Resin composition and molded product thereof

Abstract

Provided are a resin composition in which the crystallinity of a resin component is suppressed and a molded product thereof. The resin composition comprises a polyolefin resin and a nucleating agent, wherein the nucleating agent is a nucleating agent that melts at a temperature 150°C higher than the melting point of the polyolefin resin or a nucleating agent that dissolves in the polyolefin resin at a temperature 150°C higher than the melting point of the polyolefin resin; and when 0.2 parts by mass of the nucleating agent is added to 100 parts by mass of the polyolefin resin, the nucleating agent increases the crystallization temperature of the polyolefin resin by 7°C or more, and the content of the nucleating agent is 0.005 parts by mass or more and less than 0.1 parts by mass relative to 100 parts by mass of the polyolefin resin.

Description

Technical Field

[0001] The present invention relates to a resin composition and a molded article thereof, and more particularly to a resin composition and a molded article thereof in which the crystallinity of a resin component is suppressed. Background Art

[0002] When a resin material containing a crystalline resin such as a polyolefin resin or a polyamide resin is processed to produce a synthetic fiber or a film, or when such a resin material is laminated on a substrate formed of a wood or fibrous material to produce a laminate, it is desirable that the crystallinity of the resin component be sufficiently suppressed.

[0003] As a resin composition in which the crystallinity of a resin component is suppressed, for example, Patent Document 1 proposes a resin composition containing silicone oil.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 9-176407 Summary of the invention

[0007] Problem that the invention aims to solve

[0008] However, the resin composition described in Patent Document 1 contains a large amount of silicone oil in order to suppress the crystallinity of the resin component. As a result, the physical properties of a molded article obtained from the resin composition may be insufficient.

[0009] Therefore, an object of the present invention is to provide a resin composition in which the crystallinity of a resin component is suppressed, and a molded article thereof.

[0010] Solutions for solving problems

[0011] The present inventors have conducted intensive studies to solve the above problems and have found that the above problems can be solved by a polyolefin resin composition containing a nucleating agent having specific properties at a specific ratio, thereby completing the present invention.

[0012] That is, the resin composition of the present invention is characterized by comprising a polyolefin resin and a nucleating agent.

[0013] The nucleating agent is a nucleating agent that melts at a temperature 150° C. higher than the melting point of the polyolefin resin, or a nucleating agent that dissolves in the polyolefin resin at a temperature 150° C. higher than the melting point of the polyolefin resin; and

[0014] When 0.2 parts by mass of the nucleating agent is added to 100 parts by mass of the polyolefin resin, the nucleating agent increases the crystallization temperature of the polyolefin resin by 7° C. or more.

[0015] The content of the nucleating agent is 0.005 parts by mass or more and less than 0.1 parts by mass based on 100 parts by mass of the polyolefin-based resin.

[0016] In the resin composition of the present invention, the melting point of the nucleating agent is preferably 150 to 300° C. In the resin composition of the present invention, the nucleating agent preferably includes a triazine compound represented by the following general formula (1).

[0017]

[0018] Here, in the general formula (1), Ar 1 ,Ar 2 and Ar 3 Each independently represents a phenyl group having a substituent or an unsubstituted phenyl group.

[0019] Furthermore, in the resin composition of the present invention, the nucleating agent preferably further contains an acetal compound represented by the following general formula (2).

[0020]

[0021] Here, in the general formula (2), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 2 , R 3 , R 4 and R 5 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or R 2 and R 3 or R 4 and R 5 They are linked to each other to represent an alkylene group having 3 to 6 carbon atoms or an alkylenedioxy group having 1 to 4 carbon atoms, and X represents a single bond, a -CH(OH)- group or a -CH(OH)CH(OH)- group.

[0022] It should be noted that in the resin composition of the present invention, the "melting point" of the polyolefin resin is determined by measurement based on a differential scanning calorimeter, and is the temperature of the endothermic peak top observed when the polyolefin resin is heated from room temperature at a rate of 10°C / min in a nitrogen atmosphere. In addition, the "melting point" of the nucleating agent is similarly determined by measurement based on a differential scanning calorimeter, and is the temperature of the endothermic peak top observed when the nucleating agent is heated from room temperature at a rate of 10°C / min in a nitrogen atmosphere.

[0023] In the resin composition of the present invention, the crystallization temperature of the polyolefin-based resin refers to the crystallization temperature measured in accordance with JIS K 7121 using a differential scanning calorimeter.

[0024] The molded article of the present invention is characterized by being obtained by molding the resin composition of the present invention.

[0025] Effects of the Invention

[0026] According to the present invention, a resin composition in which the crystallinity of a resin component is suppressed and a molded product thereof can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The complex viscosity η obtained by measuring the dynamic viscoelasticity of the resin composition of Example 12 is * A graph plotting the measured temperature. DETAILED DESCRIPTION

[0028] Hereinafter, embodiments of the present invention will be described in detail.

[0029] <Resin composition>

[0030] The resin composition of the present invention comprises a polyolefin resin and a nucleating agent. In the composition of the present invention, the nucleating agent melts at a temperature 150°C higher than the melting point of the polyolefin resin, or dissolves in the polyolefin resin at a temperature 150°C higher than the melting point of the polyolefin resin; and, when 0.2 parts by mass of the nucleating agent is added relative to 100 parts by mass of the polyolefin resin, the crystallization temperature of the polyolefin resin is increased by more than 7°C. In addition, in the resin composition of the present invention, the content of the nucleating agent is greater than 0.005 parts by mass and less than 0.1 parts by mass relative to 100 parts by mass of the polyolefin resin. By setting the above-mentioned structure, the resin composition of the present invention can suppress the crystallinity of the resin component. The reasons are considered to be as follows.

