WO2015079896A1 - 光安定剤組成物及びその樹脂組成物 - Google Patents
光安定剤組成物及びその樹脂組成物 Download PDFInfo
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- WO2015079896A1 WO2015079896A1 PCT/JP2014/079718 JP2014079718W WO2015079896A1 WO 2015079896 A1 WO2015079896 A1 WO 2015079896A1 JP 2014079718 W JP2014079718 W JP 2014079718W WO 2015079896 A1 WO2015079896 A1 WO 2015079896A1
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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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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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
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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
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
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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
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- 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
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- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
Definitions
- the present invention relates to a light stabilizer composition preferably used for vehicle members such as instrument panels, bumpers, and linings, and more specifically, a light stabilizer composition obtained by impregnating a hindered amine compound with high water content silica and blending the same. It is related with the resin composition formed.
- the compound used as the light stabilizer is preferably a compound generally having a high melting point and small plasticization of the resin or volatilization from the resin. However, when the molecular weight is increased, the movement of the light stabilizer in the resin is suppressed, so that the stabilization effect tends to be reduced.
- a hindered amine compound obtained by reacting 2,2,6,6-tetramethylpiperidinols with a fatty acid can impart excellent weather resistance while being a low melting point compound.
- the hindered amine compound has a low molecular weight and tends to be liquid, and the surface tends to become sticky.
- Patent Document 1 discloses a method using a master batch
- Patent Document 2 describes a method based on microencapsulation
- Patent Document 3 describes an oil absorption amount of 150 ml / 100 g or more.
- a method of impregnating a powdery inorganic material has been proposed.
- the masterbatch method is a technology that, when trying to mix a high-concentration hindered amine compound, the hindered amine compound oozes out from the masterbatch and the surface becomes sticky. Challenges remained.
- the microencapsulation method is expensive, and the crystallization promotion is improved in handling compared to amorphous, but cannot be applied to liquid products. If the crystalline product has a low melting point, the effect of preventing caking is small. The improvement in sex was insufficient.
- the method described in Patent Document 3 describes a method in which a highly alkaline powder is used as a medium impregnated with a liquid resin additive. In particular, the phenolic antioxidant) may be colored.
- a method using an aluminum silicate compound has also been proposed, but since the aluminum silicate compound is relatively expensive, its utility value is low industrially.
- an object of the present invention is to provide a light stabilizer composition with improved handling of a hindered amine compound obtained by reacting 2,2,6,6-tetramethylpiperidinols with a carbonate. is there.
- the present inventor has come to solve the above problems by impregnating the hindered amine compound with silica whose water content is adjusted to a specific range.
- the present invention provides (A) a light impregnated with 10 to 300 parts by mass of a hindered amine compound represented by the following general formula (1) with respect to 100 parts by mass of silica having a water content of 2 to 7 wt%.
- a stabilizer composition is provided.
- R 1 represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, a hydroxyalkyl group, an alkoxy group, a hydroxyalkoxy group, or an oxy radical
- R 2 represents 1 to 30 represents an alkyl group, an alkenyl group having 2 to 30 carbon atoms, or a group represented by the following general formula (2)
- R 3 represents the same as R 1 in the general formula (1).
- the light stabilizer composition of the present invention is preferably such that the silica as the component (A) is silica having a particle diameter of 0.1 to 100 ⁇ m.
- the light stabilizer composition of the present invention preferably further comprises (C) 5 to 500 parts by mass of a benzoate light stabilizer represented by the following general formula (3).
- a benzoate light stabilizer represented by the following general formula (3).
- R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms
- R 6 represents an alkyl group having 8 to 30 carbon atoms. Represents an alkyl group.
- the present invention also provides a resin composition comprising 0.01 to 1 part by mass of the light stabilizer composition described above per 100 parts by mass of a resin.
- a resin composition in which the resin is a polyolefin resin is preferable.
- the present invention also provides a vehicle member formed by molding the above resin composition.
- a light stabilizer composition that has excellent handleability and can impart excellent weather resistance to a resin.
- a resin composition having excellent weather resistance can be provided, which is suitable for a vehicle member.
- silica There are natural products and synthetic products, and silica has crystalline and amorphous properties, respectively. Quartz, quartz, quartz sand, etc. can be mentioned as the crystalline nature, and diatomaceous earth, acid clay, etc. can be mentioned as the amorphous nature. Examples of synthetic products include amorphous materials such as dry silica, wet silica, and silica gel. In the present invention, among these, silica having a neutral pH of about 6 to 8 is preferred from the viewpoint of being inexpensive and not impairing the performance of the additive blended with the resin.
- the water content of (A) silica according to the present invention is 2 to 7 wt%. If it is less than 2 wt%, the powdery inorganic substance may be charged and aggregated, making handling difficult. If it is more than 7 wt%, foaming may occur during the molding process of a polyolefin resin composition containing these.
