The present invention relates to component (B) and component (C) (or component (B ') to component (A') and component (A) It also relates to a method for improving the fluidity of the diacetal by blending (C ′)). The component (A), the component (B), and the component (C) (or the component (A ′), the component (B ′), and the component (C ′)) are the above-mentioned “1. diacetal-containing composition”. And the same components as those mentioned above, and the component (A), the component (B), and the component (C) (or the component (A ′), the component (B ′), and the component (C ′ )) Various blending amounts and blending ratios are the same as the various contents and blending ratios mentioned in the above "1. Diacetal-containing composition".

  By blending component (B) and component (C) (or component (B ′) and component (C ′) with respect to component (A ′)) with respect to component (A), The powder fluidity can be improved, and bridging in the piping, the supply hopper, the feeder, and the like during the raw material supply, which is a problem specific to the component (A) diacetal, can be suppressed.

4). Polyolefin resin composition The polyolefin resin composition of the present invention contains a diacetal-containing composition and a polyolefin resin.

  The diacetal-containing composition includes the component (A), the component (B), and the component (C) (or the component (A ′), the component (B ′), and the above-mentioned “1. diacetal-containing composition”. The component similar to a component (C ')), and the diacetal containing composition which has content and content rate similar to these components are mentioned.

  Examples of the polyolefin resin according to the present invention include polyethylene resins, polypropylene resins, polybutene resins, polymethylpentene resins, and polybutadiene resins.

  Specifically, high density polyethylene, medium density polyethylene, linear polyethylene, ethylene content of 50% by weight or more, preferably 70% by weight or more, ethylene copolymer, propylene homopolymer, propylene of 50% by weight or more, preferably 70% by weight The above propylene copolymer, butene homopolymer, butene content of 50 wt% or more, preferably 70 wt% or more of butene copolymer, methylpentene homopolymer, methylpentene content of 50 wt% or more, preferably 70 wt% or more of methylpentene copolymer, Examples include polybutadiene. The copolymer may be a random copolymer or a block copolymer. Furthermore, when these resins have stereoregularity, they may be isotactic or syndiotactic.

  As the comonomer that can constitute the copolymer, specifically, an α-olefin having 2 to 12 carbon atoms such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, 1,4- Examples include bicyclo type monomers such as endomethylenecyclohexene, (meth) acrylic acid esters such as methyl (meth) acrylate and ethyl (meth) acrylate, and vinyl acetate.

  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 comprising a combination of a catalyst formed on a carrier mainly composed of magnesium halide such as magnesium and an alkylaluminum compound (triethylaluminum, diethylaluminum chloride, etc.) can also be used.

  The melt flow rate of the polyolefin resin according to the present invention (hereinafter abbreviated as “MFR”, JIS K 7210-1999) is appropriately selected depending on the molding method to be applied, but is usually about 0.01 to 200 g / 10 minutes, Preferably about 0.05 to 100 g / 10 min is recommended.

  The content of the diacetal-containing composition with respect to 100 parts by weight of the polyolefin resin is preferably about 0.05 to 0.4 parts by weight, more preferably about 0.1 to 0.3 parts by weight, and 0.15 to 0.25 parts by weight. More preferred is about part. By setting the content of the diacetal-containing composition to 0.05 parts by weight or more, the nucleating agent effect is increased, and the resin modifying effects such as improvement of transparency and mechanical properties are easily exhibited. On the other hand, when the content of the diacetal-containing composition is blended at 0.4 parts by weight or less, it does not cause deterioration of the transparency of the molded article, and is favorable from an economical viewpoint.

  The polyolefin resin composition according to the present invention may be one in which an additive is added within a range not impairing the effects of the present invention, depending on the purpose of use and the application.

  As the additive contained in the polyolefin resin composition, the same additives as those described in “1-4. Other components” can be used.

