WO2020095961A1 - Composition de caoutchouc chloroprène, et corps moulé par vulcanisation - Google Patents

Composition de caoutchouc chloroprène, et corps moulé par vulcanisation Download PDF

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Publication number
WO2020095961A1
WO2020095961A1 PCT/JP2019/043550 JP2019043550W WO2020095961A1 WO 2020095961 A1 WO2020095961 A1 WO 2020095961A1 JP 2019043550 W JP2019043550 W JP 2019043550W WO 2020095961 A1 WO2020095961 A1 WO 2020095961A1
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mass
parts
chloroprene rubber
chloroprene
rubber composition
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PCT/JP2019/043550
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English (en)
Japanese (ja)
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敦典 近藤
貴史 砂田
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デンカ株式会社
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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
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing

Definitions

  • the present invention relates to a chloroprene rubber composition containing a chloroprene rubber, a specific sulfur compound and an organic peroxide, and a vulcanized molded product of the chloroprene rubber composition.
  • Chloroprene rubber composition is widely used as a material for industrial rubber products because of its excellent mechanical properties and flame retardancy, and various improvements have been made.
  • Patent Document 1 discloses a technology of chloroprene rubber having an improved vulcanization rate.
  • Patent Documents 2 to 4 disclose the technology of chloroprene rubber having improved heat resistance.
  • JP 2001-181451 A JP, 2009-275124, A JP, 2010-106227, A JP, 2005-060546, A
  • One aspect of the present invention when obtaining a vulcanized molded body by vulcanization molding, improve the vulcanization rate while maintaining the compression set of the vulcanized body and suppressing the decrease in elongation at break after heat aging.
  • An object is to provide a chloroprene rubber composition that can be used.
  • Another object of another aspect of the present invention is to provide a vulcanized molded product that can be obtained by vulcanizing this chloroprene rubber composition.
  • One aspect of the present invention comprises 100 parts by mass of a chloroprene rubber, 0.5 to 5.0 parts by mass of a sulfur-based compound represented by the following general formula (1), and more than 4 parts by mass of an organic peroxide.
  • a chloroprene rubber composition containing 0.0 part by mass or less.
  • R 1 represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 8 carbon atoms
  • R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • One aspect of the present invention provides a vulcanized molded product of the above chloroprene rubber composition.
  • the vulcanization rate in obtaining a vulcanized molded article by vulcanization molding, while maintaining the compression set of the vulcanized molded article and suppressing the decrease in elongation at break after heat aging, the vulcanization rate It is possible to provide a chloroprene rubber composition capable of improving the above.
  • a vulcanized molded article obtained by vulcanizing and molding this chloroprene rubber composition is suitable as a vulcanized molded article for automobile rubber members (seal materials, etc.), hoses (hose materials), rubber molds, gaskets, etc. Can be used.
  • the numerical range indicated by using “to” indicates the range including the numerical values before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value of the numerical range of a certain stage can be arbitrarily combined with the upper limit value or the lower limit value of the numerical range of another stage.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • the materials exemplified in the present specification can be used alone or in combination of two or more kinds.
  • the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
  • the chloroprene rubber composition according to the present embodiment contains 100 parts by mass of a chloroprene rubber, 0.5 to 5.0 parts by mass of a specific sulfur compound described below, and 4.0 parts by mass of more than 0 parts by mass of organic peroxide. And less than or equal to parts by mass.
  • the chloroprene rubber composition according to the present embodiment when the chloroprene rubber composition is vulcanized and molded to obtain a vulcanized molded body, the compression set of the vulcanized molded body is maintained (the compression set is kept low). At the same time, it is possible to improve (accelerate) the vulcanization rate while suppressing a decrease in elongation at break after heat aging.
  • the vulcanized product according to the present embodiment is a vulcanized product of the chloroprene rubber composition according to the present embodiment, and can be obtained by vulcanizing the chloroprene rubber composition according to the present embodiment.
  • the chloroprene rubber is a chloroprene polymer (for example, chloroprene latex) having a structural unit derived from chloroprene (2-chloro-1,3-butadiene).
  • the chloroprene polymer is a homopolymer of chloroprene, a copolymer of chloroprene (a copolymer of a monomer copolymerizable with chloroprene and chloroprene), and a mixture of these polymers.
