Crystallinity inhibitor for polyolefin resin, method for inhibiting crystallinity of polyolefin resin using the same, and method for producing polyolefin resin composition

Abstract

To provide a resin composition in which crystallinity of a resin component is suppressed, and a molded article thereof.SOLUTION: The resin composition contains a polyolefin resin and a nucleating agent. The nucleating agent melts at a temperature higher by 150°C than the melting point of the polyolefin resin or dissolves in the polyolefin resin at a temperature higher by 150°C than the melting point of the polyolefin resin. The nucleating agent increases the crystallization temperature of the polyolefin resin by 7°C or more when added in an amount of 0.2 pt.mass based on 100 pts.mass of the polyolefin resin. The content of the nucleating agent is 0.005 pt.mass or more and less than 0.1 pt.mass based on 100 pts.mass of the polyolefin resin.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] When a resin material containing a crystalline resin such as polyolefin resin or polyamide resin is processed to produce a synthetic fiber or film, or when such a resin material is laminated onto a substrate made of wood, fibrous material, or the like to produce a laminate, it has been desirable to have the crystallinity of the resin component sufficiently suppressed.

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

[0004] [Patent Document 1] Japanese Patent Application Publication No. 9-176407 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the resin composition described in Patent Document 1 contains a large amount of silicone oil to suppress the crystallinity of the resin component, and as a result, the physical properties of molded articles obtained from this resin composition may not be sufficient.

[0006] SUMMARY OF THE PRESENT EMBODIMENT An object of the present invention is to provide a resin composition in which the crystallinity of the resin component is suppressed, and a molded article thereof. [Means for solving the problem]

[0007] As a result of intensive research into solving the above problems, the inventors have discovered that the above problems can be solved by a polyolefin resin composition containing a nucleating agent having specific properties in a specific ratio, and have thus completed the present invention.

[0008] That is, the resin composition of the present invention is a resin composition containing a polyolefin resin and a nucleating agent, 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 the nucleating agent is a nucleating agent that, when added in an amount of 0.2 parts by mass per 100 parts by mass of the polyolefin-based resin, increases the crystallization temperature of the polyolefin-based resin by 7° C. or more; The content of the nucleating agent relative to 100 parts by mass of the polyolefin resin is 0.005 parts by mass or more and less than 0.1 parts by mass.

[0009] In the resin composition of the present invention, the melting point of the nucleating agent is preferably 150 to 300° C. In addition, in the resin composition of the present invention, the nucleating agent preferably contains a triazine compound represented by the following general formula (1).

[0010] TIFF2025061860000002.tif52155

[0011] In the general formula (1), Ar 1 , Ar 2 and Ar 3 each independently represents a substituted or unsubstituted phenyl group.

[0012] Furthermore, in the resin composition of the present invention, it is also preferable that the nucleating agent contains an acetal compound represented by the following general formula (2).

[0013] TIFF2025061860000003.tif62155

[0014] 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 linked together to form 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.

[0015] In the resin composition of the present invention, the "melting point" of the polyolefin resin is determined by measurement using a differential scanning calorimeter, and is the endothermic peak top temperature observed when the polyolefin resin is heated from room temperature at a rate of 10°C / min under a nitrogen atmosphere. The "melting point" of the nucleating agent is determined similarly by measurement using a differential scanning calorimeter, and is the endothermic peak top temperature observed when the nucleating agent is heated from room temperature at a rate of 10°C / min under a nitrogen atmosphere.

[0016] In the resin composition of the present invention, the crystallization temperature of the polyolefin resin is the crystallization temperature measured in accordance with JIS K 7121 using a differential scanning calorimeter.

[0017] The molded article of the present invention is characterized by being obtained by molding the resin composition of the present invention. Effect of the Invention

[0018] According to the present invention, it is possible to provide a resin composition in which the crystallinity of the resin component is suppressed, and a molded article thereof. [Brief description of the drawings]

[0019] [Figure 1]1 is a graph in which the complex viscosity η* obtained by measuring the dynamic viscoelasticity of the resin composition of Example 12 is plotted against the measurement temperature. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] Hereinafter, an embodiment of the present invention will be described in detail. <Resin composition> The resin composition of the present invention includes 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 are added to 100 parts by mass of the polyolefin resin, the crystallization temperature of the polyolefin resin is increased by 7°C or more. In the resin composition of the present invention, the content of the nucleating agent to 100 parts by mass of the polyolefin resin is 0.005 parts by mass or more and less than 0.1 parts by mass. By adopting such a configuration, the resin composition of the present invention has a suppressed crystallinity of the resin component. The reason is considered to be as follows.

[0021] When the nucleating agent according to the resin composition of the present invention is added to a polyolefin resin in a conventional amount (e.g., 0.2 parts by mass per 100 parts by mass of the resin) and the resulting resin composition is plasticized by heating, the nucleating agent melts or dissolves in the polyolefin resin and diffuses into the resin matrix. When the resin melt thus obtained is cooled, the nucleating agent in the resin matrix self-organizes to form microcrystals. These microcrystals then become crystal nuclei, accelerating the crystallization of the polyolefin resin.

