WO2017061057A1 - 酸化防止剤 - Google Patents
酸化防止剤 Download PDFInfo
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- WO2017061057A1 WO2017061057A1 PCT/JP2015/078835 JP2015078835W WO2017061057A1 WO 2017061057 A1 WO2017061057 A1 WO 2017061057A1 JP 2015078835 W JP2015078835 W JP 2015078835W WO 2017061057 A1 WO2017061057 A1 WO 2017061057A1
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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
- C08K5/136—Phenols containing halogens
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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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
Definitions
- the present invention relates to an antioxidant.
- the compound represented by the formula (I) is known as an antioxidant for thermoplastic polymers such as polyolefin (for example, Patent Document 1).
- An object of the present invention is to provide an antioxidant that increases the stability of a resin.
- the present invention includes the following inventions.
- R 1 , R 2 , R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 6 carbon atoms.
- R 12 represents an alkyl cycloalkyl group, an aralkyl group having 7 to 12 carbon atoms or a phenyl group
- R 3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
- X represents a single bond, a sulfur atom or a> CH—R 6 group
- R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms
- A represents an alkylene group having 1 to 8 carbon atoms or * —C ( ⁇ O) —R 7 — group (R 7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond on the oxygen side.
- One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. . ]
- the area area of the compound represented by the formula (III) with respect to the area area 100 of the compound represented by the formula (II) is 0.01 to 5, ] Or antioxidant according to [3].
- Measurement condition column Sumipax ODS A-212 (6 mm ⁇ ⁇ 150 mm, diameter of filler: 5 ⁇ m) Column temperature: 40 ° C Mobile phase: (A liquid) 0.1 mass% ammonium acetate / water (B liquid) 0.1 mass% ammonium acetate / methanol Mobile phase gradient: 0 ⁇ 20 min (A liquid: 20 ⁇ 0 mass% (1 mass% / min), B liquid: 80 ⁇ 100 mass% (1 mass% / min)), 20 ⁇ 45 min (A liquid: 0 mass%, B liquid: 100 mass%) Flow rate: 1.0 mL / min Detection method: UV (280 nm) Sample concentration: 5 mg / mL Injection volume: 10 ⁇ L [5] In any one of the above [2] to [4], the total amount of the compound represented by the formula (II) and the compound represented by the formula (III) is 90 parts by mass or more with respect to 100 parts by mass of the antioxidant.
- thermoplastic polymer composition comprising the antioxidant according to any one of [1] to [5] and a thermoplastic polymer.
- the thermoplastic polymer according to [6] including 0.005 to 5 parts by mass of the antioxidant according to any one of [1] to [5] with respect to 100 parts by mass of the thermoplastic polymer.
- Composition [8] The thermoplastic polymer composition according to the above [6] or [7], wherein the thermoplastic polymer is a polyolefin.
- the antioxidant of the present invention contains a compound represented by the following formula (III) (hereinafter sometimes referred to as “compound (III)”).
- compound (III) By adding compound (III) to a resin such as a thermoplastic polymer, yellowing or thermal degradation of the resin can be suppressed and the stability of the resin can be increased. It is suitable as an active ingredient of an antioxidant for resins.
- Compound (III) is, for example, 2-t-butyl-4- (3-hydroxypropyl) -6-methylphenol, which is a p-hydroxyphenyl alkanol described in Japanese Patent No. 4013810, with thionyl chloride or the like. It can be produced by chlorination.
- compound (II) In addition to compound (III), it is preferable to further contain a compound represented by the following formula (II) (hereinafter sometimes referred to as “compound (II)”).
- compound (II) By including compound (II) in addition to compound (III), the processing stability of a resin such as a thermoplastic polymer is further improved.
- R 1 , R 2 , R 4 and R 5 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 12 carbon atoms.
- Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, and t-pentyl.
- cycloalkyl group having 5 to 8 carbon atoms examples include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
- alkylcycloalkyl group having 6 to 12 carbon atoms examples include 1-methylcyclopentyl group, 1-methylcyclohexyl group, 1-methyl-4-i-propylcyclohexyl group and the like.
- aralkyl group having 7 to 12 carbon atoms examples include benzyl group, ⁇ -methylbenzyl group and ⁇ , ⁇ -dimethylbenzyl group.
- R 1 , R 2 and R 4 in formula (II) are preferably each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or an alkylcycloalkyl having 6 to 12 carbon atoms. It is a group.
- R 1 and R 4 are each independently and more preferably a t-alkyl group such as a t-butyl group, a t-pentyl group and a t-octyl group, a cyclohexyl group or a 1-methylcyclohexyl group.
- R 2 is more preferably a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, t-pentyl group, etc. And an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, a t-butyl group or a t-pentyl group.
