WO2000052090A1 - Composition de materiau polymere et composition de stabilisant contenant toutes deux un compose spirochromane - Google Patents

Composition de materiau polymere et composition de stabilisant contenant toutes deux un compose spirochromane Download PDF

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Publication number
WO2000052090A1
WO2000052090A1 PCT/JP2000/001052 JP0001052W WO0052090A1 WO 2000052090 A1 WO2000052090 A1 WO 2000052090A1 JP 0001052 W JP0001052 W JP 0001052W WO 0052090 A1 WO0052090 A1 WO 0052090A1
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group
tert
butyl
organic polymer
polymer material
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PCT/JP2000/001052
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English (en)
Japanese (ja)
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Kazuki Katsuyama
Akito Tsunekage
Takeshi Inoue
Shoichi Horie
Mamoru Suga
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Yoshitomi Fine Chemicals, Ltd.
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Publication of WO2000052090A1 publication Critical patent/WO2000052090A1/fr

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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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings

Definitions

  • the present invention relates to a polymer material composition and a stabilizer composition containing a subirochroman compound.
  • the present invention relates to a stabilized organic polymer material composition. More specifically, the present invention hardly causes deterioration in quality such as changes in physical properties and appearance of an organic polymer material which is degraded by oxidation, heat and light, even when subjected to heat history during processing and use.
  • the present invention relates to a stabilized organic polymer material composition.
  • the present invention also relates to a stabilizer for an organic polymer material, which is an additive used for obtaining such a stabilized organic polymer material composition.
  • Organic polymer materials composed of organic compounds such as natural polymers, synthetic polymers, fats and oils, lubricating oils, and hydraulic oils are degraded by oxidation, heat, light, etc., reducing their usefulness. Research and development of a so-called stabilizer has been added to these organic polymers to obtain an organic polymer material composition that is resistant to deterioration.
  • Japanese Patent Publication No. 59-4443 43 discloses a compound represented by the general formula (2), which is a compound similar to an essential component of the stabilizer for an organic polymer material in the present invention.
  • R represents a substituted or unsubstituted alkyl group or a hydrogen atom
  • R 4 R 5 and R s represent a hydrogen atom, a substituted or unsubstituted alkyl group, or the like.
  • Japanese Patent Publication No. 49-209977 discloses that a compound represented by the following general formula (1) or a compound similar thereto can be used as a browning inhibitor for a color image of a color photograph. Have been.
  • a phenolic antioxidant which is another essential component of the stabilizer for organic polymer materials in the present invention, was researched and developed in the 1930s, and is well known as an antioxidant for organic polymer materials. And are widely used.
  • the phosphorus-based antioxidant used as a component of the stabilizer for organic polymer materials in the present invention was researched and developed in the 1940's, and is well known as an antioxidant for organic polymer materials. Used.
  • Japanese Patent Publication No. 56-5417 and Japanese Patent Publication No. 56-32339 disclose the use of phosphite compounds and phosphonate compounds as stabilizers during the processing of organic polymer materials. It is described that when used in combination with a hindered phenol compound, an organic polymer material having excellent stability during processing and suppressed coloring can be obtained.
  • Example 14 described in Paragraph No. 0226 of Japanese Patent Application Laid-Open No. 7-233160 3- (3,4-dimethylphenyl) 15,7-diene was added.
  • An object of the present invention is to provide an antioxidant for obtaining an organic polymer material having excellent processing stability and good heat resistance.
  • Another object of the present invention is to provide an organic polymer material having excellent processing stability and heat resistance.
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that a very small amount of a hydroxy spironic acid represented by the following general formula (1) is added to a phenol-based antioxidant and a phosphorus-based antioxidant.
  • the inventor has found that the addition of a bis-chroman compound exhibits markedly excellent effects of improving heat resistance and processing stability, thereby completing the present invention.
  • the present invention relates to the following.
  • RR 2 and R 3 may be the same or different from each other; It represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms.
  • A a compound represented by
  • the compound represented by the general formula (1) is 0.5 to 10% by weight, and the total amount of the phenolic antioxidant and the phosphorus antioxidant is 99.5 to 90% by weight based on the total amount thereof. % Of a stabilizer composition for an organic polymer material.
  • the weight ratio of the compounding amount of the phenolic antioxidant to the compounding amount of the phosphorus-based antioxidant is 1: 0.1 to 1:10, as described in [1] or [2].
  • Stabilizer composition The weight ratio of the compounding amount of the phenolic antioxidant to the compounding amount of the phosphorus-based antioxidant is 1: 0.1 to 1:10, as described in [1] or [2].
  • RR 2 and R 3 may be the same or different and each represents a hydrogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms [1]
  • the stabilizer composition according to any one of [1] to [4].
  • [8] An organic polymer material composition obtained by mixing the organic polymer with the stabilizer composition for organic polymer material according to any one of [1] to [7].
  • the phenolic antioxidant is at least one selected from Group A, and the phosphorus antioxidant is at least one selected from Group B [10] to [12] ]
  • the organic polymer material composition according to any of [1].