- the water content of the silica can be easily adjusted by placing it in an environment in which the humidity is adjusted, but can be adjusted by spraying water or drying with a vacuum or a heat source.
- the average particle diameter of (A) silica varies depending on the use of the molded product, but is preferably 0.1 to 100 ⁇ m, more preferably 0.3 to 50 ⁇ m, and further preferably 0.5 to 30 ⁇ m. If the average particle diameter is too larger than the above range, the dispersibility in the resin may be deteriorated and the physical properties of the resin may be reduced. If the average particle size is too small, dust may be easily generated and the working environment may be deteriorated. is there.
- the silica (A) is not particularly limited, and silica obtained by a known synthesis method can be used.
- Specific synthesis methods include, for example, a method of burning silicon tetrachloride in an oxygen or hydrogen flame, a method of obtaining from by-products generated during the production of metal silicon, sodium silicate and mineral acid (sulfuric acid, hydrochloric acid, etc.) Examples thereof include a neutralization reaction method and a alkoxyl hydrolysis method. By selecting the reaction conditions, silicas having different particle diameters, surface structures, pore states, etc. can be obtained.
- Preferred products of (A) silica according to the present invention include, for example, trade names manufactured by Mizusawa Chemical Co., Ltd. (Mizukasil P-78D), trade names manufactured by DSL Japan Co., Ltd. (Carplex # 80), and trade names manufactured by Evonik. (Sipernato 22S), Tosoh Silica Co., Ltd. trade names (Nipzil KP, Nipzil NS) and the like.
- the present invention is not limited by the above products.
- Hindered amine compound The hindered amine compound used in the present invention is a compound represented by the above general formula (1), and reacts 2,2,6,6-tetramethylpiperidinols with a carbonate ester. can get.
- examples of the alkyl group having 1 to 30 carbon atoms represented by R 1 and R 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, Examples include pentyl, secondary pentyl, tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
- Examples of the hydroxyalkyl group having 1 to 30 carbon atoms represented by R 1 in the general formula (1) include, for example, hydroxy group substitution of the above alkyl group such as hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and the like.
- the body can be mentioned.
- examples of the alkoxy group having 1 to 30 carbon atoms represented by R 1 in the general formula (1) include methoxy, ethoxy, propoxy, isopropoxy, butoxy, octoxy, 2-ethylhexyloxy corresponding to the alkyl group. Etc.
- the hydroxyalkoxy group having 1 to 30 carbon atoms represented by R 1 in the general formula (1) includes hydroxyethyloxy, 2-hydroxypropyloxy, 3-hydroxypropyloxy corresponding to the alkoxy group. 4-hydroxybutyloxy, 2-hydroxy-2-methylpropyloxy, 6-hydroxyhexyloxy and the like.
- examples of the alkenyl group having 2 to 30 carbon atoms represented by R 2 in the general formula (1) include vinyl, propenyl, butenyl, hexenyl, oleyl and the like.
- the position of the double bond may be the ⁇ -position, the inside, or the ⁇ -position.
- examples of the compound represented by the general formula (1) used in the present invention include compound Nos. 1-No. 9) and the like. However, the present invention is not limited by the following compounds.
- the mixed alkyl group of 8 represents a mixture of hindered amine compounds in which R 1 in the general formula (1) is an alkyl group having 15 to 17 carbon atoms.
- 9 represents a mixture of hindered amine compounds in which R 1 in the general formula (1) is an alkyl group having 15 to 19 carbon atoms.
- R 1 is preferably a hydrogen atom or a methyl group
- R 2 is a mixture of alkyl groups having 8 to 26 carbon atoms. preferable.
- the method for synthesizing the hindered amine compound represented by the general formula (1) can be obtained by reacting a fatty acid having a predetermined number of carbon atoms with an alcohol having a 2,2,6,6-tetramethylpiperidinol skeleton.
- esterification is possible by direct esterification of acid and alcohol, reaction of acid halide and alcohol, transesterification, etc., and purification methods include distillation, recrystallization, filter material, adsorbent method Etc. can be used as appropriate.
- the light stabilizer composition of the present invention 10 to 300 parts by mass, preferably 30 to 200 parts by mass of the hindered amine compound represented by the above general formula (1) with respect to 100 parts by mass of (A) silica. Impregnated by weight, more preferably 60-120 parts by weight.
- (C) Benzoate light stabilizer represents a compound represented by the following general formula (3).
- R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms
- R 6 represents an alkyl group having 8 to 30 carbon atoms. Represents an alkyl group.
- examples of the alkyl group having 1 to 12 carbon atoms represented by R 4 and R 5 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, and pentyl. Hexyl, octyl and the like, and cyclopentyl and cyclohexyl which are cycloalkyl groups.
- examples of the arylalkyl group having 7 to 30 carbon atoms represented by R 4 and R 5 include benzyl, phenylethyl, 1-methyl-1-phenylethyl and the like. it can.
