WO2016031505A1 - 熱安定剤組成物およびこれを用いた合成樹脂組成物 - Google Patents
熱安定剤組成物およびこれを用いた合成樹脂組成物 Download PDFInfo
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- WO2016031505A1 WO2016031505A1 PCT/JP2015/072149 JP2015072149W WO2016031505A1 WO 2016031505 A1 WO2016031505 A1 WO 2016031505A1 JP 2015072149 W JP2015072149 W JP 2015072149W WO 2016031505 A1 WO2016031505 A1 WO 2016031505A1
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- 0 C*C(OC1)OCC11COC(*C)OC1 Chemical compound C*C(OC1)OCC11COC(*C)OC1 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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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
- C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
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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
- C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
- C09K15/08—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen containing a phenol or quinone moiety
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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
- C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
- C09K15/322—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus
Definitions
- the present invention relates to a heat stabilizer composition and a synthetic resin composition using the same, and more particularly to a heat stabilizer composition that does not generate the odor of a phosphorus antioxidant and a synthetic resin composition using the same. .
- Organics such as thermoplastic resins, thermosetting resins, crystalline resins, non-crystalline resins, biodegradable resins, non-biodegradable resins, engineering resins, polymer alloys, natural or synthetic rubbers, lubricants, adhesives, paints, etc. It is known that when a material is subjected to the action of heat, oxygen, light, and the like, it is accompanied by deterioration of the physical properties of the organic material and deterioration of appearance such as coloring due to molecular cutting and molecular cross-linking, so that the commercial value is remarkably impaired.
- phenolic antioxidants phosphorus antioxidants, thioether antioxidants, lactone stabilizers, hydroxylamine antioxidants, vitamin E antioxidants, hindered amine stabilizers
- Organic materials are stabilized by using various stabilizers such as an agent and an ultraviolet absorber in combination.
- phosphorus antioxidants are particularly effective in preventing deterioration during processing, can exhibit synergistic effects with other stabilizers, and are resins used as plastic materials. It can be used for most resins and is widely used. Phosphorus antioxidants use compounds with various structures, but when exposed to high-temperature environments or stored for long periods, phosphite odors with unique odors may be generated over time. . When a phosphorus-based antioxidant that generates an odor is blended with a resin, an unpleasant odor may be generated during molding or an odor may be generated in a molded product.
- Patent Document 1 proposes to use a phosphite compound having a melting point exceeding 40 ° C. in a fatty acid cellulose ester resin composition.
- Patent Document 2 proposes to contain a phenolic antioxidant and a phosphite compound for the purpose of improving the odor of the epoxidized vegetable oil composition.
- Patent Document 3 proposes to contain an organic carboxylic acid zinc salt and an alkyl phosphite compound for the purpose of improving odor when an epoxidized vegetable oil is added to the vinyl chloride resin composition.
- trisnonylphenyl phosphite tris (2,4-di-tert-butylphenyl) phosphine is used for the purpose of improving the odor generated when a hose made of vinyl chloride resin is passed through. It has been proposed to contain a phosphorus-based antioxidant such as phyto in a vinyl chloride resin composition.
- Patent Document 5 a phenolic antioxidant, tris (2,4-di-tert-butylphenyl) phosphite and (2,6-di-tert- It has been proposed that a phosphorus stabilizer of butyl-4-methylphenyl) pentaerythritol-di-phosphite be included in the resin composition.
- Patent Documents 1 to 5 propose methods for improving the odor of a molded product (product), but no investigation is made on the phosphite odor of the phosphorus antioxidant itself. Moreover, although it is known to remove the phosphite odor by using an adsorbent, it is difficult to suppress the generation of the phosphite odor. Thus, the present situation is that the odor improvement of a phosphorus antioxidant is not examined concretely conventionally.
- an object of the present invention is to provide a heat stabilizer composition that does not generate the odor of a phosphorus-based antioxidant and a synthetic resin composition using the same.
- the present inventors have used a phosphorus antioxidant having a phosphite structure and a phenol antioxidant having a predetermined structure in combination at a predetermined ratio. As a result, the present inventors have found that the above problems can be solved, and have completed the present invention.
- the heat stabilizer composition of the present invention comprises 100 parts by mass of a phosphorus-based antioxidant having a phosphite structure, and the following general formula (1), (In the general formula (1), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and a is an integer of 0 to 2 And when a is 2, the plurality of R 3 may be the same or different.) 0.001 to 10 parts by mass of a phenolic antioxidant having a partial structure represented by Is contained.
- the phenolic antioxidant is represented by the following general formula (2), (In the general formula (2), R 1 , R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, a represents an integer of 0 to 2, when a is 2, the plurality of R 3 may be the same or different, and n is an integer of 1 to 4, when n is 1, X is an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, Or a combination thereof, R 4 represents a hydrogen atom, When n is 2, X is an alkylidene group having 1 to 40 carbon atoms, an arylene group having 6 to 40 carbon atoms, or the following general formula (3), (In general formula (3), R 6 and R 7 each independently represents an alkylidene group having 1 to 40 carbon atom
- R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least one R 4 represents a hydrogen atom
- X represents an alkanetriyl group having 1 to 40 carbon atoms or a trivalent cyclic group having 6 to 40 carbon atoms
- R 4 represents a hydrogen atom or 1 carbon atom.
- X represents an alkanetetrayl group having 1 to 40 carbon atoms
- R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- at least one R 4 represents Represents a hydrogen atom
- the methylene group in the alkyl group, the alkoxy group, the arylene alkyl group, the alkylidene group, the alkanetriyl group, and the alkanetetrayl group is> C ⁇ O, —O—, —S—, —CO.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is preferable that it is a compound represented by this.
- the phosphorus-based antioxidant is represented by the following general formulas (4) to (8), (In General Formula (4), R 8 and R 9 are each independently an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an arylalkyl group having 7 to 40 carbon atoms.
- R 6 and R 7 each independently represents an alkylidene group having 1 to 40 carbon atoms or an arylene group having 6 to 40 carbon atoms
- b is 3
- T represents an alkanetriyl group having 1 to 40 carbon atoms.
- R 11 and R 12 each independently represents an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms.
- R 13 and R 14 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
- R 15 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- T represents the same as T in the general formula (3)
- c represents an integer of 0 to 4
- d represents an integer of 0 to 4
- e represents 1 to When c is 2 or more, the plurality of R 13 may be the same or different, and when d is 2 or more, the plurality of R 14 are the same.
- T is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a complex having 3 to 25 carbon atoms.
- T represents an alkylidene group having 1 to 40 carbon atoms, or 6 to 40 carbon atoms.
- Arylene group, -S-, or a group represented by the above general formula (3), if e is 3, T represents alkanetriyl group of 1 to 40 carbon atoms.
- R 16 and R 17 are each independently an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, Represents an arylalkyl group having 7 to 40 carbon atoms and a heterocyclic-containing group having 3 to 25 carbon atoms, and R 18 represents an alkylidene group having 1 to 40 carbon atoms and an arylene group having 6 to 40 carbon atoms.
- F represents an integer of 1 to 3
- T is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or 3 to 25 carbon atoms.
- T represents an alkylidene group having 1 to 40 carbon atoms, an arylene group having 6 to 40 carbon atoms, -S-, or the general formula (3).
- T is an alkenyl having 1 to 40 carbon atoms.
- R 19 , R 20 and R 21 are each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or 7 to 7 carbon atoms.