[0022] On the other hand, when the resin composition of the present invention is similarly heat plasticized and then cooled, the nucleating agent cannot self-organize in the resin matrix because the nucleating agent concentration in the resin matrix is ​​sufficiently low. In addition, the strong interaction between the nucleating agent molecules and the resin molecules inhibits the expansion of the crystal domain of the resin molecules. From the above results, it is presumed that the resin composition of the present invention suppresses the crystallization of the polyolefin resin. Below, each component of the resin composition of the present invention will be described in detail.

[0023] <Polyolefin resin> The polyolefin resin according to the resin composition of the present invention can be used regardless of the molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in a solvent, degree of stereoregularity, presence or absence of catalyst residue, types and blending ratios of monomers as raw materials, types of polymerization catalysts (e.g., Ziegler catalyst, metallocene catalyst, etc.), etc. In the resin composition of the present invention, the polyolefin resin refers to one in which the proportion of polyolefins in the resin components is 70 mass% or more, preferably 80 mass% or more, more preferably 90 mass% or more, and particularly preferably 100 mass%.

[0024] Examples of polyolefin resins include 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, hemiisotactic polypropylene, maleic anhydride modified polypropylene, polybutene, cycloolefin polymer, stereoblock polypropylene, α-olefin polymers such as poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene / propylene block or random copolymers, ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate copolymers, and the like, and may be elastomers. In the resin composition of the present invention, these may be blended and used, or a block copolymer may be formed and used as a block polymer type, or the resin may be alloyed. In addition, these polyolefin resins may be chlorinated.

[0025] Examples of polyolefin-based resin elastomers include elastomers obtained by blending a polyolefin such as polypropylene or polyethylene as a hard segment and a rubber such as ethylene-propylene rubber as a soft segment, and elastomers obtained by dynamic crosslinking.

[0026] The hard segment may be, for example, at least one selected from a polypropylene homopolymer, a polypropylene block copolymer, a polypropylene random copolymer, and the like.

[0027] Examples of the soft segment include ethylene-propylene copolymer (EPM), ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer (EVA), vinyl acetate homopolymer, etc. Two or more of these may be blended and used.

[0028] <Nucleating agent> The nucleating agent in 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 melts and becomes liquid during molding of the resin composition, and is diffused 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 dissolves in the molten liquid of the plasticized polyolefin resin and is diffused in the molten liquid during molding of the resin composition.

[0029] 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-based resin or dissolves in the polyolefin-based resin at a temperature 120°C higher than the melting point of the polyolefin-based resin, more preferably a nucleating agent that melts at a temperature 100°C higher than the melting point of the polyolefin-based resin or dissolves in the polyolefin-based resin at a temperature 100°C higher than the melting point of the polyolefin-based resin, and particularly preferably a nucleating agent that melts at a temperature 70°C higher than the melting point of the polyolefin-based resin or dissolves in the polyolefin-based resin at a temperature 70°C higher than the melting point of the polyolefin-based resin.

[0030] 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 150°C or higher, the crystallinity of the resin component is more effectively suppressed. When the melting point of the nucleating agent is 300°C or lower, the molding temperature of the resin composition can be sufficiently lowered, and coloring and deterioration of physical properties of the molded product can be suppressed. The melting point of the nucleating agent is more preferably 280°C or lower, even more preferably 250°C or lower, and particularly preferably 230°C or lower. The melting point of the nucleating agent is more preferably 180°C or higher, and even more preferably 200°C or higher.

[0031] Furthermore, as described above, the nucleating agent according to the resin composition of the present invention also improves the crystallization temperature of the polyolefin resin by 7°C or more when 0.2 parts by mass of the nucleating agent is added to 100 parts by mass of the polyolefin resin. When 0.2 parts by mass of the nucleating agent is added to 100 parts by mass of the polyolefin resin, the nucleating agent molecule has an improvement in the crystallization temperature of the polyolefin resin of less than 7°C, and the interaction with the resin molecule is not sufficiently strong, and the crystal domain expansion of the resin molecule cannot be effectively inhibited. Therefore, when 0.2 parts by mass of the nucleating agent is added to 100 parts by mass of the polyolefin resin, the nucleating agent has an improvement in the crystallization temperature of the polyolefin resin of less than 7°C, and the crystallization of the polyolefin resin cannot be sufficiently suppressed. In other words, when the nucleating agent has an improvement in the crystallization temperature of the polyolefin resin of less than 7°C when 0.2 parts by mass of the nucleating agent is added to 100 parts by mass of the polyolefin resin, the crystallinity of the resin component of the resin composition is not sufficiently suppressed. The nucleating agent in the resin composition of the present invention preferably increases the crystallization temperature of the polyolefin-based resin by 9°C or more, and more preferably increases the crystallization temperature of the polyolefin-based resin 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-based resin.

