WO2013176216A1 - 安定剤組成物、樹脂組成物、およびこれを用いた成形品 - Google Patents
安定剤組成物、樹脂組成物、およびこれを用いた成形品 Download PDFInfo
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- WO2013176216A1 WO2013176216A1 PCT/JP2013/064353 JP2013064353W WO2013176216A1 WO 2013176216 A1 WO2013176216 A1 WO 2013176216A1 JP 2013064353 W JP2013064353 W JP 2013064353W WO 2013176216 A1 WO2013176216 A1 WO 2013176216A1
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- carbon atoms
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- 0 COC(CCN**)=O Chemical compound COC(CCN**)=O 0.000 description 3
- NYBCMAOFJBQXBU-UHFFFAOYSA-N CC(C#CC#CCC=C)NC(C)=[IH]=CC Chemical compound CC(C#CC#CCC=C)NC(C)=[IH]=CC NYBCMAOFJBQXBU-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/12—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen
- C09K15/14—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen containing a phenol or quinone moiety
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
-
- 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
Definitions
- the present invention relates to a stabilizer composition, a resin composition, and a molded article using the same, and more specifically, a stabilizer composition, a resin composition, and The present invention relates to a molded article using the same, a stabilizer composition for a synthetic resin that does not contain solids, has excellent heat resistance, low viscosity, and good handleability, a synthetic resin composition, and a molded article using the same. .
- stabilizer compositions comprising monoesters of bisphenol sulfide alkyl mercaptocarboxylic acid and diesters thereof are polyvinyl chloride resin, polyethylene resin, polypropylene resin, polybutene resin, polybutylene terephthalate resin, polycarbonate resin, ABS. It is known to impart an excellent stabilizing effect to various synthetic resins such as resin, nylon 6, nylon 66, ethylene-vinyl acetate copolymer, petroleum resin, coumarone resin (Patent Documents 1 to 4). ).
- monoester compounds of bisphenol sulfide alkyl mercaptocarboxylic acid, diester compounds thereof, and thiodialkylcarboxylic acid dialkyl ester compounds are polyvinyl chloride resin, polyethylene resin, polypropylene resin, polybutene resin, polybutylene terephthalate resin. It is known to impart an excellent stabilizing effect to various synthetic resins such as polycarbonate resin, ABS resin, nylon 6, nylon 66, ethylene-vinyl acetate copolymer, petroleum resin, coumarone resin ( Patent Documents 1 to 4).
- the stabilizer composition containing a monoester and a diester of an alkyl mercaptocarboxylic acid of bisphenol sulfide is not particularly problematic in terms of storage stability at room temperature of about 25 ° C.
- the stabilizer composition becomes solid and handling becomes difficult, and improvement has been demanded.
- Patent Documents 1 to 4 describe the excellent stabilization effect of such a stabilizer composition, but do not particularly mention the problem relating to the storage stability when the stabilizer composition is stored for a long period of time. No solution has been suggested.
- the viscosity of the heat stabilizer composition containing the monoester compound of the alkyl mercaptocarboxylic acid of bisphenol sulfide and the diester compound thereof is high, and there is a problem that the pump that can be used when blended in the synthetic resin is limited. was there.
- the above problem can be improved by blending a low-viscosity compound.
- layer separation occurs, turbidity or solid matter is generated in the heat stabilizer composition, and this causes problems in quality control. End up.
- the hydroxyl group contained in the heat stabilizer composition inhibits the crosslinking of synthetic resins, particularly copolymers such as polyethylene, ethylene-vinyl acetate, ethylene-ethyl acrylate, ethylene-propylene, ethylene-propylene-butadiene. Have a problem.
- an object of the present invention is a stabilizer composition containing a monoester and a diester of an alkyl mercaptocarboxylic acid of bisphenol sulfide, which does not precipitate a solid even in a low temperature environment and can maintain the handleability.
- the stabilizer composition of the present invention has the following general formula (1), (Wherein R 1 , R 2 and R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an alkyl group or an alkoxy group) Represents an aryl group having 6 to 30 carbon atoms which may be substituted with an alkenyl group, an alkenyloxy group or a hydroxy group, and R 4 and R 5 each independently represents an alkoxy group, an alkenyl group, an alkenyloxy group, a hydroxy group A diester body represented by a straight chain or branched alkyl group having 3 to 30 carbon atoms which may be substituted with a group or a cyano group, and The following general formula (2), (Wherein R 1 , R 2 and R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl
- the viscosity of the stabilizer composition of the present invention is preferably 6,000 mPa ⁇ s or less.
- a pump to charge the stabilizer composition of the present invention into a synthetic resin or the like, a known pump such as a gear pump, a diaphragm pump, a rotary pump, a screw pump, a work pump, a sine pump, or a hose pump is used.
- a special pump may be required, or the stabilizer composition may adhere to the pump or the inner wall of the pipe and increase loss. Therefore, it is preferably 6,000 mPa ⁇ s or less.
- the diester represented by the general formula (1) and the monoester represented by the general formula (2) It is necessary to adjust to a specific composition ratio.
- R 4 and R 5 in the general formula (1) and R 6 in the general formula (2) are all the same alkyl group.
- the resin composition of the present invention is characterized by blending any of the above stabilizer compositions into a synthetic resin.
- the molded product of the present invention is formed by molding the above resin composition.
- the present inventors mixed a predetermined amount of a diester compound, a monoester compound, and a thiodialkylcarboxylic acid dialkyl ester compound having a predetermined structure.
- the present inventors have found that a heat stabilizer composition capable of solving the problems can be obtained, and have completed the present invention.
- the heat stabilizer composition of the present invention has the following general formula (3), (Wherein R 11 to R 18 each independently represents an alkyl group having 1 to 18 carbon atoms which may be interrupted by a hydrogen atom, oxygen atom or sulfur atom, or cycloalkyl having 3 to 18 carbon atoms) Or an aryl group having 6 to 30 carbon atoms which may be substituted with an alkyl group, alkoxy group, alkenyl group, alkenyloxy group or hydroxy group which may be interrupted by an oxygen atom or a sulfur atom, and R 19 and R 20 each independently represents an alkoxy group, an alkenyl group, an alkenyloxy group, a hydroxy group or a cyano group, and the number of carbon atoms which may be interrupted by an oxygen atom or a sulfur atom A diester compound represented by 3 to 30 linear or branched alkyl groups), The following general formula (4), (Wherein R 11 to R 18 each independently represents an alkyl group having 1 to 18 carbon atoms
- the diester body represented by the general formula (3) in a total of 100 parts by mass of the diester body compound represented by the general formula (3) and the monoester body compound represented by the general formula (4).