- an arylalkyl group of 40 a heterocyclic group containing 3 to 25 carbon atoms, wherein R 19 , R 20 and R 21 do not simultaneously become a hydrogen atom.
- fusing point of the phosphorus antioxidant which has the said phosphite structure is 100 degrees C or less.
- R 1 in the general formula (1) is preferably a tert-butyl group
- R 2 is a hydrogen atom
- R 3 is a methyl group.
- R 1 in the general formula (2) is a tert-butyl group
- R 2 is a hydrogen atom
- R 3 is a methyl group.
- the molecular weight of the phenolic antioxidant is preferably in the range of 300 to 2,000.
- the synthetic resin composition of the present invention comprises 0.001 to 10 parts by mass of the heat stabilizer composition of the present invention with respect to 100 parts by mass of the synthetic resin.
- the heat stabilizer composition of the present invention comprises 100 parts by mass of a phosphorus-based antioxidant having a phosphite structure, and the general formula (1), And 0.001 to 10 parts by mass of a phenolic antioxidant having a partial structure represented by the formula:
- R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and a is 0 to 2 When a is 2, the plurality of R 3 may be the same or different.
- the phenolic antioxidant according to the heat stabilizer composition of the present invention will be described.
- the hydrocarbon group having 1 to 10 carbon atoms represented by R 1 , R 2 , R 3 and R 4 is a carbon atom and a hydrogen atom.
- the molecular structure includes alkanes, alkenes, cycloalkanes, aromatic hydrocarbons and the like. These hydrocarbon groups may be interrupted by an oxygen atom, sulfur atom, carbonyl group, ester group, amide group, imino group or aryl group, and the hydrogen atom in the hydrocarbon group is substituted with the following substituents It may be a thing. These interruptions or substitutions may be combined.
- Examples of the substituent for substituting the hydrogen atom in the hydrocarbon group include chain aliphatic groups such as a hydroxy group, a halogen atom, an amino group, a nitro group, a cyano group, an alkenyl group, an alkenyloxy group, an alkanoyloxy group, and an alkoxycarbonyl group.
- pyrrole furan, thiophene, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, piperidine, morpholine, 2H-pyran, 4H-pyran, phenyl, biphenyl, triphenyl, naphthalene, anthracene, pyrrolidine, pyridine, indoline, indole, iso Examples thereof include cyclic aliphatic groups such as indole, indazole, purine, quinolidine, quinoline, isoquinoline, or cycloalkyl group.
- R 1 , R 2 and R 3 are preferably alkyl groups or phenyl groups, and methyl, butyl, tert-butyl, pentyl, tert-pentyl, cycloalkyl, methylcycloalkyl, 2-phenyl- More preferred are those selected from the group of propan-2-yl.
- R 4 is preferably a hydrogen atom.
- the phenolic antioxidant is represented by the following general formula (2), The compound represented by these is preferable.
- R 1, R 2, R 3 and R 4, R 1, R 2, the same hydrogen atom and R 3 and R 4 in the general formula (1), C 1 -C ⁇ 10 hydrocarbon groups are represented.
- R 4 is at least one R 4 is a hydrogen atom.
- a represents an integer of 0 to 2
- the plurality of R 3 may be the same or different.
- N represents an integer of 1 to 4.
- X is an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, or it represents any combination thereof
- R 4 represents a hydrogen atom.
- X represents an alkylidene group having 1 to 40 carbon atoms, an arylene group having 6 to 40 carbon atoms, or a group represented by the following general formula (3)
- R 4 represents Represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and at least one R 4 represents a hydrogen atom.
- R 6 and R 7 each independently represent an alkylidene group having 1 to 40 carbon atoms or an arylene group having 6 to 40 carbon atoms.
- X represents an alkanetriyl group having 1 to 40 carbon atoms or a trivalent cyclic group having 6 to 40 carbon atoms
- R 4 represents a hydrogen atom or 1 carbon atom.
- X represents an alkanetetrayl group having 1 to 40 carbon atoms
- R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
- at least one R 4 represents Represents a hydrogen atom.
- the methylene group in the alkyl group, alkoxy group, arylalkyl group, alkylidene group, alkanetriyl group, alkanetetrayl group represented by X in the general formula (2) is> C ⁇ O, —O—, — S—, —CO—O—, —O—CO—, —O—CO—O—, —NR 5 —, phosphine, phosphinite, phosphonite, phosphite, phospholane, phosphonate or combinations thereof may be substituted. These groups may have a branch.
- R 5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- alkyl group having 1 to 40 carbon atoms represented by X in the general formula (2) examples include methyl, ethyl, propyl, iso-propyl, cyclopropyl, butyl, sec-butyl, tert-butyl, iso -Butyl, pentyl, iso-pentyl, tert-pentyl, cyclopentyl, 4-ethyl-2-methylheptyl, hexyl, 2-methylhexyl, 3-methylhexyl, cyclohexyl, 4-methylcyclohexyl, 2,4-dimethylhexyl Cyclohexyl, 1,2,4-trimethylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, nonyl, isononon
- Examples of the alkoxy group having 1 to 40 carbon atoms represented by X in the general formula (2) include methyloxy, ethyloxy, iso-propyloxy, butyloxy, sec-butyloxy, tert-butyloxy, iso-butyloxy, pentyloxy , Iso-pentyloxy, tert-pentyloxy, hexyloxy, 2-hexyloxy, 3-hexyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, heptyloxy, 2-heptyloxy, 3-heptyloxy, iso-heptyloxy Tert-heptyloxy, 1-octyloxy, iso-octyloxy, tert-octyloxy and the like.
- Examples of the aryl group having 6 to 40 carbon atoms represented by X in the general formula (2) include phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, 2-methylphenyl, 3-methylphenyl, and 4-methyl.
- Phenyl 4-vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butyl-phenyl, 4-hexylphenyl, 4-cyclohexylphenyl 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3, 4-dimethylphenyl, 3,5-dimethylphenyl, 2, -Di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amyl
- Examples of the arylalkyl group having 7 to 40 carbon atoms represented by X in the general formula (2) include benzyl, 1-methyl-1-phenylethyl, 2-phenyl-propan-2-yl, 1- Examples include naphthylmethyl, 9-anthracenylmethyl, fluorenyl, indenyl, 9-fluorenylmethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, phenethyl, styryl, and cinamyl.
- the alkylidene group having 1 to 40 carbon atoms represented by X in the general formula (2) represents a group obtained by extracting one hydrogen atom from the above-exemplified alkyl group having 1 to 40 carbon atoms.
- the arylene group having 6 to 40 carbon atoms represented by X in the general formula (2) is an aromatic hydrogen atom extracted from the group exemplified as the aryl group having 6 to 40 carbon atoms. Groups and the like.
- Examples of the alkanetriyl group having 1 to 40 carbon atoms represented by X in the general formula (2) include groups obtained by extracting two hydrogen atoms from the above exemplified alkyl groups.
- the trivalent cyclic group having 6 to 40 carbon atoms represented by X means two aromatic hydrogen atoms in the group exemplified as the aryl group having 6 to 40 carbon atoms. Examples include a drawn group, a group having an isocyanuric ring, and a group having a triazine ring.
- Examples of the alkanetetrayl group having 1 to 40 carbon atoms represented by X in the general formula (2) include groups obtained by extracting three hydrogen atoms from the above exemplified alkyl group having 1 to 40 carbon atoms. Can be mentioned.