[0032] Examples of compounds contained in the nucleating agent of the resin composition of the present invention include triazine compounds represented by the following general formula (1), acetal compounds represented by the following general formula (2), and amide compounds such as methylene bisphenylamide and trisamidobenzene. These may be contained alone in the resin composition, or two or more of them may be combined. Among these, triazine compounds represented by the following general formula (1) and acetal compounds represented by the following general formula (2) are particularly preferred. That is, it is particularly preferred that the nucleating agent contains a triazine compound represented by the following general formula (1), and it is also particularly preferred that the nucleating agent contains an acetal compound represented by the following general formula (2).

[0033] TIFF2025061860000004.tif52155TIFF2025061860000005.tif62155

[0034] In general formula (1), Ar 1 , Ar 2 and Ar 3 each independently represents a substituted or unsubstituted phenyl group.

[0035] In addition, in the general formula (2), R 1 R 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 are linked together to form 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.

[0036] Ar in general formula (1) 1 , Ar 2 and Ar 3Examples of the substituent of the above include a halogen atom, a hydroxy group, a carboxy 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 of 1 to 20 carbon atoms which may have a substituent, an aryl group of 6 to 20 carbon atoms which may have a substituent, an arylalkyl group of 7 to 20 carbon atoms which may have a substituent, an alkoxy group of 1 to 20 carbon atoms which may have a substituent, an aryloxy group of 6 to 20 carbon atoms which may have a substituent, an alkylthio group of 1 to 20 carbon atoms which may have a substituent, an arylthio group of 6 to 20 carbon atoms which may have a substituent, an acyl group of 2 to 20 carbon atoms which may have a substituent, and an acyl group of 2 to 20 carbon atoms which may have a substituent. Examples of such groups include an oxy group, an alkoxycarbonyl group having 2 to 20 carbon atoms which may have a substituent, an aryloxycarbonyl group having 7 to 20 carbon atoms which may have a substituent, an alkylaminocarbonyl group having 2 to 20 carbon atoms which may have a substituent, an arylaminocarbonyl group having 7 to 20 carbon atoms which may have a substituent, a dialkylaminocarbonyl group having 3 to 20 carbon atoms which may have a substituent, a diarylaminocarbonyl group having 13 to 20 carbon atoms which may have a substituent, an alkylarylaminocarbonyl group having 8 to 20 carbon atoms which may have a substituent, an alkylcarbonylamino group having 2 to 20 carbon atoms which may have a substituent, an arylcarbonylamino group having 7 to 20 carbon atoms which may have a substituent, and a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. In addition, the carboxy group and the sulfo group may form a salt.Preferred are alkyl groups having 1 to 20 carbon atoms which may have a substituent, aryl groups having 6 to 20 carbon atoms which may have a substituent, aminocarbonyl groups, carboxy groups, halogen atoms, cyano groups, alkylaminocarbonyl groups having 2 to 20 carbon atoms which may have a substituent, alkoxycarbonyl groups having 2 to 20 carbon atoms which may have a substituent, acyl groups having 2 to 20 carbon atoms which may have a substituent, acyloxy groups having 2 to 20 carbon atoms which may have a substituent, and arylalkyl groups having 7 to 20 carbon atoms which may have a substituent, and more preferred are alkyl groups having 1 to 20 carbon atoms which may have a substituent, aryl groups having 6 to 20 carbon atoms which may have a substituent, and aminocarbonyl groups.

[0037] Also, Ar 1 , Ar 2 and Ar 3 Examples of the substituents of the substituents of include alkyl groups, alkoxy groups, alkylthio groups, alkenyl groups, arylalkyl groups, aryl groups, aryloxy groups, arylthio groups, heterocyclic groups, halogen atoms, acyl groups, acyloxy groups, substituted amino groups, sulfonamide groups, sulfonyl groups, carboxy groups, cyano groups, sulfo groups, hydroxyl groups, nitro groups, mercapto groups, imido groups, carbamoyl groups, and sulfonamide groups, which may be further substituted. The carboxy groups and sulfo groups may form salts.

[0038] Ar 1 , Ar 2 and Ar 3 Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, 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.

[0039] Ar 1 , Ar 2 and Ar 3 Examples of the alkoxy group include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy, nonyloxy, and decyloxy.

[0040] Ar 1 , Ar 2 and Ar 3 Examples of the alkylthio group include methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tert-amylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, tert-heptylthio, n-octylthio, isooctylthio, tert-octylthio, 2-ethylhexylthio, and the like.

[0041] Ar 1 , Ar 2 and Ar 3 Examples of the arylalkyl group include benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, and cinnamyl.

[0042] Ar 1 , Ar 2 and Ar 3 Examples of the aryl group include phenyl and naphthyl.

[0043] Ar 1 , Ar 2 and Ar 3Examples of the aryloxy group include phenoxy and naphthyloxy.