  • the organic polymer is made of polyethylene resin, polypropylene resin, Admixture or compatible polymer of Tylene resin and Polypropylene resin, Compatible polymer containing Polyethylene resin and / or Polypropylene resin, Ethylene
  • the organic polymer material composition according to any one of [10] to [16], which is a vinyl acetate copolymer or an ethylene-propylene copolymer.
  • 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Refers to the group consisting of benzene.
  • the feature of the present invention is that the compound represented by the general formula (1) is 0.1% based on the total amount of the general-purpose funinol-based antioxidant, the phosphorus-based antioxidant, and the compound represented by the general formula (1). 5 to: 10% by weight, preferably 1 to 7% by weight, more preferably 1 to 5% by weight, and particularly preferably 2 to 5% by weight.
  • a feature of the present invention is that the content of the compound of the general formula (1) in the organic polymer material composition is 0.0005 to 0.025 parts by weight based on 100 parts by weight of the organic polymer material composition. It may be contained in an amount of 0.005 parts by weight, preferably 0.0005 parts by weight to 0.01 parts by weight, particularly preferably 0.0001 to 0.05 parts by weight.
  • the weight ratio of the phenol-based antioxidant to the phosphorus-based antioxidant is preferably 1: 0.1 to 1:10, more preferably 1: 0.25 to 1: 4.
  • Examples of the linear or branched alkyl group having 1 to 4 carbon atoms represented by RR 2 and R 3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a secondary group. Examples include a butyl group and a tertiary butyl group.
  • the alkoxy group having 1 to 4 carbon atoms represented by RR 2 and R 3 is linear or branched. It may be a branched alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutyloxy group, a secondary butoxy group, and a tertiary butoxy group.
  • R 1 R 2 and R 3 may be the same or different and each represents a hydrogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 4 carbon atoms.
  • R 1 is a hydroxyl group or a linear or branched alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 are hydrogen atoms. More preferably, R 1 is a hydroxyl group or a methyl group, and R 2 and R 3 are hydrogen atoms.
  • Examples of the organic polymer stabilized by the stabilizer composition of the present invention include a synthetic organic polymer and a natural organic polymer.
  • Examples of the synthetic organic polymer include synthetic resins such as a thermoplastic resin and a thermosetting resin.
  • thermoplastic resin examples include polyolefin resin, halogen-containing polymer, styrene resin, acrylic resin, thermoplastic polyester resin, polyamide resin, aromatic polycarbonate resin, polyacetal resin, polyethylene oxide resin, and polyphenylene.
  • Ether resin polysulfone resin, polyurethane resin, petroleum resin, polyvinyl acetate resin, vinyl acetal resin, cellulose (cellulose) resin, polyether sulfone resin, polyphenylene sulfide resin, polyether ketone resin, polyether imide resin, poly Oxybenzoyl resin, polyimide resin
  • examples include a polymer amide resin, a polyamide imide resin, a polyarylate resin, a fluorinated resin, an ionomer, a thermoplastic elastomer, and the like, and a mixture thereof can also be used.
  • polyolefin resin examples include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-high-molecular-weight polyethylene, polypropylene, polybutene-11, polypentene, and poly-3-methylbutylene.
  • Polyolefin homopolymer having 2 to 8 carbon atoms ethylene / provylene random copolymer, ethylene / propylene block copolymer, ethylene / butene-1 random copolymer, propylene / ethylene / butene-1
  • a monoolefin copolymer such as a random copolymer; a copolymer of a homoolefin and another monomer such as a maleic anhydride-modified polypropylene or an ethylene-vinyl acetate copolymer; Use two or more of these or a mixture of these with other compatible polymers It is also possible.
  • polyolefin-based resins have been subjected to a slight purification treatment including a step of removing catalyst residues after polymerization, and those having a relatively high degree of purification, as well as a catalyst removal step using a highly active catalyst.
  • a crystalline polyolefin resin which has not been subjected to a step may be used (see Japanese Patent Publication No. 62-41818, Japanese Patent Publication No. 3-56245, and US Pat. No. 4,156,393).
  • a polyolefin resin having a very narrow molecular weight distribution obtained by a melocene-based single-site catalyst may be used (Journal of “Ob” Polymer-Science. Polymer. Chemistry-Edition (Journa) lof Pol ymer Science. Pol ymer Chemistry Edition, Vol. 23, pp. 2151 (1985)).
  • halogen-containing polymer examples include polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and vinyl acrylate
  • examples include a kill ester copolymer and chlorinated polyethylene.
  • styrene-based resin examples include polystyrene, impact-resistant polystyrene, styrene 'acrylonitrile copolymer, styrene-MMA copolymer, ABS resin, AES resin, ACS resin, AAS resin, EES resin, and the like, and mixtures thereof. And the like.
  • acrylic resin examples include polyacrylate, polymer acrylate, and the like.
  • thermoplastic polyester resin examples include polyethylene terephthalate and polybutylene terephthalate.
  • polyamide resin examples include nylon 4, nylon 6, nylon 4.6, nylon 6-6, nylon 6.10, nylon 7, nylon 8, nylon 12, 12, nylon 12, and nylon. 11 and 12; alamide; and mixtures thereof.