- the hydrocarbon group having 1 to 10 carbon atoms represented by R 1 , R 2 , R 3 and R 4 in the general formula (2) is a carbon atom having 1 to 10 carbon atoms in the general formula (1).
- the same thing as a hydrogen group is mentioned.
- the hydrogen atom of the methylene group in the alkyl group, alkoxy group, arylalkyl group, alkylidene group, alkanetriyl group, and alkanetetrayl group may be substituted with a substituent.
- substituents examples include ethylenically unsaturated groups such as vinyl, allyl, acryl and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, Acyl groups such as phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; acetyloxy, benzoyl Acyloxy groups such as oxy; amino, ethylamino, dimethylamino, diethylamino, butylamin
- the hydrogen atom of the aryl group, arylalkylene group, arylene group or trivalent cyclic group may be substituted.
- substituents examples include ethylenically unsaturated groups such as vinyl, allyl, acryl and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, Acyl groups such as phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; acetyloxy, benzoyl Acyloxy groups such as oxy; amino, ethylamino, dimethylamino, diethylamino, butylamin
- the phenolic antioxidant according to the heat stabilizer composition of the present invention includes a compound in which X in the general formula (2) has a group represented by the following general formula (3).
- R 6 and R 7 in the general formula (3) represent an alkylidene group having 1 to 40 carbon atoms and an arylene group having 6 to 40 carbon atoms, respectively.
- Particularly preferred phenolic antioxidants in the present invention include 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -s-triazine-2,4,6 (1H, 3H , 5H) -trione, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tris (2-methyl-5-tert-butyl- 4-hydroxyphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis (methylene-3- (3,5-di-te t-4-hydroxyphenyl) propionate) methane,
- R 1 in the general formula (1) is a tert-butyl group
- R 2 is a hydrogen atom
- R 3 is a methyl group
- R 1 is a tert-butyl group
- R 2 is a hydrogen atom
- R 3 is a methyl group
- More preferred is a phenolic antioxidant having a molecular weight in the range of 300 to 2,000. If the molecular weight is less than 300, it tends to volatilize, which may adversely affect the odor and the appearance of the molded product during processing. If the molecular weight exceeds 2,000, the compatibility with the synthetic resin will be poor, or oxidation with respect to the added amount. The prevention effect may be reduced.
- any phosphorus-based antioxidant can be used as long as it has a phosphite structure, and is represented by the following general formulas (4) to (8). Compounds are preferred.
- R 8 and R 9 are each independently an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or an arylalkyl having 7 to 40 carbon atoms.
- R 10 represents a direct bond, an alkylidene group having 1 to 40 carbon atoms, or an arylene group having 6 to 40 carbon atoms.
- b represents an integer of 1 to 3, and when b is 1, T is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, Represents a heterocyclic group containing 3 to 25 carbon atoms, and when b is 2, T is an alkylidene group having 1 to 40 carbon atoms, an arylene group having 6 to 40 carbon atoms, -S-, or the following general group Represents a group of the formula (3), and when b is 3, T represents an alkanetriyl group having 1 to 40 carbon atoms.
- R 6 and R 7 each independently represents an alkylidene group having 1 to 40 carbon atoms or an arylene group having 6 to 40 carbon atoms.
- the alkyl group having 1 to 40 carbon atoms, the aryl group having 6 to 40 carbon atoms, and the arylalkyl group having 7 to 40 carbon atoms represented by R 8 and R 9 in the general formula (4) are The same as the alkyl group having 1 to 40 carbon atoms, the aryl group having 6 to 40 carbon atoms, and the arylalkyl group having 7 to 40 carbon atoms represented by X in the general formula (2).
- R 11 and R 12 each independently represents an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms.
- R 13 and R 14 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
- R 15 represents a hydrogen atom or a carbon atom having 1 to 4 carbon atoms.
- T represents the same as T in the general formula (4)
- c represents an integer of 0 to 4
- d represents an integer of 0 to 4
- e represents an integer of 1 to 3, respectively.
- T represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group having 3 to 25 carbon atoms, and e is 2
- T represents an alkylidene group having 1 to 40 carbon atoms, an arylene group having 6 to 40 carbon atoms, —S—, or a group of the above general formula (3).
- e is 3
- T is An alkanetriyl group having 1 to 40 carbon atoms is represented.
- R 16 and R 17 are each independently an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, carbon An arylalkyl group having 7 to 40 atoms, a heterocyclic-containing group having 3 to 25 carbon atoms, and R 18 represents an alkylidene group having 1 to 40 carbon atoms and an arylene group having 6 to 40 carbon atoms; f represents an integer of 1 to 3.
- T represents a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heterocyclic group having 3 to 25 carbon atoms, and f is 2
- T represents an alkylidene group having 1 to 40 carbon atoms, an arylene group having 6 to 40 carbon atoms, —S—, or a group of the above general formula (3).
- T is An alkanetriyl group having 1 to 40 carbon atoms is represented.
- R 19 , R 20 and R 21 are each independently a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms, or 7 to 40 carbon atoms.
- R 19 , R 20 and R 21 are not hydrogen atoms at the same time.
- R 8 and R 9 are alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 40 carbon atoms, and arylalkyl groups having 7 to 40 carbon atoms. The same thing as the inside can be mentioned.
- heterocyclic group having 3 to 25 carbon atoms represented by R 8 and R 9 in the general formula (4) examples include pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, Imidazolyl, benzoimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone Examples include groups having a 1-yl group, 2,4-dioxyimidazolidin-3-yl group, 2,4-dioxyoxazolidine-3-yl group
- the above-exemplified alkyl group, aryl group, arylalkyl group, heterocyclic-containing group and the like are linked to form a phosphorus atom in a cyclic structure.
- the number of carbon atoms is within the range of 3 to 25, monocyclic rings, complex rings, aggregate rings, and the like can be separately included in the above cyclic structure.
- the alkylidene group having 1 to 40 carbon atoms and the arylene group having 6 to 40 carbon atoms represented by R 10 in the general formula (4) are the same as R 6 and R 7 in the general formula (3). To express.
- the heterocyclic group having 3 to 25 carbon atoms represented by T represents the same heterocyclic group as those exemplified for R 8 and R 9 above.
- the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 40 carbon atoms represented by R 11 and R 12 in the general formula (5) include R 8 and R 9 in the general formula (4). And the same as the alkyl group having 1 to 40 carbon atoms and the aryl group having 6 to 40 carbon atoms.
- alkyl group having 1 to 10 carbon atoms represented by R 13 and R 14 in the general formula (6) examples include, for example, methyl, ethyl, propyl, iso-propyl, cyclopropyl, butyl, sec-butyl, tert -Butyl, iso-butyl, pentyl, iso-pentyl, tert-pentyl, cyclopentyl, 4-ethyl-2-methylheptyl, hexyl, 2-methylhexyl, 3-methylhexyl, cyclohexyl, 4-methylcyclohexyl, 2, Examples include 4-dimethylhexyl, cyclohexyl, 1,2,4-trimethylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-oc
- alkyl group having 1 to 4 carbon atoms represented by R 15 in the general formula (6) examples include methyl, ethyl, propyl, iso-propyl, cyclopropyl, butyl, sec-butyl, tert-butyl, iso-butyl and the like can be mentioned.
