Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/04—Monomers containing three or four carbon atoms
  • C08F10/06—Propene
• • 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
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
• • 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
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
• • 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
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
  • B29C2945/76—Measuring, controlling or regulating
  • B29C2945/76494—Controlled parameter
  • B29C2945/76531—Temperature
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
  • B29K2023/10—Polymers of propylene

Definitions

• the present invention relates to a polyolefin-based resin composition, a molded product using the polyolefin-based resin composition, and a method for producing the polyolefin-based resin composition.
• Patent Document 1 describes a polyolefin-based resin composition containing a polyolefin-based resin, a hindered amine compound, and a phenol-based antioxidant.
• the present inventors have found that in a polyolefin-based resin composition containing a polyolefin-based resin and a light stabilizer, the weather resistance can be improved by appropriately controlling the degree of color change in the weather resistance test.
• a polyolefin-based resin composition containing (A) a polyolefin-based resin and (B) a light stabilizer, wherein the (B) light stabilizer is a (B-1) hindered amine compound and The (B-2) phenol-based antioxidant is contained, and the (B-1) hindered amine compound contains one or more compounds represented by the following general formula (1), and the (B-2) phenol.
• the system antioxidant contains one or more compounds represented by the following general formula (2), and L * (0h) and L * (2040h) in the polyolefin resin composition obtained according to the following procedure.
• R 1 represents a hydrogen atom or a methyl group
• R 2 to R 5 independently represent an alkyl group having 1 to 6 carbon atoms
• R 6 represents 7 to 6 carbon atoms.
• R 7 and R 8 each independently represent an alkyl group having 1 to 6 carbon atoms
• R 9 represents a fatty acid residue having 7 to 29 carbon atoms.
• the calculation method of L * (0h) and L * (2040h) is as follows. (1) The polyolefin-based resin composition is injection-molded under molding conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C. to form a rectangular sheet-shaped test piece having dimensions of 6.0 cm ⁇ 2.7 cm ⁇ 2 mm. (2) The test piece is placed on a white calibration plate, and the reflected color is measured by the SCI method (including specular reflected light) under the conditions of a light source D65 and a viewing angle of 10 ° using a colorimeter. The L * value is calculated from the tristimulus values X, Y, and Z, and this value is defined as L * (0h).
• the weather resistance for a predetermined time is used as an index of the degree of color change in the weather resistance test.
• the color difference ⁇ E after the test as an index, it becomes possible to stably evaluate the weather resistance characteristics, and by setting such an index within a predetermined range, the weather resistance of the polyolefin resin composition can be improved.
• a polyolefin-based resin composition containing (A) a polyolefin-based resin and (B) a light stabilizer, wherein the (B) light stabilizer is a (B-1) hindered amine compound and The (B-2) phenol-based antioxidant is contained, and the (B-1) hindered amine compound contains one or more compounds represented by the general formula (1), and the (B-2) phenol.
• the system antioxidant contains one or more compounds represented by the above general formula (2), and the value of ⁇ E in the polyolefin resin composition obtained according to the following procedure is 0.05 or more.
• a polyolefin-based resin composition having a value of 0 or less is provided.
• the calculation method of ⁇ E is as follows. (1) The polyolefin-based resin composition is injection-molded under molding conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C. to form a rectangular sheet-shaped test piece having dimensions of 6.0 cm ⁇ 2.7 cm ⁇ 2 mm. (2) The test piece is placed on a white calibration plate, and the reflected color is measured by the SCI method (including specular reflected light) under the conditions of a light source D65 and a viewing angle of 10 ° using a colorimeter.
• SCI method including specular reflected light
• the L * value, a * value, and b * value are calculated from the three stimulus values X, Y, and Z, and these values are L * (0h), a * (0h), and b * (0h), respectively.
• L * (0h) and L * (2040h) in the polyolefin-based resin composition which are obtained according to the above procedure, are ⁇ 0.05.
• ⁇ [L * (2040h) -L * (0h)] / L * (0h) ⁇ 0.1 is satisfied by blending (A) a polyolefin resin and (B) a light stabilizer to form a polyolefin resin composition.
• the (B) photostabilizer comprises (B-1) a hindered amine compound and (B-2) a phenolic antioxidant, and the (B-1) hindered amine compound comprises the above general formula. It contains one or more compounds represented by (1), and the (B-2) phenolic antioxidant contains one or more compounds represented by the general formula (2).