- examples of the alkyl group having 8 to 30 carbon atoms represented by R 6 include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and the like. Can do.
- benzoate light stabilizer represented by the general formula (3) include the following compounds UV-1 to UV-4.
- the present invention is not limited by the following compounds.
- the preferred blending amount of the benzoate light stabilizer represented by the general formula (3) (C) is 5 to 500 parts by mass with respect to 100 parts by mass of the (A) silica. The more preferable amount is 10 to 300 parts by mass.
- the ratio of the benzoate light stabilizer represented by the general formula (3) to the hindered amine compound represented by the general formula (1) is expressed as a mass ratio. It is preferably in the range of 1/4 to 3/1 of the hindered amine compound. When the ratio is less than 1/4, a synergistic effect due to the combination of the hindered amine compound and the benzoate light stabilizer may not be obtained. When the ratio is more than 3/1, the light stabilization ability of the hindered amine compound may not be exhibited.
- the blending amount is 200 parts by mass or less in total with respect to 100 parts by mass of the (A) silica. It is preferable to do this.
- the method for synthesizing the compound represented by the general formula (3) is not particularly limited, and the compound can be synthesized by a normal organic synthesis method.
- esterification is possible by direct esterification of acid and alcohol, reaction of acid halide and alcohol, transesterification, etc., and as a production method, distillation, recrystallization, reprecipitation, filter agent / adsorbent is used. Methods and the like can be appropriately employed.
- Examples of the method for impregnating the (A) silica with the hindered amine compound represented by (B) the general formula (1) include the following methods. However, the present invention is not limited by these methods. 1. A method of impregnating silica by mixing a hindered amine compound heated to a liquid state as necessary with silica at atmospheric pressure or under vacuum. 2. A method in which a solid hindered amine compound is mixed with silica, and is adsorbed and sorbed on silica in the form of a solid under atmospheric pressure or vacuum. 3.
- the hindered amine compound represented by the general formula (1) (B) may be a mixture of the benzoate light stabilizer represented by the general formula (3) (C).
- the impregnation means one in which solid pores are impregnated with a liquid, or one in which solid fine particles are adsorbed and sorbed in solid pores.
- the impregnation of the hindered amine compound represented by the above general formula (1) into the above (A) silica is preferably as uniform as possible.
- Silica is preferably washed or surface-treated so that the hindered amine compound is easily impregnated.
- the impregnation may be performed under vacuum so that there is no air in the silica pores.
- the mixing ratio of the hindered amine compound represented by the general formula (1) and the silica (A) depends on the oil absorption amount of the silica, but the hindered amine compound / the above.
- the weight ratio of silica is preferably 30/70 or more, more preferably 50/50 or more.
- Resins stabilized by the light stabilizer composition of the present invention include thermoplastic resins, thermosetting resins, crystalline resins, non-crystalline resins, biodegradable resins, non-biodegradable resins, synthetic resins, natural resins Any kind of resin such as industrial resin, general-purpose resin, engineering resin, polymer alloy and the like may be used.
- Specific examples of the resin to be stabilized include polypropylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, and ethylene-propylene.
- ⁇ -olefin homopolymers or copolymers such as copolymers, copolymers of these ⁇ -olefins with polyunsaturated compounds such as conjugated or non-conjugated dienes, acrylic acid, methacrylic acid, vinyl acetate, etc.
- Copolymer of polyamide such as adipamide, liquid crystal polyamide, polyimide, polystyrene, styrene and / or ⁇ -methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.)
- polyamide such as adipamide, liquid crystal polyamide, polyimide, polystyrene, styrene and / or ⁇ -methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.)
- AS acrylonitrile styrene copolymer
- ABS acrylonitrile-butadiene-styrene copolymer
- MFS methyl methacrylate butadiene styrene copolymer
- heat-resistant ABS resin etc
- isoprene rubber butadiene rubber, butadiene-styrene copolymer rubber, butadiene-acrylonitrile copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber, copolymer rubber of ethylene and ⁇ -olefin such as butene-1
- Elastomers such as terpolymer rubbers with ethylene- ⁇ -olefins and non-conjugated dienes such as ethylidene norbornene and cyclopentadiene, ⁇ -olefin elastomers, silicone resins, etc., and these resins and / or elastomers It may also be an alloyed or blended rubber or rubber.
- the above resins are lamella crystals measured by stereoregularity, specific gravity, type of polymerization catalyst, presence / absence or degree of polymerization catalyst removal, degree of crystallization, polymerization conditions such as temperature and pressure, type of crystal, X-ray small angle scattering Size, crystal aspect ratio, solubility in aromatic or aliphatic solvents, solution viscosity, melt viscosity, average molecular weight, degree of molecular weight distribution, how many peaks in molecular weight distribution, Although it may be a block or random, a difference in the expression of the stabilizing effect may occur depending on the blending ratio of each monomer, etc., but it is applicable when any resin is selected.