[0031] In polyolefin resin, add the nucleating agent of the resin composition of the present invention in the previous addition amount (for example, 0.2 mass parts relative to 100 mass parts of resin), and when the resin composition is heated and plasticized, the nucleating agent will melt or dissolve in the polyolefin resin and diffuse in the resin matrix. When the resin melt obtained in this way is cooled, the nucleating agent in the resin matrix will self-assemble and become crystallites. And, the crystallites become crystal nuclei, thereby promoting the crystallization of polyolefin resin.

[0032] On the other hand, after the resin composition of the present invention is similarly heated and plasticized and cooled, the nucleating agent concentration in the resin matrix is ​​sufficiently low, so the nucleating agent cannot self-assemble in the resin matrix. In addition, the nucleating agent molecules interact strongly with the resin molecules, and thus the crystal domain expansion of the resin molecules is suppressed. According to the above results, it is inferred that the resin composition of the present invention can suppress the crystallization of polyolefin resins. Below, each component of the resin composition of the present invention is described in detail.

[0033] <Polyolefin resin>

[0034] The polyolefin resin of the resin composition of the present invention can be used regardless of the ratio of insoluble matter in the molecular weight, degree of polymerization, density, softening point, solvent, the degree of stereoregularity, the presence or absence of catalyst residues, the kind of monomer as raw material, blending ratio, the kind of polymerization catalyst (such as Ziegler catalyst, metallocene catalyst, etc.). It should be noted that in the resin composition of the present invention, the polyolefin resin refers to that the ratio of polyolefin is 70% by mass or more in the resin component, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass.

[0035] As polyolefin resin, for example polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, homopolypropylene, random copolymer polypropylene, block copolymer polypropylene, impact copolymer polypropylene, high impact copolymer polypropylene, isotactic polypropylene, syndiotactic polypropylene, semi-isotactic polypropylene, maleic anhydride modified polypropylene, polybutene, cycloolefin polymer, stereo block polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene and other α-olefin polymers, ethylene / propylene block or random copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer and other α-olefin copolymers etc. can be enumerated, and elastomer can also be used. In the resin composition of the present invention, these can be mixed and used in two or more kinds, can also form block copolymer and use with block polymer type, and resin can also be alloyed. In addition, it can also be the chloride of these polyolefin resins.

[0036] Examples of polyolefin resin elastomers include elastomers obtained by mixing polyolefins such as polypropylene and polyethylene as hard segments and rubbers such as ethylene-propylene rubber as soft segments, and elastomers obtained by dynamic crosslinking.

[0037] Examples of the hard segment include at least one selected from a polypropylene homopolymer, a polypropylene block copolymer, a polypropylene random copolymer, and the like.

[0038] Examples of the soft segment include ethylene-propylene copolymers (EPM), ethylene-propylene-diene copolymers (EPDM), ethylene-vinyl acetate copolymers (EVA), and vinyl acetate homopolymers, and two or more of these may be used in combination.

[0039] <Nucleating agent>

[0040] The nucleating agent of the resin composition of the present invention is a nucleating agent that melts at a temperature 150°C higher than the melting point of the polyolefin resin, or a nucleating agent that dissolves in the polyolefin resin at a temperature 150°C higher than the melting point of the polyolefin resin. When the nucleating agent melts at a temperature 150°C higher than the melting point of the polyolefin resin, the nucleating agent will melt into a liquid state during the molding process of the resin composition and diffuse in the molten liquid of the plasticized polyolefin resin. When the nucleating agent dissolves in the polyolefin resin at a temperature 150°C higher than the melting point of the polyolefin resin, the nucleating agent will dissolve in the molten liquid of the plasticized polyolefin resin during the molding process of the resin composition and diffuse in the molten liquid.

[0041] The nucleating agent contained in the resin composition of the present invention is preferably a nucleating agent that melts at a temperature 120°C higher than the melting point of the polyolefin resin, or is dissolved in the polyolefin resin at a temperature 120°C higher than the melting point of the polyolefin resin, further preferably a nucleating agent that melts at a temperature 100°C higher than the melting point of the polyolefin resin, or is dissolved in the polyolefin resin at a temperature 100°C higher than the melting point of the polyolefin resin, and particularly preferably a nucleating agent that melts at a temperature 70°C higher than the melting point of the polyolefin resin, or is dissolved in the polyolefin resin at a temperature 70°C higher than the melting point of the polyolefin resin.

[0042] In addition, the melting point of the nucleating agent contained in the resin composition of the present invention is preferably 150 to 300°C. When the melting point of the nucleating agent is above 150°C, the crystallinity of the resin component is more effectively suppressed. In addition, when the melting point of the nucleating agent is below 300°C, the molding processing temperature of the resin composition can be sufficiently reduced, and the coloring and physical property degradation of the molded product can be suppressed. The melting point of the nucleating agent is more preferably below 280°C, further preferably below 250°C, and particularly preferably below 230°C. In addition, the melting point of the nucleating agent is more preferably above 180°C, and further preferably above 200°C.

[0043] Furthermore, as described above, for the nucleating agent of the resin composition of the present invention, when 0.2 parts by mass of the nucleating agent is added relative to 100 parts by mass of the polyolefin resin, the crystallization temperature of the polyolefin resin is increased by 7°C or more. The molecules of the nucleating agent whose degree of increase in the crystallization temperature of the polyolefin resin is less than 7°C when 0.2 parts by mass of the nucleating agent is added relative to 100 parts by mass of the polyolefin resin cannot be said to have a sufficiently strong interaction with the resin molecules, and cannot effectively suppress the expansion of the crystal domain of the resin molecules. Therefore, the nucleating agent whose degree of increase in the crystallization temperature of the polyolefin resin is less than 7°C when 0.2 parts by mass of the nucleating agent is added relative to 100 parts by mass of the polyolefin resin cannot fully suppress the crystallization of the polyolefin resin. That is, when the nucleating agent is a nucleating agent whose degree of increase in the crystallization temperature of the polyolefin resin is less than 7°C when 0.2 parts by mass of the nucleating agent is added relative to 100 parts by mass of the polyolefin resin, the resin composition cannot fully suppress the crystallinity of the resin component. The nucleating agent in the resin composition of the present invention preferably increases the crystallization temperature of the polyolefin resin by 9° C. or more, more preferably by 11° C. or more, when 0.2 parts by mass of the nucleating agent is added to 100 parts by mass of the polyolefin resin.

