WO2022025187A1 - 添加剤組成物、樹脂組成物、樹脂組成物の製造方法および成形品 - Google Patents
添加剤組成物、樹脂組成物、樹脂組成物の製造方法および成形品 Download PDFInfo
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- WO2022025187A1 WO2022025187A1 PCT/JP2021/028114 JP2021028114W WO2022025187A1 WO 2022025187 A1 WO2022025187 A1 WO 2022025187A1 JP 2021028114 W JP2021028114 W JP 2021028114W WO 2022025187 A1 WO2022025187 A1 WO 2022025187A1
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Definitions
- the present invention relates to an additive composition, a resin composition, a method for producing a resin composition, and a molded product, which are excellent in powder fluidity and can impart excellent mechanical properties and excellent color tone to a molded product.
- Polyolefin-based resins have the advantages of excellent molding processability, heat resistance, mechanical properties, low specific gravity, etc., and are widely used in general miscellaneous goods, medical equipment, food packaging materials, automobile materials, and the like.
- Patent Document 1 proposes an additive composition containing an aromatic phosphoric acid ester compound and a fatty acid sodium salt as an additive composition containing a nucleating agent for a polyolefin resin.
- Patent Document 1 has room for further improvement from the viewpoint of making the color tone of the molded product sufficiently excellent.
- An object of the present invention is to provide an additive composition, a resin composition, a method for producing a resin composition, and a molded product, which have excellent powder fluidity and can impart excellent mechanical properties and excellent color tone to the molded product. To provide.
- the present invention comprises (A) an aromatic phosphate sodium salt represented by the following general formula (1), (B) a fatty acid sodium salt, and (C) talc, and the component (A) is described above.
- the mass ratio (B) / (A) of the content of the component (B) to the content of the component (B) is 0.1 or more and 3 or less, and the component (A), the component (B) and the component (C) are In an additive composition in which the mass ratio (C) / [(A) + (B) + (C)] of the content of the component (C) to the total content is 0.2 or more and 0.8 or less.
- R 1 to R 5 independently represent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, respectively.
- R 1 to R 4 are t-butyl groups and R 5 is a hydrogen atom
- the fatty acid sodium salt (B) has 12 to 30 carbon atoms. It is preferably a fatty acid sodium salt of.
- the additive composition of the present invention further contains (D) hydrotalcites, and the said (D) with respect to the total content of the said (A) component, the said (B) component and the said (C) component.
- the mass ratio (D) / [(A) + (B) + (C)] of the content of the components is preferably 0.01 or more and 20 or less.
- the resin composition of the present invention is a resin composition containing a polyolefin-based resin and the above-mentioned additive composition.
- resin compositions of the present invention include a polyolefin resin, (A) an aromatic phosphate ester sodium salt represented by the following general formula (1), (B) a fatty acid sodium salt, and (C).
- the mass ratio (B) / (A) of the content of the component (B) to the content of the component (A) including talc is 0.1 or more and 3 or less, and the component (A) is described.
- the mass ratio (C) / [(A) + (B) + (C)] of the content of the component (C) to the total content of the component (B) and the component (C) is 0.2 or more. It may be a resin composition of 0.8 or less.
- the resin composition further contains (D) hydrotalcites, and the content of the component (D) with respect to the total content of the component (A), the component (B) and the component (C).
- the mass ratio (D) / [(A) + (B) + (C)] of is preferably 0.01 or more and 20 or less.
- R 1 to R 5 independently represent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, respectively.
- the polyolefin-based resin is a polypropylene-based resin.
- the present invention is a method for producing a resin composition, which comprises a step of blending the above additive composition with a polyolefin resin.
- the present invention is a molded product obtained by molding the above resin composition.
- an additive composition, a resin composition, a method for producing a resin composition, and a molded product which are excellent in powder fluidity and can impart excellent mechanical properties and excellent color tone to a molded product are provided.
- the additive composition according to the present embodiment contains (A) an aromatic phosphate ester sodium salt represented by the following general formula (1), (B) a fatty acid sodium salt, and (C) talc.
- R 1 to R 5 independently represent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, respectively.
- the mass ratio (B) / (A) of the content of the component (B) to the content of the component (A) is 0.1 or more and 3 or less, and the component (A), the component (B) and (C).
- the mass ratio (C) / [(A) + (B) + (C)] of the content of the component (C) to the total content of the components is 0.2 or more and 0.8 or less.
- the additive composition according to the present embodiment has excellent powder fluidity, and according to the additive composition according to the present embodiment, excellent mechanical properties and excellent color tone can be imparted to the molded product.
- examples of the alkyl group having 1 to 6 carbon atoms represented by R 1 to R 5 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group and n.
- -Butyl group, sec-butyl group, tert-butyl group, isobutyl group, cyclobutyl group, n-amyl group, tert-amyl group, cyclopentyl group, n-hexyl group, cyclohexyl group and the like can be mentioned.