  • thermosetting resin examples include an unsaturated polyester resin, a phenol resin, a urine resin, a melamine resin, an epoxy resin, a polyimide resin, a silicone resin, a diyl phthalate resin, a polyurethane resin, and a furan resin.
  • a polyolefin resin in particular, a monoolefin homopolymer or a copolymer of homoolefin is particularly preferable.
  • a polyolefin resin in particular, a monoolefin homopolymer or a copolymer of homoolefin is particularly preferable.
  • an excellent antioxidant effect is exhibited.
  • Most preferred as such a single olefin is provylene or ethylene.
  • the most preferred polyolefin resin used in the present invention is polypropylene or polyethylene.
  • the phenolic antioxidant used in the present invention is represented by the general formula (3)
  • R 7 represents an alkyl group having 1 to 5 carbon atoms
  • R 8 represents an alkyl group having 1 to 4 carbon atoms
  • R 9 represents a hydrogen atom or a methyl group
  • L represents
  • a preferred example of the phenolic antioxidant is represented by the general formula (4)
  • R 7 ′ represents a tertiary butyl group
  • R 8 ′ represents a tertiary butyl group or a methyl group
  • R 9 ′ represents a hydrogen atom or a methyl group
  • L has the same meaning as described above.
  • phenolic antioxidants specifically, for example,
  • Preferred phenolic antioxidants include n-decyl decyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) probionate,
  • Particularly preferred phenolic antioxidants include:
  • particularly preferred phenolic antioxidants include:
  • one or more of these phenolic antioxidants can be used in combination.
  • the phosphorus antioxidant used in the present invention has the formula (5)
  • Preferred examples of the phosphorus antioxidant used in the present invention include the following (c-1) to (c-4).
  • Q and R 11 may be the same or different, show it that alkyl group having a carbon number to 4, R 12 is showing a hydrogen atom or a methyl group
  • Q 2 are each Is independently represented by the general formula (8)
  • R 1 D and R 11 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R 12 represents a hydrogen atom or a methyl group.
  • i represents 0 or 1 independently for each repeating unit, j represents 0 or 1, and n 1 represents an integer of 1 to 10.
  • the phosphorus-based antioxidant of (c-11) is represented by the general formula (9)
  • R 12 represents a hydrogen atom or a methyl group
  • Q 4 represents a general formula (11) independently for each repeating unit.
  • R 12 represents a hydrogen atom or a methyl group.
  • I independently represents 0 or 1 for each repeating unit, j represents 0 or 1, and n 2 represents 1-3 Indicates an integer. ] The compound represented by these.
  • R 13 represents an alkyl group or a phenyl group which may be substituted with 1 to 3 alkyl groups.
  • R 13 is an alkyl group having 1 to 18 carbon atoms, or a phenyl group which may be substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms,
  • R 13 has the general formula (13)
  • R 14 and R 15 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R 1 e represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) Shows the group represented.
  • the phosphorus-based antioxidant of (c-2) is represented by the general formula (14)
  • R 17 may be the same or different and each represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 9 carbon atoms, or a compound represented by the general formula (16) )
  • R 21 and R 22 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R 23 represents a hydrogen atom or a methyl group.
  • R 18 is an alkyl group having 1 to 18 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, a cyclohexyl group, a phenyl group, a phenyl group substituted with an alkyl group having 1 to 9 carbon atoms, or General formula (16)
  • R 21 and R 22 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R 23 represents a hydrogen atom or a methyl group.
  • R 1! Represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 2 Q represents an alkyl group having 1 to 4 carbon atoms
  • R 24 represents an alkyl group or a phenyl group which may be substituted with 1 to 3 substituents selected from the group consisting of an alkyl group, an aryl group and a phenylalkyl group.
  • R 24 represents a phenyl group which may be substituted with an alkyl group or an aryl group.
  • R 24 is selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a phenyl group, and a phenylalkyl group having 7 to 9 carbon atoms.
  • R 25 and R 28 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms, and R 27 is a hydrogen atom or a carbon atom.
  • R 25 and R 28 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms, and R 27 is a hydrogen atom or a carbon atom.
  • R 27 is a hydrogen atom or a carbon atom.
  • the phosphorus antioxidant of (c-13) is more preferably a compound represented by the following general formula (19)
  • R 31 and R 32 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and R 33 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • A represents an alkylene group having 2 to 18 carbon atoms, p-phenylene group or p-biphenylene group when q represents 2, and R 28 and R 29 represent Each independently represents an alkyl group having 1 to 4 carbon atoms;
  • R 30 independently represents an alkyl group having 1 to 18 carbon atoms;
  • R 34 and R 35 may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or a phenylalkyl group having 7 to 9 carbon atoms; and R 38 is a hydrogen atom or a carbon atom. And a group represented by the following formula (1). ] The compound represented by these.
  • R 37 represents an alkyl group having 1 to 5 carbon atoms
  • R 38 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 39 represents a hydrogen atom or a methyl group
  • 40 represents Represents a direct bond, an alkylene group having 1 to 5 carbon atoms or a sulfur atom.