[0044] As the compound contained in the nucleating agent of the resin composition of the present invention, for example, a triazine compound represented by the following general formula (1), an acetal compound represented by the following general formula (2), an amide compound such as methylenebisbenzamide and triamide benzene, etc. can be cited. These can be contained in the resin composition alone, or two or more can be combined and contained in the resin composition. Among these, a triazine compound represented by the following general formula (1) and an acetal compound represented by the following general formula (2) are particularly preferred. That is, the nucleating agent particularly preferably comprises a triazine compound represented by the following general formula (1), and also particularly preferably comprises an acetal compound represented by the following general formula (2).

[0045]

[0046] In the general formula (1), Ar 1 ,Ar 2 and Ar 3 Each independently represents a phenyl group having a substituent or an unsubstituted phenyl group.

[0047] In general formula (2), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 2 , R 3 , R 4 and R 5 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or R 2 and R 3 or R 4and R 5 They are linked to each other to represent an alkylene group having 3 to 6 carbon atoms or an alkylenedioxy group having 1 to 4 carbon atoms. X represents a single bond, a -CH(OH)- group or a -CH(OH)CH(OH)- group.

[0048] Ar in the general formula (1) 1 ,Ar 2 and Ar 3 The substituents may include a halogen atom, a hydroxyl group, a carboxyl group, an amino group which may have a substituent, an aminocarbonyl group (also referred to as a carbamoyl group), a nitro group, a cyano group, a thiol group, a sulfo group, a sulfonamide group, a formyl group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, an alkylthio group having 1 to 20 carbon atoms which may have a substituent, an arylthio group having 6 to 20 carbon atoms which may have a substituent, an acyl group having 2 to 20 carbon atoms which may have a substituent, and an acyl group having 2 to 20 carbon atoms which may have a substituent. The sulfonic acid group may be substituted with 2 to 20 carbon atoms, alkylaminocarbonyl group may be substituted with 2 to 20 carbon atoms, arylaminocarbonyl group may be substituted with 7 to 20 carbon atoms, dialkylaminocarbonyl group may be substituted with 3 to 20 carbon atoms, diarylaminocarbonyl group may be substituted with 13 to 20 carbon atoms, alkylarylaminocarbonyl group may be substituted with 8 to 20 carbon atoms, alkylcarbonylamino group may be substituted with 2 to 20 carbon atoms, arylcarbonylamino group may be substituted with 7 to 20 carbon atoms, and heterocyclic group may be substituted with 2 to 20 carbon atoms. In addition, the carboxyl group and the sulfonic acid group may form a salt. Preferred are an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aminocarbonyl group, a carboxyl group, a halogen atom, a cyano group, an alkylaminocarbonyl group having 2 to 20 carbon atoms which may have a substituent, an alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent, an acyl group having 2 to 20 carbon atoms which may have a substituent, an acyloxy group having 2 to 20 carbon atoms which may have a substituent, and an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and more preferred are an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, and an aminocarbonyl group.

[0049] In addition, as Ar 1 ,Ar 2 and Ar 3The substituents possessed by the substituted groups include alkyl, alkoxy, alkylthio, alkenyl, aralkyl, aryl, aryloxy, arylthio, heterocyclic, halogen, acyl, acyloxy, substituted amino, sulfonamide, sulfonyl, carboxyl, cyano, sulfo, hydroxyl, nitro, mercapto, imido, carbamoyl, sulfonamide, etc. These groups may be further substituted. In addition, carboxyl and sulfo groups may also form salts.

[0050] As Ar 1 ,Ar 2 and Ar 3 Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, and decyl.

[0051] As Ar 1 ,Ar 2 and Ar 3 Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, tert-pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy, nonyloxy, and decyloxy.

[0052] As Ar 1 ,Ar 2 and Ar 3 Examples of the alkylthio group include methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, pentylthio, isopentylthio, tert-pentylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio and 2-ethylhexylthio.

[0053] As Ar 1 ,Ar 2 and Ar 3 Examples of the aralkyl group include benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, and cinnamyl.

[0054] As Ar 1 ,Ar 2 and Ar 3 Examples of the aryl group include phenyl and naphthyl.

[0055] As Ar 1 ,Ar 2 and Ar3 Examples of the aryloxy group include a phenoxy group and a naphthoxy group.

[0056] As Ar 1 ,Ar 2 and Ar 3 Examples of the arylthio group include phenylthio and naphthylthio.

[0057] As Ar 1 ,Ar 2 and Ar 3 Examples of the heterocyclic group include pyridyl, pyrimidinyl, pyridazinyl, piperidinyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, phenylthio, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, isoindolyl, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, and 2,4-dioxyoxazolidin-3-yl.

[0058] As Ar 1 ,Ar 2 and Ar 3 Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

[0059] As Ar 1 ,Ar 2 and Ar 3 The acyl group possessed includes, for example, acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyl, oxalyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl and the like.