  • Examples of monomers copolymerizable with chloroprene include acrylic acid esters such as methyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; methacrylic acid such as methyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate.
  • the monomer copolymerizable with chloroprene one type may be used alone, or two or more types may be used in combination.
  • the monomer copolymerizable with chloroprene may be, for example, a polymer obtained by copolymerizing three or more kinds of monomers containing chloroprene. Also, the polymer structure of the polymer is not particularly limited.
  • Chloroprene-based rubber is chloroprene alone from the viewpoint of easily maintaining a low compression set of the vulcanized molded body, from the viewpoint of easily improving the vulcanization rate, and from the viewpoint of easily suppressing a decrease in elongation at break after heat aging.
  • the polymer includes at least one selected from a polymer and a chloroprene copolymer, and the chloroprene copolymer is at least one selected from chloroprene and 2,3-dichloro-1,3-butadiene and acrylonitrile.
  • An embodiment including a copolymer with a monomer is preferable.
  • the chloroprene rubber is a homopolymer of 2-chloro-1,3-butadiene, or is selected from 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene and acrylonitrile. It is preferably a copolymer with at least one monomer.
  • the content (copolymerization amount) of the structural unit derived from chloroprene is the compression set of the vulcanized product.
  • the following range is preferable for 100 parts by mass of the chloroprene rubber from the viewpoints of easily maintaining the low value, easily improving the vulcanization rate, and easily suppressing a decrease in elongation at break after heat aging.
  • the content of the structural unit derived from chloroprene is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, further preferably 80 parts by mass or more, particularly preferably 90 parts by mass or more, and very preferably It is 95 parts by mass or more, very preferably 97 parts by mass or more, and even more preferably 98 parts by mass or more.
  • the content of the structural unit derived from chloroprene is less than 100 parts by mass, preferably 99.5 parts by mass or less, more preferably 99.2 parts by mass or less, and further preferably 99 parts by mass or less. From these viewpoints, the content of the structural unit derived from chloroprene is preferably 50 parts by mass or more and less than 100 parts by mass.
  • the content of the structural unit derived from the monomer copolymerizable with chloroprene is 100 parts by mass of the structural unit derived from chloroprene, or 100 parts by mass of the chloroprene rubber, from the viewpoint of easily exhibiting the effect of copolymerizing these monomers without impairing the properties of the obtained chloroprene rubber composition.
  • the following range is preferable.
  • the content of the structural unit is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, particularly preferably 10 parts by mass or less, and very preferably 5 parts by mass. Or less, very preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.
  • the content of the structural unit is more than 0 parts by mass, preferably 0.5 parts by mass or more, more preferably 0.8 parts by mass or more, still more preferably 1 part by mass or more. From these viewpoints, the content of the structural unit is preferably more than 0 parts by mass and 50 parts by mass or less.
  • the method for producing chloroprene rubber includes a polymerization step of polymerizing a raw material monomer containing chloroprene.
  • Chloroprene-based rubber is used as an emulsifying dispersant, for example, in the presence of a catalyst for polymerization reaction, a catalyst activator, a polymerization initiator, a chain transfer agent, etc. It can be obtained by emulsion-polymerizing a raw material monomer as a component).
  • an alkali metal salt of a saturated or unsaturated fatty acid having 6 to 22 carbon atoms an rosin acid or an alkali metal salt of disproportionated rosin acid (eg potassium rosinate), formalin of ⁇ -naphthalenesulfonic acid
  • alkali metal salts for example, sodium salts
  • the catalyst for the polymerization reaction examples include inorganic peroxides such as potassium sulfate; organic peroxides such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides and diacyl peroxides. ..
  • catalyst activator examples include sodium sulfite, potassium sulfite, iron (II) oxide, anthraquinone, sodium ⁇ -sulfonate, formamidine sulfonic acid and L-ascorbic acid.
  • the polymerization initiator is not particularly limited, and a known polymerization initiator generally used for emulsion polymerization of a chloroprene monomer (a chloroprene monomer) can be used.
  • examples of the polymerization initiator include potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, t-butyl hydroperoxide and the like.
  • the chain transfer agent is also not particularly limited, and it is possible to use the one used for ordinary emulsion polymerization of chloroprene.