- the total content of the diester compound represented by the general formula (3) and the monoester compound represented by the general formula (4) and the general formula is greater than 65 parts by mass of the compound.
- the viscosity at 25 ° C. is preferably 3,000 mPa ⁇ s or less. Further, in the heat stabilizer composition of the present invention, the mass was 5% when heated from room temperature under the condition of a temperature increase rate of 10 ° C./min using nitrogen using differential thermal analysis (TG-DTA). The decreasing temperature is preferably 240 ° C. or higher.
- the synthetic resin composition of the present invention is characterized in that 0.01 to 5 parts by mass of the heat stabilizer composition of the present invention is blended with 100 parts by mass of the synthetic resin.
- the synthetic resin is preferably a polyolefin resin.
- the molded article of the present invention is characterized in that the synthetic resin composition of the present invention is molded.
- a solid composition does not precipitate even in a low-temperature environment, the handleability is good, the stabilizer composition, the resin composition and a molded product using the same, and the solid composition does not contain a solid and has excellent heat resistance.
- the stabilizer composition of the present invention comprises an alkyl mercaptocarboxylic acid diester of bisphenol sulfide represented by the general formula (1) and an alkyl mercaptocarboxylic acid monoester of bisphenol sulfide represented by the general formula (2).
- the content of the compound represented by the general formula (1) is more than 65 parts by mass and less than 80 parts by mass. It is characterized by.
- the stabilizer composition of the present invention is a low-viscosity liquid with good handleability, and even when stored at a low temperature, for example, in an environment of 5 ° C., solid matter precipitation is suppressed.
- the viscosity is preferably 6,000 mPa ⁇ s or less.
- the viscosity is a viscosity at 25 ° C., and can be measured by, for example, a B-type viscometer.
- the stabilizer composition of the present invention preferably consists essentially of a diester represented by the above general formula (1) and a monoester represented by the above general formula (2).
- other components such as additives generally used in the resin as described below may be included.
- the main component in the stabilizer composition of the present invention is the compound represented by the above general formula (1) and the compound represented by the general formula (2). Is preferably 1000 parts by mass or less with respect to 100 parts by mass in total of the diester represented by the general formula (1) and the monoester represented by the general formula (2).
- Examples of the optionally substituted linear or branched alkyl group having 3 to 30 carbon atoms represented by R 4 and R 5 in the general formula (1) and R 6 in the general formula (2) include: Propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, s-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, 2-ethylhexyl group, isohexyl group, heptyl group, octyl group, isooctyl group
- the alkyl group may be substituted with an alkenyl group, an alkenyloxy group, a hydroxy group, or a cyano group, and may be interrupted with an oxygen atom or a sulfur atom. These interruptions or substitutions may be combined.
- a compound having an alkyl group having less than 3 carbon atoms may bleed or fog on the surface of the molded product, which may impair the appearance of the molded product. If the alkyl group has more than 30 carbon atoms, the required stabilizing effect may not be obtained.
- a stabilizer composition containing a compound in which R 4 , R 5 and R 6 are all the same alkyl group is preferably used because it has a relatively low viscosity and good thermal stability.
- Examples of the alkyl group having 1 to 18 carbon atoms represented by R 1 , R 2 and R 3 in the general formulas (1) and (2) are the same as those described above for the alkyl group. It is done.
- Examples of the cycloalkyl group having 3 to 18 carbon atoms represented by R 1 , R 2 and R 3 in the general formulas (1) and (2) include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and cycloheptyl.
- Group, cyclooctyl group, cyclononyl group, 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,
- the alkyl group may be interrupted with an oxygen atom or a sulfur atom.
- Examples of the aryl group of 6 to 30 include phenyl group, methylphenyl group, butylphenyl group, octylphenyl group, 4-hydroxyphenyl group, 3,4,5-trimethoxyphenyl group, and 4-tert-butylphenyl.
- 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.
- the diester represented by the general formula (1) is preferably represented by the following general formula (1 ′). (In the formula, R 1 to R 5 are the same as those in the general formula (1).)
- the monoester body represented by the said General formula (2) is what is represented by the following general formula (2 '). (Wherein R 1 to R 3 and R 6 each represents the same as in general formula (2))
- Synthetic resins stabilized by the stabilizer composition of the present invention include ⁇ -olefin polymers such as polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polybutene-1, and poly-4-methylpentene. Or polyolefins such as ethylene-vinyl acetate copolymer and ethylene-propylene copolymer and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl Halogen-containing resin such as maleimide copolymer, petroleum resin, coumaro Copoly
- the stabilizer composition of the present invention is also favorably used for synthetic resins for crosslinking produced by peroxides or radiation, and foamed resins such as foamed polystyrene.
- the synthetic resin for crosslinking include polyethylene and copolymers such as ethylene-vinyl acetate, ethylene-ethyl acrylate, ethylene-propylene, and ethylene-propylene-butadiene.
- crosslinking agent examples include benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane, 2,5- Dimethyl-2,5-di (tert-butylperoxy) hexyne, 1,3-bis (tert-butylperoxyisopropyl) benzene, tert-butyl hydroperoxide, cumene hydroperoxide, polysulfone azide, azidoformate, tetramethylisophthalyl di- Examples thereof include tert-butyl bisperoxide, tetramethylisophthalyl dicumyl bisperoxide, alkanolamines such as diethanolamine and triethanolamine, hexamethylenediamine, and 4,4′-diaminodiphenylmethane.
- polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer resin are preferably used because of the excellent stabilization effect of the stabilizer composition of the present invention. That is, the stabilizer composition of the present invention is suitable as a stabilizer for polyolefin resins.
- the stabilizer composition of the present invention may contain other components other than the compound represented by the general formula (1) and the compound represented by the general formula (2).