[0060] As Ar 1 ,Ar 2 and Ar 3 Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

[0061] As Ar 1 ,Ar 2 and Ar 3Examples of the alkylaminocarbonyl group include methylaminocarbonyl, ethylaminocarbonyl, tert-butylaminocarbonyl, isobutylaminocarbonyl, cyclohexylaminocarbonyl, dimethylaminocarbonyl, N-methyl-N-ethylaminocarbonyl and diethylaminocarbonyl.

[0062] As Ar 1 ,Ar 2 and Ar 3 The amino group which may have a substituent includes, for example, amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, oct ... lauroylamino, carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino and the like.

[0063] Specific examples of the triazine compound represented by the general formula (1) include the following compounds No. 1 to No. 59. Among these, the triazine compound of compound No. 49, compound No. 50, compound No. 58 or compound No. 59 is particularly preferred.

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075] As a method for producing the triazine compound represented by the general formula (1), for example, cyanuric chloride is used as a raw material in an organic solvent, and in the presence of 1 equivalent of a base (triethylamine, sodium hydroxide, etc.), cyanuric chloride is reacted with 1 equivalent of Ar 1 ,Ar 2 ,Ar 3 A method for reacting phenolic compounds, etc.

[0076] As mentioned above, in the general formula (2), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 2 , R 3 , R 4 and R 5 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or R 2 and R 3 or R 4 and R 5 They are linked to each other to represent an alkylene group having 3 to 6 carbon atoms or an alkylenedioxy group having 1 to 4 carbon atoms. X represents a single bond, a -CH(OH)- group or a -CH(OH)CH(OH)- group.

[0077] Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group.

[0078] Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.

[0079] Examples of the alkylene group having 3 to 6 carbon atoms include propylene, butylene, pentylene, and hexylene.

[0080] Examples of the alkylenedioxy group having 1 to 4 carbon atoms include a methylenedioxy group, an ethylenedioxy group, a propylenedioxy group, and a butylenedioxy group.

[0081] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0082] Among the acetal compounds represented by the general formula (2), R 1 , R 2 , R 3 , R 4 and R 5Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a -CH(OH)- group.

[0083] Specific examples of the acetal compound represented by the general formula (2) include the following compounds No. 60 to No. 63. Among these, the acetal compound represented by compound No. 60, compound No. 61 or compound No. 62 is particularly preferred.

[0084] Compound No.60

[0085]

[0086] Compound No.61

[0087]

[0088] Compound No.62

[0089]

[0090] Compound No.63

[0091]

[0092] Examples of methods for producing the acetal compound represented by the general formula (2) include a method of subjecting an alditol compound such as sorbitol to dehydration condensation with an aryl aldehyde in the presence of an acid catalyst.

[0093] As described above, in the resin composition of the present invention, relative to 100 parts by mass of polyolefin resin, the content of nucleating agent is 0.005 parts by mass or more and less than 0.1 parts by mass. When the content of nucleating agent is less than 0.005 parts by mass, the crystallinity of resin component cannot be fully suppressed. In addition, when the content of nucleating agent is more than 0.1 parts by mass, the crystallinity of resin component can be promoted. The content of nucleating agent is more preferably more than 0.01 parts by mass, and more preferably more than 0.02 parts by mass. In addition, the content of nucleating agent is preferably less than 0.08 parts by mass, more preferably less than 0.07 parts by mass, more preferably less than 0.05 parts by mass, and particularly preferably less than 0.03 parts by mass.

[0094] The resin composition of the present invention may contain, in addition to the above-mentioned polyolefin resin and nucleating agent, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, fatty acid metal salts, ultraviolet absorbers, hindered amine compounds, flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents, fluorescent whitening agents, pigments, dyes and other additives. These additives may be included alone or in combination of two or more.

[0095] Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-methyl-4,6-bis(octylthiomethyl)phenol, 2,2'-isobutylenebis(4,6-dimethylphenol), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, hydroxyphenyl) propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,2'-oxalamide-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-ethylhexyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 2,2'-ethylenebis(4,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxy-phenylpropionic acid and C13-15 alkyl esters, 2,5-di-tert-amylhydroquinone, hindered phenol polymers (ADEKA POLYMERADDITIVES EUROPE SAS company trade name "AO.OH.98"), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methyl)propoxy]-2,4,8,10-tetra-tert-butylphenyl[d,f][1,3,2]-dioxaphosphepin, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[(3,5-di-tert-butyl-4-hydroxybenzyl)monoethyl phosphate] calcium salt, 5,7-bis(1,1-dimethyl Reaction product of 2-(3H)-benzofuranone and o-xylene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, DL-a-tocopherol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol, bis[3,3-bis-(4'-hydroxy-3'-tert-butyl-phenyl)butyric acid]diol Ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphate, tridecyl-3,5-tert-butyl-4-hydroxybenzyl thioacetate, thiodiethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-Thiobis(6-tert-butyl-m-cresol), 2-octylthio-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]diol ester, 4,4'-butylenebis(2,6-di-tert-butylphenol), 4,4'-butylenebis(6-tert-butyl-3-methylphenol), 2,2'-ethylenebis(4,6-di-tert-butylphenol), 1 ,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate,1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-Tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[2-(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxospiro[5.5]decanoate 3-(3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as cyclopentane, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, palmityl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, myristyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, and lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide. These may be included alone or in combination of two or more. The content of the phenolic antioxidant is not particularly limited, and for example, it may be 0.001 to 5 parts by mass relative to 100 parts by mass of the polyolefin resin. ,

