WO2023127938A1 - Composition de résine, article moulé et procédé de production de composition de résine - Google Patents

Composition de résine, article moulé et procédé de production de composition de résine Download PDF

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Publication number
WO2023127938A1
WO2023127938A1 PCT/JP2022/048470 JP2022048470W WO2023127938A1 WO 2023127938 A1 WO2023127938 A1 WO 2023127938A1 JP 2022048470 W JP2022048470 W JP 2022048470W WO 2023127938 A1 WO2023127938 A1 WO 2023127938A1
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Prior art keywords
resin composition
group
polyethylene
resin
composition according
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PCT/JP2022/048470
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English (en)
Japanese (ja)
Inventor
夏穂 菅井
満 友田
直人 上田
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株式会社Adeka
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Publication of WO2023127938A1 publication Critical patent/WO2023127938A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • C08K5/1575—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene

Definitions

  • the present invention relates to a resin composition with excellent transparency, a molded product using the same, and a method for producing the resin composition.
  • Polyethylene-based resins are used for various purposes such as packaging materials and containers. Since the polyethylene-based resin is a crystalline resin, it may not have sufficient transparency depending on its use.
  • Patent Document 1 proposes a resin composition containing a polyethylene-based resin and a clarifying agent composed of a diacetal compound.
  • an object of the present invention is to provide a resin composition having excellent transparency, a molded product, and a method for producing a resin composition.
  • the present inventors have made intensive studies to solve the above problems, and found that the difference in the crystallization temperature of the resin composition before and after the diacetal compound is added to the polyethylene resin is closely related to the transparency of the resin composition. found to do. As a result of further studies, the present inventors found that the above problem can be solved by setting the difference in the crystallization temperature of the resin composition before and after adding the diacetal compound to the polyethylene resin to a specific numerical range. and completed the present invention.
  • the resin composition according to the first aspect of the present invention comprises a polyethylene resin, the following general formula (1),
  • 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, or a cyano group
  • R 2 and R 3 or R 4 and R 5 are linked to each other to form represents an alkylene group or an alkylenedioxy group having 1 to 4 carbon atoms
  • X represents a single bond, -CH(OH)- group or -CH(OH)CH(OH)- group.
  • T 1 is the crystallization temperature (°C)
  • the polyethylene resin preferably has a density of 0.938 g/cm 3 or less. Further, in the resin composition according to the first aspect of the present invention, the content of high-density polyethylene in the polyethylene resin is preferably 85% by mass or less based on the total polyethylene resin, and is preferably 15% by mass. The following are more preferable. Furthermore, it is preferable that the resin composition according to the first aspect of the present invention does not contain high-density polyethylene. Furthermore, in the resin composition according to the first aspect of the present invention, the polyethylene resin is at least one selected from the group consisting of low density polyethylene (LDPE) and linear low density polyethylene (LLDPE). is preferred.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • the diacetal compound represented by the general formula (1) is the following compound No. 1 to No. It preferably contains at least one of compound No. 4. 1 to No. more preferably at least one of compound no. 1 is more preferred.
  • the resin composition according to the first aspect of the present invention preferably further contains a lubricant. Furthermore, the resin composition according to the first aspect of the present invention preferably further contains at least one selected from the group consisting of fatty acid esters and fatty acid amides.
  • the molded article according to the first aspect of the present invention is a molded article obtained by molding the above resin composition.
  • a film is suitable as the molded article according to the first aspect of the present invention.
  • the method for producing a resin composition according to the first aspect of the present invention includes adding in contrast, the following general formula (1),
  • 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, or a cyano group
  • R 2 and R 3 or R 4 and R 5 are linked to each other to form represents an alkylene group or an alkylenedioxy group having 1 to 4 carbon atoms
  • X represents a single bond, -CH(OH)- group or -CH(OH)CH(OH)- group.
  • a method for producing a resin composition including a compounding step of compounding a diacetal compound represented by (T 1 is the crystallization temperature (°C) of the resin composition determined by differential scanning calorimetry, and T
  • the resin composition according to the second aspect of the present invention comprises a polyethylene resin, the following general formula (1),
  • 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, or a cyano group
  • R 2 and R 3 or R 4 and R 5 are linked to each other to form represents an alkylene group or an alkylenedioxy group having 1 to 4 carbon atoms
  • X represents a single bond, -CH(OH)- group or -CH(OH)CH(OH)- group.
  • a diacetal compound represented by the general formula (1) wherein the content of the diacetal compound represented by the general formula (1) is 0.2 to 10 parts by mass with respect to 100 parts by mass of the polyethylene resin. It is a thing
  • the polyethylene resin has a density of 0.938 g/cm 3 or less.
  • the content of high-density polyethylene in the polyethylene-based resin is preferably 85% by mass or less of the entire polyethylene-based resin, and the polyethylene-based It is more preferably 15% by mass or less of the total resin.
  • the resin composition according to the second aspect of the present invention does not contain high-density polyethylene.
  • the polyethylene-based resin is preferably at least one selected from the group consisting of low-density polyethylene and linear low-density polyethylene.
  • the diacetal compound represented by the general formula (1) is the following compound No. 1 to No. It preferably contains at least one of compound No. 4. 1 to No. more preferably at least one of compound no. 1 is more preferred.