- R 1 to R 4 are tert-butyl groups.
- R5 is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
- the aromatic phosphate ester sodium salt may be contained alone or in combination of two or more.
- aromatic phosphate ester sodium salt examples include sodium 2,2'-methylenebis (4,6-dimethylphenyl) phosphate and sodium 2,2'-ethylidenebis (4,6-dimethylphenyl) phosphate.
- the volume average particle size of (A) aromatic phosphate sodium salt is preferably 20 ⁇ m or less, and more preferably 10 ⁇ m or less.
- the volume average particle size of the aromatic phosphate ester sodium salt may be, for example, 0.5 ⁇ m or more.
- the fatty acid sodium salt may be contained alone or in combination of two or more.
- the (B) fatty acid sodium salt is preferably a fatty acid sodium salt having 12 to 30 carbon atoms.
- the number of carbon atoms of the (B) fatty acid sodium salt is more preferably 14 or more, and further preferably 16 or more.
- the number of carbon atoms of the (B) fatty acid sodium salt is more preferably 28 or less, further preferably 26 or less, further preferably 22 or less, and 20 or less. Is particularly preferred.
- the sodium salt of (B) fatty acid is preferably a sodium salt of saturated fatty acid.
- (B) fatty acid sodium salt examples include capric acid, 2-ethylhexanoic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecic acid, palmitic acid, margaric acid, stearic acid, and 12-hydroxy.
- Sodium salts of saturated fatty acids such as stearate, nonadesyl acid, arachidic acid, heicosyl acid, bechenic acid, tricosyl acid, lignoseric acid, cellotic acid, montanic acid, melicic acid, 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid,
- unsaturated fatty acids such as ⁇ -linolenic acid, linoleic acid, ⁇ -linolenic acid, stearidonic acid, petroseric acid, oleic acid, lysynolic acid, ellagic acid, buxenic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid.
- the (B) fatty acid sodium salt is not limited thereto.
- Sodium salts of acids, ⁇ -linolenic acid, oleic acid or ricinoleic acid are more preferred, and sodium salts of myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, arachidic acid or behenic acid are more preferred, myristic acid, palmitin.
- Sodium salts of acids, stearic acids, 12-hydroxystearic acid or arachidic acid are even more preferred, with myristic acid, stearic acid or sodium salts of 12-hydroxystearic acid particularly preferred.
- the particle shape of talc is not particularly limited, but from the viewpoint of obtaining an additive composition which is more excellent in powder fluidity and can impart more excellent mechanical properties to a molded product. It is particularly preferable that it has a flat plate shape. Further, the average particle size of talc is not particularly limited, and may be, for example, 1 to 100 ⁇ m, preferably 30 ⁇ m or less from the viewpoint of improving the dispersibility in the polyolefin resin. , 20 ⁇ m or less, more preferably 10 ⁇ m or less.
- the average particle size of talc is an arithmetic average particle size calculated by a method based on JIS Z 8819-2 based on a particle size distribution measured by a laser diffraction method based on JIS Z 8825.
- the surface of the talc may be untreated, or may be surface-treated with a surfactant or the like for the purpose of improving the dispersibility in the resin.
- the surfactant used for the surface treatment of talc include silane coupling agents, titanium coupling agents, fatty acids, fatty acid esters, fatty acid amides, fatty acid metal salts and the like.
- the mass ratio (B) / (A) of the content (mass part) of the component (B) to the content (mass part) of the component (A) is 0.1 or more and 3 or less, and (A). ),
- the mass ratio of the content of the component (C) (parts by mass) to the total content (parts by mass) of the components (B) and (C) / [(A) + (B) + ( C)] is 0.2 or more and 0.8 or less.
- the value of (B) / (A) is preferably 0.14 or more, more preferably 0.33 or more. It is more preferably 0.6 or more. Further, from the viewpoint of obtaining a molded product having more excellent mechanical properties, the value of (B) / (A) is preferably 2 or less, and more preferably 1 or less. Further, from the viewpoint of obtaining a molded product having a better color tone, the value of (C) / [(A) + (B) + (C)] is preferably 0.3 or more, and 0.5 or more. It is more preferable to have. Furthermore, from the viewpoint of obtaining a molded product having more excellent mechanical properties, the value of (C) / [(A) + (B) + (C)] is preferably 0.7 or less.
- the additive composition according to the present embodiment further contains (D) hydrotalcites.
- the additive composition has excellent heat resistance. Further, in this case, it is possible to obtain a molded product having further excellent mechanical properties and excellent heat resistance.