[0096] Examples of the phosphorus antioxidant include triphenyl phosphite, diisooctyl phosphite, heptadecanyl triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyltridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tri(dipropylene glycol) phosphite, dioleyl hydrogenated phosphite, trilauryl trithiophosphite, bis(tridecyl) phosphite, tri(isodecyl) phosphite, tri(tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenyl bis(nonylphenyl) phosphite, poly(dipropylene glycol)phenyl phosphite, tetraphenyl diphosphite, Propylene glycol ester, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butyl-5-methylphenyl) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tris(decyl) phosphite, octyl diphenyl phosphite, di(decyl) monophenyl phosphite, mixture of distearyl pentaerythritol and calcium stearate, alkyl(C10) bisphenol A phosphite, tetraphenyl-tetra(tridecyl) pentaerythritol tetraphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra(tridecyl) isopropylidene bisphenol diphosphite , tetrakis(tridecyl)-4,4'-n-butylenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenyl diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphite (1-methyl-1-propenyl-3-ylidene) tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene) hexa(tridecyl) ester, phosphite 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl ester, phosphite 2,2'-methylenebis( 4,6-di-tert-butylphenyl)-octadecyl ester, 2,2'-ethylenebis(4,6-di-tert-butylphenyl)fluorophosphite, 4,4'-butylenebis(3-methyl-6-tert-butylphenylditridecyl)phosphite, tris(2-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly(4,4'-isopropylidene bisphenol C12-15 alcohol phosphite, bis(diisodecyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, bis(octadecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, etc. These may be included alone or in combination of two or more. The content of the phosphorus antioxidant is not particularly limited, and for example, it may be 0.001 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin. ,

[0097] As the sulfur-based antioxidant, for example, tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl) sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl / stearylthiodipropionate, 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-thiobis (6-tert-butyl-p-cresol), distearyl-disulfide, etc. can be mentioned. These can contain one kind alone, or two or more kinds can be contained in combination. The content of the sulfur-based antioxidant is not particularly limited, and for example, it can be 0.001 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0098] Examples of fatty acid metal salts include compounds represented by the following general formula (3). These may be contained alone or in combination of two or more.

[0099]

[0100] In the general formula (3), R 6 It represents a group formed by removing COOH from a linear or branched fatty acid having 12 to 20 carbon atoms, and the fatty acid may also be substituted with a hydroxyl group. M represents a 1-3 valent metal atom, and the metal atom may also have a hydroxyl group. n represents an integer of 1 to 3. Among the fatty acid metal salts, metal salts of lauric acid, myristic acid, palmitic acid, stearic acid, and 12-hydroxystearic acid are particularly preferred. In addition, as 1-3 valent metal atoms, for example, sodium, potassium, lithium, calcium, zinc, barium, magnesium, hydroxyaluminum, etc. can be mentioned, and sodium, lithium, potassium, calcium, and zinc are particularly preferred. The content of the fatty acid metal salt is not particularly limited, and for example, it can be 0.001 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0101] Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxybenzophenones such as 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(2-hydroxy-4-methoxybenzophenone); Bis(4-tert-octyl-6-benzotriazolephenol), polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5 -chlorobenzotriazole, 2-〔2-hydroxy-5-(2-methacryloyloxyethyl)phenyl〕benzotriazole, 2-〔2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl〕benzotriazole, 2-〔2-hydroxy-3-tert-amyl-5-(2-methacryloyloxyethyl)phenyl〕benzotriazole, 2-〔2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl〕-5-chlorobenzotriazole, 2-〔2-hydroxy-4-(2-methacryloyloxymethyl)phenyl〕benzotriazole, 2-〔2-hydroxy- 2-(2-hydroxyphenyl)benzotriazoles such as 4-(3-methacryloyloxy-2-hydroxypropyl)phenylbenzotriazole and 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenylbenzotriazole; substituted oxalanilides such as phenyl salicylate, resorcinol monobenzoate, 2-ethyl-2'-ethoxyoxalanilide and 2-ethoxy-4'-dodecyloxalanilide; cyanoacrylates such as ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate;2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, trioctyl-2,2',2"-((1,3,5-triazine-2,4,6-triyl)tris(3-hydroxybenzene-4-,1-diyl)tripronate), 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tri (2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, 1,12-bis[2-[4-(4,6-diphenyl-1,3,5-triazine-2-yl)-3-hydroxyphenoxy]ethyl] dodecanedioate and other triazines; various metal salts or metal chelates, especially nickel, chromium salts, or chelates, etc. These may be included alone or in combination of two or more. The content of the ultraviolet absorber is not particularly limited, and for example, it may be 0.01 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin. ;

[0102] Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidinyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate condensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane / 2,4-dichloro -6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazine-6-yl]-1,5 ,8-12-tetraazadodecane, 1,6,11-tris〔2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazine-6-yl〕aminoundecane, 1,6,11-tris〔2,4-bis(n-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazine-6-yl〕aminoundecane, bis{4-(1-octyloxy-2,2,6,6-tetramethyl)piperidinyl}decane diacid, bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidinyl}carbonate, etc. These may be contained alone or in combination of two or more. The content of the hindered amine compound is not particularly limited, and for example, it may be 0.001 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0103] Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-di-cresyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene)-4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetra(2,6-dimethylphenyl)phosphate, and ADEKA Corporation trade names "ADK STAB FP-500", "ADK STAB FP-600", and "ADK STAB Aromatic phosphates of "FP-800", phosphonates such as divinyl phenylphosphonate, diallyl phenylphosphonate, (1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, phosphazenes such as bis(2-allylphenoxy)phosphazene, dimethyltoluenephosphazene, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate polyphosphate), ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinyl benzyl compounds and phosphorus-containing red phosphorus and other phosphorus-based flame retardants, magnesium hydroxide, aluminum hydroxide and other metal hydroxides, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis(pentabromobenzene), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, brominated styrene and other brominated flame retardants, etc. These may be included alone or in combination of two or more. These flame retardants are preferably used in combination with drip inhibitors such as fluororesins, polyols, flame retardant aids such as hydrotalcite. The content of the flame retardant is not particularly limited, for example, it can be 1 to 100 parts by mass relative to 100 parts by mass of the polyolefin resin, and the content of the flame retardant aid is not particularly limited, for example, it can be 0.1 to 10 parts by mass relative to 100 parts by mass of the flame retardant.