- other components include additives usually used for synthetic resins.
- additives include phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet absorbers, hindered amine compounds, flame retardants, nucleating agents, fillers, lubricants, antistatic agents, Heavy metal deactivators, metal soaps, hydrotalcite, pigments, dyes, plasticizers and the like.
- the phenolic antioxidant may be the same as or different from that represented by the general formula (1).
- examples of the phenol-based antioxidant include 2,6-di-tert-butyl 4-ethylphenol, 2-tert-butyl 4,6-dimethylphenol, styrenated phenol, 2,2′-methylenebis (4- Ethyl-6-tert-butylphenol), 2,2'-thiobis- (6-tert-butyl 4-methylphenol), 2,2'-thiodiethylenebis [3- (3,5-di-tert-butyl-4) -Hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2′-isobutylidenebis (4,6-dimethylphenol), iso-octyl-3- (3 5-di-tert-butyl 4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis
- 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-di-ter
- 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 compound examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6. -Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2, 3,4-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- Peridyl) .di (tridecyl) -1,
- the flame retardant examples include aromatic phosphoric acid such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate and resorcinol bis (diphenyl phosphate) Phosphonates such as esters, 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 polyphosphate
- nucleating agent examples include carboxylic acids such as sodium benzoate, 4-tert-butylbenzoic 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-ditert-butylphenyl) phosphate and lithium-2,2′-methylenebis (4,6-di) Phosphate 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-methylcyclohexane Xyl] -1,2,3-propanetricarboxamide (RIKACLEAR PC1), N, N ′, N ′′ -tricyclohexyl 1,3,5-benzenetricarboxamide, N, N′-dicyclohexyl-
- 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 fibrous) of 5 ⁇ m or less are preferable.
- 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 above-mentioned antistatic agent is added for the purpose of reducing the chargeability of the molded product and preventing dust adhesion due to charging.
- the antistatic agent include cationic, anionic and nonionic.
- Preferred examples include polyoxyethylene alkylamines, polyoxyethylene alkylamides or their fatty acid esters, glycerin fatty acid esters, and the like.
- the range of the preferable amount of other additives used in the present invention is a range in which the improvement of the additive effect is not observed from the amount where the effect is manifested.
- the amount of each additive used is 0.1 to 20 parts by weight of a plasticizer, 1 to 50 parts by weight of a filler, and 0.001 to 1 part by weight of a surface treatment agent with respect to 100 parts by weight of a synthetic resin.
- 0.001 to 10 parts by mass of a phenolic antioxidant 0.001 to 10 parts by mass of a phosphorus antioxidant, 0.001 to 10 parts by mass of a thioether antioxidant, 0.001 to 5 parts by mass of an ultraviolet absorber Part, hindered amine compound 0.01 to 1 part by weight, flame retardant 1 to 50 part by weight, lubricant 0.03 to 2 part by weight, antistatic agent 0.03 to 2 part by weight, nucleating agent 0.0.
- the amount is preferably 01 to 10 parts by mass.
- these additives may be used individually by 1 type, and may be used in combination of 2 or more types.
- the resin composition of the present invention is obtained by blending the above-described stabilizer composition of the present invention with the above-described synthetic resin.
- the amount of the stabilizer composition of the present invention is preferably 0.01 to 5.0 parts by mass, more preferably 0.1 to 1.0 parts by mass with respect to 100 parts by mass of the synthetic resin.
- the molded product of the present invention is obtained by molding the resin composition of the present invention by a known molding method such as extrusion molding, injection molding, hollow molding, compression molding or the like.
- Uses and forms of the molded article of the present invention include automobile interior and exterior products, food containers, cosmetic and clothing containers, food bottles, beverage bottles, edible oil bottles, seasoning bottles and other bottles, food packaging materials, Examples include wrapping materials, packaging materials such as transportation packaging materials, protective films for electronic materials, sheets and films such as protective sheets for electrical appliances, fibers, daily goods, toys, and the like.
- the heat stabilizer composition of the present invention is represented by a diester compound represented by the following general formula (3), a monoester compound represented by the following general formula (4), and the following general formula (5).
- a thiodialkylcarboxylic acid dialkyl ester compound is represented by the following general formula (3), a monoester compound represented by the following general formula (4), and the following general formula (5).
- the ratio of the diester compound represented by the general formula (3) and the monoester compound represented by the general formula (4) is represented by the general formula (3).
- the diester compound represented by the general formula (3) is 65 parts by mass or more with respect to 100 parts by mass of the total amount of the diester compound and the monoester compound represented by the general formula (4).
- the amount is preferably 70 to 90 parts by mass, more preferably 70 to 85 parts by mass. This is because when the diester compound represented by the general formula (3) is less than 65 parts by mass, the viscosity of the heat stabilizer composition may increase.
- the viscosity of the heat stabilizer composition may increase, and the thiol represented by the general formula (5) This is because if the ratio of the dialkyl carboxylic acid dialkyl ester compound is more than 50, the heat stabilizer composition may have insufficient heat resistance.
- the heat stabilizer composition of the present invention is a low-viscosity liquid that does not contain solids and has good handleability, and does not inhibit crosslinking of the synthetic resin to be blended.
- the viscosity is preferably 3,000 mPa ⁇ s or less. When the viscosity exceeds 3,000 mPa ⁇ s, the pump that can be used for delivery of the heat stabilizer composition is limited, which may hinder the handling property.
- the viscosity in this invention is a viscosity in 25 degreeC, for example, can be measured with a B-type viscometer.
- the heat stabilizer composition of the present invention is preferably a diester compound represented by the general formula (3), a monoester compound represented by the general formula (4), and the general formula (5).
- the thiodialkylcarboxylic acid dialkyl ester compound represented by formula (1) may contain other components such as components generally used for the synthetic resin as long as the effects of the present invention are not impaired. Good.
- the main component in the heat stabilizer composition of the present invention is a diester compound represented by the above general formula (3), a monoester compound represented by the general formula (4), and It is a thiodialkylcarboxylic acid dialkyl ester compound represented by the general formula (5), and the content of other components is represented by the diester compound represented by the general formula (3), the general formula (4).