  • the resin composition according to the second aspect of the present invention preferably further contains a lubricant. Furthermore, the resin composition according to the second aspect of the present invention preferably further contains at least one selected from the group consisting of fatty acid esters and fatty acid amides.
  • T 1 is the crystallization temperature (°C) of the resin composition determined by differential scanning calorimetry
  • T 0 is the crystallization temperature (°C) of the polyethylene resin determined by differential scanning calorimetry.
  • a molded article according to the second aspect of the present invention is a molded article obtained by molding the above resin composition.
  • a film is suitable as the molded article according to the second aspect of the present invention.
  • the method for producing a resin composition according to the second aspect of the present invention comprises the following general formula (1),
  • 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, or a cyano group
  • R 2 and R 3 or R 4 and R 5 are linked to each other to form represents an alkylene group or an alkylenedioxy group having 1 to 4 carbon atoms
  • X represents a single bond, -CH(OH)- group or -CH(OH)CH(OH)- group.
  • T 1 is the crystallization temperature (°C) of the resin composition determined by differential scanning calorimetry
  • T 0 is the crystallization temperature (°C) of the polyethylene resin determined by differential scanning calorimetry.
  • T1 is the crystallization temperature (°C) of the resin composition determined by differential scanning calorimetry
  • T0 is the crystallization temperature (°C) of the polyethylene resin determined by differential scanning calorimetry.
  • 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 represent a hydrogen atom, a halogen atom, represents a cyano group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms
  • X represents a single bond, -CH(OH)- group or -CH(OH)CH(OH)- group.
  • the resin composition of this embodiment has excellent transparency.
  • polyethylene resin examples of the polyethylene-based resin in this embodiment include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), crosslinked polyethylene, and ultra-high molecular weight polyethylene.
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • HDPE high-density polyethylene
  • ultra-high molecular weight polyethylene ultra-high molecular weight polyethylene.
  • degree of polymerization density, softening point, ratio of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and compounding ratio of raw material monomers, catalyst used for polymerization
  • the type for example, Ziegler catalyst, metallocene catalyst, etc.
  • the content of high-density polyethylene in the polyethylene-based resin is 85% by mass or less of the entire polyethylene-based resin. It is preferably 50% by mass or less, more preferably 25% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. Furthermore, the resin composition of the present embodiment preferably does not contain high-density polyethylene from the viewpoint of further improving transparency.
  • the polyethylene-based resin is preferably at least one selected from the group consisting of low-density polyethylene and linear low-density polyethylene, from the viewpoint of further improving transparency. Further, in the resin composition of the present embodiment, the polyethylene-based resin is preferably linear low-density polyethylene from the viewpoint of providing excellent transparency and excellent mechanical properties. Linear low-density polyethylenes include those containing 1-butene as comonomers (C 4 LLDPE), those containing 1-hexene (C 6 LLDPE), those containing 4-methylpentene (iso-C 6 LLDPE), Examples include those containing 1-octene (C 8 LLDPE).
  • C 4 LLDPE, C 6 LLDPE, and iso - C 6 LLDPE is preferred, and C 4 LLDPE, C 6 LLDPE are more preferred.
  • the amount of comonomer contained in LLDPE may be, for example, 0.5 to 5 mol % with respect to the total of ethylene monomer and comonomer contained in LLDPE.
  • the polyethylene-based resin may have a density of, for example, 0.910 to 0.965 g/cm 3 .
  • the density of the polyethylene-based resin is preferably 0.938 g/cm 3 or less.
  • the resin composition becomes more excellent in transparency.
  • the difference in specific gravity between the resin composition of the present embodiment and a resin having a relatively high density such as acrylonitrile-butadiene-styrene copolymer (ABS) resin becomes large, and when the resin material is recycled, the specific gravity Sorting and collection by difference becomes easy.
  • ABS acrylonitrile-butadiene-styrene copolymer
  • the density of the polyethylene resin should be 0.910 to 0.938 g/cm 3 from the viewpoint of further improving the transparency of the resin composition and further facilitating separate collection based on the difference in specific gravity during recycling. is preferably 0.910 to 0.935 g/cm 3 , more preferably 0.910 to 0.930 g/cm 3 , and 0.915 to 0.925 g/cm 3 is even more preferred, and 0.915 to 0.923 g/cm 3 is particularly preferred.
  • the alkyl group having 1 to 4 carbon atoms in general formula (1) includes methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group.
  • Examples of the alkoxy group having 1 to 4 carbon atoms in the general formula (1) include methoxy group, ethoxy group, propoxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group and tert-butyloxy group. .
  • Examples of the alkylene group having 3 to 6 carbon atoms in the general formula (1) include a propylene group, a butylene group, a pentylene group, and a hexylene group.
  • Examples of the alkylenedioxy group having 1 to 4 carbon atoms in general formula (1) include methylenedioxy, ethylenedioxy, propylenedioxy and butylenedioxy groups.
  • the halogen atom in the general formula (1) includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 1 , R 2 , R 3 , R 4 and R 5 in the general formula (1) are each independently a hydrogen atom or a diacetal having 1 to 4 carbon atoms.
  • Alkyl groups and X is a --CH(OH)-- group are preferred.
  • the diacetal compound has excellent compatibility with the polyethylene resin and excellent diffusibility during melt-kneading. As a result, the transparency of the resin composition is further improved.