  Specifically, fluorescent whitening agents (2,5-thiophenediyl (5-tert-butyl-1,3-benzoxazole), 4,4′-bis (benzoxazol-2-yl) stilbene, etc.), Antioxidants, stabilizers (metal compounds, epoxy compounds, nitrogen compounds, phosphorus compounds, sulfur compounds, etc.), UV absorbers (benzophenone compounds, benzotriazole compounds, etc.), surfactants, lubricants (paraffin, wax, etc.) Aliphatic hydrocarbon, higher fatty acid having 8 to 22 carbon atoms, higher fatty acid metal (Al, Ca) salt having 8 to 22 carbon atoms, higher aliphatic alcohol having 8 to 22 carbon atoms, polyglycol, 4 to 22 carbon atoms Esters of higher fatty acids and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher fatty acid amides having 8 to 22 carbon atoms, silicone oils, rosin derivatives, etc.), fillers (talc) Hydrotalcite, mica, zeolite, perlite, diatomaceous earth, calcium carbonate, glass fiber, etc.), foaming agent, foaming aid, polymer additive, plasticizer (dialkyl phthalate, dialkyl hexahydrophthalate, etc.), crosslinking agent, crosslinking accelerator Various additives such as antistatic agents, flame retardants, dispersants, organic inorganic pigments (indigo compounds, phthalocyanine compounds, anthraquinone compounds, ultramarine compounds, cobalt aluminate compounds, etc.), processing aids, and other nucleating agents Agents are exemplified.

  When these optional additives are used, the amount used thereof may be used within a range that is usually used as long as the effect of the present invention is not impaired, but is preferably based on 100 parts by weight of component (A). Is used in an amount of about 0.005 to 100 parts by weight, more preferably about 0.01 to 50 parts by weight.

  In particular, the antioxidant has an effect of improving the storage stability of the diacetal-containing composition of the present invention. When the antioxidant is used for the purpose of improving the storage stability, the amount used is preferably 0.01 to 5 parts by weight, more preferably 0.1 parts by weight with respect to 100 parts by weight of the component (A). 03 to 3 parts by weight.

  Examples of such antioxidants include phenol-based antioxidants, phosphite-based compounds, sulfur-based antioxidants, and the like. Specifically, 2,6-di-t-butylphenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3 , 5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), triethylene glycol-bis- [3- (3-t -Butyl-4-hydroxy-5-methylphenyl) propionate] and the like. Among these, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is recommended.

  When these arbitrary additives are blended, the mixing method is not particularly limited as long as it can be uniformly mixed at a practical level. For example, a method of dry blending as described above to produce a uniform mixture is exemplified.

  As a preferable combination of the polyolefin resin composition of the present invention, as the polyolefin resin, a polyethylene resin, a polypropylene resin and a polybutene resin are exemplified, and more specifically, high density polyethylene, medium density polyethylene, linear Polyethylene, ethylene copolymer with ethylene content of 50% by weight or more, propylene homopolymer, propylene copolymer with 50% by weight or more of propylene, butene homopolymer, butene copolymer with butene content of 50% by weight or more, methylpentene homopolymer, methylpentene content of 50% by weight As a combination of the above methylpentene copolymer, polybutadiene and the like and a diacetal-containing composition, the components (A ′) and (B ′) mentioned in the above “1-5. Preferred combinations of diacetal-containing compositions”. , And it is preferably a combination of diacetal containing composition comprising a component (C ').

5. Production method of polyolefin resin composition Examples of the production method of the polyolefin resin composition of the present invention include the following methods:
(A) A polyolefin resin (powder, granules, flakes or pellets), the diacetal-containing composition of the present invention and, if necessary, the above-mentioned additive, a conventional mixer such as a Henschel mixer, a V blender, a ribbon blender, etc. A method for producing a dry blend type polyolefin resin composition by mixing using,
(B) This dry blend type polyolefin resin composition is melt-kneaded at a desired temperature using a conventional kneader, for example, a uniaxial or biaxial extruder, and the extruded strand is cooled. A method for producing a pellet type polyolefin resin composition by cutting a cooled strand,
(C) A method for producing a masterbatch pellet type polyolefin resin composition having a high diacetal-containing composition (about 2 to 15% by weight).

  The blending amount and blending ratio of the diacetal-containing composition in the polyolefin resin composition of the present invention are the same as the blending ratio and the blending ratio of the diacetal-containing composition in “4. Polyolefin resin composition”.

6). Resin Molded Body The resin molded body of the present invention can be obtained by molding the polyolefin resin composition of the present invention according to a conventional molding method. When molding the polyolefin resin composition according to the present invention, any conventionally known molding method such as injection molding, extrusion molding, blow molding, pressure molding, rotational molding, film molding, etc. can be employed. The molding conditions can be appropriately selected from a wide range of conventionally employed conditions.