- Hydrotalcites are complex salt compounds composed of magnesium, aluminum, hydroxyl groups, carbonic acid groups and arbitrary crystalline water known as natural products and synthetic products, and magnesium or aluminum is partially composed of alkali metals, zinc and the like. Examples thereof include those substituted with other metals and those substituted with hydroxyl groups and carbonate groups with other anionic groups. Hydrotalcites may be obtained by dehydrating crystalline water, and are higher fatty acids such as stearic acid, higher fatty acid metal salts such as oleic acid alkali metal salt, and organic sulfonic acid metals such as dodecylbenzene sulfonic acid alkali metal salt.
- hydrotalcites may be natural products or synthetic products.
- Japanese Patent Publication No. 46-2280 Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Square Root Extraction 3-36839, and Japanese Patent Application Laid-Open No. 61-174270 are used.
- hydrotalcites can be used without being limited by their crystal structure, crystal particles and the like.
- the mass ratio (D) / [(A) + (B) + (C)] of the content (parts by mass) may be, for example, 0.01 or more and 20 or less.
- the value of (D) / [(A) + (B) + (C)] is preferably 0.05 or more, preferably 0.1. The above is more preferable, 0.3 or more is further preferable, and 0.5 or more is even more preferable.
- the value of (D) / [(A) + (B) + (C)] is preferably 10 or less, preferably 5 or less. It is more preferably 3 or less, further preferably 2 or less, and particularly preferably 1.5 or less.
- the additive composition according to the present embodiment further comprises a nucleating agent other than the aromatic phosphate ester sodium salt, a phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and other additives, if necessary.
- a nucleating agent other than the aromatic phosphate ester sodium salt a phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and other additives, if necessary.
- nucleating agents other than the aromatic phosphate ester sodium salt examples include lithium 2,2'-methylenebis (4,6-dimethylphenyl) phosphate and lithium 2,2'-ethylidenebis (4,6-dimethylphenyl) phosphate.
- Ester dihydroxyaluminum salt hydroxyaluminum bis [2,2'-methylenebis (4,6-dimethylphenyl) phosphate], hydroxyaluminum bis [2,2'-ethylidenebis (4,6-dimethylphenyl) phosphate], hydroxyaluminum Bis [2,2'-methylenebis (4,6-diisopropylphenyl) phosphate], hydroxyaluminum bis [2,2'-ethylidenebis (4,6-diisopropylphenyl) phosphate], Droxyaluminum bis [2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate], hydroxyaluminum bis [2,2'-ethylidenebis (4,6-di-tert-butylphenyl) phosphate] ], Hydroxyaluminum bis [2,2'-methylenebis (4,6-di-tert-amylphenyl
- phenolic antioxidant examples include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrated phenol, and 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-
- Examples of the phosphorus antioxidant include triphenylphosphite, diisooctylphosphite, heptaxis (dipropylene glycol) triphosphite, triisodecylphosphite, diphenylisooctylphosphite, diisooctylphenylphosphite, and diphenyl.
- Tridecylphosphite triisooctylphosphite, trilaurylphosphite, diphenylphosphite, tris (dipropylene glycol) phosphite, dioleylhydrogenphosphite, trilauryltrithiophosphite, bis (tridecyl) phosphite, tris (Isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecylphosphite, dinonylphenylbis (nonylphenyl) phosphite, poly (dipropylene glycol) phenylphosphite, tetraphenyldipropylene glycol diphosphite, trisnonyl Phenyl Phenyl Phenyl Phenyl, Tris (2,4-di-tert-butylpheny
- sulfur-based antioxidant examples include tetrakis [methylene-3- (laurylthio) propionate] methane and bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl.
- antioxidants include N-benzyl- ⁇ -phenylnitrone, N-ethyl- ⁇ -methylnitrone, N-octyl- ⁇ -heptylnitrone, N-lauryl- ⁇ -undecylnitrone, N-tetradecyl- ⁇ .
- hindered amine compound examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-. Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 , 4-Butan Tetracarboxylate, Tetrakiss (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-butanetetracar
- 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).
- 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-benzotri
- Examples of the fatty acid metal salt other than the fatty acid sodium salt include metal salts of fatty acids having 12 to 30 carbon atoms including linear or branched fatty acid residues.
- Examples of the metal ion constituting the fatty acid metal salt include potassium ion, lithium ion, dihydroxyaluminum ion, calcium ion, zinc ion, barium ion, magnesium ion, hydroxyaluminum ion and the like. Among these, potassium ion, Lithium ion and calcium ion are particularly preferable.
- Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinolbis (diphenyl phosphate), (1-methylethylidene).
- Bisphenol A type epoxy resin brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromo) Ethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5- Examples thereof include triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, and brominated flame
- the lubricant examples 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, and sorbitan monopalmitite. Examples thereof include sorbitan monostearate, mannitol, stearic acid, hardened roasted oil, stearic acid amide, oleic acid amide, and ethylene bisstearic acid amide.
- 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, and sorbitan monopalmitite. Examples thereof include sorbitan monostearate,
- fillers other than talc include 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 the like.