  • diacetal compound represented by general formula (1) contained in the resin composition of the present embodiment include the following compound No. 1 to No. 4 and the like.
  • the diacetal compound represented by the general formula (1) contained in the resin composition of the present embodiment is compound No. 1 below. 1 to No. It preferably contains at least one of compound No. 4. 1 to No. more preferably at least one of compound no. 1 is more preferred.
  • the diacetal compound represented by the general formula (1) has excellent compatibility with the polyethylene resin and excellent diffusibility during melt-kneading, and as a result, the transparency of the resin composition is further excellent. It becomes a thing.
  • the diacetal compound represented by General formula (1) contained in the resin composition of this embodiment is not limited to the following specific examples.
  • Examples of methods for producing the diacetal compound represented by general formula (1) include a method of dehydration condensation of an alditol compound such as sorbitol and an arylaldehyde in the presence of an acid catalyst.
  • diacetal compounds represented by the general formula (1) commercially available ones include, for example, Gelol D (trade name), Gelol MD (trade name), and Gelol DXR (trade name) manufactured by Shin Nippon Rika Co., Ltd. , Gelall E-200 (trade name), Gelall MD-LM30G (trade name), RiKAFAST P1 (trade name), Milad 3988 (trade name) manufactured by Milliken & Company, Milad 3988i (trade name), Milad NX -8000 (trade name), Mirad NX-8000J (trade name), and the like.
  • the content of the diacetal compound represented by general formula (1) may be, for example, 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyethylene resin.
  • the content of the diacetal compound represented by the general formula (1) is It is preferably 0.1 to 10 parts by mass, more preferably 0.15 to 5 parts by mass, even more preferably 0.2 to 3 parts by mass, with respect to 100 parts by mass of the resin. .3 to 2 parts by weight is even more preferred, and 0.4 to 1 part by weight is particularly preferred.
  • the resin composition of this embodiment preferably further contains a lubricant.
  • Lubricants include fatty acid esters, fatty acid amides, stearyl alcohol, mannitol, stearic acid, hydrogenated castor oil and the like.
  • fatty acid esters include fatty acid alkyl esters such as fatty acid methyl and fatty acid ethyl; alkylene glycol fatty acid monoesters such as ethylene glycol fatty acid monoester and propylene glycol fatty acid monoester; and alkylene glycols such as ethylene glycol fatty acid diester and propylene glycol fatty acid diester.
  • Glycerol fatty acid esters such as fatty acid diesters, glycerol fatty acid monoesters, glycerol fatty acid diesters and glycerol fatty acid triesters, pentaerythritol fatty acid esters such as pentaerythritol fatty acid monoesters, pentaerythritol fatty acid diesters, pentaerythritol fatty acid triesters and pentaerythritol fatty acid tetraesters etc.
  • the fatty acid residue that constitutes the fatty acid ester may have, for example, 7 to 29 carbon atoms.
  • the fatty acid residue means a group obtained by removing a carboxyl group from a fatty acid.
  • the number of carbon atoms in the fatty acid residue is preferably 11-23, more preferably 13-21.
  • fatty acid residues include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melisic acid,
  • fatty acid residues include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid, arachidonic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melisic acid
  • groups obtained by removing the carboxyl group from fatty acids such as 12-hydroxystearic acid and ricinoleic acid.
  • groups obtained by removing the carboxyl group from lauric acid, myristic acid, palmitic acid and stearic acid are preferred, and groups obtained by removing the carb
  • glycerol fatty acid monoester is particularly preferred.
  • Specific examples of glycerol fatty acid monoesters include glycerol lauric acid monoester, glycerol myristate monoester, glycerol palmitate monoester, glycerol stearic acid monoester, glycerol oleic acid monoester, glycerol linoleic acid monoester, glycerol linolene.
  • acid monoester glycerol arachidic acid monoester, glycerol arachidonic acid monoester, glycerol behenic acid monoester, glycerol lignoceric acid monoester, glycerol cerotic acid monoester, glycerol montanic acid monoester, glycerol melisic acid monoester, glycerol 12-hydroxystearic acid monoester, glycerol ricinoleic acid monoester and the like.
  • glycerol laurate monoester glycerol myristate monoester, glycerol palmitate monoester, and glycerol stearate monoester are preferred, and glycerol stearate monoester is particularly preferred.
  • fatty acid amides include fatty acid monoamides, methylenebis fatty acid amides, alkylenebis fatty acid amides such as ethylenebis fatty acid amides, alkylol fatty acid amides such as methylol fatty acid amides and ethylol fatty acid amides, and N-alkyl fatty acid amides.
  • fatty acid residues constituting fatty acid amides include the same fatty acid residues as those exemplified above as fatty acid residues constituting fatty acid esters.
  • fatty acid amides fatty acid monoamides and alkylenebis fatty acid amides are preferred.
  • fatty acid monoamides include lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, linoleic acid amide, linolenic acid amide, arachidic acid amide, arachidonic acid amide, behenic acid amide, lignoceric acid amide, cerotic acid amide, montanic acid amide, melissic acid amide, 12-hydroxystearic acid amide, ricinoleic acid amide and the like.
  • lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, oleic acid amide and behenic acid amide are preferred, stearic acid amide, oleic acid amide and behenic acid amide are more preferred, and behenic acid amide is preferred. Especially preferred.