- the total amount of the monoester compound and the thiodialkylcarboxylic acid dialkyl ester compound represented by the general formula (5) is preferably 100 parts by mass or less.
- Examples of the alkyl group having 1 to 18 carbon atoms represented by R 11 to R 18 in the general formulas (3) and (4) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and isobutyl.
- This alkyl group may be interrupted by an oxygen atom or a sulfur atom.
- Examples of the cycloalkyl group having 3 to 18 carbon atoms represented by R 11 to R 18 in the general formulas (3) and (4) include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclo An octyl group, a cyclononyl group, a cyclodecyl group, a cyclododecyl group, a 4-methylcyclohexyl group and the like can be mentioned.
- the hydrogen atom in the cycloalkyl group is an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, a hydroxy group, Alternatively, it may be substituted with a cyano group, and this alkyl group may be interrupted with an oxygen atom or a sulfur atom.
- 6 to 6 carbon atoms which may be substituted with an alkyl group, alkoxy group, alkenyl group, alkenyloxy group or hydroxy group represented by R 11 to R 18
- the 30 aryl groups include a phenyl group, a methylphenyl group, a butylphenyl group, an octylphenyl group, a 4-hydroxyphenyl group, a 3,4,5-trimethoxyphenyl group, a 4-tert-butylphenyl group, and a biphenyl.
- the hydrogen atom in the aryl group may be substituted with an alkyl group, alkenyl group, alkenyloxy group, hydroxy group, or cyano group, and the alkyl group may be interrupted with an oxygen atom or a sulfur atom. .
- the 30 straight or branched alkyl groups include propyl, isopropyl, butyl, isobutyl, tert-butyl, s-butyl, pentyl, isopentyl, neopentyl, hexyl, 2-ethylhexyl, Examples include isohexyl group, heptyl group, octyl group, isooctyl group, nonyl group, decyl group, isodecyl group, lauryl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, tetracosyl group, and octacosyl group. .
- the alkyl group may be substituted with an alkoxy group, an alkenyl group, an alkenyloxy group, a hydroxy group, or a cyano group, and may be interrupted with an oxygen atom or a sulfur atom. These interruptions or substitutions may be combined.
- a compound having an alkyl group having less than 3 carbon atoms may bleed or fog on the surface of the molded product, which may impair the appearance of the molded product. If the alkyl group has more than 30 carbon atoms, the required stabilizing effect may not be obtained.
- linear or branched alkylene group having 1 to 8 carbon atoms which may be substituted with an alkoxy group, alkenyl group, alkenyloxy group, hydroxy group or cyano group represented by A in the general formula (5)
- alkoxy group alkenyl group, alkenyloxy group, hydroxy group or cyano group represented by A in the general formula (5)
- Examples include methylene group, ethylene group, propylene group, propane-2,2-diyl group, butylene group, isobutylene group, hexylene group and heptylene group.
- the alkylene group may be interrupted with an oxygen atom or a sulfur atom.
- the diester compound represented by the general formula (3) is preferably a compound represented by the following general formula (3 ′).
- R 11 to R 20 each represent the same as in the general formula (3).
- the monoester compound represented by the general formula (4) is preferably a compound represented by the following general formula (4 ′).
- R 11 to R 18 and R 21 are the same as those in the general formula (4).
- the thiodialkylcarboxylic acid dialkyl ester compound represented by the general formula (5) is preferably a compound represented by the following general formula (5 ′).
- R 22 represents the same as in the general formula (5).
- the specific structure of the diester compound represented by the general formula (3) is as follows. Examples of the compound include 3-1 to 3-14. However, the present invention is not limited by the following compounds.
- the compound in which R 19 and R 20 in formula (3) are C12-14 mixed alkyl groups is a compound in which R 19 and R 20 in formula (3) are alkyl groups having 12 carbon atoms, And a mixture of compounds which is an alkyl group having 14 carbon atoms.
- a compound in which R 21 in formula (4) is a C12-14 mixed alkyl group is a compound in which R 21 in formula (4) is an alkyl group having 12 carbon atoms, and a compound having 14 carbon atoms. It represents a mixture of compounds is an alkyl group, R 21 in the formula (4) is a compound having a C24-28 mixed alkyl groups, R 21 in the formula (22), carbon atoms 24-28 alkyl group Represents a mixture of compounds.
- Specific structures of the thiodialkylcarboxylic acid dialkyl ester compound represented by the general formula (5) include, for example, dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate. , Dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, mixed lauryl / stearyl-3,3′-thiodipropionate, di (2-ethylhexyl) -3, And 3'-thiodipropionate.
- the present invention is not limited by the above compounds.
- the viscosity of the heat stabilizer composition of the present invention at 25 ° C. is preferably 3,000 mPa ⁇ s or less.
- a pump to charge the heat stabilizer composition of the present invention into a synthetic resin, a gear pump, a diaphragm pump, a rotary pump, a screw pump, a work pump, a sine pump, a hose pump, a chemical pump, an air pressure pump, etc.
- a special pump is required, or it adheres to the inner wall of the pump or piping and loss increases. It is because there is a case where it is.
- the diester compound represented by the general formula (3) and the monoester compound represented by the general formula (4) It is necessary to adjust the compound and the thiodialkylcarboxylic acid dialkyl ester compound represented by the general formula (5) to the above specific composition ratio.
- the hydroxyl group contained in the heat stabilizer composition is preferably 1% by mass or less, more preferably 0.65% by mass or less of the heat stabilizer composition.
- the ratio of the hydroxyl group is higher than 1.0% by mass, it may inhibit crosslinking of polyethylene or a copolymer such as ethylene-vinyl acetate, ethylene-ethyl acrylate, ethylene-propylene, ethylene-propylene-butadiene. is there.
- the thermal stabilizer composition of the present invention is a temperature at which the mass decreases by 5% when heated from room temperature under the condition of a heating rate of 10 ° C./min under nitrogen using differential thermal analysis (TG-DTA). However, it is preferable that it is 240 degreeC or more. This is because if the temperature is less than 240 ° C., there may be cases where a sufficient stabilizing effect cannot be imparted to the synthetic resin containing the heat stabilizer composition of the present invention.