[0104] As lubricants, for example, unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmitate, sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, ethylene bis stearic acid amide, etc. These can be included alone or in combination. There is no particular limitation on the content of the lubricant, and for example, it can be 0.01 to 2 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0105] Fillers are roughly divided into organic fillers and inorganic fillers. As organic fillers, polymers of natural origin such as starch, cellulose, wood powder, bean curd residue, rice husk, wheat bran, and their modified products can be cited. In addition, as inorganic fillers, talc, calcium carbonate, zinc carbonate, wollastonite, silica, mica, aluminum oxide, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, hollow glass spheres (glass balloon), carbon black, zinc oxide, antimony trioxide, zeolite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, carbon fiber, etc. can be cited. These can contain one alone, or two or more can be combined. The content of the filler is not particularly limited, for example, it can be 0.1 to 500 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0106] Hydrotalcites are complex salt compounds containing magnesium, aluminum, hydroxyl groups, carbonate groups, and any crystal water, which are known as natural or synthetic products. Examples include those in which a part of magnesium or aluminum is replaced by other metals such as alkali metals and zinc, and those in which hydroxyl groups and carbonate groups are replaced by other anionic groups. Specifically, examples include those in which the metal of the hydrotalcite represented by the following general formula (4) is replaced by an alkali metal, etc. In addition, as Al-Li-based hydrotalcites, compounds represented by the following general formula (5) can also be used.

[0107] Mg y1 Zn y2 Al 2 (OH) 2(y1+y2)+4 (CO 3 )pH 2 O (4)

[0108] Here, in the general formula (4), y1 and y2 each represent a number satisfying the conditions shown in the following formula, and p represents 0 or a positive number.

[0109] 0≤y2 / y1<10, 2≤y1+y2≤20

[0110] [Li 1 / 3 Al 2 / 3 (OH) 2 ]·[Aq- 1 / 3q pH 2 O] (5)

[0111] Here, in the general formula (5), A q- represents a q-valent anion, and p represents 0 or a positive number. In addition, a part of the carbonate anions in the above-mentioned hydrotalcites may be replaced by other anions.

[0112] Hydrotalcites may be obtained by dehydrating crystal water, or may be coated with higher fatty acids such as stearic acid, higher fatty acid metal salts such as oleic acid alkali metal salts, organic sulfonic acid metal salts such as dodecylbenzenesulfonic acid alkali metal salts, higher fatty acid amides, higher fatty acid esters, or waxes.

[0113] Hydrotalcites can be natural or synthetic. As the synthesis method of these compounds, known methods recorded in Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-174270, Japanese Patent Publication No. 5-179052 can be cited. In addition, these hydrotalcites can be used without limiting their crystal structure, crystal particles, etc. The content of hydrotalcites is not particularly limited, for example, it can be 0.001 to 5 parts by mass relative to 100 parts by mass of polyolefin resin.

[0114] As antistatic agents, for example, low molecular weight antistatic agents based on nonionic, anionic, cationic or amphoteric surfactants, and high molecular weight antistatic agents based on polymer compounds can be cited. As nonionic surfactants, polyethylene glycol nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts can be cited; polyol nonionic surfactants such as polyethylene oxide, fatty acid esters of glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyols, and aliphatic amides of alkanolamines can be cited; as anionic surfactants, for example, carboxylates such as alkali metal salts of higher fatty acids can be cited; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates can be cited; phosphates such as higher alcohol phosphates can be cited; as cationic surfactants, quaternary ammonium salts such as alkyltrimethylammonium salts can be cited. As amphoteric surfactants, amino acid-type amphoteric surfactants such as higher alkyl amino propionates, betaine-type amphoteric surfactants such as higher alkyl dimethyl betaine and higher alkyl dihydroxyethyl betaine can be cited. These can be included alone or in combination of two or more. The content of the low molecular weight antistatic agent is not particularly limited, for example, it can be 0.1 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0115] As a polymer antistatic agent, for example, ionomers, block polymers with polyethylene glycol as a hydrophilic part, etc. can be cited. As ionomers, for example, ionomers recorded in Japanese Patent Publication No. 2010-132927, etc. can be cited. As polymers with polyethylene glycol as a hydrophilic part, for example, polyether ester amides recorded in Japanese Patent Publication No. 7-10989, polymers formed by polyolefins and polyethylene glycol recorded in U.S. Patent No. 6552131, polymers formed by polyesters and polyethylene glycol recorded in Japanese Patent Publication No. 2016-023254, etc. can be cited. These can include one alone, or two or more can be included in combination. The content of the polymer antistatic agent is not particularly limited, for example, it can be 3 to 60 parts by mass relative to 100 parts by mass of polyolefin resin.

[0116] As fluorescent brighteners, for example, benzoxazole compounds CIFluorescent Brightner 184; coumarin compounds CIFluorescent Brightner 52; diaminostilbene disulfonic acid compounds CIFluorescent Brightner 24, 85, 71, etc. can be mentioned. These can be included alone or in combination of two or more. The content of the fluorescent brightener is not particularly limited, for example, it can be 0.00001 to 0.1 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0117] As the pigment, for example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 29, 56, 60, 61, 62, 64; Pigment Commercially available pigments such as Violet 1, 15, 19, 23, 27, 29, 30, 32, 37, 40, and 50. These may be included alone or in combination of two or more. The content of the pigment is not particularly limited, and may be, for example, 0.0005 to 3 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0118] As dye, for example, azo dye, anthraquinone dye, indigo dye, triarylmethane dye, xanthene dye, alizarin dye, acridine dye, stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamine dye, oxazine dye, phthalocyanine dye, cyanine dye etc. can be mentioned. These can contain 1 kind alone, and can also contain 2 or more kinds in combination. The content of dye is not particularly limited, for example, can be 0.0005~3 mass parts relative to 100 mass parts of polyolefin resin.