- R 5 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, i An alkyl group having 1 to 5 carbon atoms such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group and t-pentyl group;
- R 3 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms are the same as those described above. R 3 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group.
- X represents a single bond, a sulfur atom or a> CH—R 6 group
- R 6 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms.
- Examples of the alkyl group having 1 to 8 carbon atoms and the cycloalkyl group having 5 to 8 carbon atoms represented by R 6 include the same ones as described above.
- X is preferably a methylene substituted with an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group. It is a group or a single bond, more preferably a single bond.
- A represents an alkylene group having 1 to 8 carbon atoms or a * —C ( ⁇ O) —R 7 — group.
- R 7 represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond on the oxygen side.
- Examples of the alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a 2,2-dimethyl-1,3-propylene group. It is done.
- A is preferably a propylene group.
- * In the * —C ( ⁇ O) —R 7 — group represents that the carbonyl group is bonded to the oxygen atom of the phosphite group.
- R 7 is preferably a single bond or an ethylene group.
- One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
- examples of the alkyl group having 1 to 8 carbon atoms include the same ones as described above.
- examples of the aralkyloxy group having 7 to 12 carbon atoms include benzyloxy group, ⁇ -methylbenzyloxy group and ⁇ , ⁇ -dimethylbenzyloxy group.
- the compound (II) include 2,4,8,10-tetra-tert-butyl-6- [3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propoxy] dibenzo [D, f] [1,3,2] dioxaphosphine, 6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -2,4,8,10- Tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphine, 6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -4, 8-di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 6- [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionyloxy] -4,8-di-t-butyl-2,
- the compound (II) is 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4-hydroxy -5-tert-Butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine is preferred.
- the content of compound (III) is preferably 0.005 to 10 parts by mass with respect to 100 parts by mass of compound (II). More preferably, the amount is 0.005 to 5 parts by mass, still more preferably 0.005 to 2 parts by mass, and particularly preferably 0.01 to 2 parts by mass.
- the content of compound (III) is within the above range, the processing stability of a resin such as a thermoplastic polymer is further improved.
- the area area of the compound (III) with respect to the area area 100 of the compound (II) is preferably 0.01 to 5, more preferably It is 0.01 to 2, particularly preferably 0.1 to 2.
- the antioxidant of the present invention may contain an additive as long as the effects of the present invention are not impaired.
- additives include UV absorbers, light stabilizers, antioxidants, metal deactivators, nucleating agents, lubricants, antistatic agents, flame retardants, fillers, pigments, plasticizers, flame retardants, anti Examples include blocking agents, surfactants, processing aids, foaming agents, emulsifiers, brighteners, neutralizing agents such as calcium stearate and hydrotalcite, and binders.
- the antioxidant of the present invention preferably contains 90 parts by mass or more, more preferably 95 parts by mass or more, and still more preferably 100 parts by mass of the antioxidant, in total of compound (II) and compound (III). Contains 98 parts by mass or more, particularly preferably 99 parts by mass or more. In addition, when the antioxidant of this invention does not contain compound (II), it is preferable that the quantity of compound (III) exists in the said range.
- the shape of the antioxidant of the present invention is not particularly limited, but is preferably powder, granule, pellet or flake.
- the antioxidant of the present invention contains compound (II) and compound (III)
- the antioxidant of the present invention can be produced, for example, by mixing compound (II) and compound (III).
- the mixing method include a method of mixing with a known mixer such as a Henschel mixer, a super mixer, or a high speed mixer.
- the compound (II) and the compound (III) are compressed and granulated with a compression granulator such as a roller compactor to obtain a flake-shaped antioxidant, and melted with a single-screw or multi-screw extruder.
- a method of obtaining a pellet antioxidant by extrusion a method of obtaining a pellet antioxidant by extruding with a semi-dry type extruder such as a disk pelleter, a method of obtaining a granular antioxidant by mixing with a binder And a method of removing the solvent under reduced pressure after dissolving or dispersing in the solvent.
- the solvent include aromatic hydrocarbons having 6 to 12 carbon atoms, alcohols having 1 to 8 carbon atoms, and aliphatic nitriles having 2 to 3 carbon atoms. What is necessary is just to mix with a compound (II) and a compound (III), when adding an additive to the antioxidant of this invention.
- the antioxidant of the present invention can increase the stability of the resin by suppressing yellowing or thermal deterioration of the resin such as a thermoplastic polymer. Accordingly, the present invention also provides a thermoplastic polymer composition containing the antioxidant of the present invention and a thermoplastic polymer.
- One type of thermoplastic polymer may be sufficient and the mixture of 2 or more types of thermoplastic polymers may be sufficient.