- Examples of the above components include phenolic antioxidants, phosphorus antioxidants, thioether antioxidants other than the compounds represented by the general formulas (3) to (5), ultraviolet absorbers, hindered amine compounds, Examples include flame retardants, nucleating agents, fillers, lubricants, antistatic agents, heavy metal deactivators, metal soaps, hydrotalcite, pigments, dyes, plasticizers, and the like.
- phenolic antioxidant phosphoric acid antioxidant, ultraviolet absorber, hindered amine compound, flame retardant, nucleating agent, filler, lubricant, and antistatic agent
- phosphoric acid antioxidant ultraviolet absorber
- hindered amine compound hindered amine compound
- flame retardant nucleating agent
- filler filler
- lubricant filler
- antistatic agent antistatic agent
- Examples of the thioether antioxidant other than the compounds represented by the general formulas (3) to (5) include tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n- Alkyl (C12 / C14) thiopropionyloxy] 5-tert-butylphenyl) sulfide, 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-thiobis (6-tert-butyl- p-cresol) and distearyl-disulfide.
- the preferable range of the amount of other components used in the present invention is a range in which the improvement of the additive effect is not observed from the amount at which the effect is manifested.
- the amount of each component used is 0.1 to 20 parts by weight of the plasticizer, 1 to 50 parts by weight of the filler, 0.001 to 1 part by weight of the surface treatment agent, and 100 parts by weight of phenol, based on 100 parts by weight of the synthetic resin.
- the hindered amine compound is preferably 0.01 to 1 part by mass
- the flame retardant is 1 to 50 parts by mass
- the lubricant is 0.03 to 2 parts by mass
- the antistatic agent is preferably 0.03 to 2 parts by mass.
- these components may be used individually by 1 type, and may be used in combination of 2 or more types.
- the synthetic resin composition of the present invention is obtained by blending 0.01 to 5 parts by mass of the heat stabilizer composition of the present invention with 100 parts by mass of the synthetic resin.
- Synthetic resins stabilized by the heat stabilizer composition of the present invention include ⁇ -olefin heavy polymers such as polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polybutene-1, and poly-4-methylpentene.
- Polymer or polyolefin such as ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene Copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride- Halogen-containing resin such as cyclohexylmaleimide copolymer, petroleum resin, coumaro Copolymer of resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and / or ⁇ -methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide
- elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, or may be included in the above resin.
- polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer resin are preferably used because they are excellent in stabilizing effect by the heat stabilizer composition of the present invention.
- the heat stabilizer composition of the present invention can also be suitably used for a synthetic resin for crosslinking produced by peroxide or radiation, and a foamed resin such as foamed polystyrene.
- a synthetic resin for crosslinking include polyethylene and copolymers such as ethylene-vinyl acetate, ethylene-ethyl acrylate, ethylene-propylene, and ethylene-propylene-butadiene.
- crosslinking agent examples include benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane, 2, 5-dimethyl-2,5-di (tert-butylperoxy) hexyne, 1,3-bis (tert-butylperoxyisopropyl) benzene-tert-butyl-hydroperoxide, cumene hydroperoxide, polysulfone azide, azidoformate, tetramethyliso
- examples include phthalyl di-tert-butyl bisper oxide, tetramethylisophthalyl dicumyl bisper oxide, alkanolamines such as diethanolamine and triethanolamine, hexamethylenediamine, and 4,4′-diaminodiphenylmethane.
- the synthetic resin composition of the present invention other components may be blended as long as the desired effects of the present invention are not impaired, in the same manner as the heat stabilizer composition of the present invention.
- the same components as those of the heat stabilizer composition of the present invention can be used.
- the molded article of the present invention is obtained by molding the above synthetic resin composition of the present invention.
- the molded product of the present invention can be molded by a known molding method such as extrusion molding, injection molding, hollow molding or compression molding.
- molded articles of the present invention automobile interior and exterior products, food containers, cosmetic and clothing containers, food bottles, beverage bottles, edible oil bottles, seasoning bottles and other bottles, food packaging materials, wrapping materials, Examples include packaging materials such as packaging materials for transportation, protective films for electronic materials, coating materials for electric wires, sheets and films such as protective sheets for electrical appliances, fibers, household goods, toys, and the like.
- Examples 1-1 to 1-5, Comparative Examples 1-1 and 1-2 As a diester represented by the general formula (1), in the general formula (1 ′), R 1 to R 3 are hydrogen atoms, and R 4 and R 5 are substituents described in the table, respectively. As the compound and the monoester represented by the general formula (2), in the general formula (2 ′), R 1 to R 3 are hydrogen atoms, and R 6 is a substituent described in the table. Each compound was added to each reagent glass bottle, stirred well, sealed, and placed in a 5 ° C. incubator. The following evaluation was performed on these samples.
- ⁇ Low temperature storage> The state of the sample was visually observed every week. Evaluation was performed by the following method. -: Liquid and solid matter is not seen. A: A solid substance slightly precipitated. B: A large solid was deposited, but more than half was liquid. C: More than half precipitated as a solid. D: The whole amount precipitated as a solid.
- the viscosity was measured under the conditions of (B-type viscometer / 4 router / 25 ° C./60 rpm) for the sample that had passed 5 months.
- the ratio of the compound represented by the formula (1) is 80 parts by mass or more with respect to 100 parts by mass of the total amount of the compounds represented by the general formula (1) and the general formula (2).
- the storage stability in a low temperature environment deteriorated, and it was confirmed that solid matter was generated after 2 months.
- the ratio of the compound represented by Formula (1) is 65 mass parts or less with respect to 100 mass parts of total amounts of the compounds represented by General Formula (1) and (2). It was confirmed that the viscosity became higher than 6,000 mPa ⁇ s. From Reference Example 1-1, no solid matter was generated when stored at room temperature even when the proportion of the compound represented by formula (1) exceeded 80 parts by mass.
- the amount of the compound represented by the formula (1) is 100 parts by mass with respect to the total amount of the compounds represented by the general formulas (1) and (2).
