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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D30/00—Producing pneumatic or solid tyres or parts thereof
  • B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
  • B29D30/0601—Vulcanising tyres; Vulcanising presses for tyres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
  • C08J3/247—Heating methods
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08K5/07—Aldehydes; Ketones
  • C08K5/08—Quinones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
• • 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
  • C08K5/14—Peroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
  • C08F214/22—Vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2315/00—Characterised by the use of rubber derivatives
  • C08J2315/02—Rubber derivatives containing halogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2265—Oxides; Hydroxides of metals of iron

Definitions

• the present invention relates to a fluororubber composition. More particularly, it relates to a fluororubber composition that provides stable product quality and can be vulcanized at high speed.
• Fluoro-rubber compositions are excellent in oil resistance and fuel resistance, and are used as seal molding materials such as oil seals, O-rings, and packings in a wide range of fields such as automobiles and industrial machinery.
• An object of the present invention is to provide a fluororubber composition that can be vulcanized at high speed and has excellent scorch stability.
• the object of the present invention is to provide per 100 parts by weight of peroxide crosslinked fluororubber, (where any two of R 1 , R 2 and R 3 are lower alkyl groups having 1 to 5 carbon atoms, the remaining one is hydrogen, and X is a methyl group or a hydroxyl group), This is achieved by a fluororubber composition containing 0.1 to 1 part by weight of a compound having a number average molecular weight Mn of 200 to 300.
• the fluororubber composition according to the present invention is capable of high-speed vulcanization and exhibits excellent scorch stability.
• the fluororubber composition of the present invention has a general formula of (where any two of R 1 , R 2 and R 3 are lower alkyl groups having 1 to 5 carbon atoms, the remaining one is hydrogen, and X is a methyl group or a hydroxyl group) It contains 0.1 to 1 part by weight of the compound.
• fluororubber peroxide-crosslinkable fluororubber is used, and a fluorine-containing olefin homopolymer or copolymer can be used.
• fluorine-containing olefins examples include vinylidene fluoride, hexafluoropropylene, pentafluoropropylene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, perfluoroacrylate, perfluoroalkyl acrylate, perfluoro methyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether and the like.
• iodine groups and/or bromine groups that enable peroxide cross-linking of fluororubber can be carried out by a copolymerization reaction in the presence of an iodine group- and/or bromine group-containing saturated or unsaturated compound.
• a bromine group and/or an iodine group is contained as a fluorine-containing copolymer side chain, for example, perfluoro(2-bromoethyl vinyl ether), 3,3,4,4,-tetrafluoro-4-bromo-1-butene , 2-bromo-1,1-difluoroethylene, bromotrifluoroethylene, perfluoro(2-iodoethylvinyl ether), iodotrifluoroethylene, and other cross-linking point-forming monomers.
• the general formula X 1 C n F 2n X 2 (X 1 : F, Br, I, X 2 : Br, I, n: 1 12) is used, and from the viewpoint of reactivity and handling balance, 1-bromoperfluoroethane, 1-bromoperfluoropropane, 1- Bromoperfluorobutane, 1-bromoperfluoropentane, 1-bromoperfluorohexane, 1-iodoperfluoroethane, 1-iodoperfluoropropane, 1-iodoperfluorobutane, 1-iodoperfluoropentane, 1-iodine A copolymer containing an iodine group and/or a bromine group derived from perfluorohexane or the like is preferably used.
• a cross-linking point can be introduced at the end of the fluorine-containing copolymer.