  • the phosphorus antioxidant of (c-4) is more preferably represented by the general formula (24)
  • R 41 represents an alkyl group having 1 to 5 carbon atoms
  • R 42 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 43 represents a hydrogen atom or a methyl group
  • R 44 represents a direct A bond, a methylene group, a CH (R 46 ) — group
  • R 48 represents an alkyl group having 1 to 4 carbon atoms
  • n 3 represents 1 or 3
  • n 3 represents 3 when R 45 represents a group represented by N (CH 2 CH 2 0-) 3, 11 3 are 1 when 1 45 is an alkyl group having a carbon number of 1-18, halogen atom, hydroxyl group, C1-8
  • An alkoxy group of R 47 (R 47 is phenyl-C 4 ) alkyl or a phenyl (Ci-C 4 ) alkylcarbonyloxy-C 4 ) alkyl group, and these groups are The phenyl may have 1 to 3 substituents selected from
  • R 1 Q and R 11 in may be the same or different and each is an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be either linear or branched, and for example, And methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tertiary butyl groups, with tertiary butyl groups being preferred. Among them, it is particularly preferred that both R 1 D and R 11 are tertiary butyl groups.
  • R 12 in the group represented by the general formula (8) is a hydrogen atom or a methyl group, and when R 12 is a methyl group, R 12 is a 5- or 6-position on the phenyl ring of the general formula (8). are particularly preferred those substituted, particularly preferred examples of the group represented by the most preferred c general formula obtained by substituting the 5-position (8), 2, 4-di-tertiary Buchirufuenokishi group, 2, 4- Di-tert-butyl-5-methylphenoxy group.
  • N 1 in the general formula (6) or the general formula (7) is an integer of 1 to 10, preferably 1 or 2, and particularly preferably 1.
  • i and j are 0 or 1, and preferably 0.
  • the compound of the general formula (6) is preferably the main component, and the compound of the general formula (7) may not be contained.
  • Examples of the compound represented by the general formula (6) or (7) include the following.
  • composition comprising tetrakis (2,4-di-tert-butyl-6-methylphenyl) 1-4,4'-biphenylenediphosphonite and the like described in JP-A-2-270892;
  • composition comprising tetrakis (2,4-di-tert-butylphenyl) -1.4,4'-biphenylenediphosphonate and the like described in JP-A-5-202708;
  • tetrax (2,4-di-tert-butylphenyl) -1,4,4,1-biphenylenediphosphonite is used in 100% by weight of the phosphorus-based antioxidant.
  • a phosphorus-based antioxidant containing 50% by weight or more, preferably 60% by weight or more, can also be used.
  • the phosphorus antioxidants are added to tetrakis (2,4-di-tert-butylphenyl) 1.4,4,1-biphenylenediphosphonite and
  • It may contain tris (2,4-di-tert-butylphenyl) phosphite.
  • Examples of the phosphorus-based antioxidant (c-11) include tetrakis (2,4-ditertiary butyl-5-methylphenyl) 14,4, -biphenyl in 100% by weight of the phosphorus-based antioxidant.
  • a phosphorus antioxidant containing 50% by weight or more, preferably 60% by weight or more of range phosphonites can also be used.
  • the phosphorus antioxidant furthermore, tetrakis (2,4-ditert-butyl-15-methylphenyl) -4,4, -biphenylenediphosphonate, the phosphorus antioxidant further
  • Tris (2,4-ditertiary butyl-5-methylphenyl) phosphite may be contained.
  • R 17 in the general formula (14) and the general formula (15) and R 18 in the general formula (14) may have a linear or branched alkyl group having 1 to 18 carbon atoms, For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, ventil, 2-pentyl, 3-pentyl, 2-methylbutane 1-yl group, 2-methylbutane-1-yl group, 2-methylbutane-13-yl group, 2-methylbutane-4-yl group, neopentyl group, hexyl group, isohexyl group, heptyl group, Octyl group, 2-ethylhexyl group, nonyl group, decyl group, pendecyl group, dodecyl group, tridecyl group, tetradecyl
  • Examples of the phenyl group substituted with an alkyl group having 1 to 9 carbon atoms for R 17 in the general formula (14) and the general formula (15) and R 18 in the general formula (14) include, for example, a methylphenyl group and an ethenylphenyl group.
  • Formula phenylalanine alkyl group 7-9 carbon atoms in R 18 of (14) may be either alkyl Le portion is a straight or branched chain, for example, a benzyl group, Hue Nechiru group, shed - methyl A benzyl group and a dimethyl benzyl group.
  • R 19 in the general formula (15) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be a straight-chain or a branched chain.
  • R 19 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.
  • R 20 in the general formula (15) is an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be any of a straight chain or a branched chain.
  • the alkyl group may be any of a straight chain or a branched chain.
  • one is preferably those substituted at the 5-position or 6-position on the phenyl ring with respect to L 1, was replaced especially the 5-position.
  • the R 2 1 and R 22 in the group represented by the general formula (1 6) may be the different from one identical or it it is an alkyl group having 1 to 4 carbon atoms, wherein the alkyl group is a straight or branched It may be any of chains, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isopropyl group and a tertiary butyl group, and a tertiary butyl group is preferable. Among them, it is particularly preferred R 2 1 and R 22 are both tertiary butyl groups.