- Propylene-based resin such as polyethylene, ethylene / ⁇ -olefin copolymer, ethylene / ethyl acrylate copolymer resin, ethylene / vinyl acetate copolymer resin, ethylene / vinyl alcohol copolymer resin, and ethylene / methyl methacrylate copolymer Resin; methylpentene polymer; poly (p-methylstyrene), poly ( ⁇ -methylstyrene), acrylonitrile / styrene copolymer resin, acrylonitrile / butadiene / styrene copolymer resin, special acrylic rubber / acrylonitrile / styrene copolymer resin, Styrenic resins such as acrylonitrile / chlorinated polyethylene / styrene copolymer resins and styrene / butadiene copolymers; halogenated polymers such as chlorinated polyethylene
- ethylene / ⁇ -olefin copolymer examples include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene -Octene copolymer, ethylene-1-decene copolymer and the like.
- ethylene resins such as polyethylene and ethylene / ⁇ -olefin copolymers are low density polyethylene (LDPE) having a density of 0.914 to 0.925 (g / cm 3 ), 0.925 to 0 .94 (g / cm 3 ) medium density polyethylene (MDPE) or 0.94 to 0.96 (g / cm 3 ) high density polyethylene (HDPE).
- LDPE low density polyethylene
- MDPE medium density polyethylene
- HDPE high density polyethylene
- an ethylene / ⁇ -olefin copolymer is sometimes referred to as linear low density polyethylene (LLDPE).
- the thermoplastic polymer is particularly preferably LLDPE.
- the ethylene / ⁇ -olefin copolymer preferably has a polyethylene crystal structure and contains 50% by mass or more of repeating units derived from ethylene.
- the ⁇ -olefin in the ethylene / ⁇ -olefin copolymer is preferably an ⁇ -olefin having 4 to 20 carbon atoms.
- the ⁇ -olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene and 4-methyl.
- Examples include 1-hexene, vinylcyclohexane, vinylcyclohexene, styrene, norbornene, butadiene, and isoprene.
- 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene are preferable. These ⁇ -olefins may be used alone or in combination of two or more.
- the ethylene resin is obtained, for example, by polymerizing ethylene and an ⁇ -olefin having 3 to 18 carbon atoms in the presence of a catalyst such as a metallocene catalyst or a Ziegler-Natta catalyst.
- a catalyst such as a metallocene catalyst or a Ziegler-Natta catalyst.
- the polymerization method include a slurry polymerization method performed in a solvent such as a hydrocarbon solvent, a solvent polymerization method, a liquid phase polymerization method without a solvent, a gas phase polymerization method, and a liquid phase-gas phase polymerization method in which these are continuously performed. Examples include legality.
- the propylene-based resin means a polyolefin-based resin having a structural unit derived from propylene.
- the propylene resin include crystalline propylene homopolymer, propylene-ethylene random copolymer, propylene- ⁇ -olefin random copolymer, propylene-ethylene- ⁇ -olefin copolymer, and polypropylene block copolymer. Is mentioned. A crystalline propylene homopolymer and a polypropylene block copolymer are preferable, and a polypropylene block copolymer is more preferable.
- One type of propylene-based resin used for the thermoplastic polymer may be used, or two or more types may be combined.
- polypropylene block copolymer examples include a propylene homopolymer or a copolymer component mainly composed of propylene, a copolymer component composed of propylene and at least one selected from the group consisting of ethylene and ⁇ -olefin, And a polypropylene block copolymer made of
- the ⁇ -olefin contained in the propylene-based resin is usually an ⁇ -olefin having 4 to 12 carbon atoms.
- Examples of the ⁇ -olefin include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, and preferably 1-butene, 1-hexene and 1 -Octene.
- propylene- ⁇ -olefin random copolymer examples include propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer, and the like.
- propylene-ethylene- ⁇ -olefin copolymer examples include propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, and the like. .
- a polypropylene block copolymer comprising a propylene homopolymer or a copolymer component mainly composed of propylene, and a copolymer component composed of propylene and at least one selected from the group consisting of ethylene and ⁇ -olefin.
- the copolymer component mainly composed of propylene include a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, and a propylene-1-hexene copolymer component.
- Examples of the copolymer component comprising propylene and at least one selected from the group consisting of ethylene and ⁇ -olefin include propylene-ethylene copolymer component, propylene-ethylene-1-butene copolymer component, propylene-ethylene- 1-hexene copolymer component, propylene-ethylene-1-octene copolymer component, propylene-1-butene copolymer component, propylene-1-hexene copolymer component, propylene-1-octene copolymer component, etc. Is mentioned.
- the content of the component derived from ethylene and ⁇ -olefin is usually 0.01 to 20% by mass.
- polypropylene block copolymer comprising a propylene homopolymer or a copolymer component mainly composed of propylene, and a copolymer component composed of at least one selected from the group consisting of propylene and ethylene and ⁇ -olefin.