- T in the general formula (6) represents the same as T in the general formula (4) except that b in the general formula (4) is replaced with e.
- the arylalkyl group having ⁇ 40 the alkyl group having 1 to 40 carbon atoms exemplified by X in the general formula (2), the alkoxy group having 1 to 40 carbon atoms, the aryl group having 6 to 40 carbon atoms, An arylalkyl group having 7 to 40 carbon atoms can be mentioned.
- the alkylidene group having 1 to 40 carbon atoms and the arylene group having 6 to 40 carbon atoms represented by R 18 in the general formula (7) are the same as R 6 and R 7 in the general formula (3). Things.
- Examples of the heterocyclic group containing 3 to 25 carbon atoms represented by R 16 and R 17 in the general formula (7) include 3 carbon atoms represented by R 8 and R 9 in the general formula (4). Examples are the same as those described above with respect to -25 heterocycle-containing groups.
- Examples of the heterocyclic group having 3 to 25 carbon atoms include the same groups as R 8 and R 9 in formula (4).
- the phosphorus antioxidant is an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, or isooctane, an alicyclic hydrocarbon such as cyclopentane, cyclohexane, or methylcyclohexane, Blended by adding to an inert solvent such as aromatic hydrocarbons such as toluene, xylene, ethylbenzene, gasoline fraction, hydrogenated diesel fraction, etc., or emulsified, blended with multiple phosphorus antioxidants Also included.
- an inert solvent such as aromatic hydrocarbons such as toluene, xylene, ethylbenzene, gasoline fraction, hydrogenated diesel fraction, etc.
- the following substitution is performed at the site of the methylene group of the alkyl group, alkoxy group, arylalkyl group, alkylidene group, alkanetriyl group, alkanetetrayl group of the phosphorus-based antioxidant. It may be substituted with a group, and these groups may have a branch.
- substituents examples include ethylenically unsaturated groups such as vinyl, allyl, acryl and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl and phenyl Acyl groups such as carbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; acetyloxy, benzoyloxy An acyloxy group such as amino, ethylamino, dimethylamino, diethylamino, butylamino
- Examples of the phosphorus-based antioxidant represented by the general formula (4) include triethyl phosphite, triphenyl phosphite, diisooctyl phosphite, heptakis triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite.
- Examples of the phosphorus-based antioxidant represented by the general formula (5) include diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (tridecyl) pentaerythritol diphosphite, and di (nonylphenyl) penta.
- Examples of the phosphorus-based antioxidant represented by the general formula (6) include 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 2,2′-methylenebis (4, 6-di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) nonyl phosphite, 2,2'-methylenebis (4,6-di) -Tert-butylphenyl) -octadecyl phosphite, 6,6 ', 6 "-[nitrilotris (ethyleneoxy)] tris (2,4,8,10-tetra-tert-butyldibenzo [d, f] [ 1,3,2] dioxaphosphepine), bis [2,2′-methylenebis (4,6-di-ter
- Examples of the phosphorus-based antioxidant represented by the general formula (7) include 5,5-diethyl-2- (2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxa. Examples include phosphinan.
- Examples of phosphorus antioxidants represented by the general formula (8) include triphenyl phosphite, octyl diphenyl phosphite, decyl diphenyl phosphite, trioctyl phenyl phosphite, octadecyl diphenyl phosphite, and tris (methylphenyl).
- Phosphite Tris (2,4-di-tert-butylphenyl) phosphite, Tris (ethylphenyl) phosphite, Trioctylphosphite, Tridecylphosphite, Triundecylphosphite, Tris (Tridecylphosphite) , Trioctadecyl phosphite, dilauryl hydrogen phosphite and the like.
- Examples of phosphorus antioxidants having a phosphite structure other than the general formulas (4) to (8) include 2,2′-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite.
- the phosphorus antioxidant having the phosphite structure according to the present invention may be used in combination of two or more.
- a compound having a melting point of 100 ° C. or lower can be preferably used because the effect of the present invention becomes remarkable.
- the phosphite compound having a melting point of 100 ° C. or lower include tridecyl phosphite, triisodecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, bisnonylphenyl pentaerythritol diphosphite.
- the heat stabilizer composition of the present invention contains 0.001 to 10 parts by mass of a phenolic antioxidant with respect to 100 parts by mass of the phosphorus antioxidant having the phosphite structure.
- the amount is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass.
- the amount is less than 0.001 part by mass, the effect of the present invention may not be obtained.
- the amount exceeds 10 parts by mass, the phenolic antioxidant may not be dissolved in the phosphorus antioxidant and may remain. If the phenolic antioxidant remains, it is not preferable because the screen may be clogged when processing is fed with a liquid during processing, which may adversely affect workability.
- resin additives can be blended within a range that does not impair the intended effect of the present invention.
- resin additives include thioether antioxidants, UV absorbers, hindered amine light stabilizers, nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, metal soaps, hydrotalcites, electrification Examples thereof include an inhibitor, a pigment, and a dye.
- These resin additives may be contained in the heat stabilizer composition of the present invention, but may be added to the synthetic resin separately from the heat stabilizer composition of the present invention.
- 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), distearyl-disulfide.
- thioether antioxidant when the above thioether antioxidant is used, when the heat stabilizer composition of the present invention is blended with a synthetic resin, 0.001 to 10 parts by mass of the thioether antioxidant is more preferable with respect to 100 parts by mass of the synthetic resin. It is preferable to use a thioether antioxidant so as to be 0.01 to 0.5 parts by mass.
- 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-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 ' Polyethylene glycol ester of methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3 -(2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-ter
- the ultraviolet absorber when the heat stabilizer composition of the present invention is blended with the synthetic resin, the ultraviolet absorber is 0.001 to 5 parts by mass, more preferably 0.001 to 100 parts by mass of the synthetic resin. It is preferable to use an ultraviolet absorber so as to be 01 to 0.5 parts by mass.
- hindered amine light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2, 6,6-Tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl- -Piperidyl) -di (tridecyl) -1,
- the hindered amine light stabilizer when used, when the heat stabilizer composition of the present invention is added to the synthetic resin, the hindered amine light stabilizer is more preferably 0.001 to 5 parts by mass, more preferably 100 parts by mass of the synthetic resin. It is preferable to use a hindered amine light stabilizer so as to be 0.005 to 0.5 parts by mass.
- 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-di-tert-butylphenyl) phosphate and lithium-2,2′-methylenebis (4,6- Phosphate metal salts such as di-tert-butylphenyl) phosphate, dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (3,4-dimethylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, and bis ( Dimethyl benzylide ) Polyhydric alcohol derivatives such as sorbitol, N, N ′, N ′′
- the nucleating agent when used, when the heat stabilizer composition of the present invention is blended with the synthetic resin, the nucleating agent is 0.001 to 5 parts by mass, more preferably 0.001 to 100 parts by mass of the synthetic resin. It is preferable to use a nucleating agent so as to be 005 to 0.5 parts by mass.
- Examples of the flame retardant 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, manufactured by ADEKA Corporation, trade name ADK STAB FP-500, manufactured by ADEKA Corporation, trade name ADK STAB FP-600, Made by ADEKA Co., Ltd.