  The polyolefin resin composition according to the present invention is applied to a field similar to the field in which a polyolefin resin composition obtained by blending diacetal as a nucleating agent has been conventionally used to form a molded body.

  The amount of the diacetal-containing composition used in the resin molded body is preferably about 0.05 to 0.4 parts by weight, more preferably about 0.1 to 0.3 parts by weight, based on 100 parts by weight of the resin. More preferably, it is about 15 to 0.25 parts by weight. By blending within these ranges, the effects of the present invention can be sufficiently obtained.

7). Molding method of polyolefin resin composition at low temperature The resin molded body according to the present invention is obtained by mixing a granular or powdered diacetal-containing composition and a polyolefin resin, and molding the resulting polyolefin resin composition. . The “granular or powdered diacetal-containing composition”, “polyolefin resin”, and “polyolefin resin composition” are the same as those mentioned above.

  Conventionally, diacetal has a high melting point, and the necessary addition amount of the diacetal-containing composition required for producing a molded article excellent in transparency under a high temperature region is not sufficiently dispersed in the low temperature region, and the transparency of the molded product It becomes a factor to worsen. On the other hand, in the present invention, by using the diacetal-containing composition mentioned in the above-mentioned “1. Diacetal-containing composition” as a nucleating agent, the transparency of the molded article can be sufficiently obtained even in a low-temperature region, and the low-temperature region. A resin molded article having sufficiently excellent transparency can be obtained even underneath.

  The specific temperature range of the low temperature region is preferably about 190 to 230 ° C, more preferably about 190 to 220 ° C, and further preferably about 190 to 210 ° C. Of course, it is possible to mold a resin molded body that is sufficiently excellent in transparency even in a conventional temperature range where the molding temperature of the resin molded body according to the present invention is higher than 240 ° C.

  The upper limit of the molding temperature is a temperature at which each component in the diacetal-containing composition and the polyolefin resin are not thermally decomposed, and is appropriately set within a range in which effects such as transparency and physical properties required as a resin molded body are not impaired. However, for example, about 260 ° C., preferably about 250 ° C. may be mentioned.

8). Uses of resin moldings The resin moldings of the present invention are used in the fields of food packaging materials and food containers, cosmetic containers, pharmaceutical containers, etc., disposable syringes sterilized by heat, radiation, etc., infusion / transfusion sets, blood collection instruments, etc. Appliances; Food and plant packaging sterilized by radiation, etc .; Various cases such as clothing cases and clothing storage containers; Cups for hot-filling foods; Retort food packaging containers; Microwave oven containers Containers for cans, bottles, etc. for beverages such as juice and tea, cosmetics, pharmaceuticals, shampoos, etc .; Containers and caps for seasonings such as miso and soy sauce; Cases for food such as water, rice, bread, pickles And useful as a container. Furthermore, the resin molded body of the present invention is also suitable as a material for miscellaneous goods such as refrigerator cases and the like; stationery; electrical / mechanical parts; automotive parts and the like.

  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.

  In the following examples and comparative examples, for diacetal-containing compositions, as evaluations regarding powder characteristics, evaluation of charging properties, evaluation of friction angle, bleed-out test, evaluation of blocking properties, evaluation of adhesion to metal (feeder) Test), shear test (evaluation of internal friction angle), and haze value were evaluated by the following methods.

1. Evaluation of chargeability The chargeability of the diacetal-containing compositions prepared in Examples and Comparative Examples was measured using an electrostatic diffusivity measuring device manufactured by Nano Seeds Co., Ltd. The diacetal-containing composition was placed on a sample plate in an environment of 20 ° C. and 40% RH, and charged with corona discharge. Then, the sample was fixed and the measurement sensor was driven to measure the attenuation of the surface potential. The smaller the value obtained after about 900 seconds, the harder it is to charge.

2. Evaluation of Friction Angle A 25 cm × 25 cm (thickness: 3 mm) glass plate on which 0.1 g of the diacetal-containing composition prepared in Examples and Comparative Examples was gradually tilted, and the angle at which the sample started to slide was measured. The smaller the numerical value obtained, the better the powder flowability.