- examples thereof include dolomite, silica, alumina, potassium titanate whiskers, warastenite, fibrous magnesium oxysulfate, etc., and the particle size (fiber diameter, fiber length, and aspect ratio in the case of fibrous form) can be appropriately selected and used. can.
- a surface-treated filler can be used if necessary.
- the antistatic agent examples include a low molecular weight antistatic agent using a nonionic, anionic, cationic or amphoteric surfactant, and a high molecular weight antistatic agent using a polymer compound.
- the nonionic surfactant include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, and polyolefin glycol ethylene oxide adduct; polyethylene oxide and fatty acid ester of glycerin.
- anionic surfactant include carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates and alkyl sulfonates. Sulfates such as paraffin sulfonates; phosphate ester salts such as higher alcohol phosphates and the like can be mentioned.
- Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts.
- Examples of the amphoteric tenside include amino acid type amphoteric tenside agents such as higher alkylaminopropionate, and betaine type amphoteric tenside agents such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine.
- anionic surfactants are preferable, and sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates are particularly preferable.
- Examples of the polymer-type antistatic agent include ionomers and block polymers having polyethylene glycol as a hydrophilic portion.
- Examples of the ionomer include the ionomer described in JP-A-2010-132927.
- Examples of the polymer having polyethylene glycol as a hydrophilic portion include the polyether ester amide described in JP-A-7-10989, the polymer composed of polyolefin and polyethylene glycol described in US Pat. No. 6,552,131, and JP-A-2016-023254. Examples thereof include a polymer composed of polyester and polyethylene glycol described in the publication.
- Optical brightener is a compound that absorbs ultraviolet rays of sunlight and artificial light, converts them into visible light of purple to blue and radiates them, and promotes the whiteness and bluish tint of the molded product.
- fluorescent whitening agent include benzoxazole compounds C.I. I. Fluorescent Fluorescenter 184; Coumarin-based compound C.I. I. Fluorescent Fluorescent 52; diaminostilbene dissulphonic acid-based compound C.I. I. Fluorescent Fluorescenter 24, 85, 71 and the like can be mentioned.
- the pigment is not particularly limited, and a commercially available pigment can also be used. Specific examples of the pigment include, for example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123.
- 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, Pigment Black 7, 11, and the like.
- Dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridin dyes, stillben dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxadin dyes, and phthalocyanine dyes. , Cyanine dyes and the like.
- the additive composition according to the present embodiment is obtained, for example, by mixing the above-mentioned component (A), (B) and (C) component, and if necessary, the above-mentioned component (D) and various additives. It may be powder. Further, the additive composition according to the present embodiment may be a one-pack composite additive further blended with a granulation aid such as a binder, a wax, a solvent, and silica, and granulated. Further, the additive composition according to the present embodiment may be a masterbatch further containing a polyolefin-based resin.
- polystyrene-based resins examples include polyethylene-based resins such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, crosslinked polyethylene, and ultra-high molecular weight polyethylene, homopolypolypoly, random copolymer polypropylene, and block copolymer.
- Polypropylene resins such as polypropylene, impact copolymer polypropylene, high impact copolymer polypropylene, maleic anhydride-modified polypropylene, polybutene-1, cycloolefin polymer, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, Examples thereof include ⁇ -olefin polymers such as poly-4-methyl-1-pentene, ethylene-methylmethacrylate copolymers, and ⁇ -olefin copolymers such as ethylene-vinyl acetate copolymers.
- One of these polyolefin resins may be used alone, or two or more thereof may be used in combination. Further, the polyolefin-based resin may be alloyed.
- polypropylene-based resin is particularly preferable as the polyolefin-based resin contained in the masterbatch.
- Molecular weight, 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 monomer, catalyst used for polymerization The type (for example, a Cheegler catalyst, a metallocene catalyst, etc.) and the like are not particularly limited and may be appropriately selected.
- the content of the polyolefin resin in the masterbatch may be, for example, 90% by mass or less, preferably 80% by mass or less, 60. It is more preferably mass% or less.
- the content of the polyolefin resin in the masterbatch may be, for example, 20% by mass or more.
- the additive composition according to this embodiment is particularly preferably used as an additive composition for a polyolefin resin.
- the resin composition according to the present embodiment includes a polyolefin-based resin and the above-mentioned additive composition.
- a molded product having excellent mechanical properties and excellent color tone can be obtained.
- Examples of the polyolefin-based resin contained in the resin composition according to the present embodiment include the same ones contained in the above-mentioned masterbatch. Among these, polypropylene-based resin is preferable. In this case, the molded product will have excellent heat resistance in addition to excellent mechanical properties and color tone.
- the content of the additive composition with respect to 100 parts by mass of the polyolefin-based resin may be, for example, 0.001 to 10 parts by mass.
- the content of the additive composition with respect to 100 parts by mass of the polyolefin resin is 0.001 part by mass or more, a molded product having more excellent mechanical properties can be obtained.