- Aromatic phosphate ester such as ADK STAB FP-800, phosphonic acid such as divinyl phenylphosphonate, diallyl phenylphosphonate, phenylphosphonic acid (1-butenyl) Phosphinic acid esters such as steal, phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, bis (2-allylphenoxy) phosphazene, dicresylphosphazene Phosphazene compounds such as melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, vinylbenzyl compounds containing phosphorus and red phosphorus Flame retardant, metal hydroxide such as magnesium hydroxide, aluminum hydroxide, bromin
- the flame retardant when the heat stabilizer composition of the present invention is blended with a synthetic resin, the flame retardant is 0.01 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the synthetic resin. It is preferable to use a flame retardant so as to be part.
- 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 lubricant when the above-mentioned lubricant is used, when the heat stabilizer composition of the present invention is blended with the synthetic resin, the lubricant is 0.01 to 2 parts by mass, more preferably 0.03 to 0.00. It is preferable to use a lubricant so as to be 5 parts by mass.
- 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, Dolomite, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate and the like can be mentioned, and the particle diameter (in the fibrous form, the fiber diameter, fiber length, and aspect ratio) can be appropriately selected and used. it can. Moreover, what was surface-treated as needed can be used for a filler.
- the filler when the heat stabilizer composition of the present invention is blended with the synthetic resin, the filler is 0.01 to 80 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the synthetic resin. It is preferable to use a filler so as to be part.
- metal soap metals such as magnesium, calcium, aluminum, and zinc, and salts of saturated or unsaturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid are used.
- the heat stabilizer composition of the present invention when blended with the synthetic resin, 0.001 to 10 parts by mass of the metal soap, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the synthetic resin. It is preferable to use it so that it may become 5 mass parts.
- the hydrotalcite is a complex salt compound composed of magnesium, aluminum, hydroxyl group, carbonate group and any crystal water known as a natural product or synthetic product.
- a part of magnesium or aluminum may be alkali metal, zinc, etc. And those having a hydroxyl group or a carbonate group substituted with another anionic group.
- the hydrotalcite represented by the following general formula (9) is replaced with an alkali metal
- Al-Li hydrotalcites include the following general formula (10): The compound represented by these can also be used.
- x1 and x2 are respectively the following formulas: 0 ⁇ x2 / x1 ⁇ 10, 2 ⁇ x1 + x2 ⁇ 20 And p represents 0 or a positive number.
- a q ⁇ represents a q-valent anion
- p represents 0 or a positive number.
- the carbonate anion in the hydrotalcites may be partially substituted with another anion.
- the hydrotalcites may be those 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 such as alkali metal dodecylbenzenesulfonate. It may be coated with a metal salt, higher fatty acid amide, higher fatty acid ester or wax.
- the hydrotalcites may be natural products or synthetic products.
- Japanese Patent Publication No. 46-2280 Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, 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 hydrotalcites can be used without being limited by their crystal structure, crystal particles and the like.
- hydrotalcite when the heat stabilizer composition of the present invention is blended with the synthetic resin, 0.001 to 5 parts by mass of the hydrotalcite with respect to 100 parts by mass of the synthetic resin, more preferably It is preferable to use hydrotalcites so as to be 0.05 to 3 parts by mass.
- 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 an antistatic agent may be used alone, or two or more kinds of antistatic agents may be used in combination.
- cationic antistatic agents such as fatty acid quaternary
- the antistatic agent when the heat stabilizer composition of the present invention is blended with the synthetic resin, the antistatic agent is 0.03 to 2 parts by mass, more preferably 0. It is preferable to use an antistatic agent so as to be 1 to 0.8 parts by mass.
- pigments can also be used as the pigment, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 9 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148,
- dyes As the above dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and a plurality of these may be used in combination.
- the heat stabilizer composition of the present invention can be treated by adding an adsorbent.
- Treatment with an adsorbent is preferable because it can further suppress odor and remove impurities.
- the adsorbent include activated clay, activated carbon, zeolite, inorganic / organic synthetic adsorbent, ion exchange resin, adsorbent resin, silica gel, silica alumina adsorbent, alumina gel, activated alumina, silicon dioxide and the like.
- the time for bringing the heat stabilizer composition into contact with the adsorbent may be appropriately determined according to the type of adsorbent and the amount used. Moreover, after making a heat stabilizer composition and an adsorbent contact, a heat stabilizer composition and an adsorbent can be isolate
- Synthetic resins that can be stabilized by the heat stabilizer composition of the present invention include, for example, thermoplastic resins, thermosetting resins, crystalline resins, non-crystalline resins, biodegradable resins, non-biodegradable resins, natural resins.
- thermoplastic resins thermosetting resins
- crystalline resins non-crystalline resins
- biodegradable resins non-biodegradable resins
- natural resins natural resins.
- examples of such resins include industrial resins, general-purpose resins, engineering resins, and polymer alloys.
- the synthetic resin composition of the present invention contains 0.001 to 10 parts by mass of the heat stabilizer composition of the present invention with respect to 100 parts by mass of the synthetic resin.
- the synthetic resin that can be used in the synthetic resin composition of the present invention include polypropylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutene-1, poly-3-methylpentene, and poly-4-methylpentene.
- ⁇ -olefin homopolymers or copolymers such as ethylene-propylene copolymers, these ⁇ -olefins and polyunsaturated compounds such as conjugated or non-conjugated dienes, acrylic acid, methacrylic acid, vinyl acetate, etc.
- Copolymers polyethylene terephthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / paraoxybenzoate, polybutylene terephthalate and other linear polyesters, acid-modified polyesters, aliphatic polyesters and other biodegradable resins, liquid crystal polyesters, polycaprolactam And polyamide such as polyhexamethylene adipamide, liquid crystal polyamide, polyimide, polystyrene, styrene and / or ⁇ -methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.
- monomers for example, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.
- acrylonitrile styrene copolymer (AS) resin acrylonitrile styrene copolymer (ABS) resin, methyl methacrylate butadiene styrene copolymer (MBS) resin, heat-resistant ABS resin, etc.
- Polyvinyl chloride polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, chloride Halogen-containing resins such as nyl-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer, (me
- 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 Or an alloy or blend of rubber.
- the synthetic resin is a lamella 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.
- the synthetic resin includes polypropylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, ethylene.
- -Polyolefin resins such as ⁇ -olefin homopolymers or copolymers such as propylene copolymers; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber 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-cyclohexyl male The effect of what is halogen-containing resins
- the method for blending the heat stabilizer composition of the present invention into the synthetic resin is not particularly limited, and a known resin additive blending technique can be used.
- a method of adding to the polymerization system in advance when polymerizing the synthetic resin a method of adding during polymerization, and a method of adding after polymerization can be used.
- a method of kneading a synthetic resin powder or pellets mixed with a Henschel mixer or the like using a processing device such as an extruder the thermal stabilizer of the present invention The method etc. which mix
- the type of processing equipment to be used, the processing temperature, the cooling conditions after processing, etc. can be used without particular limitation, and the blending conditions can be appropriately selected so that the obtained resin properties are suitable for the application.
- what was granulated by impregnating the heat stabilizer composition of this invention individually or with other resin additives or fillers can be mix
- the heat stabilizer composition of the present invention is used in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 3 parts by weight, more preferably 0.03 to 0 parts by weight based on 100 parts by weight of the synthetic resin. Within the range of 5 parts by mass. When the amount is less than 0.001 part by mass, the necessary stabilizing effect may not be obtained. When the amount exceeds 10 parts by mass, the heat stabilizer composition bleeds out from the molded product and the appearance of the molded product is impaired. There is a case. However, the amount used above represents the amount used in the molded product of the final product. For example, as in a master batch, the heat stabilizer composition can be formed by adding to the synthetic resin and molding in a later step. When the product is diluted and the blending amount of the heat stabilizer composition in the molded product falls within the numerical range of the present invention, the amount used in the master batch may exceed 10 parts by mass.
