Classifications

• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/04—Monomers containing three or four carbon atoms
  • C08F110/06—Propene
• • 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
  • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
  • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
• • 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
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• • 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
  • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
• • 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

Definitions

• the present invention relates to a method for producing an olefin resin composition for home appliance materials and automobile interior materials, and in particular, produces an olefin resin composition having good color tone and fogging resistance and suitable for home appliance materials or automobile interior materials.
• the present invention relates to a method for producing an olefin resin composition for home appliance materials and automobile interior materials.
• Olefin resin has poor stability to heat and light, and easily oxidizes / deteriorates when exposed to high-temperature molding or strong light, so that the life required for plastic products cannot be obtained.
• a stabilizer such as a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a hydroxylamine compound, a hindered amine compound, an ultraviolet absorber, an acid scavenger, etc. should be added. Is generally done.
• a method of adding a stabilizer to an olefin resin a method of dispersing the stabilizer in the olefin resin by mixing the olefin resin obtained by polymerizing the olefin monomer and the stabilizer, and melt-kneading with a molding processing apparatus such as an extruder. And a method of obtaining a stabilized olefin resin by adding a stabilizer and polymerizing before or during the polymerization of the olefin monomer.
• the method of blending the olefin resin and the stabilizer by melt-kneading is economically disadvantageous because the stabilizer must be added more than necessary to cope with the problem of poor dispersion of the stabilizer.
• the method of adding a stabilizer before or during the polymerization of the olefin monomer has a problem that the stabilizer may inhibit the polymerization of the olefin monomer.
• Olefin resins are also used in the exteriors of home appliances and automobile interiors, but these products are constantly exposed to the eyes of consumers in daily life, and in recent years, not only functionality but also design requirements have increased. There is a feature that. Therefore, with regard to olefin resins used for household appliance materials and automobile interiors, it is particularly important that the appearance is good, as well as excellent general characteristics such as heat resistance and light resistance, as well as excellent coloration resistance and fogging resistance. Is required.
• fogging refers to a phenomenon in which additives contained in automobile interior materials volatilize inside a heated vehicle and condense on the inner surface of a window glass that has been cooled by the outside air, causing it to become white and cloudy, thus hindering visibility. Not only can it be lost, but it can interfere with safety because it obstructs visibility.
• Patent Document 1 discloses (A) an olefin resin, (B) an ethylene- ⁇ -olefin copolymer rubber, and (C) an additive for a resin that satisfies specific conditions. ) Is added in an amount of 0.05 to 0.6 parts by weight and 0.05 to 0.4 parts by weight per 100 parts by weight of the total amount.
• Additives for resins corresponding to the above (C) include phenolic antioxidants having a molecular weight of 200 to 1500, phosphorus antioxidants, hindered amine light stabilizers having a molecular weight of 200 to 1000, hydroxybenzotriazole light stabilizers, carbon Several tens to 25 fatty acid amide and / or bis fatty acid amide lubricants are disclosed.
• Patent Document 2 by propylene polymerization using a metallocene catalyst as a polymerization catalyst, a by-product of a low molecular weight component is suppressed, and a propylene polymer having a narrow molecular weight distribution is obtained. It is shown that an excellent resin composition can be obtained.
• the fogging resistance of the obtained resin composition is not yet satisfactory, and further improvement has been demanded.
• the resin composition described in Patent Document 2 has a problem that the processability is lowered due to the narrow molecular weight distribution, and molding unevenness frequently occurs in a molded product having a complicated shape.
• an object of the present invention is to produce an olefin resin composition for home appliance materials and automobile interior materials that can reduce the cost by suppressing the total amount of stabilizer added, has good color tone, and has excellent fogging resistance. It is to provide a method that can.
• the present inventors can solve the above problems by adding a specific phenolic antioxidant masked with an organoaluminum compound during the polymerization of the olefin monomer.
• the present invention has been completed.
• the present inventors have disclosed olefin polymerization in existing catalyst feed tanks or polymerization tanks in JP-A-2005-206625, JP-A-2005-255953, JP-A-2006-282985, and the like.
• a method of stabilizing a polymer without reducing the activity of a polymerization catalyst by mixing a commonly used organoaluminum compound and a phenolic antioxidant and performing a masking treatment has been proposed. The effect of improving the fogging resistance was not mentioned at all.
• the method for producing an olefin resin composition for automobile interior materials is a method for producing an olefin resin composition for automobile interior materials obtained by polymerizing an olefin monomer, What is obtained by masking a phenolic antioxidant represented by the following general formula (1) with an organoaluminum compound is 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the olefin resin obtained by polymerization.