• examples of such compounds include 1-bromo-2-iodotetrafluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, monobromomonoiodoperfluoropentane, monobromomonoiodoperfluoro-n-hexane, 1,2-dibromoperfluoroethane, 1,3-dibromoperfluoropropane, 1,4-dibromoperfluorobutane, 1,5- Dibromoperfluoropentane, 1,6-dibromoperfluorohexane, 1,2-diiodoperfluoroethane
• copolymers are obtained by solution polymerization, suspension polymerization or emulsion polymerization, and are also available as commercial products such as Solvay P959, DuPont GBL-600S, GLT-600S, Daikin. industrial products such as DAIEL-G801 and DAIEL-G901;
• Per 100 parts by weight of peroxide vulcanized fluorororubber the general formula (where any two of R 1 , R 2 and R 3 are a lower alkyl group having 1 to 5 carbon atoms, preferably a butyl group or an amyl group, more preferably a tertiary butyl group or a tertiary amyl group, and , the remaining one is hydrogen, and X is a methyl group or a hydroxyl group), and a compound having a number average molecular weight Mn of 200 to 300 is blended in a proportion of 0.1 to 1 part by weight, preferably 0.1 to 0.8 part by weight. be.
• scorch stability cannot be achieved, while when used in a larger proportion, the vulcanization time becomes longer.
• Such compounds include, for example, 2,6-di-tert-butyl-4-methylphenol with a number-average molecular weight Mn of 220.35, 2,5-di-tert-butylhydroquinone with a number-average molecular weight Mn of 222.33, 2, 5-di-tertiary-amyl hydroquinone, etc., and preferably a hydroquinone derivative with a better balance of these from the scorch T5 and rheometer t90 values is used.
• Patent Document 1 10 parts of Ouchi Shinko Kagaku Nocrac NS-7 (2,5-di-tertiary-butylhydroquinone: number average molecular weight Mn molecular weight 222.33) is added as an antioxidant to 100 parts by weight of the fluoropolymer.
• An example using parts by weight is described, but in such an embodiment, the vulcanization time becomes long, and the object of the present invention cannot be achieved at all.
• Patent Document 2 describes a peroxide-vulcanizable fluorine-containing elastomer, an organic peroxide, a polyfunctional co-crosslinking agent, and one hydroxyphenyl group having one or two tertiary butyl groups in one molecule.
• a fluorine-containing elastomer vulcanized composition containing 0.1 to 10 parts by weight, preferably 0.2 to 5.0 parts by weight, based on 100 parts by weight of fluororubber, of a phenolic antioxidant containing 4 of from
• the one used in the present invention is not mentioned, and particularly preferred is tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate having a molecular weight of 784.08. It is said that there is said that there is said that there is
• the fluororubber composition consisting of the above essential components includes fillers or reinforcing agents such as carbon black and silica; processing aids such as wax, metallic soap and carnauba wax; calcium hydroxide, magnesium oxide, zinc oxide, hydrotal Additives such as acid acceptors such as sites; anti-aging agents; thermoplastic resins; colorants and the like can be added as appropriate.
• fillers or reinforcing agents such as carbon black and silica
• processing aids such as wax, metallic soap and carnauba wax
• calcium hydroxide, magnesium oxide, zinc oxide, hydrotal Additives such as acid acceptors such as sites; anti-aging agents; thermoplastic resins; colorants and the like can be added as appropriate.
• an open roll method for the process of dispersing each compounding component in the fluororubber, an open roll method, an internal kneading method, or a multi-screw extrusion kneading method can be used.
• a kneader can also be used, and in this case kneading is carried out at about 100-200°C, preferably about 140-180°C.
• a cross-linking agent is added to the mixed material to perform cross-linking molding, and a fluororubber cross-linked molding is produced.
• a peroxide cross-linking agent is used as the cross-linking agent.
• peroxide cross-linking agents examples include 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butyl peroxide, dicumyl Peroxide, tert-butyl cumyl peroxide, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(tert-butylperoxy) Hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 1,3-di(tert-butylperoxyisopropyl)benzene, tert-butylperoxybenzoate, tert-butylperoxy Oxyisopropyl carbonate, n-butyl-4,4-di(tertiary-butylperoxy
• the peroxide-based cross-linking agent is used in a proportion of about 1 to 10 parts by weight per 100 parts by weight of the fluororubber.
• a commercially available masterbatch containing raw rubber and a cross-linking agent may also be used as the peroxide cross-linking agent.
• These cross-linking agents may be used singly or in combination of two or more.
• the fluorororubber composition which is a kneaded product of these, is, for example, pressurized and heat-vulcanized to form a crosslinked molded product.