- a polyolefin resin can be preferably used as the resin because the effect of the present invention is remarkable.
- polyolefin resins include polypropylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, and ethylene-propylene copolymer.
- examples include ⁇ -olefin homopolymers and copolymers.
- the method of blending the light stabilizer composition of the present invention with the resin is not particularly limited, and a known blending technique of a stabilizer to a resin can be used.
- a method of adding to the polymerization system in advance when polymerizing the resin a method of adding during polymerization, and a method of adding after polymerization may be used.
- a method of kneading a mixture of stabilized resin powder and pellets with a Henschel mixer using a processing device such as an extruder blended into the resin after making a master batch And the like.
- the type of processing equipment to be used, processing temperature, cooling conditions after processing, and the like can be used without particular limitation, and the conditions can be selected so that the obtained resin physical properties are suitable for the application.
- the light stabilizer composition of the present invention can be granulated alone or together with other additives and then blended into the resin.
- the amount of the light stabilizer composition of the present invention to be added to the resin is 0.01 to 1 part by weight, preferably 0.02 to 0.5 part by weight with respect to 100 parts by weight of the resin.
- the amount is less than the above range, a necessary stabilization effect may not be obtained.
- it may bleed out from the surface of the molded article which shape
- various compounding agents can be used as necessary.
- Various compounding agents include, for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet absorbers, hindered amine compounds different from the above general formula (1), nucleating agents, flame retardants, Examples include flame retardant aids, lubricants, fillers, metal soaps, hydrotalcite, antistatic agents, pigments, and dyes.
- phenol-based antioxidant examples include 2,6-ditert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2′-methylenebis (4 -Ethyl-6-tert-butylphenol), 2,2'-thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2′-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- (3 , 5-Ditert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-ditert-butyl-4-l Roxyphenyl) propionamide,
- Examples of the phosphorus antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyltridecyl phosphite.
- triisooctyl phosphite trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis (tridecyl) Phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecylphosphite, dinonylphenylbis (nonylphenyl) Sphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropyl glycol diphosphite, trisnonylphenyl phosphite, tris (2,4-diterti
- thioether-based antioxidant examples include tetrakis [methylene-3- (laurylthio) propionate] methane, 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 / stearyl thiodipropionate, 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-thiobis (6-tert-butyl-p-cresol), distearyl- Disulfide is mentioned.
- 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- 3-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 2- [2-hydroxy-3- (2-acryloyl) Oxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-
- hindered amine compounds different from the general formula (1) include 2,2,6,6-tetramethyl-4-piperidylbenzoate and bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate.
- 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) Phosphate metal salts such as tert-butylphenyl) phosphate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis (dimethylbenzylidene) ) Polyhydric alcohols such as sorbitol Conductor, N, N ′,
- flame retardant examples include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis (diphenyl phosphate), (1-methylethylidene) ) -4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, ADK STAB FP-500 (manufactured by ADEKA), ADK STAB FP-600 (manufactured by ADEKA, ADK STAB) Aromatic phosphates such as FP-800 (manufactured by ADEKA Corporation), phosphonic acid esters such as divinyl phenylphosphonate, diallyl phenylphosphonate, phenylphosphonic acid (1-butenyl), diph Phosphin
- Phosphazene compounds melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, Metal hydroxide such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylene bis Tabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polypheny
- 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 scratches.
- 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 filler examples 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, Examples thereof include dolomite, mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate, etc., and the particle diameter (in the fibrous form, the fiber diameter, fiber length, and aspect ratio) is appropriately selected and used. be able to. Moreover, what was surface-treated as needed can be used for a filler.
- the hydrotalcite is a complex salt compound composed of magnesium, aluminum, a hydroxyl group, a carbonate group and any crystal water known as a natural product or a synthetic product.
- a part of magnesium or aluminum may be other metals such as alkali metals and zinc. Examples include those substituted with metal, hydroxyl groups, and carbonate groups substituted with other anionic groups.
- the hydrotalcite metal represented by the following general formula (4) is replaced with an alkali metal. The thing which was done is mentioned.
- the Al—Li hydrotalcite a compound represented by the following general formula (5) can also be used.
- x1 and x2 each represent a number satisfying the condition represented by the following formula, and p represents 0 or a positive number. 0 ⁇ x2 / x1 ⁇ 10, 2 ⁇ x1 + x2 ⁇ 20)
- a q ⁇ represents a q-valent anion, and p represents 0 or a positive number.
- the carbonate anion in the hydrotalcite may be partially substituted with another anion.
- the hydrotalcite may be obtained by dehydrating crystal water, higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal such as alkali metal dodecylbenzenesulfonate. It may be coated with a salt, higher fatty acid amide, higher fatty acid ester or wax.
- the hydrotalcite may be a natural product or a synthetic product.