- the stabilizer composition of the present invention having a ratio in the range of more than 65 parts by weight and less than 80 parts by weight is handled with a low viscosity of 6,000 mPa ⁇ s or less without generating solids even in a low temperature environment. It was confirmed that a liquid stabilizer having excellent properties could be obtained.
- R 22 is a substituent described in the table as a compound that is a substituent and a thiodialkylcarboxylic acid dialkyl ester compound represented by the general formula (5). Reagent glass for each compound In addition, one day and allowed to stand sealed for after well stirring.
- Example 2-3 In Example 2-3, except that 2-methyl-4,6-bis [(octylthio) methyl] phenol was used instead of the thiodialkylcarboxylic acid dialkyl ester compound represented by the general formula (5), Evaluation was performed in the same manner as in Example 2-3.
- the sample is heated with a differential scanning calorimeter (Thermo Plus TG8120; manufactured by Rigaku Corporation) under a nitrogen atmosphere (20 ml / min) under a temperature rising condition of 10 ° C./min, and the mass of the sample is reduced by 5%. The measured temperature was measured. The obtained results are also shown in Tables 2 and 3.
- C 12-14 mixed alkyl a compound in which R 15 and R 16 in the above general formula (3) or R 17 in the above general formula (4) is an alkyl group having 12 carbon atoms and carbon It represents a mixture of compounds which is an alkyl group having 14 atoms.
- the heat stabilizer composition of the present invention has a low viscosity, excellent handleability, good heat resistance, and an excellent liquid heat stabilizer composition free of solid matter.
- the heat stabilizer composition of this invention has few hydroxyl groups contained in a heat stabilizer composition, the effect which does not inhibit the bridge
- the mixture was kneaded with a mixing roll for 6 minutes and 30 seconds, and then compression-molded for 5 minutes under the conditions of 120 ° C. and 9.8 MPa to prepare a sheet having a thickness of 2 mm. Furthermore, a sheet having a thickness of 2 mm was compression-molded for 20 minutes under the conditions of 170 ° C. and 9.8 MPa to promote the cross-linking reaction of polyethylene, thereby producing a sheet having a thickness of 1 mm. This 1 mm thick sheet was cut into a size of 170 ⁇ 130 mm, and this sample was subjected to a thermal deterioration test in a gear oven at 150 ° C. in an air atmosphere.
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Abstract
Description
(式中、R1、R2およびR3は、各々独立して、水素原子、炭素原子数1~18のアルキル基、炭素原子数3~18のシクロアルキル基、または、アルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基またはヒドロキシ基で置換されていてもよい炭素原子数6~30のアリール基を表し、R4およびR5は各々独立に、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよい炭素原子数3~30の直鎖または分岐アルキル基を表す。)で表されるジエステル体、および、
下記一般式(2)、
(式中、R1、R2およびR3は、各々独立して、水素原子、炭素原子数1~18のアルキル基、炭素原子数3~18のシクロアルキル基、または、アルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基またはヒドロキシ基で置換されていてもよい炭素原子数6~30のアリール基を表し、R6は、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよい炭素原子数3~30の直鎖または分岐アルキル基を表す。)で表されるモノエステル体を含む安定剤組成物であって、
前記式(1)で表されるジエステル体と前記式(2)で表されるモノエステル体の合計100質量部中、前記式(1)で表されるジエステル体の含有量が、65質量部より多く、80質量部未満であることを特徴とするものである。
(式中、R11~R18は、それぞれ独立して、水素原子、酸素原子または硫黄原子で中断されていてもよい炭素原子数1~18のアルキル基、炭素原子数3~18のシクロアルキル基、または酸素原子または硫黄原子で中断されていてもよいアルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基またはヒドロキシ基で置換されていてもよい炭素原子数6~30のアリール基を表し、R19およびR20はそれぞれ独立に、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよく、また、酸素原子、または硫黄原子で中断されていてもよい炭素原子数3~30の直鎖または分岐アルキル基である。)で表されるジエステル体化合物と、
下記一般式(4)、