- propylene-ethylene block copolymers are, for example, propylene-ethylene block copolymers, (propylene)-(propylene-ethylene) block copolymers, (propylene)-(propylene-ethylene-1-butene) block copolymers, (propylene)-(propylene- (Ethylene-1-hexene) block copolymer, (propylene)-(propylene-1-butene) block copolymer, (propylene)-(propylene-1-hexene) block copolymer, (propylene-ethylene)-( Propylene-ethylene-1-butene) block copolymer, Pyrene-ethylene)-(propylene-ethylene-1-hexene) block copolymer, (propylene-ethylene)-(propylene-1-butene) block copolymer, (propylene-ethylene)-(propylene-1-hexene) Block copolymer, (propylene-1-butene)
- Propylene-based resin production methods include slurry polymerization in a solvent such as a hydrocarbon solvent, solvent polymerization, liquid phase polymerization without solvent, gas phase polymerization, and liquid phase in which these are continuously performed. Examples include a gas phase polymerization method. These production methods may be batch-wise or continuous. Moreover, the method of manufacturing in one step may be sufficient and the method of manufacturing in multiple steps of two or more steps may be sufficient.
- the polypropylene block copolymer is produced, for example, by a multistage production method in which each component constituting the polypropylene block copolymer is produced.
- the melt index (MI) value of the thermoplastic polymer is preferably 0.01 to 100 g / 10 min, more preferably 0.01 to 10 g / 10 min.
- the MI value of the ethylene-based resin is preferably 0.01 g / 10 min or more and less than 10 g / 10 min.
- the MI value of the propylene-based resin is preferably 0.01 to 100 g / 10 min from the viewpoint of moldability.
- thermoplastic polymer and the antioxidant of the present invention are dry blended and then melt-extruded with an extruder.
- the solvent include cyclohexane.
- thermoplastic polymer composition of the present invention preferably contains 0.005 to 5 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 100 parts by mass of the thermoplastic polymer. 0.01 to 1 part by mass, particularly preferably 0.03 to 1 part by mass is contained.
- the stability of the resin is determined by kneading the thermoplastic polymer composition, molding it into pellets, etc., and measuring the yellowness index (YI) value, melt index (MI) value, etc. of the molded thermoplastic polymer composition. Can be evaluated.
- the antioxidant of the present invention is particularly effective as a processing stabilizer that improves the stability of a resin during processing.
- the processing stability of the resin can be evaluated by measuring the MI value of the resin before and after processing.
- the stability of the resin can be evaluated by the following method, for example.
- the thermoplastic polymer and the antioxidant were dry blended, and the obtained thermoplastic polymer composition was kneaded in an air atmosphere at 190 ° C. and a screw rotation speed of 80 rpm using a 30 mm diameter twin screw extruder, Pellets (1) are obtained.
- the obtained pellet (1) is kneaded in an air atmosphere at 230 ° C. and a screw rotation speed of 50 rpm using a 30 mm diameter single screw extruder to obtain a pellet (2).
- the kneading and extrusion molding by this single-screw extruder is repeated 5 times to obtain pellets (3).
- the YI value is measured using a Minolta color difference meter CM-3500d based on the plastic optical property test method JIS K 7105. It is said that the smaller the YI value, the lower the yellowness and the higher the stability of the resin. Further, according to the method defined in JIS K7210-1995, the MI value is measured at 190 ° C. using a load of 21.18 N (2.16 Kg). For example, ethylene resin is considered to have higher stability as the MI value is larger. On the other hand, the propylene-based resin is considered to have higher stability as the MI value is smaller. In particular, it can be said that an ethylene-based resin having a small change in MI value when the molding is repeatedly performed 5 times at a temperature of 200 ° C. or higher using an extruder is highly stable.
- LLDPE linear low density polyethylene
- the obtained crude product was purified by silica gel column chromatography (solvent: hexane, chloroform) to obtain 2-t-butyl-4- (3-chloropropyl) -6-methylphenol. It was confirmed by 1 H-NMR that the obtained compound was 2-t-butyl-4- (3-chloropropyl) -6-methylphenol.
- Example 1 After dry blending 100 parts by weight of the thermoplastic polymer (A), 0.1 part by weight of the compound (III) -A and 0.05 part by weight of calcium stearate, a 30 mm diameter twin-screw extruder (NAS30 extruder, Was used, and kneaded in an air atmosphere at 190 ° C. and a screw rotation speed of 80 rpm to obtain pellets (1-1) as a thermoplastic polymer composition.
- the obtained pellet (1-1) was kneaded using a 30 mm diameter single screw extruder (VS30-28 type extruder, manufactured by Tanabe Plastics) in an air atmosphere at 230 ° C. and a screw rotation speed of 50 rpm. To obtain pellets (2-1).
- the kneading and extrusion molding by this single screw extruder was further repeated 5 times to obtain pellets.