  • chain transfer agents include long-chain alkyl mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, and n-octyl mercaptan; xanthogen compounds such as diisopropylxanthogen disulfide and diethylxanthogen disulfide; iodoform; benzyl 1-pyrrole dithiocarbamate (alias).
  • Benzyl 1-pyrrole carbodithioate benzyl phenyl carbodithioate, 1-benzyl-N, N-dimethyl-4-aminodithiobenzoate, 1-benzyl-4-methoxydithiobenzoate, 1-phenylethylimidazole dithiocarbamate (alias) 1-phenylethylimidazole carbodithioate), benzyl-1- (2-pyrrolidinone) dithiocarbamate (also known as benzyl-1- (2-pyrrolidinone)) Rubodithioate), benzylphthalimidyldithiocarbamate (also known as benzylphthalimidylcarbodithioate), 2-cyanoprop-2-yl-1-pyrroledithiocarbamate (also known as 2-cyanoprop-2-yl-1-pyrrolecarbodithioate) , 2-Cyanobut-2-yl-1-pyrroledithi
  • the polymerization temperature of the chloroprene rubber is not particularly limited, and is generally 0 to 50 ° C., more preferably 20 to 50 ° C., as the temperature at which emulsion polymerization is performed.
  • the final polymerization rate of the chloroprene rubber obtained in the above-mentioned polymerization step is not particularly limited, but it is preferably adjusted within the range of 30 to 100%.
  • the polymerization can be stopped by adding a polymerization terminator that stops the polymerization reaction when the desired conversion is reached.
  • the polymerization terminator is not particularly limited, and a commonly used polymerization terminator can be used.
  • Specific examples of the polymerization terminator include phenothiazine (thiodiphenylamine), 4-tert-butylcatechol, and 2,2-methylenebis-4-methyl-6-tert-butylphenol.
  • the method is not particularly limited, and examples thereof include a steam stripping method.
  • the pH is adjusted, and the chloroprene rubber can be obtained through processes such as freeze-coagulation, washing with water, and drying with hot air in a usual manner.
  • the chloroprene rubber composition according to the present embodiment contains a sulfur-based compound represented by the following general formula (1) (hereinafter referred to as "specific sulfur-based compound").
  • the specific sulfur compound can accelerate vulcanization of the resulting chloroprene rubber composition.
  • R 1 represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 8 carbon atoms
  • R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the hydrogen atom of the alkyl group of R 1 , R 2 and R 3 may be substituted with a substituent.
  • R 1 is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group of R 1 preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 or 2 carbon atoms.
  • R 2 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 3 is preferably a hydrogen atom.
  • Specific examples of the specific sulfur compound include 4-methylthiazolidine-2-thione, 3-methylthiazolidine-2-thione, 5-methylthiazolidine-2-thione, 3,4-dimethylthiazolidine-2-thione, 4, 5-dimethylthiazolidine-2-thione, 3,5-dimethylthiazolidine-2-thione, 3,4,5-trimethylthiazolidine-2-thione, 4-ethyl-3-thiazolidine-2-thione, 4-isopropyl-3 -Thiazolidine-2-thione, 4-isopropyl-3-methylthiazolidine-2-thione, 4-hydroxythiazolidine-2-thione, 5-ethyl-3-thiazolidine-2-thione, 5-isopropyl-3-thiazolidine-2 -Thion, 5-isopropyl-3-methylthiazolidine-2-thione, 5-hydroxythiazo -2-thione, 3-ethyl-thiazolidine-2-thione, 3-propyl thiazolidine-2-thione,
  • the specific sulfur compound is 4- It preferably contains at least one selected from methylthiazolidine-2-thione, 3-methylthiazolidine-2-thione, and 4-isopropyl-3-methylthiazolidine-2-thione.
  • the specific sulfur compounds can be used alone or in combination of two or more.
  • the content of the specific sulfur compound is 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the chloroprene rubber. If the content of the specific sulfur compound is less than 0.5 parts by mass, the effect of promoting vulcanization of the obtained chloroprene rubber composition is low and the vulcanization rate cannot be improved. In addition, elongation upon cutting after heat aging may decrease and compression set may deteriorate. If the content of the specific sulfur compound exceeds 5.0 parts by mass, the rubber elasticity of the obtained vulcanized molded article is lost, the elongation at break after heat aging is reduced, and the compression set is deteriorated. It may happen.