[0044] Ar 1 , Ar 2 and Ar 3 Examples of the arylthio group include phenylthio and naphthylthio.

[0045] Ar 1 , Ar 2 and Ar 3 Examples of the heterocyclic group include pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinone-1-yl, 2-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl, and 2,4-dioxyoxazolidin-3-yl.

[0046] Ar 1 , Ar 2 and Ar 3 Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

[0047] Ar 1 , Ar 2 and Ar 3 Examples of the acyl group include acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl, and the like.

[0048] Ar 1 , Ar 2 and Ar 3 Examples of the acyloxy group include acetyloxy and benzoyloxy.

[0049] Ar 1 , Ar 2 and Ar 3 Examples of the alkylaminocarbonyl group include methylaminocarbonyl, ethylaminocarbonyl, tert-butylaminocarbonyl, isobutylaminocarbonyl, cyclohexylaminocarbonyl, dimethylaminocarbonyl, N-methyl-N-ethylaminocarbonyl, and diethylaminocarbonyl.

[0050] Ar 1 , Ar 2 and Ar 3 Examples of the amino group which may have a substituent include 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, lauroylamino, carbamoylamino, and the like. Examples of the alkylamino group include ylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, and phenylsulfonylamino.

[0051] 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.

[0052] TIFF2025061860000006.tif164167TIFF2025061860000007.tif240164TIFF2025061860000008.t if239170TIFF2025061860000009.tif247170TIFF2025061860000010.tif247170TIFF20250618600 00011.tif247170TIFF2025061860000012.tif247170TIFF2025061860000013.tif247170TIFF202 5061860000014.tif247170TIFF2025061860000015.tif235170TIFF2025061860000016.tif154170

[0053] As a method for producing the triazine compound represented by the general formula (1), for example, cyanuric acid chloride is used as a raw material in an organic solvent, and 1 equivalent of Ar 1 , Ar 2 , Ar 3 and a corresponding phenol compound in the presence of 1 equivalent of a base (triethylamine, sodium hydroxide, etc.), respectively.

[0054] As described above, in the general formula (2), R 1 R 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 5are linked together to form 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.

[0055] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0056] Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, and a tert-butyloxy group.

[0057] Examples of the alkylene group having 3 to 6 carbon atoms include a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0058] 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.

[0059] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0060] In the acetal compound represented by the general formula (2), R 1 , R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X is a -CH(OH)- group.

[0061] 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.

[0062] TIFF2025061860000017.tif206159

[0063] Examples of methods for producing the acetal compound represented by the general formula (2) include a method in which an alditol compound such as sorbitol and an arylaldehyde are subjected to dehydration condensation in the presence of an acid catalyst.

[0064] As described above, in the resin composition of the present invention, the content of the nucleating agent relative to 100 parts by mass of the polyolefin resin is 0.005 parts by mass or more and less than 0.1 parts by mass. When the content of the nucleating agent is less than 0.005 parts by mass, the crystallinity of the resin component is not sufficiently suppressed. When the content of the nucleating agent is 0.1 parts by mass or more, the crystallinity of the resin component is promoted. The content of the nucleating agent is more preferably 0.01 parts by mass or more, and even more preferably 0.02 parts by mass or more. In addition, the content of the nucleating agent is preferably 0.08 parts by mass or less, more preferably 0.07 parts by mass or less, even more preferably 0.05 parts by mass or less, and particularly preferably 0.03 parts by mass or less.

[0065] In addition to the polyolefin resin and nucleating agent described above, the resin composition of the present invention may further contain additives such as phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, fatty acid metal salts, ultraviolet absorbers, hindered amine compounds, flame retardants, flame retardant assistants, lubricants, fillers, hydrosaltites, antistatic agents, fluorescent brighteners, pigments, dyes, etc. These additives may be contained alone or in combination of two or more.

[0066] Examples of phenol-based antioxidants 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(octyl sulfanylmethyl)phenol, 2,2'-isobutylidenebis(4,6-dimethylphenol), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-Hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,2'-Oxamido-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-benzenepropanoic acid and C13-15 alkyl esters, 2,5-di-tert-amylhydroquinone, hindered phenol polymers (ADEKA POLYMER ADDITIVES EUROPE SAS product 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-butylbenz[d,f][1,3,2]-dioxaphosphobin, hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate]calcium salt, 5,Reaction products of 7-bis(1,1-dimethylethyl)-3-hydroxy-2(3H)-benzofuranone with o-xylene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, DL-α-tocopherol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol, bis[3,3-bis-(4'-hydroxy-3'-tert-butyl-phenyl)butanoic acid] glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl Nyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, tridecyl-3,5-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-tert-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-tert-butyl) 1,1,3-tris(2-methyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester, 4,4'-butylidenebis(2,6-di-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenol), rt-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-tetraoxaspiro[5.5]undecane, 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, lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, and other 3-(3,5-dialkyl-4-hydroxyphenyl)propionic acid derivatives. These may be contained alone or in combination of two or more. The content of the phenol-based antioxidant is not particularly limited, and may be, for example, 0.001 to 5 parts by mass relative to 100 parts by mass of the polyolefin-based resin.