[0119] The method for manufacturing the resin composition of the present invention is not particularly limited, and examples thereof include a method of dry-mixing a polyolefin resin powder or pellet, a nucleating agent, and other additives as required, and a method of melt-mixing after dry-mixing. The nucleating agent and other additives may be added to the polyolefin resin simultaneously or separately. In addition, the nucleating agent and other additives may also be added to the polyolefin resin in the form of a masterbatch.

[0120] <Molded products>

[0121] Next, the molded product of the present invention will be described.

[0122] The molded article of the present invention is a molded article obtained by molding the resin composition of the present invention.

[0123] As the molded product of the present invention, there can be mentioned molded products in which the crystallinity of the resin component is fully suppressed during manufacture. As such molded products, more specifically, there can be mentioned, for example, a laminated body formed by laminating synthetic fibers, films, and resins on a substrate formed by a wood / fibrous material, etc.

[0124] The method for producing the molded product of the present invention is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, blow molding, calendaring, slash molding, immersion molding, foaming, etc. Among the molding methods, extrusion molding and calendaring are particularly preferred.

[0125] Example

[0126] Hereinafter, the present invention will be described in further detail using Examples, but the present invention is not limited to these.

[0127] (Experimental Examples 1 to 6 and Reference Example 1)

[0128] <Confirmation of Crystallization Temperature When 0.2 Parts by Mass of Nucleating Agent is Added to 100 Parts by Mass of Polyolefin Resin>

[0129] The crystallization temperature of the polyolefin resin when 0.2 parts by mass of the following nucleating agents 1 to 6 are added to 100 parts by mass of the polyolefin resin was confirmed. The following polyolefin resin, nucleating agent, antioxidant and fatty acid metal salt were mixed in the proportions shown in Table 1, mixed using a Henschel mixer, and then melt-kneaded and granulated at an extrusion temperature of 230°C using a twin-screw extruder (TEX-28V manufactured by Nippon Steel Works, Ltd.), thereby obtaining the resin composition pellets of Experimental Examples 1 to 6 and Reference Example 1. The unit of the compounding amount of each component in Table 1 is parts by mass. For the obtained resin composition pellets, the crystallization temperature was measured according to the following steps.

[0130] Polyolefin resin: cylinder temperature 230°C, homopolypropylene with a melt flow rate of 7.7 g / 10 min under a load of 2.16 kg, melting point 160°C

[0131] Nucleating agent 1: triazine compound of compound No. 59, melting point 202.7°C

[0132] Nucleating agent 2: triazine compound of compound No. 58, melting point 189.3°C

[0133] Nucleating agent 3: triazine compound of compound No. 50, melting point 217.7°C

[0134] Nucleating agent 4: acetal compound of compound No. 60, melting point 274.8°C

[0135] Nucleating agent 5: acetal compound of compound No. 61, melting point 244.7°C

[0136] Nucleating agent 6: 2,2'-methylenebis(4,6-di-tert-butylphenyl) lithium phosphate, melting point above 400°C (no endothermic peak observed)

[0137] Antioxidant 1: Tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane

[0138] Antioxidant 2: tris(2,4-di-tert-butylphenyl) phosphite

[0139] Fatty acid metal salt: calcium stearate

[0140] The “melting point” of the nucleating agent is the temperature (° C.) of an endothermic peak observed when the nucleating agent is heated from 50° C. to 400° C. at 10° C. / min in a nitrogen atmosphere using a differential scanning calorimeter (Diamond, manufactured by PerkinElmer).

[0141] <Crystallization temperature>

[0142] The obtained resin composition pellets were crushed into smaller pieces and 5 mg was filled in an aluminum pan, and the crystallization temperature was measured using a differential scanning calorimeter (Diamond manufactured by PerkinElmer). The temperature was raised from 50°C to 230°C at a rate of 10°C / min, maintained for 5 minutes, and then cooled to 50°C at a rate of 10°C / min. The temperature (°C) of the exothermic peak observed during the cooling process was determined as the crystallization temperature. The results are shown in Table 1.

[0143] [Table 1]

[0144]

[0145] According to the results shown in Table 1, the crystallization temperature of the resin compositions of Experimental Examples 1 to 6 is 7° C. or higher than the crystallization temperature of the resin composition of Reference Example 1. Therefore, nucleating agents 1 to 6 are nucleating agents that increase the crystallization temperature of the polyolefin resin by 7° C. or higher when added at 0.2 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0146] (Examples 1 to 10, Comparative Examples 1 to 7)

[0147] <Preparation and property evaluation of resin composition>

[0148] The polyolefin resin, nucleating agent, antioxidant and fatty acid metal salt were mixed in the proportions shown in Tables 2 to 4, mixed using a Henschel mixer, and then melt-kneaded and granulated at an extrusion temperature of 230° C. using a twin-screw extruder (TEX-28V manufactured by Nippon Steel Works, Ltd.), thereby obtaining resin composition pellets of Examples 1 to 10 and Comparative Examples 1 to 7. The unit of the amount of each component in Tables 2 to 4 is parts by mass. In addition, the crystallization temperature of the obtained resin composition pellets was measured in the same procedure as in Experimental Example 1. The results are shown in Tables 2 to 4.