• the method includes a step of adding before or during the polymerization of the olefin monomer.
• R is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon atom. Represents an aryl group of formula 6-18.
• the manufacturing method of the olefin resin composition for household appliances of this invention is a manufacturing method of the olefin resin composition for household appliances formed by superposing
• the method includes a step of adding before or during the polymerization of the olefin monomer.
• R is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon atom. Represents an aryl group of formula 6-18.
• the organoaluminum compound is preferably trialkylaluminum.
• the organoaluminum compound is preferably trialkylaluminum.
• a phosphorus-based antioxidant before or during polymerization of a monomer having an ethylenically unsaturated bond.
• a phosphorus-based antioxidant before or during the polymerization of a monomer having an ethylenically unsaturated bond.
• the automobile interior material of the present invention is formed by molding the olefin resin composition for automobile interior materials produced by the above-described method for producing an olefin resin composition for automobile interior materials.
• the home appliance exterior material of the present invention is characterized in that it is formed by molding the olefin resin composition for home appliances produced by the above-described method for producing the olefin resin composition for home appliances.
• the present invention provides a method for producing an olefin resin composition for home appliance materials and automobile interior materials that can reduce the cost by suppressing the total amount of stabilizer added, has good color tone, and has excellent fogging resistance. It becomes possible to do.
• the olefin resin composition for home appliance materials and automobile interior materials obtained by the production method of the present invention does not exhibit fogging resistance in a fogging resistance test based on ISO6452.
• the manufacturing method of the olefin resin composition for automobile interior materials of the present invention and the manufacturing method of the olefin resin composition for household electrical appliance materials each masked the phenolic antioxidant represented by the following general formula (1) with organoaluminum. These are blended before or during the polymerization of the olefin monomer so as to be 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the polymer obtained by polymerization.
• R is an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 12 carbon atoms, and an optionally substituted carbon atom. Represents an aryl group of formula 6-18.
• alkyl group having 1 to 30 carbon atoms which may have a branch and represented by R in the general formula (1) include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, sec-butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, hexyl, heptyl, n-octyl, isooctyl, t-octyl, nonyl, isononyl, decyl Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like.
• Phenol antioxidants with fewer than 12 carbon atoms in the alkyl group may easily volatilize, and if the alkyl group has more than 24 carbon atoms, the ratio of phenol to the molecular weight of the phenolic antioxidant will decrease. Therefore, the stabilization effect may be reduced.
• alkyl groups may be interrupted by an oxygen atom, a sulfur atom, or the following aryl group, and a hydrogen atom in the alkyl group is a chain fatty acid such as a hydroxy group, a cyano group, an alkenyl group, or an alkenyloxy group.
• Examples of the optionally substituted cycloalkyl group having 3 to 12 carbon atoms represented by R in the general formula (1) include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclo An octyl group, a cyclononyl group, a cyclodecyl group, and the like, and a hydrogen atom in the cycloalkyl group may be substituted with an alkyl group, an alkenyl group, an alkenyloxy group, a hydroxy group, or a cyano group, It may be interrupted by an oxygen atom or a sulfur atom.
• Examples of the aryl group having 6 to 18 carbon atoms which may have a substituent represented by R in the general formula (1) include, for example, a phenyl group, a methylphenyl group, a butylphenyl group, and an octylphenyl group. 4-hydroxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-t-butylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, phenanthryl group, benzyl, phenylethyl group, 1- And phenyl-1-methylethyl group.
• a hydrogen atom in the aryl group may be substituted with an alkyl group, an alkenyl group, an alkenyloxy group, a hydroxy group, or a cyano group, and the alkyl group may be interrupted with an oxygen atom or a sulfur atom. Good.
• Examples of the specific structure of the phenolic antioxidant represented by the general formula (1) include the following compound No. 1-No. 16 is mentioned. However, the present invention is not limited by the following compounds.
• the phenolic antioxidant is 0.001 to 0.5 parts by mass, preferably 0.001 to 0.3 parts per 100 parts by mass of a polymer obtained by polymerization (hereinafter also simply referred to as polymer). Add so that it becomes a mass part.
• stearyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide palmityl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propion Acid amide, myristyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide, etc.
• An amide compound of 3- (3,5-dialkyl-4-hydroxyphenyl) propionic acid represented by the general formula (1) is preferable because of its excellent stabilizing effect and color tone of the resulting olefin resin composition.