[0067] Examples of phosphorus-based antioxidants include triphenyl phosphite, diisooctyl phosphite, heptakis(dipropylene glycol)triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctylphenyl phosphite, diphenyl tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropylene glycol)phosphite, dioleylhydrogen phosphite, trilauryl trithiophosphite, bis(tridecyl)phosphite, phosphite, tris(isodecyl)phosphite, tris(tridecyl)phosphite, diphenyldecylphosphite, dinonylphenylbis(nonylphenyl)phosphite, poly(dipropylene glycol)phenylphosphite, tetraphenyldipropylene glycol diphosphite, trisnonylphenylphosphite, 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-hydro (5-methylphenylthio)-5-methylphenyl) phosphite, tri(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) isopropylidenediphenol diphosphite tetra(tridecyl)-4,4'-n-butylidenebis(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)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propenyl-3-ylidene)tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexatridecyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, 4,4'-butylidenebis(3-methyl- 6-tert-butylphenylditridecyl)phosphite, tris(2-[(2,4,8,10-tetrakis-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-diphosphespiro[5,5]undecane, 2,4,6-tri-tert-butyl Examples of such phosphite include phenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly4,4'-isopropylidenediphenol 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, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite. These may be used alone or in combination of two or more. The content of the phosphorus-based antioxidant is not particularly limited, and may be, for example, 0.001 to 10 parts by mass per 100 parts by mass of the polyolefin-based resin.

[0068] Examples of sulfur-based antioxidants include 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 / stearyl thiodipropionate, 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-thiobis(6-tert-butyl-p-cresol), distearyl disulfide, etc. These may be contained alone or in combination of two or more. The content of the sulfur-based antioxidant is not particularly limited, and may be, for example, 0.001 to 10 parts by mass relative to 100 parts by mass of the polyolefin-based resin.

[0069] 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.

[0070] TIFF2025061860000018.tif17159

[0071] In general formula (3), R 6represents a group obtained by removing COOH from a linear or branched fatty acid having 12 to 20 carbon atoms, and the fatty acid may be substituted with a hydroxyl group. M represents a monovalent to trivalent metal atom, and the metal atom may have a hydroxyl group. n represents an integer of 1 to 3. Among fatty acid metal salts, metal salts of lauric acid, myristic acid, palmitic acid, stearic acid, and 12-hydroxystearic acid are particularly preferred. Examples of monovalent to trivalent metal atoms include sodium, potassium, lithium, calcium, zinc, barium, magnesium, and hydroxyaluminum, and sodium, lithium, potassium, calcium, and zinc are particularly preferred. The content of the fatty acid metal salt is not particularly limited, and may be, for example, 0.001 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0072] Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 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(4-tert-octyl-6-benzotriazolylphenol), 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) 2-(2-hydroxyphenyl)benzotriazoles such as 2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole, and 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole;Substituted oxanilides such as phenyl salicylate, resorcinol monobenzoate, 2-ethyl-2'-ethoxyoxanilide, and 2-ethoxy-4'-dodecyloxanilide; 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-triazin-2-yl)-5-hexyloxyphenol, 2-(2-hydroxy-4-octoxyphenyl)-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)tripropionate), 2-(4, Examples of the ultraviolet absorbing agent include triazines such as 6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, and 1,12-bis[2-[4-(4,6-diphenyl-1,3,5-triazin-2-yl)-3-hydroxyphenoxy]ethyl]dodecanedioate; and various metal salts or metal chelates, particularly nickel and chromium salts or chelates. These may be contained alone or in combination of two or more. The content of the ultraviolet absorbing agent is not particularly limited, and may be, for example, 0.01 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0073] 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)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, Bis(1,2,2,6,6-pentamethyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, Bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis( N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, bis{4-(1-octyloxy-2,2,6,Examples of the hindered amine compound include bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidyl}decanedionate and bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidyl}carbonate. These may be used alone or in combination of two or more. The content of the hindered amine compound is not particularly limited, and may be, for example, 0.001 to 10 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0074] Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene)-4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetrakis(2,6-dimethylphenyl)phosphate, and ADEKA Corporation products under the trade names "ADK STAB FP-500", "ADK STAB FP-600", and "ADK STAB FP-700". Aromatic phosphate esters such as Tab FP-800, phosphonate esters such as divinyl phenylphosphonate, diallyl phenylphosphonate, and 1-butenyl phenylphosphonate, phosphinate esters such as phenyl diphenylphosphinate, methyl diphenylphosphinate, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene, melamine phosphate, melamine pyrophosphate, and melamine polyphosphate. Phosphorus-based flame retardants such as melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds and red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resins, brominated phenol novolac type epoxy resins, hexabromobenzene, pentabromotoluene, ethylene bis(pentabromophenyl), ethylene bistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethylene) Examples of the brominated flame retardants include brominated flame retardants such as 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, tribromophenylmaleimide, tribromophenylacrylate, tribromophenylmethacrylate, tetrabromobisphenol A dimethacrylate, pentabromobenzyl acrylate, and brominated styrene. These may be used alone or in combination of two or more.These flame retardants are preferably used in combination with anti-drip agents such as fluororesins, and flame retardant assistants such as polyhydric alcohols, hydrotalcites, etc. The content of the flame retardant is not particularly limited, and may be, for example, 1 to 100 parts by mass per 100 parts by mass of the polyolefin resin, and the content of the flame retardant assistant is also not particularly limited, and may be, for example, 0.1 to 10 parts by mass per 100 parts by mass of the flame retardant.