3. Bleed-out test The test piece (thickness: 1 mm) obtained by injection molding in the examples and comparative examples was suspended in a gear oven at about 80 ° C. and left to stand for about 10 days. A: A bleedout was not observed, B: A slight bleedout was observed, and C: A bleedout was observed.

4). Evaluation of blocking property A polyethylene bag of 5.6 cm x 5.6 cm was filled with 3.5 g of the diacetal-containing composition prepared in Examples and Comparative Examples, and then a 2 kg load was applied to the sealed ones. It left still in the gear oven of about 60 degreeC. Three weeks later, each sample is taken out from the bag and visually checked for blocking status. A: Three-stage evaluation: A: almost no blocking, B: slight blocking, C: blocking is noticeable. Went.

5. Evaluation of adhesion to metal (feeder test)
After 300 g of the diacetal-containing composition prepared in Examples and Comparative Examples was put into a twin screw type feeder (KF-C2000 manufactured by Kubota Corporation), the motor screw output (MV1) was set to 10%, and the agitator was The diacetal-containing composition was fed out by driving. Then, the adhesion state of the diacetal containing composition to the screw was confirmed visually. FIG. 1 schematically shows a biaxial screw feeder. The upper part of FIG. 1 shows a front view of the twin screw type feeder part, and the lower part of FIG. 1 shows a top view. In FIG. 1, 1 indicates a hopper, 2 indicates an agitator, and 3 indicates a biaxial screw.

6). Shear test (Evaluation of internal friction angle)
The internal friction angles of the diacetal-containing compositions prepared in Examples and Comparative Examples were measured using a powder layer shear force measuring device (NS-S500 type) manufactured by Nano Seeds Co., Ltd. The height of the cell used for the shear test was 30 mm, and measurements were performed by applying forces of 50 N, 100 N, and 150 N under vertical load. The cell indentation speed was 0.2 mm / sec, the indentation gap was 0.2 mm, and the side sliding speed was 10 μm / sec. The smaller the slope (internal friction angle) of the obtained chart, the smaller the adhesion between the diacetal-containing compositions and the better the powder flowability.

7). Evaluation of haze value (%) The haze value of the test piece (thickness: 2 mm) obtained by injection molding in Examples and Comparative Examples was measured using a haze meter manufactured by Toyo Seiki Seisakusho, JIS K7136 (2000). It measured according to. The smaller the numerical value obtained, the better the transparency.

Example 1
1,3: 2,4-Bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol (hereinafter also referred to as “3,4DDMDBS”) as component (A) and poly (B) Oxyethylene (average number of moles of ethylene oxide added: 20) sorbitan tristearate and zinc stearate as component (C) were mixed so as to have the blending amounts shown in Table 1, and methanol was further added to reflux conditions in methanol. Under stirring for 1 hour, a white paste-like mixture was obtained. Next, most of the methanol was removed under reduced pressure, followed by vacuum drying with stirring at 133 Pa and 80 ° C. for 4 hours. Next, the coarse particles were removed by sieving with a 70 mesh JIS standard sieve (aperture 212 μm) to obtain a powdery diacetal-containing composition. The obtained diacetal-containing composition was evaluated for chargeability, friction angle, internal friction angle, and blocking test. The obtained evaluation results are shown in Table 1.

Examples 2-4
The same as in Example 1 except that the amount of polyoxyethylene (ethylene oxide average addition moles: 20) sorbitan tristearate of component (B) was used as shown in Table 1 with respect to 100 parts by weight of component (A). The diacetal-containing composition of the present invention was obtained. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 1.

Example 5
In place of polyoxyethylene (ethylene oxide average addition mole number: 20) sorbitan tristearate as component (B), polyoxyethylene (ethylene oxide average addition mole number: 20) sorbitan monostearate is used, and component (A) 100 Except having used 1.0 weight part of component (B) with respect to the weight part, it carried out similarly to Example 1 and obtained the diacetal containing composition of this invention. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 1.

Example 6
As component (B), instead of polyoxyethylene (average number of moles of ethylene oxide added: 20) sorbitan tristearate, polyoxyethylene (average number of moles of ethylene oxide added: 20) sorbitan monooleate was used, and component (A) 100 Except having used 1.0 weight part of component (B) with respect to the weight part, it carried out similarly to Example 1 and obtained the diacetal containing composition of this invention. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 1.