  • R 23 in the group represented by the general formula (16) is a hydrogen atom or a methyl group. When R 23 is a methyl group, R 23 is preferably substituted at the 5- or 6-position on the phenyl ring. .
  • Preferable examples of the group represented by the general formula (1 6), 2, 4-di-tert-Kyubu Chirufueniru group, 2, 4-di-tertiary-butyl-6-methylphenyl c general formula group (1 Preferred examples of R 17 in 4) are dodecyl group, octadecyl group, phenyl group, nonylphenyl group, 2,4-di-tert-butylphenyl group, 2,4-di-tert-butyl group. And a methylphenyl group.
  • R 18 in the general formula (14) include a methyl group, an ethyl group, a dodecyl group, an octadecyl group, a phenyl group, a nonylphenyl group, a 2,4-ditertiary butylphenyl group, and a 2,4- Di-tertiary butyl-6-methylphenyl group.
  • R 17 in the general formula (15) include a dodecyl group, a tridecyl group, an octadecyl group, a phenyl group, a nonylphenyl group, a 2,4-ditertiary-butylphenyl group, and a 2,4- Di-tert-butyl-6-methylphenyl group; and more preferably tridecyl group.
  • Examples of the phosphorus antioxidant of (c-2) include:
  • R 31 and R 32 in the group represented by the general formula (21) may be the same or different and each is an alkyl group having 1 to 4 carbon atoms, and the alkyl group is linear or branched. It may be any of a chain, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isopropyl group, a tertiary butyl group, and a methyl group and a tertiary butyl group are preferable. .
  • R 33 in the group represented by the general formula ( 21) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be either linear or branched. Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group.
  • R 33 is preferably a hydrogen atom or a tertiary butyl group. If R 33 is an alkyl group having 1 to 4 carbon atoms is preferably one R 33 is substituted at the 5-position or 6-position on the Hue cycloalkenyl ring, those substituted especially 6-position is preferred.
  • Preferred examples of the group represented by the general formula (21) include a 2,4,6-tri-tert-butylphenyl group, a 2,4-di-tert-butylphenyl group, and a 2,6-di-tert-butylphenyl group.
  • a tertiary butyl group includes a 4-methylphenyl group.
  • the alkylene group having 2 to 18 carbon atoms in A in the general formula (19) may be linear or branched, and may be, for example, an ethylene group, an ethylidene group, a trimethylene group, an isopropylidene group, Examples include a methylene group, a pentamethylene group, and a hexmethylene group.
  • A When q represents 1, preferred examples of A include 2, 4, 6-tri-tert-butyl. Examples thereof include a phenyl group, a 2,4-di-tert-butylphenyl group, and a 2,6-di-tert-butyl-4-methylphenyl group.
  • Q in the general formula (19) is preferably 1.
  • R 28 and 29 in the general formula (19) may be the same or different and each is an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be either linear or branched. Often, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tertiary butyl group are exemplified.
  • the alkyl group having 1 to 18 carbon atoms at R 3 ° in the general formula (20) may be linear or branched, and may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutane-1-yl, 2-methylbutane-1-yl, 2-methylbutane-3-yl, 2-methylbutane-4-yl, neopentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, Isodecyl group, pentadecyl group, dodecyl group, tridecyl group, tetradecyl group, pendecyl group, hexa
  • the alkyl portion may be either linear or branched, and examples thereof include a benzyl group, a phenethyl group, a paramethylbenzyl group, a paramethyldimethylbenzyl group, and the like. You.
  • the alkyl group having 1 to 4 carbon atoms at R 34 and R 35 in the general formula (22) may be either linear or branched, for example, methyl, ethyl, propyl, isopropyl, butyl Groups, an isobutyl group and a tertiary butyl group, and a methyl group and a tertiary butyl group are preferable.
  • the phenylalkyl group having 7 to 9 carbon atoms at R 34 and R 35 in the general formula (22) may have a linear or branched alkyl moiety. Phenyl, phenethyl, monomethylbenzyl, a, monodimethylpentyl and the like.
  • R 36 in the group represented by the general formula (22) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group may be linear or branched, for example, methyl Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and tertiary butyl group. 3 e is preferably a hydrogen atom or a tertiary butyl group. If R 38 is an alkyl group having 1 to 4 carbon atoms, which R 36 is substituted with preferably those substituted at the 5-position or 6-position of Hue sulfonyl ⁇ , especially 6-position is preferred.
  • R 3 D examples include 2,4-ditertiary butylphenyl group, 2,6-ditertiary butyl-4-methylphenyl group, 2,4-di (1-phenyl-1,1-dimethyl) Methyl) phenyl group, 2,4,6-tri-tert-butylphenyl group, octadecyl group, and isodecyl group.
  • Examples of the phosphorus antioxidant of (c-3) include:
  • phosphorus antioxidant of (c-3) preferably, Bis (2,4-di-tertiary butyl phenyl) pentaerythritol diphosphite,
  • Distearyl pentyl erythritol diphosphate is mentioned.