[0075] Examples of the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmitate, sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearin amide, oleic acid amide, and ethylene bisstearic acid amide. These may be contained alone or in combination of two or more. The content of the lubricant is not particularly limited, and may be, for example, 0.01 to 2 parts by mass per 100 parts by mass of the polyolefin resin.

[0076] Fillers are broadly classified into organic fillers and inorganic fillers. Examples of organic fillers include naturally derived polymers such as starch, cellulose, wood flour, soybean pulp, rice husks, and bran, and modified products thereof. Examples of inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, mica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloons, carbon black, zinc oxide, antimony trioxide, zeolite, metal fibers, metal whiskers, ceramic whiskers, potassium titanate, boron nitride, graphite, and carbon fibers. These may be contained alone or in combination of two or more. The content of the filler is not particularly limited, and may be, for example, 0.1 to 500 parts by mass per 100 parts by mass of the polyolefin resin.

[0077] Hydrotalcites are known as natural or synthetic compounds, and are complex salt compounds consisting of magnesium, aluminum, hydroxyl groups, carbonate groups, and any water of crystallization. Examples include those in which part of the magnesium or aluminum has been replaced with other metals such as alkali metals or zinc, and those in which the hydroxyl groups and carbonate groups have been replaced with other anion groups. Specific examples include those in which the metal in hydrotalcite represented by the following general formula (4) has been replaced with an alkali metal. In addition, as Al-Li-based hydrotalcites, compounds represented by the following general formula (5) can also be used.

[0078] TIFF2025061860000019.tif11159

[0079] In the general formula (4), y1 and y2 are each represented by the following formula: 0≦y2 / y1<10,2≦y1+y2≦20 represents the number that satisfies the condition expressed by, and p represents 0 or a positive number.

[0080] TIFF2025061860000020.tif11159

[0081] In the general formula (5), A q- represents a q-valent anion, and p represents 0 or a positive number. In addition, the carbonate anion in the hydrotalcites may be partially substituted with another anion.

[0082] The hydrotalcites may be those from which water of crystallization has been dehydrated, or may be those coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal salt of oleic acid, an organic sulfonic acid metal salt such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, or a wax.

[0083] The hydrotalcites may be natural products or synthetic products. Methods for synthesizing these compounds include known methods described in JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, JP-B-3-36839, JP-A-61-174270, and JP-A-5-179052. These hydrotalcites can be used without being limited by their crystal structure, crystal particles, and the like. The content of the hydrotalcites is not particularly limited, and may be, for example, 0.001 to 5 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0084] Examples of the antistatic agent include low molecular weight antistatic agents based on nonionic, anionic, cationic or amphoteric surfactants, and polymeric antistatic agents based on polymeric compounds. Examples of the nonionic surfactant include polyethylene glycol type 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; polyhydric alcohol type nonionic surfactants such as polyethylene oxide, fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and fatty amides of alkanolamines; examples of the anionic surfactant include carboxylates such as alkali metal salts of higher fatty acids; sulfate ester salts such as higher alcohol sulfate ester salts, higher alkyl ether sulfate ester salts, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphate ester salts; examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of amphoteric surfactants include amino acid type amphoteric surfactants such as higher alkylaminopropionate salts, betaine type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine. These may be used alone or in combination of two or more. The content of the low molecular weight antistatic agent is not particularly limited, and may be, for example, 0.1 to 10 parts by mass per 100 parts by mass of the polyolefin resin.

[0085] Examples of the polymer-type antistatic agent include ionomers and block polymers having polyethylene glycol as a hydrophilic part. Examples of the ionomer include the ionomer described in JP-A-2010-132927. Examples of the polymer having polyethylene glycol as a hydrophilic part include the polyether ester amide described in JP-A-7-10989, the polymer of polyolefin and polyethylene glycol described in U.S. Pat. No. 6,552,131, and the polymer of polyester and polyethylene glycol described in JP-A-2016-023254. These may be contained alone or in combination of two or more. The content of the polymer-type antistatic agent is not particularly limited, and may be, for example, 3 to 60 parts by mass relative to 100 parts by mass of the polyolefin resin.