- the use of the synthetic resin composition of the present invention is not particularly limited, it can be used for automobile parts, building materials, agricultural materials, packaging materials, household goods, household electrical appliance materials, housings, textile materials, toys and the like. . In particular, it is useful for odor sensitive applications such as food packaging materials, beverage bottle containers, and seasoning containers.
- the synthetic resin composition of the present invention can be molded by a known molding method.
- known molding techniques such as extrusion molding, injection molding, hollow molding, blow molding, film, and sheet can be used.
- Comparative Example 1-1 to Comparative Example 1-10 10 g of a heat stabilizer composition having the composition shown in Tables 1 to 4 was prepared, put in a glass 100 mL sample bottle, sealed, allowed to stand in an oven at 50 ° C., and heat stabilizer composition by 10 panelists. A sensory test on the odor was conducted.
- Comparative Example 1-1 was evaluated without adding anything other than triisodecyl phosphite.
- Comparative Example 1-2 was evaluated without adding anything other than triisodecyl phosphate.
- Comparative Example 1-10 2% by mass of Kyowa Chemical Industry Co., Ltd. trade name Kyoward 300 was added as an adsorbent to triisodecyl phosphite, stirred for 5 minutes with a stirrer, and then filtered off with a filter paper. was evaluated using separated triisodecyl phosphite.
- Phenol-based antioxidant 1 1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanephenol-based antioxidant 2: 4,4′-butylidenebis (3-methyl-6) -Tert-butylphenol)
- Phenolic antioxidant 3 n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate
- HALS-1 4-hydroxy-2,2,6,6-tetramethylpiperidyl-1-oxylthioether-1: 4,6-bis (octylthiomethyl) -o-cresolamine-1: tri-2-propanol
- Amine adsorbent-1 Product name Kyoward 300 manufactured by Kyowa Chemical Industry Co., Ltd.
- Example 1-10 the odor was suppressed by adding a phenolic antioxidant to 100 parts by mass of the phosphorous antioxidant having a phosphite structure, and in a heating environment. It was confirmed that deterioration of odor could be suppressed. Further, from Example 1-10, no turbidity was observed in the heat stabilizer composition in which 10 parts by mass of the phenolic antioxidant was added to 100 parts by mass of the phosphorous antioxidant having the phosphite structure, and the heat stabilizer It was confirmed that there was no problem in use as a composition.
- Example 2-1 Comparative Example 2-1 was evaluated by granulating in the same manner as in Example 2-1, except that the heat stabilizer composition was not blended.
- melt flow rate (MFR: g / 10 min) was measured according to JIS K 7210 (temperature: 190 ° C., 2.16 kg load).
- the resin composition using the heat stabilizer composition of the present invention can suppress the generation of odor during processing and maintain the MFR of the resin. I was able to confirm. It was confirmed that the synthetic resin composition containing the heat stabilizer composition of the present invention suppresses odor during processing and has excellent heat resistance to the resin.
- Example 3-1 to Example 3-7 Comparative Example 3-1 to Comparative Example 3-5> 100 parts by weight of vinyl chloride resin having a degree of polymerization of 1,050, 50 parts by weight of diisononyl phthalate, 3 parts by weight of epoxidized soybean oil (trade name Adeka Stub O-130P manufactured by ADEKA Corporation), barium / zinc stabilizer (Inc. ADEKA product name AP-551) 0.5 parts by mass and blended with 1 part by mass of the heat stabilizer composition described in Table 6 and Table 7 in advance, a processing temperature of 170 ° C. and a roll rotation speed of 30 rpm Then, roll processing was performed under conditions of roll kneading time of 5 minutes to obtain a sheet having a thickness of 0.7 mm.
- the heat stabilizer composition described in Table 6 and Table 7 was evaluated using a composition that was placed in a sample bottle and allowed to stand in an oven at 50 ° C. for 30 days.
- roll processing was performed in the same manner as in Example 3-1, except that the heat stabilizer composition was not blended.
- Comparative Example 3-5 was a phenol-based antioxidant in phosphite. The phosphite and the phenolic antioxidant were separately added to the vinyl chloride resin so as to have the same composition as that of the heat stabilizer composition of Example 3-2.
- a sheet having a thickness of 0.7 mm was obtained by performing roll processing in the same manner as in Example 3-1, except for adding to the above.
- the molded product of the synthetic resin composition of the present invention can suppress the generation of odor in the molded product placed in a heating environment under processing, and is stable in heat. It was confirmed that coloring of the molded product could be suppressed more than Comparative Example 3-1, in which no agent composition was added.
- this invention provides the heat stabilizer composition which suppressed the phosphite odor, and the synthetic resin composition of this invention which mix
- blended the said heat stabilizer composition is the time of processing and a heating environment.
- Generation of phosphite odor in the molded product can be suppressed, coloring of the molded product can be suppressed, and the heat stabilization effect is excellent.
- the heat stabilizer composition of the present invention and the synthetic resin composition formed by blending it are particularly useful in applications where phosphite odor is avoided.