- the pellets obtained in the first, third, and fifth iterations and the pellet (2-1) were filled in a plastic bag, respectively, and a plastic optical property test method JIS K 7105 using a Minolta color difference meter CM-3500d.
- the YI value was measured based on Further, the MI value of the pellets obtained in the fifth repetition was measured at 190 ° C. under a load of 21 using a melt indexer (manufactured by Techno Seven Co., Ltd., model L246-3537) according to the method specified in JIS K7210-1995.
- the processing stability of the polymer composition was evaluated by measuring at .18N (2.16 Kg). The results are shown in Table 1.
- thermoplastic polymer composition was prepared in the same manner as in Example 1 except that compound (I) -A was used in place of compound (III) -A, and the resulting polymer composition had improved processing stability and yellowing. evaluated. The results are shown in Table 1.
- Example 2 [Preparation of Antioxidant (A)]
- Compound (II) -A and compound (III) -A were mixed in the proportions shown in Table 2 to obtain antioxidant (A).
- the liquid chromatography measurement was performed on the antioxidant (A) under the following measurement conditions.
- Table 2 shows the area area of Compound (III) -A with respect to area area 100 of Compound (II) -A.
- LC Measurement Device Shimadzu Corporation LC-10Avp Column: Sumipax ODS A-212 (6 mm ⁇ ⁇ 150 mm, filler diameter: 5 ⁇ m) Column temperature: 40 ° C Mobile phase: (A liquid) 0.1 mass% ammonium acetate / water (B liquid) 0.1 mass% ammonium acetate / methanol Mobile phase gradient: 0 ⁇ 20 min (A liquid: 20 ⁇ 0 mass% (1 mass% / min), B liquid: 80 ⁇ 100 mass% (1 mass% / min)), 20 ⁇ 45 min (A liquid: 0 mass%, B liquid: 100 mass%) Flow rate: 1.0 mL / min Detector: SPD-10Avp Detection method: UV (280 nm) Sample concentration: 5 mg / mL Injection volume: 10 ⁇ L
- thermoplastic polymer composition After dry blending 100 parts by weight of the thermoplastic polymer (A), 0.1 part by weight of the antioxidant (A) and 0.05 part by weight of calcium stearate, a 30 mm diameter twin screw extruder (NAS30 extruder) (Manufactured by Nakatani Co., Ltd.) in an air atmosphere at 190 ° C. and a screw rotation speed of 80 rpm to obtain pellets (1-2) as a thermoplastic polymer composition. The obtained pellet (1-2) was kneaded using a 30 mm diameter single screw extruder (VS30-28 type extruder, manufactured by Tanabe Plastics Co., Ltd.) in an air atmosphere at 230 ° C.
- NAS30 extruder Manufactured by Nakatani Co., Ltd.
- pellets (2-2) The kneading and extrusion molding by this single screw extruder was further repeated 5 times to obtain pellets (3-2).
- the MI value of the pellet (3-2) was measured at 190 ° C. under a load of 21.18 N (2) using a melt indexer (manufactured by Techno Seven Co., Ltd., model L246-3537) according to the method defined in JIS K7210-1995. .16 Kg), the processing stability of the polymer composition was evaluated. The results are shown in Table 2.
- Examples 3 to 6, Comparative Example 2 In Examples 3 to 6, an antioxidant and a thermoplastic polymer composition were used in the same manner as in Example 2 except that the parts shown in Table 2 were used as Compound (II) -A and Compound (III) -A. The product was obtained and the area area and the processing stability of the polymer composition were evaluated. Comparative Example 2 is an example in which no antioxidant was used. The results of Examples 3 to 6 and Comparative Example 2 are shown in Table 2.
- the antioxidant of the present invention composed of the compound represented by the formula (III) has a low YI value even after repeated kneading and extrusion molding, and the conventional antioxidant [(I) Compared with -A], the effect of suppressing yellowing was high. Further, it was confirmed that the MI value after repeated kneading and extrusion molding was high, and the processing stability of the resin was excellent. Furthermore, as shown in Table 2, when the compound represented by the formula (II) was included, it was confirmed that the stability of the resin was higher.