• a method for producing a polyolefin-based resin composition is provided.
• the value of ⁇ E in the polyolefin-based resin composition obtained according to the above procedure is 0.05 or more and 2.0 or less
• A includes a step of blending a polyolefin-based resin and (B) a light stabilizer to obtain a polyolefin-based resin composition, wherein the (B) light stabilizer is (B-1) a hindered amine compound and (B-2).
• the (B-1) hindered amine compound contains one or more compounds represented by the general formula (1)
• the (B-2) phenolic antioxidant contains a phenolic antioxidant.
• a polyolefin-based resin composition having excellent weather resistance a molded product using the polyolefin-based resin composition, and a method for producing the polyolefin-based resin composition are provided.
• the polyolefin-based resin composition of this embodiment is outlined.
• the polyolefin-based resin composition of the present embodiment contains (A) a polyolefin-based resin and (B) a photostabilizer, and (B) the photostabilizer is (B-1) a hindered amine compound and (B-2).
• the (B-1) hindered amine compound contains one or more compounds represented by the following general formula (1)
• the (B-2) phenolic antioxidant contains the following. It contains one kind or two or more kinds of compounds represented by the general formula (2).
• R 1 represents a hydrogen atom or a methyl group
• R 2 to R 5 independently represent an alkyl group having 1 to 6 carbon atoms
• R 6 represents 7 to 6 carbon atoms. Represents 29 fatty acid residues.
• R 7 and R 8 each independently represent an alkyl group having 1 to 6 carbon atoms, and R 9 represents a fatty acid residue having 7 to 29 carbon atoms.
• L * (0h) and L * (2040h) in the polyolefin-based resin composition which are obtained according to the following procedure, are -0.05 ⁇ [L * (2040h) -L. * (0h)] / L * (0h) ⁇ 0.1 is configured to be satisfied.
• the lower limit of [L * (2040h) ⁇ L * (0h)] / L * (0h) is ⁇ 0.05 or higher, preferably ⁇ 0.02 or higher, and more preferably ⁇ 0.01 or higher.
• the upper limit of [L * (2040h) -L * (0h)] / L * (0h) is less than 0.1, preferably 0.09 or less, more preferably 0.07 or less, still more preferably 0. It is 06 or less. Within such a range, the weather resistance of the polyolefin resin composition can be improved.
• the lower limit of ⁇ E is 0.05 or more, preferably 0.08 or more, more preferably 0.1 or more, still more preferably 0.2 or more.
• the upper limit of ⁇ E is 2.0 or less, preferably 1.9 or less, more preferably 1.7 or less, and further preferably 1.5 or less. Within such a range, the weather resistance of the polyolefin resin composition can be improved.
• the L * value is calculated as the a * value and the b * value, and these values are L * (0h), a * (0h), and b * (0h), respectively. .. (3) Weather resistance test of the above test piece using a weather resistance tester under the conditions of irradiation intensity 0.55 W / m 2 at a wavelength of 340 nm, continuous irradiation, black panel temperature 89 ° C ⁇ 3 ° C, and no rainfall. Is carried out for 2040 hours.
• L * (0h) is, for example, 50 or less, preferably 40 or less, and more preferably 30 or less. This makes it possible to provide a polyolefin-based resin composition having further excellent long-term weather resistance.
• the present embodiment for example, by appropriately selecting the type and blending amount of each component contained in the polyolefin-based resin composition, the method for preparing the polyolefin-based resin composition, and the like, the above-mentioned brightness increase ratio [L * (2040h)). -L * (0h)] / L * (0h), color difference ⁇ E, and L * (0h) can be controlled.
• a predetermined (B-1) hindered amine compound and a predetermined (B-2) phenol-based antioxidant may be used in combination, and (A) photostability with respect to 100 parts by mass of (A) polyolefin-based resin.
• the polyolefin-based resin composition contains (A) one or more types of polyolefin-based resin.
• Examples of the (A) polyolefin-based resin include polyethylene-based resins such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, crosslinked polyethylene, and ultrahigh-molecular-weight polyethylene, homopolypolypoly, random copolymer polypropylene, and block copolymer polypropylene.
• Polypropylene resins such as 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, poly- Examples thereof include ⁇ -olefin polymers such as 4-methyl-1-pentene, ethylene-methylmethacrylate copolymers, and ⁇ -olefin copolymers such as ethylene-vinyl acetate copolymers.