[0086] Examples of the fluorescent brightener include benzoxazole-based compound CI Fluorescent Brightner 184, coumarin-based compound CI Fluorescent Brightner 52, and diaminostilbene disulfonic acid-based compounds CI Fluorescent Brightner 24, 85, and 71. These may be used alone or in combination of two or more. The content of the fluorescent brightener is not particularly limited, and may be, for example, 0.00001 to 0.1 parts by mass relative to 100 parts by mass of the polyolefin-based resin.

[0087] Examples of pigments include 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, 2 09, 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; Commercially available pigments such as Pigment 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 Violet 1, 15, 19, 23, 27, 29, 30, 32, 37, 40, 50 can be used. These may be used 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.

[0088] Examples of dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, etc. These may be contained alone or in combination of two or more. The content of the dye is not particularly limited, and may be, for example, 0.0005 to 3 parts by mass per 100 parts by mass of the polyolefin resin.

[0089] The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method of dry-blending a polyolefin resin powder or pellets with a nucleating agent and, if necessary, other additives, and a method of melt-kneading after dry-blending. The nucleating agent and other additives may be added to the polyolefin resin simultaneously or separately. The nucleating agent and other additives may also be added to the polyolefin resin as a master batch.

[0090] <Molded products> Next, the molded article of the present invention will be described. The molded article of the present invention is a molded article obtained by molding the resin composition of the present invention.

[0091] The molded article of the present invention includes molded articles that require the crystallinity of the resin component to be sufficiently suppressed during production, and more specifically, examples of such molded articles include laminates formed by laminating synthetic fibers, films, and resins onto substrates made of wood, fibrous materials, etc.

[0092] The method for producing the molded article of the present invention is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, inflation molding, calendar molding, slush molding, dip molding, foam molding, etc. Among these, extrusion molding and calendar molding are particularly preferred as molding methods. EXAMPLES

[0093] The present invention will be described in more detail below using examples, but the present invention is not limited to these.

[0094] (Experimental Examples 1 to 6 and Reference Example 1) <Confirmation of crystallization temperature when 0.2 parts by mass of nucleating agent is added to 100 parts by mass of polyolefin resin> The crystallization temperature of the polyolefin resin was confirmed when 0.2 parts by mass of the following nucleating agents 1 to 6 were added to 100 parts by mass of the polyolefin resin. The following polyolefin resin, nucleating agent, antioxidant, and fatty acid metal salt were blended in the ratios shown in Table 1, mixed using a Henschel mixer, and then melt-kneaded at an extrusion temperature of 230°C using a twin-screw extruder (TEX-28V, manufactured by Japan Steel Works, Ltd.), and granulated to obtain resin composition pellets of Experimental Examples 1 to 6 and Reference Example 1. In Table 1, the blending amount of each component is expressed in parts by mass. The crystallization temperature of the obtained resin composition pellets was measured by the following procedure.

[0095] Polyolefin resin: homopolypropylene with a melt flow rate of 7.7 g / 10 min at a cylinder temperature of 230°C and a load of 2.16 kg, melting point of 160°C Nucleating agent 1: Compound No. 59, triazine compound, melting point 202.7°C Nucleating agent 2: Compound No. 58, triazine compound, melting point 189.3°C Nucleating agent 3: Compound No. 50, triazine compound, melting point 217.7℃ Nucleating agent 4: Acetal compound of Compound No. 60, melting point 274.8°C Nucleating agent 5: Acetal compound of Compound No. 61, melting point 244.7°C Nucleating agent 6: Lithium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, melting point 400°C or higher (no endothermic peak observed) Antioxidant 1: Tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane Antioxidant 2: Tris(2,4-di-tert-butylphenyl)phosphite Fatty acid metal salts: Calcium stearate The "melting point" of the nucleating agent is the temperature (°C) of the endothermic peak observed when the nucleating agent is heated from 50°C to 400°C at a rate of 10°C / min in a nitrogen atmosphere using a differential scanning calorimeter (Diamond, manufactured by PerkinElmer).

[0096] <Crystallization temperature> The obtained resin composition pellets were broken into small pieces, 5 mg of which were packed in an aluminum pan, and the crystallization temperature was measured using a differential scanning calorimeter (Diamond, manufactured by PerkinElmer). The crystallization temperature was determined as the temperature (°C) of the exothermic peak observed during the cooling process when the temperature was raised from 50°C to 230°C at a rate of 10°C / min, held for 5 minutes, and then cooled to 50°C at a rate of 10°C / min. The results are shown in Table 1.

[0097] [Table 1]

[0098] From the results shown in Table 1, the crystallization temperatures of the resin compositions of Experimental Examples 1 to 6 were 7°C or more higher than the crystallization temperature of the resin composition of Reference Example 1. Therefore, nucleating agents 1 to 6 were nucleating agents that increased the crystallization temperature of the polyolefin resin by 7°C or more when added in an amount of 0.2 part by mass per 100 parts by mass of the polyolefin resin.