- the content of the additive composition with respect to 100 parts by mass of the polyolefin resin is 10 parts by mass or less, the aggregation of the components contained in the additive composition in the polyolefin resin can be sufficiently suppressed.
- the content of the additive composition with respect to 100 parts by mass of the polyolefin resin is 10 parts by mass or less, the generation of fish eyes in the molded product can be sufficiently suppressed.
- the content of the additive composition with respect to 100 parts by mass of the polyolefin resin is preferably 0.01 part by mass or more, preferably 0.02 part by mass or more. It is more preferable to have.
- the content of the additive composition with respect to 100 parts by mass of the polyolefin resin is 5 parts by mass or less. It is preferably 3 parts by mass or less, more preferably 1 part by mass or less, further preferably 0.5 part by mass or less, and particularly preferably 0.2 part by mass or less. ..
- the content of talc contained in the resin composition according to the present embodiment may be, for example, 0.0001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin-based resin, and may be 100 parts by mass of the polyolefin-based resin. On the other hand, it is preferably 0.0001 to less than 1 part by mass. In this case, it is possible to obtain a molded product having excellent scratch resistance and a small specific gravity as compared with the case where the talc content is out of the above range.
- the content of talc contained in the resin composition is more preferably 0.8 parts by mass or less, still more preferably 0.5 parts by mass or less, and 0.1 parts by mass with respect to 100 parts by mass of the polyolefin resin. It is even more preferably less than or equal to parts by mass, and even more preferably less than or equal to 0.08 parts by mass.
- the resin composition according to the present embodiment includes a polyolefin resin, (A) an aromatic phosphate ester sodium salt represented by the above general formula (1), (B) a fatty acid sodium salt, and (C).
- the mass ratio (B) / (A) of the content of the component (B) to the content of the component (A) including talc is 0.1 or more and 3 or less, and the components (A) and (B) And the mass ratio (C) / [(A) + (B) + (C)] of the content of the component (C) to the total content of the component (C) is 0.2 or more and 0.8 or less. It may be a thing.
- a molded product having excellent mechanical properties and excellent color tone can be obtained.
- the content of the (A) aromatic phosphate ester sodium salt with respect to 100 parts by mass of the polyolefin-based resin may be, for example, 0.001 to 10 parts by mass.
- the content of the (A) aromatic phosphate ester sodium salt with respect to 100 parts by mass of the polyolefin resin is preferably 0.01 part by mass or more. It is more preferably 0.02 parts by mass or more.
- the content of the (A) aromatic phosphate ester sodium salt with respect to 100 parts by mass of the polyolefin resin is 5. It is preferably less than or equal to parts by mass, more preferably less than 3 parts by mass, further preferably less than 1 part by mass, further preferably less than 0.5 parts by mass, and even more preferably 0.2 parts by mass. The following is particularly preferable.
- the value of (B) / (A) is preferably 0.14 or more, more preferably 0.33 or more, and more preferably 0.6 or more. Is even more preferable. Further, in the resin composition according to the present embodiment, the value of (B) / (A) is preferably 2 or less, preferably 1 or less, from the viewpoint of obtaining a molded product having more excellent mechanical properties. Is more preferable.
- the value of (C) / [(A) + (B) + (C)] is preferably 0.3 or more, preferably 0.5 or more. Is more preferable. Furthermore, from the viewpoint of obtaining a molded product having more excellent mechanical properties, the value of (C) / [(A) + (B) + (C)] is preferably 0.7 or less.
- the content of the (B) fatty acid sodium salt with respect to 100 parts by mass of the polyolefin resin may be, for example, 0.001 to 10 parts by mass, and the content of (C) talc with respect to 100 parts by mass of the polyolefin resin may be. For example, it may be 0.0001 to 10 parts by mass.
- the resin composition according to the present embodiment further contains (D) hydrotalcites. In this case, it is possible to obtain a molded product having further excellent mechanical properties and excellent heat resistance.
- the mass ratio (D) / [(A) + (B) + (C)] of the amount (part by mass) may be, for example, 0.01 or more and 20 or less.
- the value of (D) / [(A) + (B) + (C)] is preferably 0.05 or more, preferably 0.1 or more. Is more preferable, 0.3 or more is further preferable, and 0.5 or more is even more preferable.
- the value of (D) / [(A) + (B) + (C)] is preferably 10 or less, and 5 It is more preferably 3 or less, further preferably 2 or less, and particularly preferably 1.5 or less.
- the content of (D) hydrotalcites with respect to 100 parts by mass of the polyolefin resin may be, for example, 0.001 to 10 parts by mass.
- the resin composition according to the present embodiment further comprises a nuclear agent other than the aromatic phosphate ester sodium salt, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and other antioxidants, if necessary.
- a nuclear agent other than the aromatic phosphate ester sodium salt e.g., a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and other antioxidants, if necessary.