• the type for example, Ziegler catalyst, metallocene catalyst, etc.
• the type are not particularly limited and may be appropriately selected.
• the polyolefin-based resin may contain one or more types of polyolefin-based thermoplastic elastomers.
• the molded product obtained by molding the polyolefin-based resin composition has excellent impact resistance.
• Specific examples of the polyolefin-based thermoplastic elastomer include, for example, an ethylene-propylene copolymer elastomer, an ethylene-propylene-diene copolymer elastomer, an ethylene-1-butene copolymer elastomer, and an ethylene-1-hexene copolymer elastomer.
• the (A) polyolefin-based resin contains a polyolefin-based thermoplastic elastomer
• the total content thereof is, for example, 50% by mass or less, preferably 30% by weight or less, more preferably of the entire (A) polyolefin-based resin. Is 20% by weight or less.
• the polyolefin-based resin may contain a polypropylene-based resin.
• the heat resistance of the polyolefin-based resin composition becomes more excellent.
• the polypropylene-based resins block copolymer polypropylene, impact copolymer polypropylene, and high impact copolymer polypropylene may be used, and in particular, impact copolymer polypropylene may be used.
• polystyrene resin examples include polyamide resin, polyester resin, polyacetal resin, polylactic acid, polyphenylene sulfide, polycarbonate resin, styrene resin, acrylic resin, urethane resin, halogen-containing resin, petroleum resin, and kumaron resin.
• examples thereof include polyvinyl alcohol, polyvinyl acetate, polyphenylene oxide and the like.
• the blending amount thereof is, for example, 50 parts by mass or less, preferably 30 parts by weight or less, more preferably 20 parts by weight, in total with respect to 100 parts by mass of the polyolefin-based resin (A). It is less than a part.
• the polyolefin-based resin composition may contain an elastomer other than the above-mentioned polyolefin-based thermoplastic elastomer.
• the molded product obtained by molding the polyolefin-based resin composition has excellent impact resistance.
• the elastomer other than the above-mentioned polyolefin-based thermoplastic elastomer include isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, synthetic rubber such as silicone rubber, polystyrene-based thermoplastic elastomer, and polychloride.
• thermoplastic elastomers other than the above-mentioned polyolefin-based thermoplastic elastomers such as vinyl-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyamide-based thermoplastic elastomers.
• thermoplastic elastomers other than the above-mentioned polyolefin-based thermoplastic elastomers, from the viewpoint of improving the processability of the polyolefin-based resin composition and further reducing the weight of the molded product obtained by molding the polyolefin-based resin composition.
• Thermoplastic elastomers are preferred.
• the blending amount thereof is, for example, 50 parts by mass or less, preferably 30 parts by mass or less, in total with respect to 100 parts by mass of the (A) polyolefin-based resin. More preferably, it is 20 parts by mass or less.
• the lower limit of the content of the (A) polyolefin resin in the polyolefin resin composition is, for example, 10% by mass or more, preferably 50% by mass or more, more preferably 70% by mass in 100% by mass of the polyolefin resin composition. That is all.
• the upper limit of the content of the (A) polyolefin resin in the polyolefin-based resin composition is not particularly limited, and may be, for example, 99.99% by mass.
• the polyolefin-based resin composition contains (B) a light stabilizer.
• the lower limit of the content of the (B) light stabilizer with respect to 100 parts by mass of the (A) polyolefin resin may be, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more. , More preferably 0.1 parts by mass or more.
• the upper limit of the content of the (B) light stabilizer may be, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 1 part by mass or less.
• the (B) light stabilizer contains at least a (B-1) hindered amine compound and a (B-2) phenolic antioxidant, and may further contain a (B-3) benzoate compound, if necessary. ..
• the light stabilizer contains (B-1) a hindered amine compound.
• the hindered amine compound contains one or more compounds represented by the following general formula (1).
• R 1 represents a hydrogen atom or a methyl group
• R 2 to R 5 independently represent an alkyl group having 1 to 6 carbon atoms
• R 6 represents 7 to 6 carbon atoms. Represents 29 fatty acid residues.
• Alkyl groups having 1 to 6 carbon atoms include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, sec-pentyl group, tert. -Pentyl group and hexyl group can be mentioned.