  • alkylenebis fatty acid amide examples include methylenebislauric acid amide, methylenebismyristate amide, methylenebispalmitic acid amide, methylenebisstearic acid amide, methylenebisoleic acid amide, methylenebislinoleic acid amide, methylenebislinolenic acid amide, methylenebisarachidic acid amide, methylenebisarachidonic acidamide, methylenebisbehenic acid amide, methylenebislignoceric acid amide, methylenebiscerotic acid amide, methylenebismontanamide, methylenebismelicic acid amide, methylenebis 12-hydroxystearic acid amide, methylenebisricinoleic acid amide, ethylenebislauric acid amide, ethylenebismyristate amide, ethylenebispalmitic acid amide, ethylenebisstearic acid amide, ethylenebisoleic acid amide, ethylenebislinoleic
  • the content of the lubricant may be, for example, 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, with respect to 100 parts by mass of the polyethylene resin. , more preferably 0.05 to 1 part by mass.
  • the resin composition of the present embodiment preferably further contains at least one selected from the group consisting of fatty acid esters and fatty acid amides, and may contain fatty acid amides. more preferred.
  • the content of these additives may be, for example, 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, and 0.05 to 1 Parts by mass are more preferred.
  • the resin composition of the present embodiment further contains a nucleating agent other than the diacetal compound represented by the general formula (1), a phenol antioxidant, a phosphorus antioxidant, a sulfur antioxidant, Various additives such as other antioxidants, hindered amine compounds, ultraviolet absorbers, fatty acid metal salts, flame retardants, flame retardant aids, fillers, hydrotalcites, antistatic agents, fluorescent brighteners, pigments and dyes may be included.
  • a nucleating agent other than the diacetal compound represented by the general formula (1) a phenol antioxidant, a phosphorus antioxidant, a sulfur antioxidant,
  • additives such as other antioxidants, hindered amine compounds, ultraviolet absorbers, fatty acid metal salts, flame retardants, flame retardant aids, fillers, hydrotalcites, antistatic agents, fluorescent brighteners, pigments and dyes may be included.
  • Nucleating agents other than the diacetal compound represented by general formula (1) include, for example, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, lithium 2,2'-methylenebis(4 ,6-di-tert-butylphenyl)phosphate, dihydroxyaluminum 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, hydroxylaluminum bis[2,2'-methylenebis(4,6-di -tert-butylphenyl)phosphate], sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate, disodium bicyclo[2.2.1]heptane-2, 3-dicarboxylate, carboxylic acid metal salts such as calcium cyclohexane-1,2-dicarboxylate, N,N′,N′′-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide
  • Phenolic antioxidants include, for example, 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(octylsulfanylmethyl)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-
  • Phosphorus antioxidants include, for example, triphenylphosphite, diisooctylphosphite, heptakis (dipropylene glycol) triphosphite, triisodecylphosphite, diphenylisooctylphosphite, diisooctylphenylphosphite, diphenyl tridecylphosphite, triisooctylphosphite, trilaurylphosphite, diphenylphosphite, tris(dipropyleneglycol)phosphite, dioleylhydrogenphosphite, trilauryltrithiophosphite, bis(tridecyl)phosphite, tris (isodecyl)phosphite, tris(tridecyl)phosphite, diphenyldecylphosphite, din
  • 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-dipropionate sulfide and the like.
  • antioxidants include, for example, N-benzyl- ⁇ -phenyl nitrone, N-ethyl- ⁇ -methyl nitrone, N-octyl- ⁇ -heptyl nitrone, N-lauryl- ⁇ -undecyl nitrone, N-tetradecyl - ⁇ -tridecyl nitrone, N-hexadecyl- ⁇ -pentadecyl nitrone, N-octyl- ⁇ -heptadecyl nitrone, N-hexadecyl- ⁇ -heptadecyl nitrone, N-octadecyl- ⁇ -pentadecyl nitrone, N-heptadecyl - nitrone compounds such as ⁇ -heptadecyl nitrone, N-octadecyl- ⁇ -heptadecyl nitrone, 3-arylbenz
  • Hindered amine compounds include, for example, 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-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 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-butanet
  • UV absorbers include, for example, 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-acryloyloxy e
  • fatty acid metal salts include metal salts of fatty acids having 12 to 20 carbon atoms containing linear or branched fatty acid residues.
  • metal ions constituting fatty acid metal salts include sodium ions, potassium ions, lithium ions, dihydroxyaluminum ions, calcium ions, zinc ions, barium ions, magnesium ions, and hydroxyaluminum ions. ions, potassium ions, lithium ions, calcium ions are particularly preferred.
  • fatty acid metal salts include sodium laurate, sodium myristate, sodium palmitate, sodium stearate, sodium oleate, sodium linoleate, sodium linolenate, sodium arachidate, sodium 12-hydroxystearate, and lauric acid.
  • sodium myristate, sodium stearate, sodium 12-hydroxystearate, lithium myristate, lithium stearate, lithium 12-hydroxystearate, calcium myristate, calcium stearate, calcium 12-hydroxystearate are preferred, and myristic Lithium oxide, lithium stearate, lithium 12-hydroxystearate, calcium myristate, calcium stearate and calcium 12-hydroxystearate are more preferable, and lithium myristate, lithium stearate and lithium 12-hydroxystearate are more preferable.