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Abstract
Description
本発明の目的は、樹脂の安定性を高くする酸化防止剤を提供することにある。
[1]式(III)で示される化合物を含む酸化防止剤。
Xは単結合、硫黄原子又は>CH-R6基(R6は水素原子、炭素数1~8のアルキル基又は炭素数5~8のシクロアルキル基を示す)を表し、
Aは炭素数1~8のアルキレン基又は*-C(=O)-R7-基(R7は単結合又は炭素数1~8のアルキレン基を表し、*は酸素側の結合手であることを表す)を表し、
Y及びZは、いずれか一方がヒドロキシル基、炭素数1~8のアルコキシ基又は炭素数7~12のアラルキルオキシ基を表し、他の一方が水素原子又は炭素数1~8のアルキル基を表す。〕
[3]式(II)で示される化合物100質量部に対して、式(III)で示される化合物を0.005~10質量部含む、前記[2]に記載の酸化防止剤。
[4]下記測定条件における液体クロマトグラフィー測定において、式(II)で示される化合物のエリア面積100に対する、式(III)で示される化合物のエリア面積が0.01~5である、前記[2]又は[3]に記載の酸化防止剤。
測定条件
カラム:Sumipax ODS A-212(6mmφ×150mm、充填剤の径:5μm)
カラム温度:40℃
移動相:(A液)0.1質量%酢酸アンモニウム/水
(B液)0.1質量%酢酸アンモニウム/メタノール
移動相勾配:0→20min(A液:20→0質量%(1質量%/min)、B液:80→100質量%(1質量%/min))、20→45min(A液:0質量%、B液:100質量%)
流速:1.0mL/min
検出方法:UV(280nm)
試料濃度:5mg/mL
注入量:10μL
[5]酸化防止剤100質量部に対して、式(II)で示される化合物と式(III)で示される化合物を合計90質量部以上含む、前記[2]~[4]のいずれかに記載の酸化防止剤。
[6]前記[1]~[5]のいずれかに記載の酸化防止剤と熱可塑性ポリマーとを含む熱可塑性ポリマー組成物。
[7]熱可塑性ポリマー100質量部に対して、前記[1]~[5]のいずれかに記載の酸化防止剤を0.005~5質量部含む、前記[6]に記載の熱可塑性ポリマー組成物。
[8]熱可塑性ポリマーがポリオレフィンである、前記[6]又は[7]に記載の熱可塑性ポリマー組成物。
[9]熱可塑性ポリマーの安定性を向上させるための、前記[1]~[5]のいずれかに記載の酸化防止剤の使用。
炭素数1~8のアルキル基としては、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、t-ブチル基、t-ペンチル基、i-オクチル基、t-オクチル基及び2-エチルヘキシル基等が挙げられる。炭素数5~8のシクロアルキル基としては、シクロペンチル基、シクロヘキシル基、シクロヘプチル基及びシクロオクチル基等が挙げられる。炭素数6~12のアルキルシクロアルキル基としては、1-メチルシクロペンチル基、1-メチルシクロヘキシル基及び1-メチル-4-i-プロピルシクロヘキシル基等が挙げられる。炭素数7~12のアラルキル基としては、ベンジル基、α-メチルベンジル基及びα,α-ジメチルベンジル基等が挙げられる。
<測定条件>
カラム:Sumipax ODS A-212(6mmφ×150mm、充填剤の径:5μm)
カラム温度:40℃
移動相:(A液)0.1質量%酢酸アンモニウム/水
(B液)0.1質量%酢酸アンモニウム/メタノール
移動相勾配:0→20min(A液:20→0質量%(1質量%/min)、B液:80→100質量%(1質量%/min))、20→45min(A液:0質量%、B液:100質量%)
流速:1.0mL/min
検出方法:UV(280nm)
試料濃度:5mg/mL
注入量:10μL
化合物(II)のエリア面積100に対する化合物(III)のエリア面積が前記範囲内であると、熱可塑性ポリマー等の樹脂の加工安定性がより向上する。
本発明において、熱可塑性ポリマーはポリオレフィン系の樹脂であることが好ましく、中でも、エチレン系樹脂及びプロピレン系樹脂がより好ましく、エチレン系樹脂がさらに好ましい。
熱可塑性ポリマーに用いられるプロピレン系樹脂は、1種類でもよいし、2種以上を組み合わせてもよい。
エチレン系樹脂のMI値は、好ましくは0.01g/10分以上10g/10分未満である。プロピレン系樹脂のMI値は、成型加工性等の観点から、0.01~100g/10分であると好ましい。
熱可塑性ポリマーと酸化防止剤とをドライブレンドし、得られた熱可塑性ポリマー組成物を、30mm径の二軸押出成形機を用いて、空気雰囲気下、190℃、スクリュー回転数80rpmで混練し、ペレット(1)を得る。得られたペレット(1)を、30mm径の単軸押出成形機を用いて、空気雰囲気下、230℃、スクリュー回転数50rpmで混練し、ペレット(2)を得る。この単軸押出成形機による混練・押出成形を5回繰り返し、ペレット(3)を得る。得られたペレット(3)について、ミノルタ製色差計CM-3500dを用いて、プラスックの光学的特性試験方法JIS K 7105に基づいてYI値を測定する。YI値が小さいほど黄色みが少なく、樹脂の安定性が高いとされる。また、JIS K7210-1995に規定された方法に従い、190℃にて荷重21.18N(2.16Kg)を用いてMI値を測定する。例えば、エチレン系樹脂はMI値が大きいほど安定性が高いとされる。一方、プロピレン系樹脂はMI値が小さいほど安定性が高いとされる。特に、押出成形機を用いて、200℃以上の温度で5回繰り返し成形を実施した際のMI値の変化が少ないエチレン系樹脂は、安定性が高いといえる。