  • the content of the specific sulfur compound is preferably 0.75 parts by mass or more, more preferably 1.0 parts by mass or more, from the viewpoint of easily improving the vulcanization rate.
  • the content of the specific sulfur-based compound is preferably 4.5 parts by mass or less, from the viewpoint of easily suppressing a decrease in elongation at break after heat aging, and from the viewpoint of easily keeping the compression set of the vulcanized molded product low.
  • the content of the specific sulfur compound is preferably 0.75 to 3.0 parts by mass, more preferably 1.0 to 2.0 parts by mass.
  • the content of the specific sulfur-based compound is preferably more than 1.0 part by mass, more preferably 1.5 parts by mass or more, and further preferably 2.0 parts by mass, from the viewpoint that the vulcanization rate is more easily improved.
  • the content of the specific sulfur-based compound from the viewpoint of easily maintaining a low compression set of the vulcanized molded article, from the viewpoint of easily improving the vulcanization rate, and from the viewpoint of easily suppressing a decrease in elongation at break after heat aging.
  • the total amount of the sulfur-based compound (the total amount of the sulfur-based compound contained in the chloroprene rubber composition according to the present embodiment), it is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably Is 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 99% by mass or more.
  • the sulfur-based compound in the chloroprene rubber composition according to the present embodiment may be substantially composed of the specific sulfur-based compound (substantially 100% by mass of the sulfur-based compound is the specific sulfur-based compound).
  • the chloroprene rubber composition according to this embodiment may contain a sulfur-based compound other than the specific sulfur-based compound.
  • a sulfur compound for example, a vulcanization accelerator generally used for vulcanizing chloroprene rubber can be used.
  • the vulcanization accelerator include thiourea-based, guanidine-based, thiuram-based, thiazole-based vulcanization accelerators; dimethylammonium hydrogen isophthalate; 1,2-dimercapto-1,3,4-thiadiazole derivative and the like. ..
  • Examples of the thiourea-based vulcanization accelerator include ethylenethiourea, diethylthiourea, trimethylthiourea, triethylthiourea, N, N'-diphenylthiourea, and the like, and at least one selected from trimethylthiourea and ethylenethiourea is preferable.
  • the sulfur compounds may be used alone or in combination of two or more.
  • the content of the sulfur-based compound (the total amount of the sulfur-based compound contained in the chloroprene rubber composition according to this embodiment) is preferably in the following range with respect to 100 parts by mass of the chloroprene rubber.
  • the content of the sulfur-based compound is preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass or more, and further preferably 1.0 parts by mass or more, from the viewpoint of easily improving the vulcanization rate. Is.
  • the content of the sulfur-based compound is preferably 5.0 parts by mass or less from the viewpoint of easily suppressing a decrease in elongation at break after heat aging, and from the viewpoint of easily keeping the compression set of the vulcanized molded product low.
  • the content of the sulfur-based compound is preferably 0.5 to 5.0 parts by mass.
  • the content of the sulfur-based compound is preferably more than 1.0 part by mass, more preferably 1.5 parts by mass or more, and further preferably 2.0 parts by mass or more, from the viewpoint of further improving the vulcanization rate.
  • the chloroprene rubber composition according to the present embodiment contains an organic peroxide.
  • the organic peroxide can accelerate the vulcanization of the obtained chloroprene rubber composition by a synergistic effect with the above-mentioned specific sulfur compound.
  • organic peroxide examples include dialkyl peroxide, diacyl peroxide, peroxyketal, peroxyester, and butyl 4,4-bis [(t-butyl) peroxy] pentanoate.
  • the organic peroxide is a dialkylperoxide from the viewpoint of easily keeping the compression set of the vulcanized molded article low, from the viewpoint of easily increasing the vulcanization rate, and from the viewpoint of easily suppressing a decrease in elongation at break after heat aging. It preferably contains at least one selected from oxides, peroxyketals and butyl 4,4-bis [(t-butyl) peroxy] pentanoate.
  • dialkyl peroxides examples include dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne. -3,1,3-bis (t-butylperoxyisoprobyl) benzene, 1,4-bis (t-butylperoxyisoprobyl) benzene, t-butylcumyl peroxide, di-t-butylperoxide, etc. Is mentioned.