  • Flame retardants include, for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene).
  • fillers include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, and dolomite. , silica, alumina, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, etc., and the particle size (in the fibrous form, the fiber diameter, fiber length and aspect ratio) can be appropriately selected and used. can.
  • talc is particularly preferably used because it has an excellent effect of imparting rigidity and is easily available.
  • the filler may be surface-treated as necessary.
  • Hydrotalcites are complex salt compounds consisting of magnesium, aluminum, hydroxyl group, carbonate group, and water of crystallization, which are known as natural or synthetic products. Examples thereof include those substituted with a metal, and those in which a hydroxyl group or a carbonate group is substituted with another anionic group. Hydrotalcites may be those obtained by dehydrating water of crystallization, and include higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, and organic metal sulfonates such as alkali metal dodecylbenzenesulfonate. It may be coated with a salt, higher fatty acid amide, higher fatty acid ester, wax, or the like.
  • Hydrotalcites may be natural products or synthetic products. Methods for synthesizing hydrotalcites include JP-B-46-2280, JP-B-50-30039, JP-B-51-29129, JP-B-3-36839, and JP-A-61-174270. , and the known methods described in JP-A-5-179052. In addition, hydrotalcites can be used without being limited by their crystal structure, crystal grains, and the like.
  • antistatic agents include low-molecular-weight antistatic agents such as nonionic, anionic, cationic or amphoteric surfactants, and high-molecular-weight antistatic agents based on polymer compounds.
  • nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polyolefin glycol ethylene oxide adducts; polyethylene oxide, fatty acid esters of glycerin; , pentaerythrityl fatty acid esters, sorbit or sorbitan fatty acid esters, polyhydric alcohol type nonionic surfactants such as alkyl ethers of polyhydric alcohols, and aliphatic amides of alkanolamine.
  • anionic surfactants include carboxylates such as alkali metal salts of higher fatty acids; sulfate salts such as higher alcohol sulfates and higher alkyl ether sulfates; alkylbenzenesulfonates; sulfonates such as paraffin sulfonates; and phosphate salts such as higher alcohol phosphate salts.
  • Cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts.
  • Amphoteric surfactants include amino acid type amphoteric surfactants such as higher alkylaminopropionates, and betaine type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkyldihydroxyethylbetaines.
  • anionic surfactants are preferred, and sulfonates such as alkylbenzenesulfonates, alkylsulfonates and paraffin sulfonates are particularly preferred.
  • Polymer-type antistatic agents include ionomers and block polymers with polyethylene glycol as the hydrophilic part.
  • ionomers include ionomers described in JP-A-2010-132927.
  • polymers having polyethylene glycol as a hydrophilic portion include, for example, polyether ester amide described in JP-A-7-10989, a polymer composed of polyolefin and polyethylene glycol described in US Pat. No. 6,552,131, and JP-A-2016-023254. Examples thereof include polymers composed of polyester and polyethylene glycol described in publications.
  • a fluorescent whitening agent is a compound that enhances the whiteness and bluishness of molded products through the fluorescent effect of absorbing ultraviolet rays from sunlight and artificial light, converting them into violet to blue visible rays and radiating them.
  • a fluorescent brightening agent a benzoxazole compound C.I. I. Fluorescent Brightener 184; coumarin compound C.I. I. Fluorescent Brightener 52; diaminostilbene disulfonic acid compound C.I. I. Fluorescent Brightener 24, 85, 71 and the like.
  • the pigment is not particularly limited, and commercially available pigments can also be used. Specific 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, 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,
  • 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, and phthalocyanine dyes. , cyanine dyes, and the like.
  • T1 is the crystallization temperature (°C) of the resin composition determined by differential scanning calorimetry
  • T0 is the crystallization temperature (°C) of the polyethylene resin determined by differential scanning calorimetry.
  • the specific method for determining the crystallization temperature (°C) of the resin composition is as follows. That is, the resin composition is introduced into a differential scanning calorimetry (DSC) device, heated from room temperature to 200° C. at a rate of 50° C./min under a nitrogen atmosphere, held for 20 minutes, and then heated at a rate of ⁇ 10° C./min. is cooled to 50° C. and subjected to DSC measurement, and the peak top temperature of the exothermic peak in the cooling process is defined as the crystallization temperature (° C.) of the resin composition.
  • DSC differential scanning calorimetry
  • the value of ⁇ T (° C.) is determined, for example, by appropriately selecting the type of the diacetal compound represented by the polyethylene resin and the general formula (1) contained in the resin composition, and the general formula for the polyethylene resin It can be controlled by appropriately adjusting the content of the diacetal compound represented by (1).
  • the value of ⁇ T (° C.) may be, for example, 3.0 to 30.0, and from the viewpoint of improving the transparency of the resin composition, 4.0 to 25.0. is preferably 5.0 to 20.0, more preferably 5.5 to 15.0, and even more preferably 6.0 to 10.0.
  • the diacetal compound represented by the general formula (1) is added to the polyethylene resin so that the value of ⁇ T (° C.) is 3.0 or more. It includes a blending step of blending.
  • a resin composition with excellent transparency can be produced.
  • the polyethylene resin may be blended with the diacetal compound represented by the general formula (1), as well as the various additives described above, if necessary.