Example 7
As component (B), polyoxyethylene (average number of moles of ethylene oxide added: 20) sorbitan monolaurate was used instead of polyoxyethylene (average number of moles of ethylene oxide added: 20) sorbitan tristearate, and component (A) 100 Except having used 1.0 weight part of component (B) with respect to the weight part, it carried out similarly to Example 1 and obtained the diacetal containing composition of this invention. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 1.

Example 8
In place of polyoxyethylene (ethylene oxide average addition mole number: 20) sorbitan tristearate as component (B), polyoxyethylene (ethylene oxide average addition mole number: 6) sorbitan monostearate is used, and component (A) 100 Except having used 1.0 weight part of component (B) with respect to the weight part, it carried out similarly to Example 1 and obtained the diacetal containing composition of this invention. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 1.

Comparative Example 1
Each component was evaluated about the diacetal of a component (A), without adding a component (B) and a component (C), and the obtained result was shown in Table 1.

Comparative Example 2
The same as in Example 1 except that 0.04 parts by weight of the component (B) polyoxyethylene (ethylene oxide average added mole number: 20) sorbitan tristearate was used with respect to 100 parts by weight of the component (A). And a diacetal-containing composition was obtained. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 1.

Comparative Example 3
The same as in Example 1 except that 6.0 parts by weight of component (B) polyoxyethylene (ethylene oxide average added mole number: 20) sorbitan tristearate was used with respect to 100 parts by weight of component (A). And a diacetal-containing composition was obtained. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 1.

Comparative Example 4
As component (B), sorbitan monooleate was used in place of polyoxyethylene (ethylene oxide average added mole number: 20) sorbitan tristearate, and component (B) was added to 1.100 parts by weight of component (A). Except having used 0 weight part, it carried out similarly to Example 1 and obtained the diacetal containing composition. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 1.

Comparative Example 5
Except not adding a component (C), it carried out like Example 3 and the diacetal containing composition was obtained. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 1.

Comparative Example 6
The diacetal-containing composition was carried out in the same manner as in Example 1 except that 5.0 parts by weight of component (C) (zinc stearate) was used with respect to 100 parts by weight of component (A) without adding component (B). Got. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 1.

  In Table 1, the kind, compounding quantity, and each evaluation result of the diacetal containing composition obtained in Examples 1-8 and Comparative Examples 1-6 are shown. In Table 1, the abbreviations of the types of component (A), component (B), and component (C) are as follows.

a1: 1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol b1: polyoxyethylene (average number of moles of ethylene oxide added: 20) sorbitan tristearate b2: polyoxy Ethylene (moles with average ethylene oxide: 20) sorbitan monostearate b3: Polyoxyethylene (moles with average ethylene oxide: 20) sorbitan monooleate b4: Polyoxyethylene (moles with average ethylene oxide: 20) sorbitan monolaurate b5: polyoxyethylene (average number of moles of ethylene oxide: 6) sorbitan monostearate b6: sorbitan monooleate c1: zinc stearate

  The above Example 2 and Comparative Example 1 were measured according to “5. Evaluation of Adhesion to Metal (Feeder Test)”. FIG. 2 shows a photograph showing the state of attachment to the screw of Example 2, and FIG. 3 shows a photograph showing the state of attachment to the screw of Comparative Example 1.

  Further, for Example 2 and Comparative Example 1 described above, the vertical stress was plotted on the horizontal axis and the shear stress was plotted on the vertical axis according to “6. Shear Test (Internal Friction Angle)”. The measurement results are shown in FIG. Similarly, the measurement results for Examples 1, 3 to 8, 17 to 20, 28, 29, and Comparative Examples 5, 16, 24, and 25 are shown in FIGS.

  It can be seen from Table 1 that the charging property in the powder properties is suppressed by containing a predetermined amount of the component (B) which is a surfactant. Moreover, it turns out that such an effect is high about the component (B) which is a nonionic surfactant to which ethylene oxide is added.

  Regarding chargeability, component (A), component (B) (comparative example 5), component (A) and component (C) (comparative example 6) are compared with component (A) alone (comparative example 1). In the two-component system), a charging effect was observed, but as in Examples 1 to 8, the three-component diacetal-containing composition confirmed a dramatic charging effect as compared with the comparative example.