- additives such as agents, hindered amine compounds, ultraviolet absorbers, fatty acid metal salts other than fatty acid sodium salts, flame retardants, flame retardant aids, lubricants, fillers other than talc, antistatic agents, fluorescent whitening agents, pigments and dyes. It may contain an agent. Examples of these various additives include the same as those exemplified as the additives that may be contained in the above-mentioned additive composition.
- the method for producing a resin composition according to the present embodiment includes a step of blending the above-mentioned additive composition with a polyolefin-based resin.
- the above-mentioned additive composition has excellent powder fluidity, it is excellent in transportability, workability and measurableness. Therefore, according to the method for producing a resin composition according to the present embodiment, a molded product having excellent mechanical properties and color tone can be efficiently produced with stable quality.
- the additive composition is blended with the polyolefin resin.
- the blending method is not particularly limited, and for example, a polyolefin resin, an additive composition, and if necessary, various additives described above are added, and then a Henschel mixer, a mill roll, a Banbury mixer, a super mixer, or the like is used. Examples thereof include a method of mixing using a mixing device.
- at least one component of the components constituting the additive composition and the above-mentioned various additives is added before or during the polymerization of the polyolefin resin monomer or oligomer, and the remaining components are added to the obtained polymer. May be added.
- the method for producing the resin composition may be a method including a melt-kneading step in which the mixture obtained by the above method is further melt-kneaded using a melt-kneading device such as a single-screw extruder or a twin-screw extruder. ..
- the temperature of the melt-kneading may be, for example, 220 to 280 ° C.
- the method for producing the resin composition may be a method including a granulation step of granulating the kneaded product obtained by melt-kneading.
- the granulation method is not particularly limited, and examples thereof include a method using a granulation device such as a granulator.
- the shape of the resin composition obtained by granulation is not particularly limited, and may be, for example, pellet-shaped.
- the above-mentioned component (A), (B) and (C) component, and if necessary, the above-mentioned component (D) and various additives are blended with the polyolefin-based resin. It may be a method including a step.
- the molded product according to the present embodiment is obtained by molding the above-mentioned resin composition.
- the molded product according to the present embodiment has excellent mechanical properties and excellent color tone.
- Examples of the molded product according to this embodiment include an injection molded product, a fiber, a flat yarn, a biaxially stretched film, a uniaxially stretched film, a non-stretched film, a sheet, a thermoforming molded product, an extrusion blow molded product, and an injection blow molded product. , Injection stretch blow molded products, deformed extrusion molded products, rotary molded products and the like, and more specifically, automobile exterior parts, automobile interior parts, housings, containers, pipes and the like.
- Examples of automobile exterior parts include bumpers, radiator grilles, front grilles, front panels, fenders, pillars, pillar covers, door mirror stay covers, glass run channels, door mirror housings, lamp housings, wheel covers, spoilers, air spoilers, weather strips, etc. Examples include window moldings, belt moldings, sunroofs, front end modules, door modules, back door modules, and outer panels. Examples of automobile interior parts include instrument panels, door trim panels, pillar trims, door trims, pillar garnishes, package trays, rear trays, console boxes, air conditioning ducts, and the like.
- Examples of the housing include a housing for home appliances, a housing for arcade game machines, a housing for home game machines, a housing for portable game machines, a housing for cameras, a housing for mobile phones, and a housing for smartphones. , Electronic device housings, secondary battery housings, safety breaker housings, and the like.
- Examples of the container include tableware, delicatessen containers, frozen food containers, microwave heat-resistant containers, frozen storage containers, retort containers, cups, chilled confectionery cups and other food containers, beverage bottles, infusion bottles, medical hollow bottles and the like. Examples thereof include containers for physicochemical tests such as containers, beakers and measuring cylinders, chemical containers, medical containers, detergent containers, cosmetic containers, perfume containers, toner containers and the like.
- piping examples include water pipes, gas pipes, infrastructure pipes, factory utility pipes, vehicle fuel delivery pipes, vehicle air intake pipes, and other pipes, cosmetic / perfume spray tubes, medical tubes, and infusion tubes.
- Various tubes such as water hoses, various hoses such as air duct hoses for vehicles, and the like can be mentioned.
- the molding method of the molded product according to the present embodiment is not particularly limited, and for example, an injection molding method, an extrusion molding method, a blow molding method, a rotary molding method, a vacuum molding method, an inflation molding method, and a calendar molding method. , Slash forming method, dip forming method, thermoforming forming method and the like.
- Example 17 to 24 (A) Sodium 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate as aromatic phosphate ester sodium salt, (B) Sodium stearate as fatty acid sodium, (C) Average particle size as talc 4.75 ⁇ m talc (Hayashi Kasei Co., Ltd. product name: Micron White # 5000S) and (D) Hydrotalsites with an average particle size of 0.45 ⁇ m (Kyowa Chemical Industry Co., Ltd.