・熱可塑性ポリマー(A):線状低密度ポリエチレン(LLDPE)(MI値:1.05g/10分、住友化学製)
・化合物(I)-A:n-オクタデシル-3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオネート
・化合物(II)-A:2,4,8,10-テトラ-t-ブチル-6-〔3-(3-メチル-4-ヒドロキシ-5-t-ブチルフェニル)プロポキシ〕ジベンゾ〔d,f〕〔1,3,2〕ジオキサホスフェピン(スミライザー(登録商標)GP、住友化学製)
・化合物(III)-A:2-t-ブチル-4-(3-クロロプロピル)-6-メチルフェノール
特許第4013810号に記載された方法に準じて、2-t-ブチル-4-(3-ヒドロキシプロピル)-6-メチルフェノールを合成した。2-t-ブチル-4-(3-ヒドロキシプロピル)-6-メチルフェノール250g、ピリジン9g及びトルエン650mLを混合し、得られた混合物に塩化チオニル171gを滴下し、その後、78℃で3時間撹拌混合した。得られた混合物を室温まで冷却した後、水及び5%炭酸水素ナトリウム水溶液で分液洗浄し、その後、溶媒を減圧留去することで粗生成物を得た。得られた粗生成物を、シリカゲルカラムクロマトグラフィー(溶媒:ヘキサン、クロロホルム)で精製し、2-t-ブチル-4-(3-クロロプロピル)-6-メチルフェノールを得た。得られた化合物が2-t-ブチル-4-(3-クロロプロピル)-6-メチルフェノールであることを1H-NMRによって確認した。
熱可塑性ポリマー(A)100質量部、化合物(III)-A0.1質量部及びステアリン酸カルシウム0.05質量部をドライブレンドした後、さらに、30mm径の二軸押出成形機(NAS30型押し出し機、ナカタニ社製)を用いて、空気雰囲気下、190℃、スクリュー回転数80rpmで混練し、熱可塑性ポリマー組成物であるペレット(1-1)を得た。得られたペレット(1-1)を、30mm径の単軸押出成形機(VS30-28型押し出し機、田辺プラスチックス社製)を用いて、空気雰囲気下、230℃、スクリュー回転数50rpmで混練し、ペレット(2-1)を得た。この単軸押出成形機による混練・押出成形をさらに5回繰り返してペレットを得た。繰り返し1、3、5回目で得られたペレット、及び、ペレット(2-1)をそれぞれポリ袋に充填し、ミノルタ製色差計CM-3500dを用いて、プラスックの光学的特性試験方法JIS K 7105に基づいてYI値を測定した。また、繰り返し5回目で得られたペレットのMI値を、メルトインデクサ(株式会社テクノ・セブン製、型式L246-3537)を用いて、JIS K7210-1995に規定された方法に従い、190℃、荷重21.18N(2.16Kg)で測定することでポリマー組成物の加工安定性を評価した。結果を表1に示す。
化合物(III)-Aの代わりに化合物(I)-Aを用いた以外は実施例1と同様にして熱可塑性ポリマー組成物を調製し、得られたポリマー組成物の加工安定性および黄変を評価した。結果を表1に示す。
〔酸化防止剤(A)の調製〕
化合物(II)-Aと化合物(III)-Aを表2に記載の割合で混合し酸化防止剤(A)を得た。酸化防止剤(A)に対して、下記測定条件で液体クロマトグラフィー測定を行った。化合物(II)-Aのエリア面積100に対する化合物(III)-Aのエリア面積を表2に示す。
LC測定装置:島津製作所 LC-10Avp
カラム:Sumipax ODS A-212(6mmφ×150mm、充填剤の径:5μm)
カラム温度:40℃
移動相:(A液)0.1質量%酢酸アンモニウム/水
(B液)0.1質量%酢酸アンモニウム/メタノール
移動相勾配:0→20min(A液:20→0質量%(1質量%/min)、B液:80→100質量%(1質量%/min))、20→45min(A液:0質量%、B液:100質量%)
流速:1.0mL/min
検出器:SPD-10Avp
検出方法:UV(280nm)
試料濃度:5mg/mL
注入量:10μL
熱可塑性ポリマー(A)100質量部、酸化防止剤(A)0.1質量部及びステアリン酸カルシウム0.05質量部をドライブレンドした後、さらに、30mm径の二軸押出成形機(NAS30型押し出し機、ナカタニ社製)を用いて、空気雰囲気下、190℃、スクリュー回転数80rpmで混練し、熱可塑性ポリマー組成物であるペレット(1-2)を得た。得られたペレット(1-2)を、30mm径の単軸押出成形機(VS30-28型押し出し機、田辺プラスチックス社製)を用いて、空気雰囲気下、230℃、スクリュー回転数50rpmで混練し、ペレット(2-2)を得た。この単軸押出成形機による混練・押出成形をさらに5回繰り返してペレット(3-2)を得た。ペレット(3-2)のMI値を、メルトインデクサ(株式会社テクノ・セブン製、型式L246-3537)を用いて、JIS K7210-1995に規定された方法に従い、190℃、荷重21.18N(2.16Kg)で測定することでポリマー組成物の加工安定性を評価した。結果を表2に示す。