• the obtained fluororubber composition is usually heated at a temperature of about 150 to 200° C. for about 3 to 300 minutes using an injection molding machine, a compression molding machine, a vulcanizing press, an oven, or the like (
• a fluororubber crosslinked molding is obtained by primary vulcanization. If necessary, heat treatment is performed in an oven at a temperature of about 200 to 300° C. for about 1 to 20 hours for secondary vulcanization.
• the resulting crosslinked molding is effectively used as a seal member or the like.
• Example 1 Fluororubber Solvay product P959 100 parts by weight MT carbon black (Cancarb product) 15 ⁇ Iron oxide (BROWN#601, a product of Resinocolor) 35 ⁇ Fatty acid ester compound (Dupont product VPA#2) 1.5 ⁇ Triallyl isocyanurate (Nippon Kaseisei Taiku M-60) 2 Same as above 2,5-dimethyl-2,5-bis(tert-butylperoxy) 3 ⁇ Hexane (NOF PERHEXA25B-40) 2,6-Di-tert-butyl-4-methylphenol 0.2 ⁇ (Ouchi Shinko Chemical Industrial Product Nocrack 200 : number average molecular weight Mn 220.35) Each of the above components was kneaded using a kneader and an open roll, and the kneaded product was vulcanized by a cross-linking press at 180° C. for 4 minutes to obtain a cross-linked product.
• Scorch T5 Measure the time (T5) for the torque to rise by 5M at a temperature of 125°C.
• Rheometer t90 According to JIS K6300 corresponding to ISO 289-1, measure the cross-linking curve at 180°C for 10 minutes, and measure the torque equivalent to 90% of the maximum torque value MH. Time to achieve t90 was obtained If t90 is less than 4 minutes, the cross-linking time is sufficiently short, ⁇ , because it is effective in reducing CO 2 and cost 4 minutes or more is evaluated as ⁇
• Example 2 In Example 1, when the amount of 2,6-di-tert-butyl-4-methylphenol was changed to 0.1 parts by weight, T5 was 18 (evaluation ⁇ ) and t90 was 1.01 (evaluation ⁇ ). .
• Example 3 In Example 1, when the amount of 2,6-di-tert-butyl-4-methylphenol was changed to 0.5 parts by weight, T5 was 40 or more (evaluation ⁇ ) and t90 was 1.78 (evaluation ⁇ ). rice field.
• Example 4 In Example 1, when the amount of 2,6-di-tert-butyl-4-methylphenol was changed to 1 part by weight, T5 was 40 or more (evaluation ⁇ ) and t90 was 3.42 (evaluation ⁇ ). rice field.
• Example 5 In Example 1, 2,5-di-tert-butylhydroquinone (Nocrac NS-7, a product of Ouchi Shinko Chemical Industry Co., Ltd.: number average molecular weight Mn 222.33) was used instead of 2,6-di-tert-butyl-4-methylphenol. When the same amount (0.2 parts by weight) was used, T5 was 20 (evaluation ⁇ ) and t90 was 1.50 (evaluation ⁇ ).
• Nocrac NS-7 a product of Ouchi Shinko Chemical Industry Co., Ltd.: number average molecular weight Mn 222.33
• Example 6 In Example 1, the same amount of 2,5-di-tertiary-amylhydroquinone (Ouchi Shinko Kagaku Kogyo product Nocrack DAH: number average molecular weight Mn 250.38) was used instead of 2,6-di-tert-butyl-4-methylphenol. (0.2 parts by weight) was used, giving a T5 of 26 (good rating) and a t90 of 1.58 (good rating).
• 2,5-di-tertiary-amylhydroquinone Ouchi Shinko Kagaku Kogyo product Nocrack DAH: number average molecular weight Mn 250.38
• Example 3 tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane (ADEKA When the same amount (0.2 parts by weight) of Adekastab AO-60, a product of Co., Ltd., having a number average molecular weight Mn of 1178) was used, T5 was 10 (evaluation ⁇ ) and t90 was 1.03 (evaluation ⁇ ).

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