Example 9
Preparation of polyolefin resin composition An isotactic random polypropylene resin having an ethylene content of 3.0% by weight (MFR = 20 g / 10 min., Hereinafter abbreviated as “r-PP”). 0.2 parts by weight of the diacetal-containing composition prepared in Step 1, 0.05 parts by weight of calcium stearate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane ( Trade name: Irganox (registered trademark) 1010, manufactured by Ciba Specialty Chemicals Co., Ltd. 0.05 parts by weight and Tris (2,4-di-t-butylphenyl) phosphite (trade name, Irgaphos (registered trademark) 168) 0.05 parts by weight (BASF) was blended and dry blended with a Henschel mixer. Next, it is melt-kneaded using a twin-screw extruder (15 mmφ, L / D = 45 (675 mm / 15 mm), rotation speed = 250 rpm) at a resin temperature of 190 ° C., extruded, and the resulting strand is cooled with water, It cut | disconnected and pelletized and obtained the polyolefin-type resin composition of this invention.

Molding of polyolefin resin composition The polyolefin resin composition obtained was injection molded under the conditions of a resin temperature of 190 ° C. and a mold temperature of 40 ° C. to obtain a polyolefin resin molded body (test piece) of 40 mm × 70 mm × 2 mm. Obtained. Using the obtained test piece, the haze value (%) was evaluated (ppm) and the bleed-out test was evaluated. The obtained evaluation results are shown in Table 2.

Examples 10-16
Except having replaced the diacetal containing composition with what was prepared in the Example shown in Table 2, it carried out similarly to Example 9 and obtained the polyolefin resin composition and resin molding of this invention. Each of these evaluation items was evaluated, and the results obtained are shown in Table 2.

Comparative Example 7
Except not adding a diacetal containing composition, it carried out similarly to Example 9 and obtained the polyolefin resin composition and the resin molding. Each of these evaluation items was evaluated, and the results obtained are shown in Table 2.

Comparative Examples 8-13
Except having replaced the diacetal containing composition with what was prepared by the comparative example shown in Table 2, it carried out similarly to Example 9 and obtained the polyolefin resin composition and the resin molding. Each of these evaluation items was evaluated, and the results obtained are shown in Table 2.

Comparative Example 14
A polyolefin resin composition and a resin were prepared in the same manner as in Example 9 except that polyoxyethylene (average number of moles of ethylene oxide added: 20) sorbitan tristearate (component (b1)) was added instead of the diacetal-containing composition. A molded body was obtained. Each of these evaluation items was evaluated, and the results obtained are shown in Table 2.

  In Table 2, the compounding quantity of each component of the polyolefin resin composition and resin molding which were obtained in Examples 9-16 and Comparative Examples 7-14, and each evaluation result are shown.

  From Examples 9 to 16, it can be seen that the molded product obtained from the specific polyolefin resin composition of the present application is suppressed from bleeding out from the molded product that adversely affects the transparency of the molded product over time. .

Example 17
A diacetal-containing composition was obtained in the same manner as in Example 4 except that 0.5 part by weight of component (C) zinc stearate was used with respect to 100 parts by weight of component (A). Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 3.

Example 18
A diacetal-containing composition was obtained in the same manner as in Example 4 except that 15.0 parts by weight of component (C) zinc stearate was used with respect to 100 parts by weight of component (A). Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 3.

Example 19
The same procedure as in Example 4 was conducted except that magnesium stearate was used instead of zinc stearate and 5.0 parts by weight of magnesium stearate of component (C) was used with respect to 100 parts by weight of component (A). A composition was obtained. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 3.

Example 20
The same procedure as in Example 4 was carried out except that lithium stearate was used instead of zinc stearate and 5.0 parts by weight of lithium stearate of component (C) was used with respect to 100 parts by weight of component (A). A composition was obtained. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 3.

Comparative Example 15
A diacetal-containing composition was obtained in the same manner as in Example 4 except that 0.4 part by weight of component (C) zinc stearate was used with respect to 100 parts by weight of component (A). Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 3.

Comparative Example 16
With respect to 100 parts by weight of component (A), 1.5 parts by weight of component (B) polyoxyethylene (average number of moles of ethylene oxide added: 20) sorbitan tristearate and 25 parts of component (C) (zinc stearate) Except having used 0.0 weight part, it carried out similarly to Example 1 and obtained the diacetal containing composition. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 3.