- Japanese Patent Publication No. 46-2280 Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-174270, Known methods described in, for example, Japanese Laid-Open Patent Application No. 5-179052 are listed.
- the said hydrotalcite can be used without being restrict
- antistatic agent examples include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate esters, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic type Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfates, 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 alkyl allyl ether; amphoteric antistatic agents such as amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine and imidazoline type amphoteric activators. Such antistatic agents may be used alone, or two or more kinds of antistatic agents may be used in combination.
- the range of the preferable amount of the additive used in the resin composition of the present invention is a range in which the improvement of the additive effect is not seen from the amount where the effect is manifested.
- the final use amount of each additive in a molded product molded using the resin composition of the present invention is, in the case of polyolefin resin, 0.1% of phenolic antioxidant with respect to 100 parts by mass of polyolefin resin.
- the content is preferably 1 part by weight, 1 to 50 parts by weight of a flame retardant, 0.03 to 2 parts by weight of a lubricant, 0.03 to 2 parts by weight of hydrotalcite, and 0.03 to 2 parts by weight of an antistatic agent.
- the resin composition of the present invention can be suitably used as a vehicle member.
- vehicle member examples include an automobile, an industrial vehicle, a personal vehicle, a self-propelled vehicle body, a vehicle interior / exterior member such as a railroad, a vehicle outer plate, a vehicle resin window, and the like.
- the resin composition of the present invention may be such a resin base material or may be used as a protective film.
- vehicle exterior member examples include a door molding, a frame frame of a door mirror, a wheel cap, a spoiler, a bumper, a winker lens, a pillar garnish, a rear finisher, a head lamp cover, and the like.
- Examples of the vehicle interior member include an instrument panel, a console box, a meter cover, a door lock pzel, a steering wheel, a power window switch base, a center cluster, a dashboard, and a bonnet.
- Examples of the vehicle outer plate include a front fender, a door panel, a roof panel, a hood panel, a trunk lid, and a back door panel.
- Examples of the vehicle resin window include a sunroof, a windshield, a side glass, a rear glass, a rear water glass, and a rear door water glass.
- Example 1-1 From Comparative Examples 1-1 to 1-4, when the moisture content of silica is not within the numerical range of 2 to 7 wt%, there remains a problem in the handleability of the light stabilizer composition, whereas Example 1-1 From 1-7, it was confirmed that the light stabilizer composition of the present invention using silica having a silica water content of 2-7 wt% showed excellent handling properties.
- Example 2-1 Stabilization of polypropylene 70 parts by mass of polypropylene resin (MFR: 30 g / 10 min, density: 0.9 g / cm 3 ), 10 parts by mass of Dow's trade name Engage 8100 as an elastomer, and talc (product of Nippon Talc Co., Ltd.) as a filler Name P-4) 20 parts by mass, 0.05 parts by mass of tetrakis (3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxymethyl) methane as a phenolic antioxidant, phosphorus antioxidant As a pigment, 0.05 part by weight of tris (2,4-ditert-butylphenyl) phosphite, 0.05 part by weight of calcium stearate, and as a pigment, beige masterbatch (product name: PPCM700V-118) 3 manufactured by Tokyo Ink Co., Ltd.
- MFR polypropylene resin
- Engage 8100 as an elasto
- Example 1-1 0.1 parts by mass of the light stabilizer composition of Example 1-1 described in [Table 1] below, and mix well. And melt-kneaded at a resin temperature of 230 ° C. to pellet while vented through-screw extruder, and injection molded at 230 ° C., to obtain a test piece of 60mm ⁇ 20mm ⁇ 2mm.
- Comparative Example 2-1 A test piece was obtained in the same procedure as in Example 2-1 except that 0.1 part by weight of the light stabilizer composition of Example 1-1 was not blended.
- Example 2-1 the impregnation treatment of the hindered amine compound into silica was not performed instead of the light stabilizer composition of Example 1-1, but the same light stabilizer composition as in Example 1-1 was used.
- a test piece was obtained in the same procedure by blending 0.1 part by mass of the composition.
- test piece was subjected to a weather resistance test using a sunshine weatherometer under conditions of 83 ° C. and rain (ion exchange water was sprayed for 6 hours / day). The test piece was taken out every 120 hours and evaluated by the gloss maintenance rate of the test piece. Immediately after the evaluation, the test piece was set in a weather tester and the weather test was resumed.
- Comparative Example 2-1 since the surface of the test piece deteriorated significantly after 1320 hours, the subsequent evaluation was cancelled. From Example 2-1 and Comparative Example 2-2, it was confirmed that the light stabilizer composition of the present invention in which silica was impregnated with a hindered amine compound exhibited an excellent stabilizing effect. The result of good gloss maintenance suggests that blooming on the surface of the molded article by the hindered amine compound is suppressed, and the resin composition of the present invention is a vehicle member, particularly a vehicle interior member, in which appearance is important. Can be suitably used.