- ⁇ Preparation of resin composition> As a polyolefin resin, 100 parts by mass of homopolypropylene having a melt flow rate of 8 g / 10 min at a measurement temperature of 230 ° C. and a load of 2.16 kg measured in accordance with ISO standard 1133, Examples 1 to 24 and Comparative Examples 1 to 6 0.1 part by mass of the additive composition of the above, tetrakis [methylene-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane as a phenolic antioxidant, 0.05.
- the pellets of the obtained resin composition were injection-molded using an injection molding machine (EC100-2A manufactured by Toshiba Machine Co., Ltd.) under the conditions of an injection temperature of 200 ° C. and a mold temperature of 50 ° C., and the dimensions were 80 mm ⁇ 10 mm ⁇ .
- a 4 mm bending test test piece was prepared. After allowing this test piece to stand in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% for 48 hours, the test piece is taken out from the constant temperature and humidity chamber, and the flexural modulus FM (MPa) of the test piece is set to ISO-178. Measured in compliance. The obtained results are shown in Tables 1 to 4.
- the additive composition of the present invention has excellent powder fluidity and can impart excellent mechanical properties and excellent color tone to the molded product.
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Abstract
Description
(一般式(1)中、R1~R5はそれぞれ独立に水素原子または炭素原子数1~6のアルキル基を表す。)
(一般式(1)中、R1~R5はそれぞれ独立に水素原子または炭素原子数1~6のアルキル基を表す。)
まず、添加剤組成物について説明する。
本実施形態に係る添加剤組成物は、(A)下記一般式(1)で表される芳香族リン酸エステルナトリウム塩と、(B)脂肪酸ナトリウム塩と、(C)タルクとを含む。
ここで、一般式(1)中、R1~R5はそれぞれ独立に水素原子または炭素原子数1~6のアルキル基を表す。
本実施形態に係る樹脂組成物は、ポリオレフィン系樹脂と、上述した添加剤組成物とを含む。
本実施形態に係る樹脂組成物の製造方法は、ポリオレフィン系樹脂に対し、上述した添加剤組成物を配合する工程を含む。
まず、上述したポリオレフィン系樹脂と、上述した添加剤組成物とを準備する。
次に、添加剤組成物をポリオレフィン系樹脂に配合する。配合の方法としては特に限定されるものではなく、例えば、ポリオレフィン系樹脂、添加剤組成物および必要に応じて上述の各種添加剤を添加した後、ヘンシェルミキサー、ミルロール、バンバリーミキサー、スーパーミキサー等の混合装置を用いて混合する方法などが挙げられる。ここで、添加剤組成物を構成する成分および上述の各種添加剤のうち少なくとも一つの成分が、ポリオレフィン系樹脂モノマーまたはオリゴマーの重合前または重合中に添加され、得られた重合体に残りの成分が添加されてもよい。
本実施形態に係る成形品は、上述した樹脂組成物を成形して得られるものである。本実施形態に係る成形品は、優れた力学的特性および優れた色調を備えるものとなる。
(実施例1~16および比較例1~6)
(A)芳香族リン酸エステルナトリウム塩としてナトリウム 2,2’-メチレンビス(4,6-ジ-tert-ブチルフェニル)ホスフェート、(B)脂肪酸ナトリウムとしてステアリン酸ナトリウム、および、(C)タルクとして平均粒子径4.75μmのタルク(林化成社製 商品名:ミクロンホワイト#5000S)を、表1~表3に示す割合で配合し、フードブレンダー(象印マホービン社製 BM-RE08)を用いて1分間混合することにより、実施例1~16および比較例1~6の添加剤組成物を得た。なお、表1~表3において、配合量の単位は質量部である。
(A)芳香族リン酸エステルナトリウム塩としてナトリウム 2,2’-メチレンビス(4,6-ジ-tert-ブチルフェニル)ホスフェート、(B)脂肪酸ナトリウムとしてステアリン酸ナトリウム、(C)タルクとして平均粒子径4.75μmのタルク(林化成社製 商品名:ミクロンホワイト#5000S)、および、(D)ハイドロタルサイト類として平均粒子径0.45μmのハイドロタルサイト(協和化学工業社製 商品名:DHT-4A)を、表4に示す割合で配合し、フードブレンダー(象印マホービン社製 BM-RE08)を用いて1分間混合することにより、実施例17~24の添加剤組成物を得た。なお、表4において、配合量の単位は質量部である。
実施例1~24および比較例1~6の添加剤組成物を試料とし、内容積500mLの円筒型容器を備える流動表面角測定器(筒井理化学器械社製 FSA-100S)に、円筒型容器の半分まで試料を満たした後、2.0rpmの回転速度で円筒型容器を回転させた。円筒型容器が回転すると、円筒型容器内の試料は回転する円筒型容器に沿って持ち上げられ、高い位置から試料が崩れ落ちる。崩れ落ちた試料で形成される斜面が一定の状態になったとき、試料の斜面と水平面とがなす角度を測定し、試料の回転安息角とした。こうして測定された回転安息角の値を、添加剤組成物の粉体流動性の指標とした。得られた結果を表1~表4に示す。
実施例3および実施例17~24の添加剤組成物を試料とし、試料1gを直径15mmの15mLガラス試験管に仕込み、ブロックバスを用いて、空気雰囲気下、230℃で30分加熱した。加熱前後の試料の黄色度(Y.I.)を、分光測色計(日本電色工業社製 SD3000)により測定し、下記式により算出されるΔY.I.の値を、添加剤組成物の耐熱性の指標とした。得られた結果を表4に示す。
ΔY.I.=(加熱後のY.I.)-(加熱前のY.I.)