  • R 4 1 in the general formula (24) are each alkyl groups of the same or different and 1 carbon atoms which may have 1-5, the alkyl group may be either straight or branched chain, e.g., methyl Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, 2-pentyl group, 3-pentyl group, 2-methylbutane-1-yl group And 2-methylbutane-2-yl group, 2-methylbutane-3-yl group, 2-methylbutane-4-yl group, neopentyl group and the like.
  • R 41 is preferably a tertiary butyl group.
  • R 42 in the general formula (24) may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • the alkyl group may be any of a straight chain or a branched chain. And methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tertiary butyl groups.
  • the R 42, tert-butyl group is preferable.
  • R 43 in the general formula (24) may be the same or different and is a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • R 4 8 in the general formula (24) is an alkyl group having 1-4 carbon atoms
  • the Al kill group may be either straight or branched chain, for example, a methyl group, Echiru group, a propyl group , Isopropyl, butyl, isobutyl and tertiary butyl groups
  • No. R 46 is preferably a methyl group.
  • R 44 in the general formula (24) include a direct bond, a methylene group, and an ethylidene group.
  • the alkyl group having 1 to 18 carbon atoms at R 45 in the general formula (24) may be a straight-chain or branched-chain alkyl group, for example, a methyl group, an ethyl group, a propyl group, a isovrovir tomb, butyl Group, isobutyl group, secondary butyl group, tertiary butyl group, benzyl group, 2-pentyl group, 3-pentyl group, 2-methylbutane-1-yl group, 2-methylbutane-1-yl group, 2 —Methylbutane-3-yl, 2-methylbutane-4-yl, neopentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl And benzyl, dodecyl, dodecyl, tridecyl, tetradecyl, pendec
  • Examples of the halogen atom for R 45 in the general formula (24) include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom, and a fluorine atom is preferable.
  • the alkoxy group having 1 to 8 carbon atoms in R 45 in the general formula (24) may be straight-chain or branched, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, Butoxy group, secondary butyloxy group, tertiary butyloxy group, pentyloxy group, hexyloxy group, heptyloxydi group, octyloxy group, 2-ethylhexyloxy group, etc., and preferably 2-ethylhexyloxy group. .
  • R 45 when n 3 is 1, preferred examples of R 45 include a fluorine atom and a 2-ethylhexyloxy group.
  • Examples of the phosphorus antioxidant of (c-4) include:
  • Preferred phosphorus antioxidants include:
  • Particularly preferred phosphorus antioxidants include:
  • one or more of these phosphorus-based antioxidants can be used in combination.
  • phenolic antioxidants and phosphorus antioxidants are known compounds, and most of them are sold as antioxidants and are generally available.
  • a sulfur-based antioxidant By further blending a sulfur-based antioxidant with the organic polymer material composition of the present invention, an organic polymer material having more excellent stability can be obtained.
  • the sulfur-based antioxidant is not particularly limited, but is preferably
  • One or more sulfur-based antioxidants can be added to the organic polymer material composition of the present invention.
  • the sulfur-based antioxidant is preferably added in a proportion of 0.005 to 5 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the organic polymer material composition. can do. Where two or more sulfur-based antioxidants are used In this case, it is preferable to add them so that the total amount is within the above range.
  • an organic polymer material composition of the present invention By further blending an ultraviolet absorber or a light stabilizer with the organic polymer material composition of the present invention, an organic polymer material having more excellent stability can be obtained.
  • ultraviolet absorber or light stabilizer examples include salicylic acid compounds, benzophenone compounds, benzotriazole compounds, benzoate compounds, cyanoacrylate compounds, nickel compounds, and beveridine compounds.
  • Salicylic acid-based compounds that can be used as an ultraviolet absorber include phenyl salicylate,
  • Benzophenone-based compounds that can be used as ultraviolet absorbers include 2,4-dihydroxypentazophenone,
  • cyanoacrylate compound that can be used as an ultraviolet absorber
  • ethyl 2-cyano-1,3,3-diphenyl acrylate Octyl '2-cyano-1,3-diphenyl acrylate.
  • nickel-based compound that can be used as an ultraviolet absorber
  • biperidine compound that can be used as a light stabilizer
  • Preferred compounds that can be used as ultraviolet absorbers or light stabilizers include 2-hydroxy 41-n-octyloxy benzophenone,
  • One or more ultraviolet absorbers or light stabilizers can be added to the organic polymer material composition of the present invention.
  • the ultraviolet absorber or light stabilizer is preferably added in an amount of 0.005 to 5 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the organic polymer material composition. be able to.
  • two or more UV absorbers or light stabilizers are used, they are preferably added so that the total amount is within the above range.
  • the phenolic antioxidant, and the phosphorus-based antioxidant if necessary, a sulfur-based antioxidant, an ultraviolet absorber, and a light stabilizer are added to the organic More stabilized organic compound by blending with molecular material A child material composition can be obtained.
  • additives that do not significantly impair the performance of the organic polymer material composition of the present invention, for example, hydrated talcites, metal stones such as calcium stearate, hydrazine compounds, etc.