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- 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)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
Description
(A)シリカ
シリカは、天然品と合成品がありそれぞれ結晶質と非晶質の性質を有する。天然品の結晶質としては、石英、水晶、珪砂等を挙げることができ、天然品の非晶質としては、珪藻土、酸性白土等を挙げることができる。合成品としては、乾式シリカ、湿式シリカ、シリカゲル等の非晶質を挙げることができる。本発明においては、これらの中でも安価であることと樹脂と一緒に配合される添加剤の性能を阻害させない観点から、pHが6~8程度の中性にあるシリカが好ましい。
本発明で用いられるヒンダードアミン化合物は、上記一般式(1)で表される化合物であり、2,2,6,6-テトラメチルピペリジノール類と炭酸エステルとを反応させて得られる。
上記一般式(1)において、R1及びR2で表される炭素原子数1~30のアルキル基としては、例えばメチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、第二ブチル、第三ブチル、ペンチル、第二ペンチル、第三ペンチル、ヘキシル、ヘプチル、オクチル、イソオクチル、2-エチルヘキシル、第三オクチル、ノニル、イソノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル等を挙げることができる。R1及びR2は、同じものであってもよく、相違してもよい。
本発明に用いられる(C)ベンゾエート系光安定剤は、下記一般式(3)で表される化合物を表す。
また本発明の光安定剤組成物において、上記(C)一般式(3)で表されるベンゾエート系光安定剤と上記一般式(1)で表されるヒンダードアミン化合物との比率は、質量比でヒンダードアミン化合物の1/4~3/1の範囲内が好ましい。1/4より少ないと、ヒンダードアミン化合物とベンゾエート系光安定剤の組合せによる相乗効果が得られない場合があり、3/1より多いと、ヒンダードアミン化合物の光安定化能を発揮できない場合がある。
1.必要に応じて加熱して液体状態にしたヒンダードアミン化合物を、大気圧もしくは真空下に、シリカと混合してシリカに含浸させる方法。
2.固体のヒンダードアミン化合物をシリカと混合して、大気圧もしくは真空下に、固体のままシリカに吸着・収着させる方法。
3.ヒンダードアミン化合物を溶媒に溶解した溶液をシリカと混合して、大気圧もしくは真空下に、シリカに含浸させた後、溶媒を留去する方法。
4.ヒンダードアミン化合物をシリカの表面に担持させ、加圧によりヒンダードアミン化合物をシリカの細孔の内部に移動・吸着させる方法
5.ヒンダードアミン化合物を気化させ、気体状態でシリカに吸着・含浸させる方法
6.シリカの存在下で、ヒンダードアミン化合物を合成して、生成物としてヒンダードアミン化合物をシリカに含浸させる方法。
尚、上記(B)一般式(1)で表されるヒンダードアミン化合物は、上記(C)一般式(3)で表されるベンゾエート系光安定剤と混合したものであってもよく、本発明でいう含浸とは、固体の細孔に液体を含浸させたもの、又は、固体の細孔に固体の微粒子が吸着、収着したものを表す。
含浸は、回分式でも、半回分式でも、連続式で行われていてもよい。
安定化される樹脂として具体的には、例えば、ポリプロピレン、低密度ポリエチレン、直鎖低密度ポリエチレン、高密度ポリエチレン、ポリブテン-1、ポリ-3-メチルペンテン、ポリ-4-メチルペンテン、エチレン-プロピレン共重合体等のα-オレフィンの単重合体又は共重合体、これらのα-オレフィンと共役ジエン又は非共役ジエン等の多不飽和化合物、アクリル酸、メタクリル酸、酢酸ビニル等との共重合体、ポリエチレンテレフタレート、ポリエチレンテレフタレート・イソフタレート、ポリエチレンテレフタレート・パラオキシベンゾエート、ポリブチレンテレフタレート等の直鎖ポリエステルや酸変性ポリエステル、脂肪族ポリエステル等の生分解性樹脂、液晶ポリエステル、ポリカプロラクタム及びポリヘキサメチレンアジパミド等のポリアミド、液晶ポリアミド、ポリイミド、ポリスチレン、スチレン及び/又はα-メチルスチレンと他の単量体(例えば、無水マレイン酸、フェニルマレイミド、メタクリル酸メチル、ブタジエン、アクリロニトリル等)との共重合体(例えば、アクリロニトリルスチレン共重合体(AS)樹脂、アクリロニトリル-ブタジエン-スチレン共重合体(ABS)樹脂、メチルメタクリレートブタジエンスチレン共重合体(MBS)樹脂、耐熱ABS樹脂等)、ポリ塩化ビニル、ポリ塩化ビニリデン、塩素化ポリエチレン、塩素化ポリプロピレン、ポリフッ化ビニリデン、塩化ゴム、塩化ビニル-酢酸ビニル共重合体、塩化ビニル-エチレン共重合体、塩化ビニル-塩化ビニリデン共重合体、塩化ビニル-塩化ビニリデン-酢酸ビニル三元共重合体、塩化ビニル-アクリル酸エステル共重合体、塩化ビニル-マレイン酸エステル共重合体、塩化ビニル-シクロヘキシルマレイミド共重合体等の含ハロゲン樹脂、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸オクチル等の(メタ)アクリル酸エステルの重合物、ポリエーテルケトン、ポリビニルアセテート、ポリビニルホルマール、ポリビニルブチラール、ポリビニルアルコール、直鎖又は分岐のポリカーボネート、石油樹脂、クマロン樹脂、ポリフェニレンオキサイド、ポリフェニレンサルファイド、熱可塑性ポリウレタン、繊維素系樹脂等の熱可塑性樹脂;エポキシ樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル樹脂、熱硬化性ポリウレタン等の熱硬化性樹脂;天然ゴム、3-ヒドロキシブチラート等の微生物産製脂肪族ポリエステル、微生物産製脂肪族ポリアミド、デンプン、セルロース、キチン・キトサン、グルテン・ゼラチン等天然産製樹脂、汎用樹脂、エンジニアリング樹脂、ポリマーアロイ等、いずれの種類の樹脂でもよい。ここでいうポリマーアロイとは高分子多成分系のことであり、共重合によるブロックポリマーであってもよく、混合等によるポリマーブレンドでもよい。