• the hydrogen of the phenolic hydroxyl group of the phenolic antioxidant can be easily replaced with the organoaluminum compound, and the phenolic antioxidant Can be masked with organoaluminum.
• the organoaluminum compound an organoaluminum compound that can be regenerated into phenol by treating the masked phenolic antioxidant with a hydrogen-donating compound such as water, alcohol, or acid is used.
• the organoaluminum compound for example, alkylaluminum, alkylaluminum hydride and the like can be used, but alkylaluminum is preferable, and trialkylaluminum is particularly preferable, and specifically, trimethylaluminum, triethylaluminum, tri-n. -Propyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum and the like. Any of the organoaluminum compounds can be used as a mixture. Moreover, the aluminoxane obtained by reaction of alkylaluminum or alkylaluminum hydride and water can be used similarly.
• the masked phenolic antioxidant is added before or during the polymerization of the olefin monomer.
• the addition site include a polymerization system, a catalyst system, and a compounding tube. .
• the masking method may be simply mixing and stirring the organoaluminum compound and the phenolic antioxidant in an inert solvent.
• the by-product compound when the by-product compound does not affect the polymer, it can be used as it is, but when the by-product compound inhibits the polymerization, it should be used after removing the compound by distillation under reduced pressure or the like. Is preferred.
• the mixing ratio of the organoaluminum compound and the phenolic antioxidant represented by the general formula (1) is preferably 1/5 to 100/1 by mass ratio. If it is less than 1/5, there is a problem that an excessive phenolic antioxidant adversely affects the catalyst activity. If it is more than 100/1, an aluminum compound remains in the polymer after polymerization, and the physical properties of the polymer are lowered. In some cases, the desired polymerization cannot be performed due to the influence of the component ratio of the catalyst metal.
• the inert solvent examples include aliphatic and aromatic hydrocarbon compounds.
• the aliphatic hydrocarbon compound examples include saturated hydrocarbon compounds such as n-pentane, n-hexane, n-heptane, n-octane, isooctane and purified kerosene, and cyclic saturated hydrocarbons such as cyclopentane, cyclohexane and cycloheptane.
• the aromatic hydrocarbon compound include compounds such as benzene, toluene, ethylbenzene, and xylene. Of these compounds, n-hexane or n-heptane is preferably used.
• the concentration of the trialkylaluminum salt in the inert solvent is preferably in the range of 0.001 to 0.5 mol / L, particularly preferably 0.01 to 0.1 mol / L.
• a phosphorus-based antioxidant is further added before or during polymerization of a monomer having an ethylenically unsaturated bond. Is preferably added.
• Examples of the phosphorus antioxidant include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tris (2,4-ditertiarybutyl-5- Methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenylphos Phyto, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythr
• phosphorus-based antioxidants such as tris (2,4-ditertiarybutylphenyl) phosphite that do not adversely affect the polymerization even when added before polymerization are preferred.
• the amount of the phosphorus antioxidant used is 0.001 to 1 part by mass, and more preferably 0.001 to 0.5 part by mass with respect to 100 parts by mass of the polymer obtained by polymerization.
• the phosphorus-based antioxidant When the phosphorus-based antioxidant is added before or during the polymerization of the ethylenically unsaturated monomer, it is mixed with the inert solvent and used in advance.
• the phenol represented by the general formula (1) is used in advance. It may be mixed with an inert solvent together with the system antioxidant, or mixed with the inert solvent separately from the phenolic antioxidant represented by the general formula (1) to form a polymerization system, catalyst It may be added to the system or piping.
• Examples of the monomer having an ethylenically unsaturated bond include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, Examples thereof include vinylcycloalkane, styrene, and derivatives thereof.
• one of the above monomers having an ethylenically unsaturated bond is used alone.
• Polymerization of the ethylenically unsaturated monomer needs to be performed in an inert gas atmosphere such as nitrogen in the presence of a polymerization catalyst, but may be performed in the above inert solvent.
• an active hydrogen compound, a particulate carrier, an organoaluminum compound, an ion exchange layered compound, and an inorganic silicate may be added as long as polymerization is not inhibited.
• the polymerization catalyst is not particularly limited, and a known polymerization catalyst can be used.
• transition metals of Group 3 to 11 of the periodic table for example, titanium, zirconium, hafnium, vanadium, iron, nickel, Lead, platinum, yttrium, samarium, etc.
• typical examples include Ziegler catalysts, Ziegler-Natta catalysts comprising a titanium-containing solid transition metal component and an organometallic component, and at least one cyclopentadienyl.