  • Heavy metal deactivator trialkyltin tris (octyl thioglycolate), dialkyltin tris (octyl thioglycolate), monoalkyltin tris (monoalkyl maleate) or dialkyltin Organotin stabilizers such as tris (monoalkyl maleate), epoxy compounds such as epoxidized soybean oil or epoxyoctyl stearate, various organic pigments, flame retardants such as phosphate esters, cationic or anionic Antistatic agents such as surfactants, low aliphatic amides or fatty acids Lubricants such as grade alcohol esters, acrylic polymer processing aids, plasticizers such as di-2-ethylhexyl sulfate or di
  • a crystal nucleating agent, a clarifying agent, and the like can be added to the organic polymer material composition of the present invention, if necessary.
  • the method of blending the stabilizer with the organic polymer is not particularly limited, and includes, for example, a conventionally known method. For example, after mixing the organic polymer and the stabilizer, kneading and extrusion are performed. For example, a method of performing treatment through a step such as polishing.
  • the stabilizer composition of the present invention can be prepared by mixing a compound represented by the general formula (1), a phenolic antioxidant, and a phosphorus antioxidant stabilizer by a conventionally known method. .
  • the mixed stabilizer composition has no change in appearance or stickiness even after long-term storage of one year or more, and no change in powder properties is observed. Also, regarding the processing stability of the organic polymer material composition using the stabilizer composition after long-term storage, there is no difference in performance as compared with the case where the stabilizer composition was used immediately after mixing.
  • a compound represented by the general formula (1) a compound represented by the general formula (1), a phenolic antioxidant and a phosphorus-based antioxidant, and if necessary, a sulfur-based antioxidant.
  • An agent, an ultraviolet absorber, a light stabilizer, or another additive may be weighed in a predetermined amount and mixed with the organic polymer, and may be mixed and kneaded.
  • mixing there are mixing machines conventionally used for mixing additives with organic polymers, such as ball mills, bebble mills, tumble mixers, methane dimixers, super mixers (Henschel mixers), and the like.
  • the kneading machine conventionally used for kneading additives into an organic polymer for example, a mixing roll, a pan burr mixer, a blade-type mixer, a high-speed twin-screw continuous mixer, An extruder-type kneader and the like can be mentioned.
  • the organic polymer material composition according to the present invention can be prepared by various known methods for forming organic polymer materials, for example, injection molding, extrusion molding, calender molding, blow molding, and compression molding. By such means, it can be formed into the desired product.
  • Products are not particularly limited and may be used indoors or outdoors.
  • parts for electrical products, parts for electronic products, parts for agricultural machinery, agricultural products, fisheries products Examples include machine parts, marine products, car parts, daily necessities, sundries, etc.
  • Ml Melt index
  • yellowness (hereinafter also referred to as YI) is generally widely used as a measure of the degree of discoloration. Yellowness (YI) is measured by colorimetry, and a larger value indicates a greater degree of discoloration or coloring, and a smaller value indicates less coloring during processing and is considered to be superior.
  • Table 1 shows the measurement results.
  • AO-2 Tetrakis [3- (3,5-di-tert-butyl-14-hydroxyphenyl) propionyloxymethyl] methane (Yoshitomi Fine Chemical Co., Ltd., product name: "Tominox TT”)
  • ⁇ —1 Tris (2,4-di-tert-butylphenyl) phosphite (manufactured by Yoshitomi Fine Chemical Co., Ltd., trade name: “Tomiphos 202”)
  • MI 2 The Ml value measured by the beret obtained at the second time was shown.
  • MI 3 Ml value measured by the pellet obtained at the third time was shown.
  • Pellet could not be obtained because the resin could not be picked up by the strand method due to deterioration of the resin.
  • AO—2 Tetrakis [3- (3,5-di-tert-butyl-1-hydroxyphenyl) propyl-niloxymethyl] methane (manufactured by Yoshitomi Fine Chemical Co., Ltd., trade name: “Tominox TT”)
  • compositions of the present invention (formulations 6 and 7) containing the spirochroman compound (S-17 or S-18) had a lower I.sub.I than the composition of the comparative example (formulation 10). It is clear that the value of is small and the processing stability is excellent. It can be seen that by adding a small amount of the spirochroman compound, a synergistic effect is exhibited and good processing stability is exhibited.
  • the blends prepared according to the blending recipes shown in Table 3 were mixed in the same manner as in Example 1, repeatedly extruded, and Ml was measured on the pellets obtained by granulation. Further, the yellowness (YI) of the pellets extruded each time was measured according to JISK 7103. Table 3 shows the measurement results. In all compositions, the total amount of antioxidants was 0.1% by weight.
  • Ml The Ml value measured by the pellet obtained at the first time was shown.
  • MI 2 The MI value measured by the pellet obtained the second time was shown.
  • Y I 1 Y I value measured by the first pellet obtained.
  • Y I 2 Y I value measured by the second pellet obtained.
  • the composition of the present invention (formulations 11, 12, 13, and 14) containing the subirochroman compound (S-17) had a higher Ml than the composition of the comparative example (formulation 15). It is clear that the value is small and the processing stability is excellent. It can be seen that a small amount of the spirochroman compound shows a synergistic effect and shows good processing stability.