また、上記ハイドロタルサイトにおける炭酸アニオンは、一部を他のアニオンで置換したものでもよい。
下記〔表1〕又は〔表2〕記載のヒンダードアミン化合物をFMミキサー(FM-20型,日本コークス株式会社製)を用いて40℃で20分間撹拌することにより、ヒンダードアミン化合物が溶融状態になったのを確認後、重量比(ヒンダードアミン化合物/シリカ)で、30/70、40/60、50/50の割合となるように常圧下にてシリカを加え、各々の比率で調製された光安定剤組成物を得た。
(1)性状
得られた光安定剤組成物をビーカーに加え、ガラス棒でビーカーの底に円を描くようにかき混ぜた後、性状を目視により評価した。
◎:サラサラの粉末状
○:しっとり感のある粉末状
△:ベトツキ感は低いが塊状
×:粘着性のノリ状
尚、粉末状であるものは取扱性が良好で樹脂中に均一分散させることが比較的容易であるが、塊状、ノリ状の光安定剤組成物は分散不良となる場合があり、充分な耐候性を付与することができないばかりか成形品の外観に悪影響を与える場合がある。
シリカとヒンダードアミン化合物をFMミキサーに投入する際に、シリカの帯電性を目視により下記条件に従って評価した。
○:問題なく投入ができる。
△:帯電により、FMミキサー内部にシリカが付着し、シリカの投入に支障がでる。
×:帯電により、FMミキサー周囲へのシリカの拡散が目立つ
得られた光安定剤組成物において、シリカとヒンダードアミン化合物の混ざりやすさについて目視により下記条件に従って評価した。
○:シリカがヒンダードアミン化合物を吸収して分離していない。
×:シリカとヒンダードアミン化合物が分離している。
ポリプロピレン樹脂(MFR:30g/10分、密度:0.9g/cm3)70質量部、エラストマーとして、ダウ社製商品名エンゲージ8100を10質量部、充填剤として、タルク(日本タルク株式会社製商品名P-4)20質量部、フェノール系酸化防止剤としてテトラキス(3-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシメチル)メタン0.05質量部、リン系酸化防止剤として、トリス(2,4-ジ第三ブチルフェニル)ホスファイト0.05質量部、ステアリン酸カルシウム0.05質量部、顔料として、東京インキ株式会社製ベージュマスターバッチ(製品名:PPCM700V-118)3質量部及び下記〔表1〕に記載の実施例1-1の光安定剤組成物0.1質量部を添加してよく混合し、二軸押出機によりベントしながら樹脂温度230℃で溶融混練してペレットとし、230℃で射出成形して、60mm×20mm×2mmの試験片を得た。
上記実施例2-1において、実施例1-1の光安定剤組成物0.1質量部を配合しなかった以外は、同一の手順にて試験片を得た。
上記実施例2-1において、実施例1-1の光安定剤組成物の代わりに、シリカへのヒンダードアミン化合物の含浸処理を実施しないが、実施例1-1の光安定剤組成物と同一の組成のものを0.1質量部配合して、同一の手順にて試験片を得た。
上記の得られた試験片を、サンシャインウェザオメーターで83℃、雨有(イオン交換水を6時間/1日散水)の条件で、耐候試験を行った。試験片は、120時間毎に取り出して試験片のグロス維持率で評価した。評価後は、直ちに試験片を耐候試験機にセットして耐候試験を再開した。
試験片の表面の光沢度(グロス)を、日本電色工業株式会社製光沢計(VG-2000)を用いて測定角度60°で測定して試験片のグロス維持率を評価した。グロス維持率は、初期のグロスの数値に対する測定値の比率を表す。これらの結果について、下記〔表3〕に示す。
実施例2-1と比較例2-2より、シリカにヒンダードアミン化合物を含浸させた本発明の光安定剤組成物は、優れた安定化効果を示すことが確認できた。グロス維持率が良好な結果から、ヒンダードアミン化合物による成形品表面へのブルーミングが抑制されることを示唆しており本発明の樹脂組成物は、外観を重視される車両用部材、特に、車両内装部材において好適に用いることができる。
Claims (6)
- 上記(A)成分であるシリカが、体積平均粒子径0.1~100μmのシリカである請求項1記載の光安定剤組成物。
- 樹脂100質量部に対し、請求項1~3の何れか1項記載の光安定剤組成物0.01~1質量部を配合してなることを特徴とする樹脂組成物。
- 上記樹脂が、ポリオレフィン系樹脂である請求項4記載の樹脂組成物。
- 請求項4又は5記載の樹脂組成物を成形してなる車両用部材。
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BR112016007012-7A BR112016007012B1 (pt) | 2013-11-26 | 2014-11-10 | Composição de estabilizante à luz, composição de resina, e, peça de veículo |