  • the dialkyl peroxides can be used alone or in combination of two or more.
  • diacyl peroxide examples include dibenzoyl peroxide, di-p-methylbenzoyl peroxide, di-o-methylbenzoyl peroxide and the like.
  • the diacyl peroxides can be used alone or in combination of two or more.
  • peroxyketals examples include 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, n-butyl-4,4-di (t-butylperoxy) valerate and the like.
  • the peroxyketals may be used alone or in combination of two or more.
  • peroxyesters examples include 2,5-dimethyl-2,5-di (t-benzoylperoxy) hexane, t-hexylperoxybenzoate, t-butylperoxybenzoate and the like.
  • the peroxyesters may be used alone or in combination of two or more.
  • the content of organic peroxide is more than 0 parts by mass and 4.0 parts by mass or less based on 100 parts by mass of chloroprene rubber.
  • the content of the organic peroxide is 0 part by mass, the effect of promoting vulcanization of the obtained chloroprene rubber composition is low and the vulcanization rate cannot be improved.
  • elongation upon cutting after heat aging may decrease and compression set may deteriorate.
  • the content of the organic peroxide exceeds 4.0 parts by mass, the rubber elasticity of the obtained vulcanized molded product may be lost, and the elongation at break after heat aging may be reduced.
  • the content of the organic peroxide is from the viewpoint of easily keeping the compression set of the vulcanized molded article low, from the viewpoint of easily increasing the vulcanization rate, and from the viewpoint of easily suppressing a decrease in elongation at break after heat aging.
  • the content of the organic peroxide is preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, and further preferably from the viewpoint of easily suppressing a decrease in elongation at break after heat aging.
  • the content of the organic peroxide is preferably 0.05 to 4.0 parts by mass, more preferably 0.1 to 3.0 parts by mass, still more preferably 0.1 to 3.0 parts by mass.
  • the amount is 2.0 parts by mass, and particularly preferably 0.3 to 1.0 part by mass.
  • the content of the organic peroxide is preferably 0.75 parts by mass or more, from the viewpoint of easily maintaining the compression set of the vulcanized molded article even lower and from the viewpoint of further improving the vulcanization rate, and It is preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, particularly preferably 2.0 parts by mass or more, very preferably 2.5 parts by mass or more, and very preferably Is 3.0 parts by mass or more.
  • the chloroprene rubber composition according to the present embodiment may contain a filler or a reinforcing agent, a plasticizer, a vulcanizing agent, a vulcanization aid, a processing aid, an antioxidant, and the like.
  • filler or reinforcing agent examples include carbon black, silica, clay, talc, calcium carbonate and the like. Each of the filler and the reinforcing agent may be used alone or in combination of two or more.
  • the content of the filler or the reinforcing agent is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the chloroprene rubber or 100 parts by mass of the chloroprene rubber composition.
  • the plasticizer is not particularly limited as long as it is compatible with chloroprene rubber, vegetable oil (rapeseed oil, etc.), phthalate plasticizer, DOS, DOA, ester plasticizer, ether / ester plasticizer, Examples include thioether plasticizers, aromatic oils, naphthene oils and the like.
  • the plasticizer may be used alone or in combination of two or more, depending on the properties required for the chloroprene rubber composition.
  • the content of the plasticizer is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the chloroprene rubber or 100 parts by mass of the chloroprene rubber composition.
  • the vulcanizing agent is not particularly limited, but a metal oxide is preferable. Specific examples of the metal oxide include zinc oxide, magnesium oxide, lead oxide, trilead tetroxide, iron trioxide, titanium dioxide, calcium oxide, hydrotalcite and the like.
  • the vulcanizing agents may be used alone or in combination of two or more.
  • the content of the vulcanizing agent is preferably 3 to 15 parts by mass with respect to 100 parts by mass of the chloroprene rubber or 100 parts by mass of the chloroprene rubber composition. Vulcanization can be performed more effectively by using a vulcanizing agent in combination with the above-mentioned vulcanization accelerator.
  • the chloroprene rubber composition according to the present embodiment as a vulcanization aid, at least one selected from a difunctional ester compound and a trifunctional ester compound from the viewpoint of improving the vulcanization rate or vulcanization density. Can be included.