実施例3~6においては、化合物(II)-A及び化合物(III)-Aとして、表2に記載した部数を用いた以外は、実施例2と同様にして酸化防止剤及び熱可塑性ポリマー組成物を得て、エリア面積及びポリマー組成物の加工安定性を評価した。比較例2は、酸化防止剤を使用しなかった例である。実施例3~6および比較例2の結果を表2に示す。
2)化合物(II)-Aのエリア面積を100として算出した。
Claims (9)
- 式(II)で示される化合物をさらに含む、請求項1に記載の酸化防止剤。
Xは単結合、硫黄原子又は>CH-R6基(R6は水素原子、炭素数1~8のアルキル基又は炭素数5~8のシクロアルキル基を示す)を表し、
Aは炭素数1~8のアルキレン基又は*-C(=O)-R7-基(R7は単結合又は炭素数1~8のアルキレン基を表し、*は酸素側の結合手であることを表す)を表し、
Y及びZは、いずれか一方がヒドロキシル基、炭素数1~8のアルコキシ基又は炭素数7~12のアラルキルオキシ基を表し、他の一方が水素原子又は炭素数1~8のアルキル基を表す。〕 - 式(II)で示される化合物100質量部に対して、式(III)で示される化合物を0.005~10質量部含む、請求項2に記載の酸化防止剤。
- 下記測定条件における液体クロマトグラフィー測定において、式(II)で示される化合物のエリア面積100に対する、式(III)で示される化合物のエリア面積が0.01~5である、請求項2又は3に記載の酸化防止剤。
測定条件
カラム:Sumipax ODS A-212(6mmφ×150mm、充填剤の径:5μm)
カラム温度:40℃
移動相:(A液)0.1質量%酢酸アンモニウム/水
(B液)0.1質量%酢酸アンモニウム/メタノール
移動相勾配:0→20min(A液:20→0質量%(1質量%/min)、B液:80→100質量%(1質量%/min))、20→45min(A液:0質量%、B液:100質量%)
流速:1.0mL/min
検出方法:UV(280nm)
試料濃度:5mg/mL
注入量:10μL - 酸化防止剤100質量部に対して、式(II)で示される化合物と式(III)で示される化合物を合計90質量部以上含む、請求項2~4のいずれかに記載の酸化防止剤。
- 請求項1~5のいずれかに記載の酸化防止剤と熱可塑性ポリマーとを含む熱可塑性ポリマー組成物。
- 熱可塑性ポリマー100質量部に対して、請求項1~5のいずれかに記載の酸化防止剤を0.005~5質量部含む、請求項6に記載の熱可塑性ポリマー組成物。
- 熱可塑性ポリマーがポリオレフィンである、請求項6又は7に記載の熱可塑性ポリマー組成物。
- 熱可塑性ポリマーの安定性を向上させるための、請求項1~5のいずれかに記載の酸化防止剤の使用。
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US3280070A (en) * | 1961-07-31 | 1966-10-18 | Geigy Chem Corp | Stabilization of unstable organic material with phosphonates, phosphates and/or thiodipropionates |
US3281505A (en) * | 1963-09-12 | 1966-10-25 | Geigy Chem Corp | Dialkylhydroxyethanephosphonates and dialkylhydroxybenzylphosphonates |
JP2001081250A (ja) * | 1999-07-14 | 2001-03-27 | Mitsui Chemicals Inc | ポリオレフィン樹脂組成物 |
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US3280070A (en) * | 1961-07-31 | 1966-10-18 | Geigy Chem Corp | Stabilization of unstable organic material with phosphonates, phosphates and/or thiodipropionates |
US3281505A (en) * | 1963-09-12 | 1966-10-25 | Geigy Chem Corp | Dialkylhydroxyethanephosphonates and dialkylhydroxybenzylphosphonates |
JP2001081250A (ja) * | 1999-07-14 | 2001-03-27 | Mitsui Chemicals Inc | ポリオレフィン樹脂組成物 |
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