Comparative Example 17
A diacetal-containing composition was obtained in the same manner as in Example 4 except that calcium stearate was used instead of component (C) zinc stearate and 5.0 parts by weight of component (C) calcium stearate was used. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 3.

Comparative Example 18
A diacetal-containing composition was obtained in the same manner as in Example 4 except that sodium stearate was used instead of zinc stearate of component (C) and 5.0 parts by weight of sodium stearate of component (C) was used. It was. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 3.

  In Table 3, the kind, compounding quantity, and each evaluation result of the diacetal containing composition obtained in Examples 17-20 and Comparative Examples 15-18 are shown. For comparison, Table 3 also shows the types, blending amounts, and evaluation results of the diacetal-containing compositions of Example 4 and Comparative Example 1 shown in Table 1 above. In Table 3, the abbreviations of the component (A) type a1, the component (B) type b1, and the component (C) type c1 are the same as those in Table 1 above. Furthermore, the abbreviations of the other components in Table 3 are as follows.

c2: Magnesium stearate c3: Lithium stearate c4: Calcium stearate c5: Sodium stearate

Examples 21-24
Except having replaced the diacetal containing composition with what was prepared in the Example shown in Table 4, it carried out similarly to Example 9 and obtained the polyolefin resin composition and the resin molding. Each evaluation item was evaluated, and the results obtained are shown in Table 4.

Comparative Examples 19-22
Except having replaced the diacetal containing composition with what was prepared by the comparative example shown in Table 4, it carried out similarly to Example 9 and obtained the polyolefin resin composition and the resin molding. Each evaluation item was evaluated, and the results obtained are shown in Table 4.

Comparative Example 23
Instead of the diacetal-containing composition, zinc stearate (component (c1)) was added, and 0.01 part by weight of zinc stearate (component (c1)) was used with respect to 100 parts by weight of r-PP. In the same manner as in Example 9, a polyolefin resin composition and a resin molded body were obtained. Each evaluation item was evaluated, and the results obtained are shown in Table 4.

  In Table 4, the compounding quantity of each component of the polyolefin resin composition and resin molding which were obtained in Examples 21-24 and Comparative Examples 19-23, and each evaluation result are shown. For comparison and reference, the amounts of the components of the polyolefin resin composition and resin molded body of Example 12, Comparative Example 7, and Comparative Example 8 shown in Table 2 above, and the evaluation results are also shown in Table 4. Show.

Example 25
Instead of the diacetal-containing composition prepared in Example 2, the same procedure as in Example 9 was performed except that 0.1 part by weight of the diacetal-containing composition was used with respect to 100 parts by weight of r-PP. A resin molded body was obtained. Each of these evaluation items was evaluated, and the results obtained are shown in Table 5.

Example 26
In place of the diacetal-containing composition prepared in Example 2, the same procedure as in Example 9 was carried out except that 0.3 part by weight of the diacetal-containing composition was used with respect to 100 parts by weight of r-PP. A resin molded body was obtained. Each of these evaluation items was evaluated, and the results obtained are shown in Table 5.

Example 27
The same procedure as in Example 10 was carried out except that the resin temperature during the production of the polyolefin resin composition was 240 ° C. and the resin temperature during the molding of the polyolefin resin composition was 240 ° C. Obtained. Each of these evaluation items was evaluated, and the results obtained are shown in Table 5.

  In Table 5, the compounding quantity of each component of the polyolefin resin composition and resin molding which were obtained in Examples 25-27, and each evaluation result are shown. For comparison and reference, the blending amounts of the components of the polyolefin resin composition and the resin molded product of Example 10, Comparative Example 7, and Comparative Example 8 shown in Table 2 above, and the evaluation results are also shown in Table 5. Show.

Example 28
In place of component (A) 1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O— (p— Using ethylbenzylidene) -D-sorbitol, 100 parts by weight of component (A) and 1.0 part by weight of polyoxyethylene (ethylene oxide average added mole number: 20) sorbitan tristearate of component (B) A diacetal-containing composition was obtained in the same manner as in Example 1 except that 5.0 parts by weight of zinc stearate (C) was used. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 6.