• the metallocene catalyst include a transition metal compound of Group 4 to Group 6 of the periodic table having a skeleton and a promoter component. Use of an electron donating compound is preferable because a high-quality polymer can be obtained.
• titanium trichloride or titanium trichloride composition obtained by reducing titanium tetrachloride with organoaluminum or the like is treated with an electron-donating compound and further activated (for example, JP-A-47). -34478, JP-A-58-23806, JP-A-63-146906), obtained by reducing titanium tetrachloride with an organoaluminum compound and further treating with various electron donors and electron acceptors.
• Catalysts comprising the obtained titanium trichloride composition, an organoaluminum compound and an aromatic carboxylic acid ester (Japanese Patent Laid-Open Nos.
• a supported catalyst comprising magnesium halide, titanium tetrachloride and various electron donors (Japanese Patent Kokai 57-63310) JP, 58-157808, JP 58-83006, JP 58-5310, JP 61-218606, JP 63-43915, JP 63 -83116) and the like.
• metallocene catalyst examples include, for example, transition metal metallocene catalysts described in JP-A-9-12621, JP-A-5-043616, JP-A-5-295022, JP-A-5-301919, JP-A-6-239914, JP-A-6-239915, JP-A-6-239917, JP-A-7-082311, JP-A-7-228621, JP-A-7-330820, JP-A-8 -059724, JP-A-8-085707, JP-A-8-085708, JP-A-8-127613, JP-A-10-226712, JP-A-10-259143, JP-A-10-265490.
• Examples of the electron donating compound include ether compounds, ester compounds, ketone compounds, alkoxysilane compounds, and the like. A single compound may be added to the electron donor compound, or a plurality of compounds may be added as necessary.
• ether compounds include diethyl ether, dipropyl ether, diisopropyl ether, di-n-butyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, ethylene oxide, tetrahydrofuran, 2,2,5,5-tetramethyltetrahydrofuran, dioxane and the like. Is mentioned.
• ester compound examples include methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, methyl propionate, ethyl propionate, propionate-n-propyl, methyl methacrylate, ethyl methacrylate, methacrylic acid- n-propyl, ethyl phenylacetate, methyl benzoate, ethyl benzoate, phenyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, methyl methoxybenzoate, ethyl methoxybenzoate, methyl methacrylate, Examples thereof include ethyl methacrylate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, ⁇ -butyrol
• ketone compound examples include acetone, diethyl ketone, methyl ethyl ketone, acetophenone, and the like.
• alkoxysilane compounds include tetramethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, t-butyltrimethoxysilane, i-butyltrimethoxysilane, phenyltrimethoxysilane, cyclohexyltri Methoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butyl-n-propyldimethoxysilane, t-butylisopropyldimethoxysilane Cyclohexylmethyldimethoxysilane, tetraeth
• carriers such as an inorganic oxide
• carriers such as porous polyolefin
• the inorganic carrier include silica, alumina, magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium oxide, and zinc oxide.
• Other inorganic carriers include magnesium halides such as magnesium chloride and magnesium bromide, magnesium alkoxides such as magnesium ethoxide, and ion-exchangeable layered compounds.
• the ion-exchangeable layered compound has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak binding force, and represents a compound in which contained ions can be exchanged.
• Specific examples of the ion-exchangeable layered compound include, for example, kaolin, bentonite, talc, kaolinite, vermiculite, montmorillonite group, mica group, ⁇ -Zr (HAsO 4 ) 2 .H 2 O, ⁇ -Zr (HPO 4 ) 2 ⁇ H 2 O, ⁇ -Sn (HPO 4 ) 2 ⁇ H 2 O, ⁇ -Ti (NH 4 PO 4 ) 2 ⁇ H 2 O, and the like.
• organic carrier examples include polyethylene, polypropylene, polystyrene, ethylene-butene copolymer, ethylene-propylene copolymer, polymethacrylic acid ester, polyacrylic acid ester, polyacrylonitrile, polyamide, polycarbonate, and polyethylene terephthalate.
• examples thereof include polyester, polyvinyl chloride, and the like, and these may be crosslinked, for example, as a styrene-divinylbenzene copolymer.
• a catalyst in which a catalyst is chemically bonded to these organic supports can be used.
• the particle diameter (volume average) of these carriers is usually from 0.1 to 300 ⁇ m, preferably from 1 to 200 ⁇ m, more preferably from 10 to 100 ⁇ m. If the particle size is smaller than 1 ⁇ m, a finely powdered polymer is likely to be formed, and if it is too large, coarse particles are produced. Therefore, the particle size of the carrier should be selected according to the desired particle shape.