• a methyl group, a tert-butyl group and a tert-pentyl group are preferable, and a methyl group is particularly preferable.
• the fatty acid residue having 7 to 29 carbon atoms is, for example, an alkyl group having 7 to 29 carbon atoms or an alkenyl group having 7 to 29 carbon atoms, preferably an alkyl group having 9 to 25 carbon atoms. It is preferably an alkyl group having 11 to 21 carbon atoms.
• alkyl groups for example, a decyl group, an undecylic group, a dodecyl group, a tridecylic group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecylic group and the like may be used.
• R 1 is preferably a methyl group.
• the polyolefin-based resin composition has further excellent weather resistance and further excellent NOx resistance.
• the compound represented by the general formula (1) is obtained, for example, by reacting piperidinols with a fatty acid.
• a fatty acid for example, a saturated fatty acid or an unsaturated fatty acid may be used, and any one or more of a linear fatty acid and a branched fatty acid may be used.
• a method for purifying a fatty acid a method using distillation, recrystallization, a filter medium, an adsorbent, or the like can be appropriately used.
• the (B-1) hindered amine compound is, for example, the following compound No. A1 to No. It may contain one or more selected from the group consisting of A6.
• the light stabilizer contains (B-2) a phenolic antioxidant.
• Phenolic antioxidant contains one or more compounds represented by the following general formula (2).
• R 7 and R 8 each independently represent an alkyl group having 1 to 6 carbon atoms, and R 9 represents a fatty acid residue having 7 to 29 carbon atoms.
• alkyl group having 1 to 6 carbon atoms in the general formula (2) those exemplified as the alkyl group having 1 to 6 carbon atoms in the general formula (1) can be used.
• alkyl group having 1 to 6 carbon atoms in the general formula (2) a methyl group, a tert-butyl group or a tert-pentyl group is preferable, and a tert-butyl group is particularly preferable.
• fatty acid residue having 7 to 29 carbon atoms in the general formula (2) those exemplified as the fatty acid residue having 7 to 29 carbon atoms in the general formula (1) can be used.
• the fatty acid residue having 7 to 29 carbon atoms an alkyl group having 8 to 22 carbon atoms is preferable, and an alkyl group having 14 to 20 carbon atoms is more preferable.
• the content of the (B-1) hindered amine compound and the (B-2) phenolic antioxidant in the (B) light stabilizer is preferably 50% by mass or more, for example, in 100% by mass of the (B) light stabilizer. Is 70% by mass or more, more preferably 90% by mass or more.
• the blending ratio ((B-2) / (B-1)) of the (B-2) phenol-based antioxidant to the (B-1) hindered amine compound is, for example, 0 in terms of mass. It is 1.1 or more and 4.0 or less, preferably 0.15 or more and 2.5 or less, and more preferably 0.2 or more and 1.5 or less. By keeping it within such a range, the weather resistance can be further improved.
• the (B) light stabilizer may contain a (B-3) benzoate compound.
• the (B-3) benzoate compound may contain one or more compounds represented by the following general formula (3).
• R 10 and R 11 each independently represent an alkyl group having 1 to 6 carbon atoms, and R 12 represents a fatty acid residue having 7 to 29 carbon atoms.
• alkyl group having 1 to 6 carbon atoms in the general formula (3) those exemplified as the alkyl group having 1 to 6 carbon atoms in the general formula (1) can be used.
• alkyl group having 1 to 6 carbon atoms in the general formula (3) a methyl group, a tert-butyl group or a tert-pentyl group is preferable, and a tert-butyl group is particularly preferable.
• fatty acid residue having 7 to 29 carbon atoms in the general formula (3) those exemplified as the fatty acid residue having 7 to 29 carbon atoms in the general formula (1) can be used.
• the fatty acid residue having 7 to 29 carbon atoms an alkyl group having 8 to 22 carbon atoms is preferable, and an alkyl group having 10 to 20 carbon atoms is more preferable.
• the (B-3) benzoate compound is, for example, the following compound No. C1-No. It may contain one or more selected from the group consisting of C5.
• the content of the (B-3) benzoate compound is, for example, 0.01 parts by mass or more and 5 parts by mass or less, preferably 0.02 parts by mass or more and 0.5 parts by mass with respect to 100 parts by mass of the (A) polyolefin resin. It is less than a part.