  • One or two or more of the diacetal compound represented by the general formula (1) and various additives are further blended with granulation aids such as binders, waxes, solvents, silica, etc., and granulated one-pack It may be blended in the form of a composite additive or a masterbatch containing a resin component.
  • the method of blending the diacetal compound represented by the general formula (1) and various additives is not particularly limited.
  • a method of mixing using a mixing device such as an FM mixer, a mill roll, a Banbury mixer, a super mixer, or the like can be used.
  • the mixture obtained in the blending step is melt-kneaded using a melt-kneading device such as a single screw extruder or a twin screw extruder.
  • the method may further include a step.
  • the melt-kneading temperature in the melt-kneading step may be, for example, 180 to 280°C.
  • the method for producing the resin composition of the present embodiment may further include a granulation step of granulating the kneaded product obtained in the melt-kneading step.
  • the granulation method is not particularly limited, and examples thereof include a method using a granulation apparatus such as a pelletizer.
  • the shape of the resin composition obtained by granulation is not particularly limited, and may be, for example, a pellet shape.
  • at least one of the diacetal compound represented by the general formula (1) and optionally other additives is added before or after the polymerization of the ethylene-based monomer or oligomer. A method of adding the components during polymerization and adding the remaining components to the obtained polymer may also be used.
  • a molded article of the first embodiment is obtained by molding the resin composition described above.
  • the molded product of this embodiment has excellent transparency.
  • the molded article of the present embodiment include, for example, injection molded articles, fibers, flat yarns, films, sheets, thermoforming molded articles, extrusion blow molded articles, injection blow molded articles, injection stretch blow molded articles, and profile extrusion.
  • examples include molded articles and rotationally molded articles.
  • films are particularly preferred. When the molded article is a film, it is possible to effectively utilize the feature of having excellent transparency. Examples of films include biaxially stretched films, uniaxially stretched films, non-stretched films, and the like.
  • the method for producing the molded article is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, inflation molding, calendar molding, and slush molding. , a dip molding method, a thermoforming molding method, and the like.
  • the resin composition of the second embodiment contains a polyethylene-based resin and the diacetal compound represented by the general formula (1) described above, and the content of the diacetal compound represented by the general formula (1) is It is 0.2 to 10 parts by mass with respect to 100 parts by mass of polyethylene resin.
  • the resin composition of this embodiment has excellent transparency.
  • the polyethylene-based resin and the diacetal compound represented by general formula (1) may be the same as those exemplified for the resin composition of the first embodiment.
  • the content of high-density polyethylene in the polyethylene resin is preferably 85% by mass or less of the entire polyethylene resin, It is more preferably 50% by mass or less, even more preferably 25% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. Furthermore, the resin composition of the present embodiment preferably does not contain high-density polyethylene from the viewpoint of further improving transparency.
  • the polyethylene-based resin is preferably at least one selected from the group consisting of low-density polyethylene and linear low-density polyethylene, from the viewpoint of further improving transparency. Further, in the resin composition of the present embodiment, the polyethylene-based resin is preferably linear low-density polyethylene from the viewpoint of providing excellent transparency and excellent mechanical properties. Furthermore, when the resin composition is formed into a film, from the viewpoint that the film can be easily torn by hand and can be torn linearly, C 4 LLDPE is used as the linear low-density polyethylene. , C 6 LLDPE and iso-C 6 LLDPE are preferred, and C 4 LLDPE and C 6 LLDPE are more preferred. The amount of comonomer contained in LLDPE may be, for example, 0.5 to 5 mol % with respect to the total of ethylene monomer and comonomer contained in LLDPE.
  • the polyethylene-based resin may have a density of, for example, 0.910 to 0.965 g/cm 3 .
  • the density of the polyethylene-based resin is preferably 0.938 g/cm 3 or less.
  • the resin composition becomes more excellent in transparency.
  • the difference in specific gravity between the resin composition of the present embodiment and a resin having a relatively high density such as acrylonitrile-butadiene-styrene copolymer (ABS) resin becomes large, and when the resin material is recycled, the specific gravity Sorting and collection by difference becomes easy.
  • ABS acrylonitrile-butadiene-styrene copolymer
  • the density of the polyethylene resin should be 0.910 to 0.938 g/cm 3 from the viewpoint of further improving the transparency of the resin composition and further facilitating separate collection based on the difference in specific gravity during recycling. is preferably 0.910 to 0.935 g/cm 3 , more preferably 0.910 to 0.930 g/cm 3 , and 0.915 to 0.925 g/cm 3 is even more preferred, and 0.915 to 0.923 g/cm 3 is particularly preferred.
  • the diacetal compound represented by general formula (1) contained in the resin composition of the present embodiment is compound No. 1 to No. It preferably contains at least one of compound No. 4. 1 to No. more preferably at least one of compound no. 1 is more preferred.
  • the diacetal compound represented by the general formula (1) has excellent compatibility with the polyethylene resin and excellent diffusibility during melt-kneading, and as a result, the resin composition has further excellent transparency. become a thing.
  • the content of the diacetal compound represented by general formula (1) is 0.2 to 10 parts by mass with respect to 100 parts by mass of the polyethylene resin.
  • the content of the diacetal compound represented by the general formula (1) is It is preferably 0.25 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, even more preferably 0.4 to 3 parts by mass, with respect to 100 parts by mass of the resin. 0.45 to 2 parts by weight is even more preferred, and 0.5 to 1 part by weight is particularly preferred.