(式中、R11~R18は、それぞれ独立して、水素原子、酸素原子または硫黄原子で中断されていてもよい炭素原子数1~18のアルキル基、炭素原子数3~18のシクロアルキル基、または酸素原子または硫黄原子で中断されていてもよいアルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基またはヒドロキシ基で置換されていてもよい炭素原子数6~30のアリール基を表し、R11はアルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよく、また、酸素原子、または硫黄原子で中断されていてもよい炭素原子数3~30の直鎖または分岐アルキル基である。)で表されるモノエステル体化合物と、
下記一般式(5)、
(式中、R22は、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよく、また、酸素原子、または硫黄原子で中断されていてもよい炭素原子数3~30の直鎖または分岐アルキル基であり、Aは、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよい炭素原子数1~8の直鎖または分岐のアルキレン基を表す。)で表されるチオジアルキルカルボン酸ジアルキルエステル化合物と、を含む熱安定剤組成物であって、
前記一般式(3)で表されるジエステル体化合物と、前記一般式(4)で表されるモノエステル体化合物と、の合計100質量部中、前記一般式(3)で表されるジエステル体化合物の含有量が、65質量部より多く、かつ、前記一般式(3)で表されるジエステル体化合物と前記一般式(4)で表されるモノエステル体化合物と、の合計と前記一般式(5)で表されるチオジアルキルカルボン酸ジアルキルエステル化合物の質量比が、{(3)+(4)}/(5)=95/5~50/50の範囲内であることを特徴とするものである。
本発明の安定剤組成物は、上記一般式(1)で表されるビスフェノールスルフィドのアルキルメルカプトカルボン酸ジエステルおよび一般式(2)で表されるビスフェノールスルフィドのアルキルメルカプトカルボン酸モノエステルを含むものであり、式(1)の化合物と式(2)の化合物の合計量100質量部中、一般式(1)で表される化合物の含有量が、65質量部より多く80質量部未満であることを特徴とするものである。本発明の安定剤組成物は、取扱性の良好な低粘度の液状であり、低温下、例えば5℃の環境下、において保存しても、固形分の析出が抑制される。粘度は、好ましくは6,000mPa・s以下である。粘度は、25℃における粘度であり、例えばB型粘度計によって測定することができる。
本発明の熱安定剤組成物は、下記一般式(3)で表されるジエステル体化合物および下記一般式(4)で表されるモノエステル体化合物、および、下記一般式(5)で表されるチオジアルキルカルボン酸ジアルキルエステル化合物を含むものである。
本発明の合成樹脂組成物は、合成樹脂100質量部に対して、上記本発明の熱安定剤組成物が0.01~5質量部配合されてなるものである。本発明の熱安定剤組成物によって安定化される合成樹脂としては、ポリプロピレン、高密度ポリエチレン、低密度ポリエチレン、直鎖低密度ポリエチレン、ポリブテン-1、ポリ-4-メチルペンテン等のα-オレフィン重合体またはエチレン-酢酸ビニル共重合体、エチレン-プロピレン共重合体等のポリオレフィンおよびこれらの共重合体、ポリ塩化ビニル、ポリ塩化ビニリデン、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、石油樹脂、クマロン樹脂、ポリスチレン、ポリ酢酸ビニル、アクリル樹脂、スチレンおよび/または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、AS樹脂、ABS樹脂、MBS樹脂、耐熱ABS樹脂等)、ポリメチルメタクリレート、ポリビニルアルコール、ポリビニルホルマール、ポリビニルブチラール、ポリエチレンテレフタレート、ポリブチルテレフタレート、ポリテトラメチルテレフタレート等の直鎖ポリエステル、ポリフェニレンオキサイド、ポリカプロラクタムおよびポリヘキサメチレンアジパミド等のポリアミド、ポリカーボネート、分岐ポリカーボネート、ポリアセタール、ポリフェニレンサルファイド、ポリウレタン、繊維素系樹脂等の熱可塑性樹脂、およびこれらの混合物、または、フェノール樹脂、ユリア樹脂、メラミン樹脂、エポキシ樹脂、不飽和ポリエステル樹脂等の熱硬化性樹脂を挙げることができる。さらに、イソプレンゴム、ブタジエンゴム、アクリロニトリル-ブタジエン共重合ゴム、スチレン-ブタジエン共重合ゴム等のエラストマーであってもよく、上記樹脂に含むものであってもよい。
一般式(1)で表されるジエステル体として、上記一般式(1’)中、R1~R3が水素原子であり、R4およびR5がそれぞれ表中に記載された置換基である化合物、および、一般式(2)で表されるモノエステル体として、上記一般式(2’)中、R1~R3が水素原子であり、R6が表中に記載された置換基である化合物をそれぞれ試薬ガラス瓶に加え、よく撹拌したのちに密栓して5℃の恒温器内に静置した。これらの試料に対して、以下の評価を行った。
表1の比較例1-1の試料については、5℃の恒温器を用いずに、常温(25℃)で放置し、以下の評価を行った。
一週間毎に試料の状態を目視観察した。評価は、下記の方法で行った。
-:液状で固形物がみられない。
A:わずかに固形物が析出した。
B:大きな固形物が析出したが、半分以上は液状。
C:半分以上が固形物で析出した。
D:全量が固形物として析出した。
試料を100gフラスコに入れ、25℃(常温)にてフラスコを逆さにして試料の97gが受け皿であるビーカーに落ちるまでの時間を測定した。97gが落ちるまでの時間が5分以内の場合を○、5分経過後8分以内の場合を△、8分超経過した場合を×として評価した。これらの結果について表1に示す。
一般式(3)で表されるジエステル体化合物として、上記一般式(3’)中の、R11およびR17が第三ブチル基、R13およびR15がメチル基、R12、R14、R16、R18が水素原子であり、R19およびR20がそれぞれ表中に記載された置換基である化合物、一般式(4)で表されるモノエステル体化合物として、上記一般式(4’)中、R11およびR17が第三ブチル基、R13およびR15がメチル基、R12、R14、R16、R18が水素原子であり、R21が、表中に記載された置換基である化合物、および、上記一般式(5)で表されるチオジアルキルカルボン酸ジアルキルエステル化合物として、上記一般式(5’)中、R22が表中に記載された置換基である化合物をそれぞれ試薬ガラス瓶に加え、よく撹拌したのちに密栓して一昼夜静置した。
比較例2-2において、上記一般式(5)で表されるチオジアルキルカルボン酸ジアルキルエステル化合物の代わりに、2-メチル-4,6-ビス[(オクチルチオ)メチル]フェノールを用いた以外は、比較例2-2と同様にして評価した。
実施例2-3において、上記一般式(5)で表されるチオジアルキルカルボン酸ジアルキルエステル化合物の代わりに、2-メチル-4,6-ビス[(オクチルチオ)メチル]フェノールを用いた以外は、実施例2-3と同様にして評価した。
(B型粘度計/4号ルーター/25℃/60rpm)の条件で粘度を測定した。得られた結果を表2および3に併記する。
試料を、示差走査熱量測定機(サーモプラスTG8120;(株)リガク製)にて、窒素雰囲気下(20ml/min)、10℃/minの昇温条件で加熱し、試料の質量が5%減少した温度を測定した。得られた結果を表2および3に併記する。
目視で観察し、濁りまたは固形状のものが確認された場合は×、透明であった場合は○として評価した。得られた結果を表2および3に併記する。
熱安定剤組成物に含まれる各々の化合物の分子量に対する水酸基の割合を求め、熱安定剤組成物に含まれる水酸基の割合を算出した。得られた結果を表2および3に併記する。
本発明の熱安定剤組成物の合成樹脂に対する優れた安定化効果を見るために、本発明の熱安定剤組成物の安定化効果について検討を行った。未安定の低密度ポリエチレン(NUC-8000;日本ユニカー株式会社製)100質量部、架橋剤として、ジクミルパーオキサイド2質量部、一般式(3)で表されるジエステル体化合物と一般式(4)で表されるモノエステル体化合物および一般式(5)で表されるチオジアルキルカルボン酸ジアルキルエステル化合物を表3に記載された質量比で0.3質量部を、120℃、20rpmの条件にてミキシングロールで6分30秒間混練し、次いで120℃、9.8MPaの条件で5分間圧縮成形を行い厚さ2mmのシートを作成した。さらに、厚み2mmのシートを170℃、9.8MPaの条件で20分間圧縮成形を行い、ポリエチレンの架橋反応を促進させて、厚み1mmのシートを作成した。この厚み1mmのシートを170×130mmの大きさに切断し、この試料を150℃のギヤーオーブン中、空気雰囲気下で熱劣化試験を行った。評価方法は、552時間後に取り出した試験片において、試験片の面積に対して、赤茶色に変色していない箇所の面積の比率を未燃焼率として算出し安定化効果を評価した。これらの結果について、下記表4に示す。