• a resin additive usually generally used can be blended as long as the effect of the present invention is not impaired.
• the resin additive include phosphorus-based antioxidants, thioether-based antioxidants, ultraviolet absorbers, nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, metal soaps, hydrotalcites, and antistatic agents.
• examples include inhibitors, pigments, dyes and the like.
• Examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite and tris [2-tertiary butyl-4- (3-third butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl].
• Phosphite Tridecylphosphite, Octyldiphenylphosphite, Di (decyl) monophenylphosphite, Di (tridecyl) pentaerythritol diphosphite, Di (nonylphenyl) pentaerythritol diphosphite, Bis (2,4-di) Tertiary Butylphenyl) Pentaerythritol diphosphite, bis (2,6-ditriary butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritrith butylphenyl) pentaerythritoldi Phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropyridene diphenol diphosphite, tetra (tride
• thioether-based antioxidant examples include tetrakis [methylene-3- (laurylthio) propionate] methane and bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butyl.
• Phenyl) Sulfide Ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipro Pionate, lauryl / stearylthiodipropionate, 4,4'-thiobis (6-tert-butyl-m-cresol), distealyl-disulfide and the like can be mentioned.
• ultraviolet absorber examples include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, salicylic acid ester-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. These may be used alone or in combination of two or more.
• benzophenone-based ultraviolet absorbers are used.
• benzotriazole-based ultraviolet absorbers are used, and for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole are used.
• 2- (2-Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole
• 2- (2-Hydroxy-3-dodecyl-5-methylphenyl) benzotriazole 2- (2-hydroxy-3-tert-butyl-5-alkoxycarbonylethylphenyl) triazole, 2- (2-hydroxy-3) , 5-Dicumylphenyl) Benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl
• triazine-based ultraviolet absorbers examples thereof include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-triazine.
• 2,4,6,-Tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,6) 4-Dimethylphenyl) -1,3,5-triazine, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- (octyloxy) Examples thereof include phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- (hexyloxy) phenol and the like.
• Known salicylic acid ester-based ultraviolet absorbers are used, and examples thereof include ethylene glycol salicylate, phenyl salicylate, octyl salicylate, benzyl salicylic acid, p-tert-butylphenyl salicylate, and homomentyl salicylate.
• cyanoacrylate-based ultraviolet absorbers are used, and for example, ethyl- ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl). Examples include acrylate.
• nucleating agent examples include carboxylic acids such as sodium benzoate, 4-tert-butyl benzoic acid aluminum salt, sodium adipate and disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate.
• Metal salts sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate and lithium-2,2'-methylenebis (4,6-- Phosphate metal salts such as di-tert-butylphenyl) phosphate, dibenzylene sorbitol, bis (methylbenzylene) sorbitol, bis (3,4-dimethylbenzylene) sorbitol, bis (p-ethylbenzylene) sorbitol, and bis (p-ethylbenzylene) sorbitol.
• Polyvalent alcohol derivatives such as dimethylbenzylene) sorbitol, N, N', N'-tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N, N', N''-tricyclohexyl-
• amide compounds such as 1,3,5-benzenetricarbochimid, N, N'-dicyclohexylnaphthalenedicarboxamide, and 1,3,5-tri (2,2-dimethylpropanamide) benzene.
• Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinolbis (diphenyl phosphate), (1-methylethylidene). ) -4,1-Phenyltetraphenyldiphosphate, 1,3-Phenyltetrakis (2,6-dimethylphenyl) phosphate, ADEKA Co., Ltd. trade name Adecastab FP-500, ADEKA Co., Ltd.
• Adecastab FP- 600 Aromatic phosphate ester such as ADEKA Co., Ltd. trade name Adecastab FP-800, phosphonic acid ester such as divinyl phenylphosphonate, diallyl phenylphosphonate, phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, Methyl diphenylphosphinate, phosphinic acid esters such as 9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide derivative, phosphazene compounds such as bis (2-allylphenoxy) phosphazene, dicredylphosphazene, phosphates.
• phosphonic acid ester such as divinyl phenylphosphonate, diallyl phenylphosphonate, phenylphosphonic acid (1-butenyl
• phenyl diphenylphosphinate Methyl diphenylphosphinate
• Phenyl flame retardants such as melamine, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compound and red phosphorus, magnesium hydroxide, water.