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Abstract
Description
(一般式(1)中、R1、R2、R3およびR4は、各々独立して、水素原子、炭素原子数1~10の炭化水素基を表し、aは、0~2の整数を表し、aが2の場合、複数のR3は同じであってもよく、異なるものであってもよい。)で表される部分構造を有するフェノール系酸化防止剤0.001~10質量部が含有されてなることを特徴とするものである。
(一般式(2)中、R1、R2およびR3は、各々独立して、水素原子、炭素原子数1~10の炭化水素基を表し、aは、0~2の整数を表し、aが2の場合、複数のR3は同じものであっても異なるものであってもよく、nは1~4の整数であり、
nが1の場合、Xは、炭素原子数1~40のアルキル基、炭素原子数1~40のアルコキシ基、炭素原子数6~40のアリール基、炭素原子数7~40のアリールアルキル基、またはこれらの組み合わせを表し、R4は水素原子を表し、
nが2の場合、Xは、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基、または下記一般式(3)、
(一般式(3)中、R6およびR7は、各々独立して、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基を表す。)で表される基を表し、R4は、水素原子または炭素原子数1~10の炭化水素基を表すが、少なくとも一つのR4は水素原子を表し、
nが3の場合、Xは、炭素原子数1~40のアルカントリイル基、炭素原子数6~40の三価の環状基の何れかを表し、R4は、水素原子または炭素原子数1~10の炭化水素基を表すが、少なくとも一つのR4は水素原子を表し、
nが4の場合、Xは、炭素原子数1~40のアルカンテトライル基を表し、R4は、水素原子または炭素原子数1~10の炭化水素基を表すが、少なくとも一つのR4は水素原子を表し、
前記アルキル基、前記アルコキシ基、前記アリーレンアルキル基、前記アルキリデン基、前記アルカントリイル基、および前記アルカンテトライル基中のメチレン基は、>C=O、-O-、-S-、-CO-O-、-O-CO-、-O-CO-O-、-NR5-、ホスフィン、ホスフィナイト、ホスホナイト、ホスファイト、ホスホラン、ホスホネートまたはこれらの組み合わせで置換されていてもよく、また分岐を有するものであってもよく、R5は、水素原子または炭素原子数1~4のアルキル基を表す。)で表される化合物であることが好ましい。
(一般式(4)中、R8およびR9は、各々独立して、炭素原子数1~40のアルキル基、炭素原子数6~40のアリール基、炭素原子数7~40のアリールアルキル基、炭素原子数3~25の複素環含有基、またはこれらの組み合わせを表し、R8およびR9は結合して環状基を形成してもよく、R10は、直接結合、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基を表し、bは、1~3の整数であり、Tは、bが1の場合、水素原子、炭素原子数1~40のアルキル基、炭素原子数6~40のアリール基、炭素原子数3~25の複素環含有基を表し、bが2の場合、Tは、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基、-S-、または下記一般(3)、
(一般式(3)中、R6およびR7は、各々独立して、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基を表す。)を表し、bが3の場合、Tは、炭素原子数1~40のアルカントリイル基を表す。)
(一般式(5)中、R11およびR12は、各々独立して、炭素原子数1~40のアルキル基、炭素原子数6~40のアリール基を表す。)
(一般式(6)中、R13およびR14は、各々独立して、水素原子、または炭素原子数1~10のアルキル基を表し、R15は、水素原子または炭素原子数1~4のアルキル基を表し、Tは、前記一般式(3)中のTと同じものを表し、cは、0~4の整数を表し、dは、0~4の整数を表し、eは、1~3の整数を表し、cが2以上の場合、複数あるR13は、同じものであっても異なるものであってもよく、dが2以上の場合、複数あるR14は、同じものであっても異なるものであってもよく、eが1の場合、Tは、水素原子、炭素原子数1~40のアルキル基、炭素原子数6~40のアリール基、炭素原子数3~25の複素環含有基を表し、eが2の場合、Tは、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基、-S-、または前記一般式(3)で表される基を表し、eが3の場合、Tは、炭素原子数1~40のアルカントリイル基を表す。)
(一般式(7)中、R16およびR17は、各々独立して、炭素原子数1~40のアルキル基、炭素原子数1~40のアルコキシ基、炭素原子数6~40のアリール基、炭素原子数7~40のアリールアルキル基、炭素原子数3~25の複素環含有基を表し、R18は、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基を表し、fは、1~3の整数を表し、fが1の場合、Tは、水素原子、炭素原子数1~40のアルキル基、炭素原子数6~40のアリール基、炭素原子数3~25の複素環含有基を表し、fが2の場合、Tは、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基、-S-、または前記一般式(3)で表される基を表し、fが3の場合、Tは、炭素原子数1~40のアルカントリイル基を表す。)
(一般式(8)中、R19、R20およびR21は、各々独立して、水素原子、炭素原子数1~40のアルキル基、炭素原子6~40のアリール基、炭素原子数7~40のアリールアルキル基、炭素原子数3~25の複素環含有基を表すが、R19、R20およびR21は同時に水素原子にならない。)で表される化合物を少なくとも1種含むことが好ましい。
本発明の熱安定剤組成物は、ホスファイト構造を有するリン系酸化防止剤100質量部、および一般式(1)、
で表される部分構造を有するフェノール系酸化防止剤0.001~10質量部が含有されてなるものである。ここで、一般式(1)中、R1、R2、R3およびR4は、それぞれ独立して、水素原子、炭素原子数1~10の炭化水素基を表し、aは、0~2の整数を表し、aが2の場合、複数のR3は同じであってもよく、異なるものであってもよい。
上記一般式(1)で表されるフェノール系酸化防止剤において、R1、R2、R3およびR4で表される炭素原子数1~10の炭化水素基とは、炭素原子と水素原子で構成される官能基を表し、その分子構造としては、アルカン、アルケン、シクロアルカン、芳香族炭化水素等が挙げられる。これら炭化水素基は、酸素原子、硫黄原子、カルボニル基、エステル基、アミド基、イミノ基またはアリール基で中断されていてもよく、炭化水素基中の水素原子が下記の置換基で置換されたものであってもよい。これら中断または置換は組み合わされていてもよい。
で表される化合物が好ましい。ここで、一般式(2)中、R1、R2、R3およびR4は、一般式(1)のR1、R2、R3およびR4と同じ水素原子、炭素原子数1~10の炭化水素基を表す。ただし、R4は、少なくとも一つのR4は水素原子である。また、上記一般式(2)中のaは、0~2の整数を表し、aが2の場合、複数のR3は同じものであってもよく、異なるものであってもよい。また、nは1~4の整数を表す。
本発明の熱安定剤組成物においては、リン系酸化防止剤は、ホスファイト構造を有するものであればいずれも使用することができるが、下記一般式(4)~(8)で表される化合物が好ましい。
本発明の合成樹脂組成物は、合成樹脂100質量部に対して、本発明の熱安定剤組成物を0.001~10質量部含有する。本発明の合成樹脂組成物に使用できる合成樹脂としては、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または共重合体、これらのα-オレフィンと共役ジエンまた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およ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、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、直鎖また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。
表1~表4に示す配合で熱安定剤組成物を10g調製し、ガラス製の100mLサンプル瓶に入れて密封し、50℃のオーブンに静置し、10名のパネラーにより熱安定剤組成物の臭気に関する官能試験を行った。
比較例1-2は、トリイソデシルホスフェート以外は何も加えずに評価した。
比較例1-10は、トリイソデシルホスファイトに対し、吸着剤として協和化学工業株式会社製商品名キョーワード300を2質量%加え、5分間スターラーで撹拌したあと濾紙で濾別し、吸着剤を分離したトリイソデシルホスファイトを用いて評価した。
臭気の評価は、熱安定剤組成物の調製直後、50℃のオーブンに静置して14日経過後、および、30日経過後のそれぞれの時点において、サンプル瓶の蓋を僅かに開けて、瓶口の臭気を嗅ぐ方法で下記の評価基準に従って評価した。結果を表1~表4に併記する。
5:不快になるほどの強い臭気を感じた。
4:強い臭気を感じた。
3:臭気を感じた。
2:僅かに臭気を感じた。
1:殆ど臭気が感じられなかった。
濁りの評価は、熱安定剤組成物を調製した際に、濁りの有無について目視で評価した。結果を表1~表4に併記する。
フェノール系酸化防止剤2:4,4’-ブチリデンビス(3-メチル-6-tert-ブチルフェノール)