ES14865751T ES2754475T3 (es) | 2013-11-26 | 2014-11-10 | Composición estabilizante de la luz, y composición de resina que la contiene |
CN201480055538.0A CN105612241B (zh) | 2013-11-26 | 2014-11-10 | 光稳定剂组合物以及其树脂组合物 |
JP2015550633A JP6570449B2 (ja) | 2013-11-26 | 2014-11-10 | 光安定剤組成物及びその樹脂組成物 |
EP14865751.3A EP3075815B1 (en) | 2013-11-26 | 2014-11-10 | Light stabilizer composition and resin composition containing same |
KR1020167009087A KR102242620B1 (ko) | 2013-11-26 | 2014-11-10 | 광안정제 조성물 및 그 수지 조성물 |
US15/026,767 US20160237241A1 (en) | 2013-11-26 | 2014-11-10 | Light stabilizer composition and resin composition containing same |
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Cited By (2)
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WO2016159103A1 (ja) * | 2015-03-30 | 2016-10-06 | 株式会社Adeka | 光安定剤マスターバッチおよびその製造方法 |
WO2023199986A1 (ja) * | 2022-04-13 | 2023-10-19 | 株式会社Adeka | 光安定剤組成物、これを含む樹脂組成物の製造方法、光安定剤組成物の耐ブロッキング性向上方法、およびこれらに用いるヒンダードアミン化合物 |
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JP6630461B1 (ja) * | 2019-08-09 | 2020-01-15 | 株式会社Adeka | 農業用フィルム、農業用フィルム形成用樹脂組成物、及びそれを用いた植物の育成方法 |
JPWO2022075442A1 (ja) * | 2020-10-08 | 2022-04-14 | ||
CN112646152B (zh) * | 2020-12-10 | 2023-04-28 | 利安隆凯亚(河北)新材料有限公司 | 受阻胺类光稳定剂的制备方法 |
CN112877072A (zh) * | 2021-01-14 | 2021-06-01 | 柴松锋 | 一种长效性农林保水剂及其制备方法 |
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- 2014-11-10 EP EP14865751.3A patent/EP3075815B1/en active Active
- 2014-11-10 ES ES14865751T patent/ES2754475T3/es active Active
- 2014-11-10 US US15/026,767 patent/US20160237241A1/en not_active Abandoned
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WO2023199986A1 (ja) * | 2022-04-13 | 2023-10-19 | 株式会社Adeka | 光安定剤組成物、これを含む樹脂組成物の製造方法、光安定剤組成物の耐ブロッキング性向上方法、およびこれらに用いるヒンダードアミン化合物 |
Also Published As
Publication number | Publication date |
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BR112016007012B1 (pt) | 2022-02-01 |
US20160237241A1 (en) | 2016-08-18 |
EP3075815A1 (en) | 2016-10-05 |
KR102242620B1 (ko) | 2021-04-21 |
CN105612241B (zh) | 2018-09-25 |
EP3075815A4 (en) | 2017-09-13 |
ES2754475T3 (es) | 2020-04-17 |
JPWO2015079896A1 (ja) | 2017-03-16 |
CN105612241A (zh) | 2016-05-25 |
KR20160090792A (ko) | 2016-08-01 |
TWI630199B (zh) | 2018-07-21 |
JP6570449B2 (ja) | 2019-09-04 |
TW201527280A (zh) | 2015-07-16 |
EP3075815B1 (en) | 2019-10-09 |
BR112016007012A2 (pt) | 2017-08-01 |
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