• Metal hydroxides such as aluminum oxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1, 2 -Dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris ( Tribromophenoxy) -1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A-type dimethacrylate, pentabromo
• the above lubricant is added for the purpose of imparting slipperiness to the surface of the molded product and enhancing the scratch prevention effect.
• the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearate amide. These may be used alone or in combination of two or more.
• the filler examples include silica, talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, and glass fiber.
• examples thereof include clay, dolomite, 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.
• Examples of the metal soap include fatty acid metal salts having 1 to 40 carbon atoms.
• Fatty acids of fatty acid metal salts include acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, enant acid, capric acid, pelargonic acid, capric acid, 2-ethylhexanoic acid, undecylic acid, lauric acid and tridecyl.
• Saturated fatty acids such as acid, myristic acid, pentadecic acid, partiminic acid, margaric acid, stearic acid, nonadesilic acid, arachidic acid, heicosyl acid, behenic acid, tricosyl acid, lignoseric acid, cellotic acid, montanic acid, melicic acid, 4- Decenoic acid, 4-dodecenoic acid, palmitoleic acid, ⁇ -linolenic acid, linoleic acid, ⁇ -linolenic acid, stearidonic acid, petroseric acid, oleic acid, elladic acid, baxenoic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid Examples thereof include linear unsaturated fatty acids such as, aromatic fatty acids such as trimesic acid, and the like. In the present invention, an aliphatic group having 7 to 21 carbon atoms is prefer
• Examples of the metal of the fatty acid metal salt include alkali metal, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, ittrium, barium, hafnium and the like.
• alkali metals such as sodium, lithium and potassium are particularly preferably used.
• the hydrotalcites are complex salt compounds composed of magnesium, aluminum, hydroxyl groups, carbonate groups and arbitrary crystalline water known as natural products or 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.
• the 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 acids such as dodecylbenzene sulfonic acid alkali metal salt. It may be coated with a metal salt, a higher fatty acid amide, a higher fatty acid ester, a wax or the like.
• the above hydrotalcites may be natural products or synthetic products.
• Examples of the method for synthesizing such a compound include Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, and Japanese Patent Application Laid-Open No. 61-174270. , A known method described in JP-A-5-179052 and the like. Further, the hydrotalcites can be used without being limited by their crystal structure, crystal particles and the like.
• antistatic agent examples include cationic antistatic agents such as quaternary ammonium ion salt of fatty acid and quaternary polyamine salt; higher alcohol phosphate ester salt, higher alcohol EO adduct, polyethylene glycol fatty acid ester, and anionic type.
• Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfate esters, higher alcohol ethylene oxide adduct sulfates, higher alcohol ethylene oxide adduct phosphates; polyhydric alcohol fatty acid esters, polyglycol phosphates, poly Nonionic antistatic agents such as oxyethylene alkylallyl ethers; amphoteric alkyl betaines such as alkyldimethylaminoacetic acid betaine, and amphoteric antistatic agents such as imidazoline amphoteric activators can be mentioned.
• Such an antistatic agent may be used alone, or may be used in combination of two or more kinds of antistatic agents.
• a commercially available pigment may be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147
• the polyolefin-based resin composition is obtained, for example, by mixing the above-mentioned constituent components and then melt-kneading.
• the method for producing the polyolefin resin composition is as follows: dry blend with a mixer such as a Henshell mixer or a tumbler, and use an extruder, a Banbury mixer, a roll, a Brabender plastograph, a kneader or the like to process the processing temperature 100. It may include a step of kneading at ° C. to 280 ° C. It is preferable to use a Henschel mixer as the mixer and an extruder, particularly a twin-screw extruder, as the processing machine.
• L * (0h) and L * (2040h) in the polyolefin-based resin composition, which are obtained according to the above procedure are ⁇ 0.05 ⁇ [L. * (2040h) -L * (0h)] / L *
• Another example of the method for producing the polyolefin-based resin composition of the present embodiment is such that the value of ⁇ E in the polyolefin-based resin composition obtained according to the above procedure is 0.05 or more and 2.0 or less (A).
• a step of blending a polyolefin-based resin and (B) a light stabilizer to obtain a polyolefin-based resin composition is included.
• the blending amount of the (B) light stabilizer with respect to 100 parts by mass of the (A) polyolefin resin is, for example, 0.01 part by mass or more and 10 parts by mass or less, preferably 0.1 part by mass or more and 1 part by mass.