フェノール系酸化防止剤3:n-オクタデシル-3-(3’,5’-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート
チオエーテル-1:4,6-ビス(オクチルチオメチル)-o-クレゾール
アミン-1:トリ-2-プロパノールアミン
吸着剤-1:協和化学工業株式会社製商品名キョーワード300
次に、本発明の熱安定剤組成物を合成樹脂に配合した場合の熱安定化効果について、以下の手順で評価した。
造粒して得られたペレットを採取し、JIS K 7210(温度:190℃,2.16kg加重)に準拠して、メルトフローレート(MFR:g/10min)を測定した。
造粒時における臭気について、下記の評価基準に基づいて評価した。結果を表5に併記する。
5:不快になるほどの強い臭気を感じた。
4:強い臭気を感じた。
3:臭気を感じた。
2:僅かに臭気を感じた。
1:殆ど臭気が感じられなかった。
重合度1,050の塩化ビニル樹脂100質量部に対し、ジイソノニルフタレート50質量部、エポキシ化大豆油(株式会社ADEKA製商品名アデカスタブO-130P)3質量部、バリウム/亜鉛系安定剤(株式会社ADEKA製商品名AP-551)0.5質量部、および、予め表6および表7に記載の熱安定剤組成物1質量部を調整したものをブレンドし、加工温度170℃、ロール回転数30rpm、ロール混練時間5分間の条件でロール加工を行い、厚み0.7mmのシートを得た。
得られたシートを重ねて180℃に加熱して、プレスして厚み2mmのシートを作成し、これを試験片とした。試験片は室温環境下で1日静置後、分光測色計(SC-T;スガ試験機株式会社製)を用いて着色性(Y.I.)を評価した。また、ロール加工時の臭気の有無、および、試験片の加熱後の臭気について下記の方法で評価した。これらの結果について下記表6、7に示す。
試験片を1平方センチ大に切断したもの10gをサンプル瓶に入れて密封し、50℃のオーブンに24時間経過後、サンプル瓶を取り出して蓋を僅かに開け、瓶口の臭気について下記の方法で評価した。
5:不快になるほどの強い臭気を感じた。
4:強い臭気を感じた。
3:臭気を感じた。
2:僅かに臭気を感じた。
1:殆ど臭気が感じられなかった。
Claims (8)
- 前記フェノール系酸化防止剤が、下記一般式(2)、
(一般式(2)中、R1、R2およびR3は、各々独立して、水素原子、炭素原子数1~10の炭化水素基を表し、aは、0~2の整数を表し、aが2の場合、複数のR3は同じものであっても異なるものであってもよく、nは1~4の整数であり、
nが1の場合、Xは、炭素原子数1~40のアルキル基、炭素原子数1~40のアルコキシ基、炭素原子数6~40のアリール基、炭素原子数7~40のアリールアルキル基、またはこれらの組み合わせを表し、R4は水素原子を表し、
nが2の場合、Xは、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基、または下記一般式(3)、
(一般式(3)中、R6およびR7は、各々独立して、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基を表す。)で表される基を表し、R4は、水素原子または炭素原子数1~10の炭化水素基を表すが、少なくとも一つのR4は水素原子を表し、
nが3の場合、Xは、炭素原子数1~40のアルカントリイル基、炭素原子数6~40の三価の環状基の何れかを表し、R4は、水素原子または炭素原子数1~10の炭化水素基を表すが、少なくとも一つのR4は水素原子を表し、
nが4の場合、Xは、炭素原子数1~40のアルカンテトライル基を表し、R4は、水素原子または炭素原子数1~10の炭化水素基を表すが、少なくとも一つのR4は水素原子を表し、
前記アルキル基、前記アルコキシ基、前記アリーレンアルキル基、前記アルキリデン基、前記アルカントリイル基、および前記アルカンテトライル基中のメチレン基は、>C=O、-O-、-S-、-CO-O-、-O-CO-、-O-CO-O-、-NR5-、ホスフィン、ホスフィナイト、ホスホナイト、ホスファイト、ホスホラン、ホスホネートまたはこれらの組み合わせで置換されていてもよく、また分岐を有するものであってもよく、R5は、水素原子または炭素原子数1~4のアルキル基を表す。)で表される化合物である請求項1記載の熱安定剤組成物。 - 前記リン系酸化防止剤が、下記一般式(4)~(8)、
(一般式(4)中、R8およびR9は、各々独立して、炭素原子数1~40のアルキル基、炭素原子数6~40のアリール基、炭素原子数7~40のアリールアルキル基、炭素原子数3~25の複素環含有基、またはこれらの組み合わせを表し、R8およびR9は結合して環状基を形成してもよく、R10は、直接結合、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基を表し、bは、1~3の整数であり、Tは、bが1の場合、水素原子、炭素原子数1~40のアルキル基、炭素原子数6~40のアリール基、炭素原子数3~25の複素環含有基を表し、bが2の場合、Tは、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基、-S-、または下記一般(3)、
(一般式(3)中、R6およびR7は、各々独立して、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基を表す。)を表し、bが3の場合、Tは、炭素原子数1~40のアルカントリイル基を表す。)
(一般式(5)中、R11およびR12は、各々独立して、炭素原子数1~40のアルキル基、炭素原子数6~40のアリール基を表す。)
(一般式(6)中、R13およびR14は、各々独立して、水素原子、または炭素原子数1~10のアルキル基を表し、R15は、水素原子または炭素原子数1~4のアルキル基を表し、Tは、前記一般式(3)中のTと同じものを表し、cは、0~4の整数を表し、dは、0~4の整数を表し、eは、1~3の整数を表し、cが2以上の場合、複数あるR13は、同じものであっても異なるものであってもよく、dが2以上の場合、複数あるR14は、同じものであっても異なるものであってもよく、eが1の場合、Tは、水素原子、炭素原子数1~40のアルキル基、炭素原子数6~40のアリール基、炭素原子数3~25の複素環含有基を表し、eが2の場合、Tは、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基、-S-、または前記一般式(3)で表される基を表し、eが3の場合、Tは、炭素原子数1~40のアルカントリイル基を表す。)
(一般式(7)中、R16およびR17は、各々独立して、炭素原子数1~40のアルキル基、炭素原子数1~40のアルコキシ基、炭素原子数6~40のアリール基、炭素原子数7~40のアリールアルキル基、炭素原子数3~25の複素環含有基を表し、R18は、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基を表し、fは、1~3の整数を表し、fが1の場合、Tは、水素原子、炭素原子数1~40のアルキル基、炭素原子数6~40のアリール基、炭素原子数3~25の複素環含有基を表し、fが2の場合、Tは、炭素原子数1~40のアルキリデン基、炭素原子数6~40のアリーレン基、-S-、または前記一般式(3)で表される基を表し、fが3の場合、Tは、炭素原子数1~40のアルカントリイル基を表す。)
(一般式(8)中、R19、R20およびR21は、各々独立して、水素原子、炭素原子数1~40のアルキル基、炭素原子6~40のアリール基、炭素原子数7~40のアリールアルキル基、炭素原子数3~25の複素環含有基を表すが、R19、R20およびR21は同時に水素原子にならない。)で表される化合物を少なくとも1種含む請求項1記載の熱安定剤組成物。 - 前記ホスファイト構造を有するリン系酸化防止剤の融点が100℃以下である請求項1記載の熱安定剤組成物。
- 前記一般式(1)中のR1がtert-ブチル基、R2が水素原子、R3がメチル基である請求項1記載の熱安定剤組成物。
- 前記一般式(2)中のR1がtert-ブチル基、R2が水素原子、R3がメチル基である請求項2記載の熱安定剤組成物。
- 前記フェノール系酸化防止剤の分子量が、300~2,000の範囲内である請求項1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1記載の熱安定剤組成物が0.001~10質量部含有されてなることを特徴とする合成樹脂組成物。
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US15/506,384 US10654990B2 (en) | 2014-08-27 | 2015-08-04 | Thermal stabilizer composition and synthetic resin composition comprising same |
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KR20170045316A (ko) | 2017-04-26 |
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BR112017003356A2 (ja) | 2018-01-23 |
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WO2016031505A8 (ja) | 2017-03-16 |
EP3187565A1 (en) | 2017-07-05 |
JP6433726B2 (ja) | 2018-12-05 |
EP3187565A4 (en) | 2018-03-28 |
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