  • a composition containing 0.002% by weight of a spirochroman compound (S-17) based on 100% by weight of an organic polymer material composition (formulation 12), and a composition containing 0.005% by weight ( Formulation 13) shows significantly better Ml and YI values than the comparative composition (formulation 15).
  • the product (formulation 14) showed a better MI value than the comparative composition (formulation 15).
  • the composition containing 0.001% by weight of the spirochromane compound (S—17) relative to 100% by weight of the organic polymer material composition (formulation 11) was a comparative example. It shows a better YI value than the composition (Formulation 15).
  • Table 4 shows the formulation.
  • AO-1 n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by Yoshitomi Fine Chemical Co., Ltd., trade name: TOMINOX SS)
  • P-2 Tetrakis (2,4-di-tert-butyl-5-methylphenyl) 1-4,4'-biphenylenediphosphonite (manufactured by Yoshitomi Fine Chemical Co., Ltd., trade name: "GS Y-P101”) )
  • the stabilizer composition of the present invention as a stabilizer for organic polymer materials (especially synthetic resins), an extremely useful stabilized organic polymer having excellent processing stability and heat resistance.
  • a material (especially synthetic resin) composition can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de stabilisant pour matériaux polymères organiques, qui comprend (a) un composé représenté par la formule générale (1) (dans laquelle R?1, R2 et R3¿ représentent chacun hydrogène, hydroxy, alcoxy C¿1-4?, ou alkyle C1-4 linéaire ou ramifié), (b) un antioxydant phénolique, et (c) un antioxydant à composé phosphore, la quantité de l'ingrédient (a) et la somme des ingrédients (b) et (c) étant respectivement de 0,5 à 10 % en poids et de 99,5 à 90 % en poids, par rapport à la quantité totale des ingrédients (a), (b) et (c) ; et une composition de matériau polymère organique obtenue par compoundage d'un polymère organique avec la composition de stabilisant. L'utilisation de la composition de stabilisant en tant que stabilisant pour un matériau polymère organique permet la production d'un matériau polymère organique présentant une stabilité au traitement excellente et une résistance à la chaleur satisfaisante.
PCT/JP2000/001052 1999-02-26 2000-02-24 Composition de materiau polymere et composition de stabilisant contenant toutes deux un compose spirochromane WO2000052090A1 (fr)

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JP11/51769 1999-02-26
JP5176999A JP2000248113A (ja) 1999-02-26 1999-02-26 スピロクロマン化合物を含有する高分子材料組成物

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002105301A (ja) * 2000-10-03 2002-04-10 Sumitomo Dow Ltd ゴム強化ポリカーボネート樹脂組成物
JP2017036423A (ja) * 2015-08-13 2017-02-16 味の素株式会社 熱硬化性樹脂組成物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6513372B2 (ja) * 2014-11-07 2019-05-15 日本化薬株式会社 フェノール樹脂、エポキシ樹脂、エポキシ樹脂組成物およびそれらの硬化物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52119652A (en) * 1976-02-05 1977-10-07 Ciba Geigy Ag Triarylphosphiteephenol series compound stabilizers
JPS54109083A (en) * 1978-02-16 1979-08-27 Konishiroku Photo Ind Antioxidant
GB2260764A (en) * 1991-10-11 1993-04-28 Sandoz Ltd Stabilizing composition for polymers
WO1999018154A1 (fr) * 1997-10-02 1999-04-15 Yoshitomi Fine Chemicals, Ltd. Composition stabilisante pour materiaux polymeres organiques contenant des composes 6-hydroxychroman et compositions de materiaux polymeres organiques correspondantes
WO1999054394A1 (fr) * 1998-04-17 1999-10-28 Yoshitomi Fine Chemicals, Ltd. Stabilisant et composition de materiau polymere organique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52119652A (en) * 1976-02-05 1977-10-07 Ciba Geigy Ag Triarylphosphiteephenol series compound stabilizers
JPS54109083A (en) * 1978-02-16 1979-08-27 Konishiroku Photo Ind Antioxidant
GB2260764A (en) * 1991-10-11 1993-04-28 Sandoz Ltd Stabilizing composition for polymers
WO1999018154A1 (fr) * 1997-10-02 1999-04-15 Yoshitomi Fine Chemicals, Ltd. Composition stabilisante pour materiaux polymeres organiques contenant des composes 6-hydroxychroman et compositions de materiaux polymeres organiques correspondantes
WO1999054394A1 (fr) * 1998-04-17 1999-10-28 Yoshitomi Fine Chemicals, Ltd. Stabilisant et composition de materiau polymere organique

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002105301A (ja) * 2000-10-03 2002-04-10 Sumitomo Dow Ltd ゴム強化ポリカーボネート樹脂組成物
JP4535413B2 (ja) * 2000-10-03 2010-09-01 住友ダウ株式会社 ゴム強化ポリカーボネート樹脂組成物
JP2017036423A (ja) * 2015-08-13 2017-02-16 味の素株式会社 熱硬化性樹脂組成物

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