• the pore volume of the carrier is usually from 0.1 to 5 cm 2 / g, preferably from 0.3 to 3 cm 2 / g.
• the pore volume can be measured by, for example, the BET method or the mercury intrusion method.
• a conventionally used method can be employed.
• aliphatic hydrocarbons such as butane, pentane, hexane, heptane, isooctane
• alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane
• aromatic hydrocarbons such as toluene, xylene, ethylbenzene, gasoline fraction
• hydrogen A method for carrying out polymerization in the liquid phase in the presence of an inert solvent such as a liquefied diesel fraction, a method for carrying out polymerization using the liquefied olefin itself as a medium, and a method for carrying out polymerization in the gas phase under conditions where there is substantially no liquid phase
• a polymerization method in which two or more of these are combined can also be used.
• the polymerization may be either a batch type or a continuous type, and may be a one
• a continuous reaction tank in an existing polymerization facility may be used as it is, and the present invention is not particularly limited to conventional polymerization facilities in terms of size, shape, material, and the like.
• the above polymer can be blended with other ordinary additives as required.
• other additives can be added at the time of polymerization of the olefin monomer as long as they do not inhibit the polymerization.
• another additive may be mixed with the olefin resin in a blending amount according to the purpose, and melt-kneaded with a molding machine such as an extruder, and granulated and molded.
• additives include, for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, UV absorbers, heavy metal deactivators, nucleating agents, flame retardants, metal soaps, hydrotalcite , Fillers, lubricants, antistatic agents, pigments, dyes, plasticizers and the like.
• phenolic antioxidant examples include 2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-t-butyl- 4-hydroxyphenyl) propionate, distearyl (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-t-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [ (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5 -Di-t-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-t-butylphenol) Bis [3,3-bis (4-hydroxy-3-t-
• Examples of the phosphorus antioxidant include the same compounds as those exemplified above.
• thioether-based antioxidant examples include tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-t-butyl.
• Phenyl) sulfide ditridecyl-3,3′-thiodipropionate, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipro Pionate, lauryl / stearyl thiodipropionate, 4,4'-thiobis (6-t-butyl-m-cresol), 2,2'-thiobis (6-t-butyl-p-cresol), distearyl- Disulfide is mentioned.
• the amount of the thioether-based antioxidant used is preferably 0.001 to 0.3 parts by mass, more preferably 0.01 to 0.3 parts by mass with respect to 100 parts by mass of the polymer.
• ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone).
• 2-hydroxybenzophenones such as 2-; 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-tertiary Octyl-6-benzotriazolylphenol), polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5
• hindered amine light stabilizer 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-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,
• nucleating agent examples include carboxylic acids such as sodium benzoate, aluminum 4-tert-butylbenzoate, 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-ditert-butylphenyl) phosphate and lithium-2,2′-methylenebis (4,6-di) Phosphoric acid ester metal salts such as tert-butylphenyl) phosphate, polyhydric alcohol derivatives such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis (dimethylbenzylidene) sorbitol, N, N ′, N ′′ -tris [2-methylcyclohexyl 1,2,3-prop
• the flame retardant examples include aromatic phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, and resorcinol bis (diphenyl phosphate).
• aromatic phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, and resorcinol bis (diphenyl phosphate).
• Esters such as divinyl phenylphosphonate, diallyl phenylphosphonate and phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phospha Phosphinic acid esters such as phenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, Melamine phosphate, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, bromine Phenol novolac epoxy resin, hexabromobenzene
• Examples of the filler 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, Dolomite, mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate and the like are preferable.
• these fillers those having an average particle diameter (spherical or flat) or an average fiber diameter (needle or fiber) of 5 ⁇ m or less are preferable.
• the amount of the filler used can be appropriately used as long as the present invention is not impaired.
• the above-mentioned lubricant is added for the purpose of imparting lubricity to the surface of the molded body and enhancing the effect of preventing damage.
• the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide. These may be used alone or in combination of two or more.
• the addition amount of the lubricant is in the range of 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass, with respect to 100 parts by mass of the polymer. If the amount is less than 0.03 parts by mass, the desired lubricity may not be obtained. If the amount exceeds 2 parts by mass, the lubricant component may bleed on the surface of the polymer molded product or cause a decrease in physical properties.
• the above-mentioned antistatic agent is added for the purpose of reducing the chargeability of the molded product and preventing dust adhesion due to charging.