• the following compounding ratio may be used.
• the (B) photostabilizer used in the method for producing a polyolefin resin composition contains (B-1) a hindered amine compound and (B-2) a phenolic antioxidant, and (B-1) a hindered amine compound is a compound.
• the compound represented by the general formula (1) is contained in one or more kinds, and the (B-2) phenolic antioxidant contains one or more kinds of compounds represented by the general formula (2). include.
• a masterbatch containing (A) a polyolefin resin and (B) a light stabilizer may be used as a method for producing a polyolefin resin composition.
• This masterbatch may be configured such that the content of (B) the light stabilizer with respect to (A) 100 parts by mass of the polyolefin resin is larger than 10 parts by mass.
• the molding method of the polyolefin resin composition can be formed by using a known molding method, and for example, an injection molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an inflation molding method, a calendar molding method, etc.
• a slash molding method, a dip molding method, a foam molding method, or the like can be used. In this way, a molded product obtained by molding the polyolefin-based resin composition can be obtained.
• the polyolefin resin composition is used, for example, for automobile resin parts such as bumpers, dashboards, instrument panels, moldings, interior skins, and packings, resin parts for home appliances such as refrigerators, washing machines, and vacuum cleaners, and tableware.
• Buckets household items such as bathing items, connection parts such as connectors, miscellaneous items such as toys, storage containers such as tanks and bottles, medical packs, syringes, catheters, medical items such as medical tubes, wall materials, etc. Examples thereof include floor materials, window frames, building materials such as wallpaper, electric wire covering materials, agricultural materials such as houses and tunnels, food packaging materials such as wraps and trays, various molded products such as films and sheets, and fibers.
• the (B) light stabilizer is It contains (B-1) a hindered amine compound and (B-2) a phenolic antioxidant.
• the (B-1) hindered amine compound contains one or more compounds represented by the general formula (1).
• the (B-2) phenolic antioxidant contains one or more compounds represented by the general formula (2).
• the content of the (B) light stabilizer with respect to 100 parts by mass of the (A) polyolefin resin is 0.01 parts by mass or more and 10 parts by mass or less.
• L * (0h) and L * (2040h) in the polyolefin resin composition obtained according to the following procedure are -0.05 ⁇ [L * (2040h) -L * (0h)] / L * (0h). ) ⁇ Satisfy 0.1, Polyolefin-based resin composition. [Calculation method of L * (0h) and L * (2040h)] (1)
• the polyolefin-based resin composition is injection-molded under molding conditions of a resin temperature of 230 ° C.
• the test piece is placed on a white calibration plate, and the reflected color is measured by the SCI method (including specular reflected light) under the conditions of a light source D65 and a viewing angle of 10 ° using a colorimeter.
• the L * value is calculated from the tristimulus values X, Y, and Z, and this value is defined as L * (0h).
• the (B) light stabilizer is It contains (B-1) a hindered amine compound and (B-2) a phenolic antioxidant.
• the (B-1) hindered amine compound contains one or more compounds represented by the general formula (1).
• the (B-2) phenolic antioxidant contains one or more compounds represented by the general formula (2).
• the content of the (B) light stabilizer with respect to 100 parts by mass of the (A) polyolefin resin is 0.01 parts by mass or more and 10 parts by mass or less.
• the value of ⁇ E in the polyolefin-based resin composition obtained according to the following procedure is 0.05 or more and 2.0 or less.
• Polyolefin-based resin composition [Calculation method of ⁇ E] (1) The polyolefin-based resin composition is injection-molded under molding conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C. to form a rectangular sheet-shaped test piece having dimensions of 6.0 cm ⁇ 2.7 cm ⁇ 2 mm. (2) The test piece is placed on a white calibration plate, and the reflected color is measured by the SCI method (including specular reflected light) under the conditions of a light source D65 and a viewing angle of 10 ° using a colorimeter.
• SCI method including specular reflected light
• the L * value, a * value, and b * value are calculated from the three stimulus values X, Y, and Z, and these values are L * (0h), a * (0h), and b * (0h), respectively. .. (3) Weather resistance test of the test piece using a weather resistance tester under the conditions of irradiation intensity 0.55 W / m 2 at a wavelength of 340 nm, continuous irradiation, black panel temperature 89 ° C ⁇ 3 ° C, and no rainfall. Is carried out for 2040 hours.