  • the resin composition of this embodiment preferably further contains a lubricant.
  • the transparency of the resin composition is further improved.
  • the lubricant may be the same as those exemplified as the lubricant that the resin composition of the first embodiment may contain.
  • the content of the lubricant may be, for example, 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, with respect to 100 parts by mass of the polyethylene resin. , more preferably 0.05 to 1 part by mass.
  • the resin composition of the present embodiment preferably further contains at least one selected from the group consisting of fatty acid esters and fatty acid amides, and may contain fatty acid amides. more preferred.
  • the content of these additives may be, for example, 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, and 0.05 to 1 Parts by mass are more preferred.
  • the resin composition of the present embodiment further contains a nucleating agent other than the diacetal compound represented by the general formula (1), a phenol antioxidant, a phosphorus antioxidant, a sulfur antioxidant, Various additives such as other antioxidants, hindered amine compounds, ultraviolet absorbers, fatty acid metal salts, flame retardants, flame retardant aids, fillers, hydrotalcites, antistatic agents, fluorescent brighteners, pigments and dyes may be included. These various additives may be the same as those exemplified as the various additives that may be contained in the resin composition of the first embodiment.
  • the value of ⁇ T (°C) described above is preferably 3.0 or more from the viewpoint of further improving transparency.
  • the value of ⁇ T (° C.) may be, for example, 3.0 to 30.0, preferably 4.0 to 25.0, more preferably 5.0 to 20.0, and 5 It is more preferably 0.5 to 15.0, and even more preferably 6.0 to 10.0.
  • the content of the diacetal compound represented by the general formula (1) is 0.2 to 10 parts by mass with respect to 100 parts by mass of the polyethylene resin.
  • (2) includes a blending step of blending the diacetal compound represented by the general formula (1) with the polyethylene resin.
  • a resin composition with excellent transparency can be produced.
  • the polyethylene resin may be blended with the diacetal compound represented by the general formula (1), as well as the various additives described above, if necessary.
  • One or two or more of the diacetal compound represented by the general formula (1) and various additives are further blended with granulation aids such as binders, waxes, solvents, silica, etc., and granulated one-pack It may be blended in the form of a composite additive or a masterbatch containing a resin component.
  • the method of blending the diacetal compound represented by the general formula (1) and various additives is not particularly limited.
  • a method of mixing using a mixing device such as an FM mixer, a mill roll, a Banbury mixer, a super mixer, or the like can be used.
  • the mixture obtained in the blending step is melt-kneaded using a melt-kneading device such as a single screw extruder or a twin screw extruder.
  • the method may further include a step.
  • the melt-kneading temperature in the melt-kneading step may be, for example, 180 to 280°C.
  • the method for producing the resin composition of the present embodiment may further include a granulation step of granulating the kneaded product obtained in the melt-kneading step.
  • the granulation method is not particularly limited, and examples thereof include a method using a granulation apparatus such as a pelletizer.
  • the shape of the resin composition obtained by granulation is not particularly limited, and may be, for example, a pellet shape.
  • at least one of the diacetal compound represented by the general formula (1) and optionally other additives is added before or after the polymerization of the ethylene-based monomer or oligomer. A method of adding the components during polymerization and adding the remaining components to the obtained polymer may also be used.
  • ⁇ T (° C.) may be, for example, 3.0 to 30.0, preferably 4.0 to 25.0, more preferably 5.0 to 20.0, and 5 It is more preferably 0.5 to 15.0, and even more preferably 6.0 to 10.0.
  • a molded article of the second embodiment is obtained by molding the resin composition described above.
  • the molded product of this embodiment has excellent transparency.
  • the molded article of the present embodiment include, for example, injection molded articles, fibers, flat yarns, films, sheets, thermoforming molded articles, extrusion blow molded articles, injection blow molded articles, injection stretch blow molded articles, and profile extrusion.
  • examples include molded articles and rotationally molded articles.
  • films are particularly preferred. When the molded article is a film, it is possible to effectively utilize the feature of having excellent transparency. Examples of films include biaxially stretched films, uniaxially stretched films, non-stretched films, and the like.
  • the method for producing the molded article is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, rotational molding, vacuum molding, inflation molding, calendar molding, and slush molding. , a dip molding method, a thermoforming molding method, and the like.
  • the polyethylene resin, diacetal compound and lubricant used in this example are as follows.
  • DA-1 1,2,3-trideoxy-4,6:5,7-o-bis(4-propylbenzylidene)nonitol
  • DA-2 bis (3,4-dimethylbenzylidene) sorbitol
  • LB-1 Glycerol stearic acid monoester
  • LB-2 Oleic acid amide
  • LB-3 Ethylene bis-stearic acid amide
  • LB-4 Behenic acid amide
  • LB-5 Stearic acid amide
  • Crystallization temperature The crystallization temperatures of the resin compositions of Examples 1-14 and Comparative Examples 1-4 were measured by differential scanning calorimetry (DSC). Specifically, the resin compositions of Examples 1 to 14 and Comparative Examples 1 to 4 were introduced into a differential scanning calorimeter (Diamond, manufactured by PerkinElmer), under a nitrogen atmosphere, from room temperature at a rate of 50 ° C./min. The temperature was raised to 230°C at , held for 20 minutes, and then cooled to 50 °C at a rate of -10°C/min. .