ポリオレフィン系樹脂として、ISO規格1133に準拠して測定した測定温度230℃、荷重2.16kgでのメルトフローレート8g/10minのホモポリプロピレンを100質量部、実施例1~24および比較例1~6の添加剤組成物を0.1質量部、フェノール系酸化防止剤としてテトラキス[メチレン-3-(3’,5’-ジ-tert-ブチル-4’-ヒドロキシフェニル)プロピオネート]メタンを0.05質量部、リン系酸化防止剤としてトリス(2,4-ジ-tert-ブチルフェニル)ホスファイトを0.1質量部、脂肪酸ナトリウム塩以外の脂肪酸金属塩としてステアリン酸カルシウムを0.05質量部配合し、ヘンシェルミキサーを用いて、1000rpmの回転速度で1min混合後、二軸押出機(日本製鋼所社製 TEX-28V)を用いて、押出温度230℃、スクリュー回転速度150rpm、フィード速度7.5kg/hの条件で溶融混練し、樹脂組成物のペレットを得た。
得られた樹脂組成物のペレットを、射出成形機(東芝機械社製 EC100-2A)を用いて、射出温度200℃、金型温度50℃の条件で射出成形することにより、寸法80mm×10mm×4mmの曲げ試験用試験片を作製した。この試験片を温度23℃、湿度50%の恒温恒湿器内に48時間静置した後、恒温恒湿器から試験片を取り出し、試験片の曲げ弾性率FM(MPa)をISO-178に準拠して測定した。得られた結果を表1~表4に示す。
得られた樹脂組成物のペレットを、射出成形機(東芝機械社製 EC100-2A)を用いて、射出温度200℃、金型温度50℃の条件で射出成形することにより、寸法60mm×60mm×2mmの正方形シートを作製し、試験片とした。この試験片を温度23℃、湿度50%の恒温恒湿器内に48時間静置した後、恒温恒湿器から試験片を取り出し、試験片の黄色度(Y.I.)を分光測色計(X-rite社製 Color-Eye 7000A)により測定した。得られた結果を表1~表4に示す。
Claims (10)
- R1~R4がt-ブチル基であって、R5が水素原子である請求項1記載の添加剤組成物。
- 前記(B)脂肪酸ナトリウム塩が、炭素原子数12~30の脂肪酸ナトリウム塩である請求項1または2記載の添加剤組成物。
- さらに、(D)ハイドロタルサイト類を含み、前記(A)成分、前記(B)成分および前記(C)成分の含有量の合計に対する前記(D)成分の含有量の質量比(D)/[(A)+(B)+(C)]が、0.01以上20以下である請求項1~3のうちいずれか一項記載の添加剤組成物。
- ポリオレフィン系樹脂と、
請求項1~4のうちいずれか一項記載の添加剤組成物と、
を含む樹脂組成物。 - さらに、(D)ハイドロタルサイト類を含み、前記(A)成分、前記(B)成分および前記(C)成分の含有量の合計に対する前記(D)成分の含有量の質量比(D)/[(A)+(B)+(C)]が、0.01以上20以下である請求項6記載の樹脂組成物。
- 前記ポリオレフィン系樹脂がポリプロピレン系樹脂である請求項5~7のうちいずれか一項記載の樹脂組成物。
- ポリオレフィン系樹脂に対し、請求項1~4のうちいずれか一項記載の添加剤組成物を配合する工程を含む樹脂組成物の製造方法。
- 請求項5~8のうちいずれか一項記載の樹脂組成物が成形されてなる成形品。
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- 2021-07-29 US US18/018,649 patent/US20240043655A1/en active Pending
- 2021-07-29 EP EP21850554.3A patent/EP4190850A4/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| JP7802002B2 (ja) | 2026-01-19 |
| US20240043655A1 (en) | 2024-02-08 |
| EP4190850A4 (en) | 2024-09-04 |
| EP4190850A1 (en) | 2023-06-07 |
| JPWO2022025187A1 (ja) | 2022-02-03 |
| CN116323779A (zh) | 2023-06-23 |
| TW202216880A (zh) | 2022-05-01 |
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