• the test piece after the weather resistance test is carried out is placed on a white calibration plate, and the SCI method (including specular reflected light) is performed under the conditions of a light source D65 and a viewing angle of 10 ° using a colorimeter.
• the reflected color was measured by the above, and the L * value, a * value, and b * value were calculated from the obtained tristimulus values X, Y, and Z, and these values were calculated as L * (2040h) and a * (2040h, respectively). ), B * (2040h).
• ⁇ E [ ⁇ L * (2040h) -L * (0h) ⁇ 2 + ⁇ a * (2040h) -a * (0h) ⁇ 2 + ⁇ b * (2040h) -b * (0h) ⁇ 2 ] 1 / 2 3A. 1A. Or 2A.
• the (B) light stabilizer comprises (B-3) a benzoate compound.
• L * (0h) and L * (2040h) obtained by blending a light stabilizer and according to the following procedure are -0.05 ⁇ [L * (2040h) -L * (0h)] / L * (0h).
• the (B) light stabilizer is It contains (B-1) a hindered amine compound and (B-2) a phenolic antioxidant.
• the (B-1) hindered amine compound contains one or more compounds represented by the general formula (1).
• the (B-2) phenolic antioxidant contains one or more compounds represented by the general formula (2).
• a method for producing a polyolefin resin composition [Calculation method of L * (0h) and L * (2040h)] (1)
• the polyolefin-based resin composition is injection-molded under molding conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C. to form a rectangular sheet-shaped test piece having dimensions of 6.0 cm ⁇ 2.7 cm ⁇ 2 mm.
• the test piece is placed on a white calibration plate, and the reflected color is measured by the SCI method (including specular reflected light) under the conditions of a light source D65 and a viewing angle of 10 ° using a colorimeter.
• the L * value is calculated from the tristimulus values X, Y, and Z, and this value is defined as L * (0h).
• the test piece after the weather resistance test is carried out is placed on a white calibration plate, and the SCI method (including specular reflected light) is performed under the conditions of a light source D65 and a viewing angle of 10 ° using a colorimeter.
• the reflected color is measured by the above, and the L * value is calculated from the obtained tristimulus values X, Y, and Z, and this value is defined as L * (2040h).
• C Filler (C-1) Talc (Made by Japan Talc, Micro Ace P-4) Masterbatch containing (D) black pigment and (D-1a) black pigment (manufactured by NP Kasei Co., Ltd., OM250)
• D-1b Masterbatch containing dark gray pigment (manufactured by NP Kasei Co., Ltd., PG0501)
• D-1c Masterbatch containing light beige pigment (manufactured by NP Kasei Co., Ltd., PC8501)
• D-1d Masterbatch containing light gray pigment (manufactured by NP Kasei Co., Ltd., PK8201)
• E Lubricants, (E-1) Glycerol monostearate, (E-2) Ethylene bisstearic acid amide
• the reflected color was measured by the SCI method (including specular reflected light), and the L * value was calculated from the obtained tristimulus values X, Y, and Z, and this value was defined as L * (0h).
• an irradiation intensity of 0.55 W / m 2 at a wavelength of 340 nm, continuous irradiation, and black panel temperature using a weather resistance tester (device name: Ci4000, manufactured by ATLAS).
• the weather resistance test was carried out for 2040 hours under the conditions of 89 ° C. ⁇ 3 ° C. and no rainfall.
• the reflected color is measured by the SCI method (including positively reflected light), and the L * value, a * value, and b * value are calculated from the obtained tristimulus values X, Y, and Z, and these values are L * (each). 0h), a * (0h), b * (0h).
• a weathering tester device name: Ci4000, manufactured by ATLAS
• irradiation intensity 0.55 W / m 2 at a wavelength of 340 nm, continuous irradiation, black panel temperature 89 ° C ⁇ 3 ° C.
• the weather resistance test was carried out for 2040 hours under the condition of no rainfall.
• the polyolefin-based resin compositions of Examples 1 to 20 showed a longer crack generation time and excellent weather resistance than the polyolefin-based resin compositions of Comparative Examples 1 to 3. Further, comparing Examples 2, 4 and 6 in which the composition ratios of the components (A) to (C) are the same, the black polyolefin resin composition having an L * (0h) value of 50 or less is better. , The result was more weather resistant.

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