[0099] (Examples 1 to 10, Comparative Examples 1 to 7) <Preparation of resin composition and evaluation of its properties> Polyolefin resin, nucleating agent, antioxidant and fatty acid metal salt were blended in the ratios shown in Tables 2 to 4, mixed using a Henschel mixer, and then melt-kneaded at an extrusion temperature of 230°C using a twin-screw extruder (TEX-28V, manufactured by Japan Steel Works, Ltd.) and granulated to obtain resin composition pellets of Examples 1 to 10 and Comparative Examples 1 to 7. In Tables 2 to 4, the blending amount of each component is expressed in parts by mass. In addition, the crystallization temperature of the obtained resin composition pellets was measured in the same manner as in Experimental Example 1. The results are shown in Tables 2 to 4.

[0100] [Table 2]

[0101] [Table 3]

[0102] [Table 4]

[0103] (Examples 11 to 12, Comparative Example 8) Polyolefin resin, nucleating agent, antioxidant and fatty acid metal salt were blended in the ratio shown in Table 5, mixed using a Henschel mixer, and then melt-kneaded at an extrusion temperature of 230°C using a twin-screw extruder (Labo Plastomill Micro, manufactured by Toyo Seiki Seisakusho) and granulated to obtain resin composition pellets of Examples 11 to 12 and Comparative Example 8. In Table 5, the unit of the blending amount of each component is parts by mass. The obtained resin composition pellets were melt-compressed using a 50t press under conditions of 230°C, 10 MPa, and 5 minutes to obtain a square sheet with a side length of 10 cm and a thickness of 1.0 mm. A disk-shaped test piece with a diameter of 25 mm was cut out from the obtained sheet, and the flow field crystallization temperature of this test piece was measured by the following procedure.

[0104] First, the above test piece was placed in a rotational rheometer (TA Instruments DHR2) equipped with parallel plates with a diameter of 25 mm, and heated at 200 ° C for 3 minutes under a nitrogen atmosphere, after which the gap was set to 0.9 mm and excess resin was removed. Next, the dynamic viscoelasticity measurement was performed by setting the device under the conditions of strain amount 1%, angular velocity 1 rad / s, starting temperature 200 ° C, and cooling temperature 5 ° C / min. Then, the complex viscosity value η * (Pa · s) obtained by the measurement was plotted against the measurement temperature ( ° C). For the resin composition of Example 12, a graph plotting η * (Pa · s) against the measurement temperature ( ° C) is shown in Figure 1. Here, in Figure 1, the vertical axis is a common logarithmic scale. As shown in Figure 1, the slope of the tangent line of the graph changes significantly around the temperature at which the resin component crystallizes. Tangents were drawn at the points immediately before and after the tangent slope changed significantly, and the temperature corresponding to the intersection of these two tangents was determined as the flow field crystallization temperature TC (°C) and was used as an index of the crystallinity of the resin component in the flow field. Similar graphs were also created for the resin compositions of Example 11 and Comparative Example 8, and the flow field crystallization temperature TC was determined. The results are shown in Table 5.

[0105] [Table 5]

[0106] From the results shown in Tables 2 to 4, the resin compositions of Examples 1 to 10 had lower crystallization temperatures and suppressed the crystallinity of the resin components compared to the resin composition of Comparative Example 7. On the other hand, the resin compositions of Comparative Examples 1 to 6 had higher crystallization temperatures and did not suppress the crystallinity of the resin components compared to the resin composition of Comparative Example 7. Furthermore, from the results shown in Table 5, the resin compositions of Examples 11 and 12 had lower flow field crystallization temperatures TC and suppressed the crystallinity of the resin components compared to the resin composition of Comparative Example 8.

[0107] From the above, it was confirmed that the resin composition of the present invention has a resin component with suppressed crystallinity.

Claims

1. A crystallinity inhibitor for polyolefin resins, characterized by containing a triazine compound represented by the following general formula (1): (In general formula (1), AR 1 , AR 2 and AR 3 each independently represent a phenyl group having an aminocarbonyl group, a phenyl group having an alkyl group of 1 to 20 carbon atoms which may have a substituent, or a phenyl group having an aryl group of 6 to 20 carbon atoms which may have a substituent.)

2. A method for suppressing crystallinity of polyolefin-based resins, characterized by blending the crystallinity inhibitor for polyolefin-based resins described in claim 1 so that the blending ratio of the triazine compound is 0.005 parts by mass or more and 0.08 parts by mass or less per 100 parts by mass of polyolefin-based resin.

3. A method for producing a polyolefin resin composition in which the crystallinity of the resin component is suppressed, characterized by comprising a step of blending the crystallinity inhibitor for polyolefin resin described in claim 1 so that the blending ratio of the triazine compound is 0.005 parts by mass or more and 0.08 parts by mass or less per 100 parts by mass of polyolefin resin.

Images