  • DSC differential scanning calorimetry
  • T 1 (° C.), T 0 (° C.) and ⁇ T (° C.) of the resin compositions of Examples 1-14 and Comparative Examples 1-4 are also shown in Tables 1, 2 and 3.
  • the haze values (%) of the films obtained by molding the resin compositions of Examples 1 to 14 and Comparative Examples 1 to 4 were measured and used as an indicator of the transparency of the resin compositions.
  • the resin compositions of Examples 1 to 14 and Comparative Examples 1 to 4 are melted and kneaded by connecting a small single screw extruder (D1220B manufactured by Toyo Seiki Co., Ltd.) and a T-die (MT60B manufactured by Toyo Seiki Co., Ltd.). (Laboplastomill Micro manufactured by Toyo Seiki Co., Ltd.), melted and kneaded under conditions of a melting temperature of 200° C.
  • the resin composition of the present invention has excellent transparency.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine présentant une excellente transparence, un article moulé et un procédé de production d'une composition de résine.　Cette composition de résine contient une résine de polyéthylène et un composé diacétal représenté par la formule générale (1), la valeur de ∆T (°C) définie par ∆T = T1-T0 étant supérieure ou égale à 3,0. T1 et T0 représentent respectivement les températures de cristallisation (°C) de la composition de résine et de la résine de polyéthylène qui sont déterminées par calorimétrie différentielle à balayage.　Dans la formule : R1 représente un atome d'hydrogène ou un groupe alkyle ; R2 à R5 représentent indépendamment un atome d'hydrogène, un atome d'halogène, un groupe cyano, un groupe alkyle ou un groupe alcoxy, ou R2 et R3 ou R4 et R5 sont reliés l'un à l'autre et représentent un groupe alkylène ou un groupe alkylènedioxy ; et X représente une liaison simple, un groupe -CH(OH)- ou un groupe -CH(OH)CH(OH)-.
PCT/JP2022/048470 2021-12-28 2022-12-28 Composition de résine, article moulé et procédé de production de composition de résine WO2023127938A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61133252A (ja) * 1984-12-04 1986-06-20 Ube Ind Ltd 射出成形法
JPH06122789A (ja) * 1992-10-12 1994-05-06 Mitsubishi Kasei Corp ポリエチレン組成物
JPH0812817A (ja) * 1994-07-01 1996-01-16 Sumitomo Chem Co Ltd レトルト包装用フィルム
JPH09507083A (ja) * 1993-11-08 1997-07-15 モービル・オイル・コーポレーション エチレン重合体または共重合体とソルビトール誘導体とのブレンドを含んで成る組成物
JP2001192513A (ja) * 2000-01-14 2001-07-17 Chisso Corp 高密度ポリエチレン樹脂組成物およびその成形品
JP2006328121A (ja) * 2005-05-24 2006-12-07 Tokyo Printing Ink Mfg Co Ltd 造核剤含有ポリエチレン樹脂組成物及びその製造方法
JP2017125111A (ja) * 2016-01-13 2017-07-20 株式会社Adeka ポリエチレン樹脂組成物の製造方法
WO2019132694A1 (fr) * 2017-12-27 2019-07-04 Public Joint Stock Company "Sibur Holding" Composition de polyéthylène
JP2021502275A (ja) * 2017-11-13 2021-01-28 カウンスィル オブ サイエンティフィック アンド インダストリアル リサーチＣｏｕｎｃｉｌ Ｏｆ Ｓｃｉｅｎｔｉｆｉｃ ＆ Ｉｎｄｕｓｔｒｉａｌ Ｒｅｓｅａｒｃｈ ポリマーの反りのない３ｄ印刷

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61133252A (ja) * 1984-12-04 1986-06-20 Ube Ind Ltd 射出成形法
JPH06122789A (ja) * 1992-10-12 1994-05-06 Mitsubishi Kasei Corp ポリエチレン組成物
JPH09507083A (ja) * 1993-11-08 1997-07-15 モービル・オイル・コーポレーション エチレン重合体または共重合体とソルビトール誘導体とのブレンドを含んで成る組成物
JPH0812817A (ja) * 1994-07-01 1996-01-16 Sumitomo Chem Co Ltd レトルト包装用フィルム
JP2001192513A (ja) * 2000-01-14 2001-07-17 Chisso Corp 高密度ポリエチレン樹脂組成物およびその成形品
JP2006328121A (ja) * 2005-05-24 2006-12-07 Tokyo Printing Ink Mfg Co Ltd 造核剤含有ポリエチレン樹脂組成物及びその製造方法
JP2017125111A (ja) * 2016-01-13 2017-07-20 株式会社Adeka ポリエチレン樹脂組成物の製造方法
JP2021502275A (ja) * 2017-11-13 2021-01-28 カウンスィル オブ サイエンティフィック アンド インダストリアル リサーチＣｏｕｎｃｉｌ Ｏｆ Ｓｃｉｅｎｔｉｆｉｃ ＆ Ｉｎｄｕｓｔｒｉａｌ Ｒｅｓｅａｒｃｈ ポリマーの反りのない３ｄ印刷
WO2019132694A1 (fr) * 2017-12-27 2019-07-04 Public Joint Stock Company "Sibur Holding" Composition de polyéthylène

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