Claims (11)
- 下記一般式(1)、
(式中、R1、R2およびR3は、各々独立して、水素原子、炭素原子数1~18のアルキル基、炭素原子数3~18のシクロアルキル基、または、アルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基またはヒドロキシ基で置換されていてもよい炭素原子数6~30のアリール基を表し、R4およびR5は各々独立に、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよい炭素原子数3~30の直鎖または分岐アルキル基を表す。)で表されるジエステル体、および、
下記一般式(2)、
(式中、R1、R2およびR3は、各々独立して、水素原子、炭素原子数1~18のアルキル基、炭素原子数3~18のシクロアルキル基、または、アルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基またはヒドロキシ基で置換されていてもよい炭素原子数6~30のアリール基を表し、R6は、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよい炭素原子数3~30の直鎖または分岐アルキル基を表す。)で表されるモノエステル体を含む安定剤組成物であって、
前記式(1)で表されるジエステル体と前記式(2)で表されるモノエステル体の合計100質量部中、前記式(1)で表されるジエステル体の含有量が、65質量部より多く、80質量部未満であることを特徴とする安定剤組成物。 - 粘度が、6,000mPa・s以下である請求項1記載の安定剤組成物。
- 前記一般式(1)中のR4、R5、および、前記一般式(2)中のR6が、全て同一のアルキル基である請求項1記載の安定剤組成物。
- 請求項1記載の安定剤組成物を合成樹脂に配合してなることを特徴とする樹脂組成物。
- 請求項4記載の樹脂組成物を成形してなることを特徴とする成形品。
- 下記一般式(3)、
(式中、R11~R18は、それぞれ独立して、水素原子、酸素原子または硫黄原子で中断されていてもよい炭素原子数1~18のアルキル基、炭素原子数3~18のシクロアルキル基、または酸素原子または硫黄原子で中断されていてもよいアルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基またはヒドロキシ基で置換されていてもよい炭素原子数6~30のアリール基を表し、R19およびR20はそれぞれ独立に、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよく、また、酸素原子、または硫黄原子で中断されていてもよい炭素原子数3~30の直鎖または分岐アルキル基である。)で表されるジエステル体化合物と、
下記一般式(4)、
(式中、R11~R18は、それぞれ独立して、水素原子、酸素原子または硫黄原子で中断されていてもよい炭素原子数1~18のアルキル基、炭素原子数3~18のシクロアルキル基、または酸素原子または硫黄原子で中断されていてもよいアルキル基、アルコキシ基、アルケニル基、アルケニルオキシ基またはヒドロキシ基で置換されていてもよい炭素原子数6~30のアリール基を表し、R11はアルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよく、また、酸素原子、または硫黄原子で中断されていてもよい炭素原子数3~30の直鎖または分岐アルキル基である。)で表されるモノエステル体化合物と、
下記一般式(5)、
(式中、R22は、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよく、また、酸素原子、または硫黄原子で中断されていてもよい炭素原子数3~30の直鎖または分岐アルキル基であり、Aは、アルコキシ基、アルケニル基、アルケニルオキシ基、ヒドロキシ基またはシアノ基で置換されていてもよい炭素原子数1~8の直鎖または分岐のアルキレン基を表す。)で表されるチオジアルキルカルボン酸ジアルキルエステル化合物と、を含む熱安定剤組成物であって、
前記一般式(3)で表されるジエステル体化合物と、前記一般式(4)で表されるモノエステル体化合物と、の合計100質量部中、前記一般式(3)で表されるジエステル体化合物の含有量が、65質量部より多く、かつ、前記一般式(3)で表されるジエステル体化合物と前記一般式(4)で表されるモノエステル体化合物と、の合計と前記一般式(5)で表されるチオジアルキルカルボン酸ジアルキルエステル化合物の質量比が、{(3)+(4)}/(5)=95/5~50/50の範囲内であることを特徴とする熱安定剤組成物。 - 25℃における粘度が、3,000mPa・s以下である請求項6記載の熱安定剤組成物。
- 示差熱分析(TG-DTA)を用いて、窒素下、10℃/minの昇温速度の条件で室温から加熱したときに、質量が5%減少する温度が、240℃以上である請求項6記載の熱安定剤組成物。
- 合成樹脂100質量部に対して、請求項6記載の熱安定剤組成物が0.01~5質量部配合されてなることを特徴とする合成樹脂組成物。
- 前記合成樹脂がポリオレフィン樹脂である請求項9記載の合成樹脂組成物。
- 請求項10記載の合成樹脂組成物が成形されてなることを特徴とする成形品。
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BR112014028924-7A BR112014028924B1 (pt) | 2012-05-24 | 2013-05-23 | composição estabilizadora, composição de resina e produto moldado usando a mesma |
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JPS5170192A (ja) | 1974-12-17 | 1976-06-17 | Adeka Argus Chemical Co Ltd | Kosankazai |
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US4101479A (en) * | 1975-09-18 | 1978-07-18 | Chevron Research Company | Polyolefin photostabilizer composition |
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JPS5170192A (ja) | 1974-12-17 | 1976-06-17 | Adeka Argus Chemical Co Ltd | Kosankazai |
JPS52154851A (en) | 1976-06-17 | 1977-12-22 | Adeka Argus Chem Co Ltd | Stabilized crosslinkable ethylenic polymer composition |
JPS5483950A (en) | 1977-12-16 | 1979-07-04 | Adeka Argus Chem Co Ltd | Antioxidant composition |
JPS55149338A (en) | 1979-05-09 | 1980-11-20 | Adeka Argus Chem Co Ltd | Resin composition |
JPS57190098A (en) * | 1981-05-18 | 1982-11-22 | Adeka Argus Chem Co Ltd | Oiling agent composition for treating fiber |
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