• antistatic agents such as cationic, anionic and nonionic.
• Preferred examples include polyoxyethylene alkylamines, polyoxyethylene alkylamides or their fatty acid esters, glycerin fatty acid esters, and the like. These may be used alone or in combination of two or more.
• the addition amount of the antistatic agent is preferably 0.03 to 2 parts by mass, more preferably 0.04 to 1 part by mass with respect to 100 parts by mass of the polymer. When the amount of the antistatic agent is too small, the antistatic effect is insufficient. On the other hand, when the amount is too large, bleeding to the surface and deterioration of physical properties of the polymer may be caused.
• the olefin resin composition for automobile interior materials obtained by the method for producing an olefin resin composition for automobile interior materials of the present invention is suitable as a plastic material used for automobile interiors.
• automobile interiors include air bag covers, door modules, steering handles, console boxes, glove boxes, heater cases, indoor lamp housings, room mirrors, assist grips, various lever grips, instrument panels, steering members, and air conditioners. Cockpit modules that integrate systems, airbag systems, various displays, switches, audio, and the like.
• the olefin resin composition for home appliances obtained by the method for producing an olefin resin composition for home appliances according to the present invention is suitable as a plastic material used for home appliance materials, in particular, interior and exterior of home appliances.
• the home appliance include a TV, a video deck, a DVD deck, a Blu-ray player, an audio, a component, a refrigerator, a microwave oven, a rice cooker, a washing machine, a dishwasher, a vacuum cleaner, and an air conditioner.
• a manufacture example represents the polymerization method of an ethylenically unsaturated monomer
• an Example and a comparative example represent evaluation of the olefin resin composition obtained by superposing
• Production Example B In the polymerization of Production Example A, a phosphite solution was prepared by the following method, and Production Example A was added except that the phenoxide solution and the phosphite solution were added so as to have the composition of the stabilizer composition described in Table 1. Polymerization was carried out in the same procedure as above to obtain a polyolefin resin composition.
• Thermal stability The above pellets were put into a twin screw extruder (Plastomill Micro manufactured by Toyo Seiki Seisakusho, extrusion temperature 230 ° C., screw rotation speed 50 rpm) and kneaded repeatedly 5 times, and gel permeation chromatograph (apparatus: GPC2000 type manufactured by Waters) , Column: 2 Styragel HT6E and 1 Styragel HT2 manufactured by Waters, measurement temperature 135 ° C., solvent: orthodichlorobenzene, concentration: 6 mg / 10 g), and the weight average molecular weight was measured. These results are shown in Table 1 below.
• AO-1 Compound No. 1 4
• AO-2 Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate
• AO-3 Tetrakis [methylenebis-3- (3,5-di-t-butyl- 4'-hydroxyphenyl) propionate] methane 4)
• P-1 Tris (2,4-di-t-butylphenyl) phosphite 5)
• Ca-St calcium stearate
• Comparative Examples 1 to 9 a polyolefin resin composition obtained by a production method different from the production method of the present invention was not obtained that satisfies all of the thermal stability, coloration resistance and fogging resistance. On the other hand, as is clear from Examples 1 and 2, it was confirmed that the polyolefin resin composition obtained by the production method of the present invention was excellent in thermal stability, color tone and fogging resistance. Further, in Examples 1 and 2, although the total amount of the antioxidant used was the same as that of Comparative Examples 6 and 7, respectively, the obtained polymers had high thermal stability and excellent coloration resistance. It was.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polymerisation Methods In General (AREA)
• Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=49222370

Family Applications (1)

Country Status (8)

Families Citing this family (2)

Citations (49)

Family Cites Families (13)

• 2012
  • 2012-03-23 JP JP2012067832A patent/JP2013199551A/ja active Pending
• 2013
  • 2013-02-15 IN IN1990MUN2014 patent/IN2014MN01990A/en unknown
  • 2013-02-15 CN CN201380015833.9A patent/CN104203991B/zh not_active Expired - Fee Related
  • 2013-02-15 KR KR20147029815A patent/KR20140139066A/ko not_active Ceased
  • 2013-02-15 EP EP13764537.0A patent/EP2829554A4/en not_active Withdrawn
  • 2013-02-15 WO PCT/JP2013/053748 patent/WO2013140905A1/ja not_active Ceased
  • 2013-02-15 US US14/387,465 patent/US20150065649A1/en not_active Abandoned
  • 2013-03-05 TW TW102107647A patent/TWI582149B/zh not_active IP Right Cessation

Patent Citations (49)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events