Example 29
In place of component (A) 1,3: 2,4-bis-O- (3 ′, 4′-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis-O— (p— Using methylbenzylidene) -D-sorbitol, 100 parts by weight of component (A) and 1.0 part by weight of component (B) polyoxyethylene (average number of moles of ethylene oxide added: 20) sorbitan tristearate A diacetal-containing composition was obtained in the same manner as in Example 1 except that 5.0 parts by weight of zinc stearate (C) was used. Each evaluation item of the obtained diacetal-containing composition was evaluated, and the obtained results are shown in Table 6.

Comparative Example 24
Without adding component (B) and component (C), each evaluation item was evaluated for 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol of component (A), The results obtained are shown in Table 6.

Comparative Example 25
Without adding component (B) and component (C), each evaluation item was evaluated for 1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol of component (A), The results obtained are shown in Table 6.

  Table 6 shows the types, blending amounts, and evaluation results of the diacetal-containing compositions obtained in Examples 28 to 29 and Comparative Examples 24 to 25. In Table 6, the abbreviations of b1 of the component (B) and c1 of the type of the component (C) are the same as in Table 1 above. Further, abbreviations of a2 and a3 of the types of component (A) in Table 6 are as follows.

a2: 1,3: 2,4-bis-O- (p-ethylbenzylidene) -D-sorbitol a3: 1,3: 2,4-bis-O- (p-methylbenzylidene) -D-sorbitol

Examples 30 and 31
Except having replaced the diacetal containing composition with what was prepared in the Example shown in Table 7, it carried out similarly to Example 9 and obtained the polyolefin resin composition and the resin molding. Each of these evaluation items was evaluated, and the results obtained are shown in Table 7.

  In Table 7, the compounding quantity of each component of the polyolefin resin composition and resin molding which were obtained in Example 30 and 31 and each evaluation result are shown.

1 Hopper 2 Agitator 3 Twin screw

Claims (7)

Component (A): General formula (1):

[In Formula (1), R ¹ and R ² are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms, or a linear or branched carbon number 1 to 1, respectively. 3 represents an alkoxy group or a halogen atom. m and n each represent an integer of 1 to 3. ]
At least one diacetal represented by:
Component (B): polyoxyethylene sorbitan _C 8 _{-C 22} fatty acid ester, and component _(C): a C 12 _{-C 22} fatty acid, zinc, consisting of at least one metal selected from the group consisting of magnesium and lithium fatty acid Metal salts,
A composition comprising:
The composition ratio in the composition is in the range of 0.05 to 5 parts by weight of component (B) and 0.5 to 15 parts by weight of component (C) with respect to 100 parts by weight of component (A) or Powdered diacetal-containing composition. The granular or powdery diacetal-containing composition according to claim 1, comprising 0.1 to 300 parts by weight of the component (C) with respect to 1 part by weight of the component (B). Component (B), polyoxyethylene sorbitan C ₈ -C ₂₂ fatty acid triester according to claim 1 or 2 granular or powdery diacetal containing composition according to. A polyolefin resin composition containing the granular or powdered diacetal-containing composition according to any one of claims 1 to 3 and a polyolefin resin. The resin molding obtained by shape | molding the polyolefin resin composition of Claim 4. Component (A): General formula (1):

[In Formula (1), R ¹ and R ² are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms, or a linear or branched carbon number 1 to 1, respectively. 3 represents an alkoxy group or a halogen atom. m and n each represent an integer of 1 to 3. ]
In at least one diacetal represented by
Component (B): polyoxyethylene sorbitan _C 8 _{-C 22} fatty acid ester, and component _(C): a C 12 _{-C 22} fatty acid, zinc, consisting of at least one metal selected from the group consisting of magnesium and lithium fatty acid Metal salts,
Is a method for improving the fluidity of diacetal by blending,
The composition ratio in the diacetal-containing composition is in the range of 0.05 to 5 parts by weight of component (B) and 0.5 to 15 parts by weight of component (C) with respect to 100 parts by weight of component (A). A method for improving the fluidity of diacetal. A polyolefin resin, characterized by mixing the granular or powdered diacetal-containing composition according to any one of claims 1 to 3 and a polyolefin resin, and molding the obtained polyolefin resin composition at 190 to 240 ° C. Molding method.

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