[0149] [Table 2]

[0150]

[0151] [Table 3]

[0152]

[0153] [Table 4]

[0154]

[0155] (Examples 11-12, Comparative Example 8)

[0156] The polyolefin resin, nucleating agent, antioxidant and fatty acid metal salt were mixed in the proportions shown in Table 5, mixed using a Henschel mixer, and then melt-kneaded and granulated at an extrusion temperature of 230°C using a twin-screw extruder (Labo plastomill Micro manufactured by Toyo Seiki Seisaku-sho, Ltd.), thereby obtaining the resin composition pellets of Examples 11 to 12 and Comparative Example 8. The unit of the compounding amount of each component in Table 5 is parts by mass. Using a 50t punch, the obtained resin composition pellets were melt-compressed at 230°C, 10MPa, and 5 minutes to obtain a square sheet with a side length of 10cm and a thickness of 1.0mm. A disc-shaped test piece with a diameter of 25mm was cut out from the obtained sheet, and the flow field crystallization temperature of the test piece was measured according to the following steps.

[0157] First, the test piece was placed on a rotational rheometer (DHR2 manufactured by TAINSTRUMENTS) with parallel plates of 25 mm in diameter, and heated at 200°C for 3 minutes under a nitrogen atmosphere, and then the gap was set to 0.9 mm to remove the remaining resin. Then, the device was set to the conditions of strain 1%, angular velocity 1 rad / s, starting temperature 200°C, and cooling temperature 5°C / min to perform dynamic viscoelasticity measurement. Then, the complex viscosity value η obtained by the measurement was * (Pa·s) versus the measurement temperature (°C) is plotted. * The graph of (Pa·s) versus the measured temperature (°C) is shown in Figure 1 Here, Figure 1 The vertical axis is a common logarithmic scale. Figure 1 As shown in the figure, the slope of the tangent line changes significantly before and after the temperature at which the resin component crystallizes. Tangent lines are drawn at the point just before and just after the tangent line slope changes significantly, and the temperature corresponding to the intersection of these two tangent lines is taken as the flow field crystallization temperature T C (°C) and used as an index of the crystallinity of the resin component in the flow field. The same graph was prepared for the resin compositions of Example 11 and Comparative Example 8 and the flow field crystallization temperature T was determined. C The results are shown in Table 5.

[0158] [Table 5]

[0159]

[0160] According to the results shown in Tables 2 to 4, the crystallization temperatures of the resin compositions of Examples 1 to 10 are lower than those of the resin composition of Comparative Example 7, and the crystallization of the resin component is suppressed. On the other hand, the crystallization temperatures of the resin compositions of Comparative Examples 1 to 6 are higher than those of the resin composition of Comparative Example 7, and it is not considered that the crystallization of the resin component is suppressed. In addition, according to the results shown in Table 5, the flow field crystallization temperatures T of the resin compositions of Examples 11 and 12 are higher than those of the resin composition of Comparative Example 8. C The crystallinity of the resin component is suppressed.

[0161] From the above, it was confirmed that the crystallinity of the resin component in the resin composition of the present invention is suppressed.

Claims

1. A method for inhibiting crystallization of a polyolefin resin, characterized in that: The method comprises the step of mixing a polyolefin resin with a nucleating agent, The nucleating agent melts or dissolves in the polyolefin resin at a temperature 150° C. higher than the melting point of the polyolefin resin, and When 0.2 parts by mass of the nucleating agent is added to 100 parts by mass of the polyolefin resin, the nucleating agent increases the crystallization temperature of the polyolefin resin by 7° C. or more. The nucleating agent is a triazine compound represented by the following general formula (1) or an acetal compound represented by the following general formula (2), In the general formula (1), Ar 1 ,Ar 2 and Ar 3 Each independently represents a substituted phenyl group or an unsubstituted phenyl group, In the general formula (2), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 2 , R 3 , R 4 and R 5 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or R 2 and R 3 or R 4 and R 5 are connected to each other to represent an alkylene group having 3 to 6 carbon atoms or an alkylenedioxy group having 1 to 4 carbon atoms, X represents a single bond, a -CH(OH)- group or a -CH(OH)CH(OH)- group, In the compounding step, the amount of the nucleating agent compounded is 0.005 parts by mass or more and less than 0.1 parts by mass based on 100 parts by mass of the polyolefin-based resin.

2. The method for inhibiting crystallization of a polyolefin resin according to claim 1, wherein: The melting point of the nucleating agent is 150-300°C.

3. A method for producing a polyolefin resin composition, characterized in that: The present invention provides a method for producing a polyolefin resin composition in which the crystallization of the polyolefin resin is suppressed. The production method includes a step of mixing the polyolefin resin with a nucleating agent. The nucleating agent melts or dissolves in the polyolefin resin at a temperature 150° C. higher than the melting point of the polyolefin resin, and When 0.2 parts by mass of the nucleating agent is added to 100 parts by mass of the polyolefin resin, the nucleating agent increases the crystallization temperature of the polyolefin resin by 7° C. or more. The nucleating agent is a triazine compound represented by the following general formula (1) or an acetal compound represented by the following general formula (2), In the general formula (1), Ar 1 ,Ar 2 and Ar 3 Each independently represents a substituted phenyl group or an unsubstituted phenyl group, In the general formula (2), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 2 , R 3 , R 4 and R 5 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, or R 2 and R 3 or R 4 and R 5 are connected to each other to represent an alkylene group having 3 to 6 carbon atoms or an alkylenedioxy group having 1 to 4 carbon atoms, X represents a single bond, a -CH(OH)- group or a -CH(OH)CH(OH)- group, In the compounding step, the amount of the nucleating agent compounded is 0.005 parts by mass or more and less than 0.1 parts by mass based on 100 parts by mass of the polyolefin-based resin.

4. The method for producing a polyolefin resin composition according to claim 3, wherein: The melting point of the nucleating agent is 150-300°C.

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