  • vulcanization aid examples include trimethylolpropane, ethylene glycol dimethacrylate, triallyl isocyanate, triallyl cyanate, and maleimide compounds.
  • the vulcanization aids may be used alone or in combination of two or more.
  • maleimide compounds include N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, 2-methyl-N-phenylmaleimide, 2,3-dimethylmaleimide, 2 -Ethyl maleimide, 2-n-butyl maleimide, N-benzyl maleimide, N, N'-1,2-ethyl bismaleimide, N, N'-1,2-hexyl bismaleimide, N-propionic acid maleimide, 4, 4'-bismaleimidodiphenylmethane, 6,7-methylenedioxy-4-methyl-3-coumaric acid maleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N-bromomethyl-2,3- Dichloromaleimide, N- (3-maleimidobenzoyloxy) succinic acid, N (3-maleimido
  • the content of the vulcanization aid is preferably in the following range with respect to 100 parts by mass of the chloroprene rubber or 100 parts by mass of the chloroprene rubber composition.
  • the content of the vulcanization aid is preferably 0.2 parts by mass or more, and more preferably 0.5 parts by mass or more, from the viewpoint of easily obtaining the effect of adding the vulcanization aid.
  • the content of the vulcanization aid is preferably 5 parts by mass or less, and more preferably 4 parts by mass or less, from the viewpoint of easily suppressing the hardness of the obtained vulcanized product from becoming excessively high. From these viewpoints, the content of the vulcanization aid is preferably 0.2 to 5 parts by mass, more preferably 0.5 to 4 parts by mass.
  • processing aids include fatty acids such as stearic acid; paraffin-based processing aids such as polyethylene; fatty acid amides.
  • the processing aids may be used alone or in combination of two or more.
  • the content of the processing aid is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the chloroprene rubber or 100 parts by mass of the chloroprene rubber composition.
  • an amine antiaging agent an imidazole antiaging agent, a carbamate metal salt, a phenol antiaging agent, a wax, an ozone antiaging agent (for example, N-phenyl-N '-(1,3- Dimethylbutyl) -p-phenylenediamine) and the like.
  • the anti-aging agent is preferably an amine-based anti-aging agent from the viewpoint of a large effect of improving heat resistance, and at least one selected from 4,4′-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine and octylated diphenylamine. Is more preferable, and 4,4′-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine is even more preferable.
  • the antioxidants can be used alone or in combination of two or more.
  • the chloroprene rubber composition according to the present embodiment may contain phenothiazine from the viewpoint of improving the processing stability of the chloroprene rubber composition.
  • the content of phenothiazine is preferably 0.1 to 2 parts by mass, more preferably 0.3 to 1.5 parts by mass based on 100 parts by mass of the chloroprene rubber or 100 parts by mass of the chloroprene rubber composition. .. By using phenothiazine in these ranges, the effect of improving the processing stability of the obtained chloroprene rubber composition is high.
  • the chloroprene rubber composition according to the present embodiment can be obtained by kneading the above compound at a temperature below its vulcanization temperature.
  • a mixer, a Banbury mixer, a kneader mixer, a two-roll mill or the like can be used as the kneading device.
  • the molded body according to this embodiment is a molded body of the chloroprene rubber composition according to this embodiment, and can be obtained by molding the chloroprene rubber composition according to this embodiment.
  • the vulcanized molded product according to the present embodiment is a vulcanized molded product of the chloroprene rubber composition according to the present embodiment.
  • a method for molding a vulcanized molded body from the chloroprene rubber composition a method such as press molding, extrusion molding or calender molding can be used.
  • the temperature for vulcanizing the chloroprene rubber composition may be set appropriately according to the composition, and is preferably 140 to 220 ° C, more preferably 150 to 180 ° C.
  • the vulcanization time may also be appropriately set depending on the composition or shape of the chloroprene rubber composition, and may be 10 to 60 minutes.
  • the vulcanized molded article according to the present embodiment is obtained by vulcanizing and molding the chloroprene rubber composition according to the present embodiment, and its compression set is maintained despite the high vulcanization rate. At the same time, the decrease in elongation at break after heat aging was suppressed.
  • the polymerization rate of the chloroprene-acrylonitrile copolymer latex was calculated from the dry mass of the chloroprene-acrylonitrile copolymer latex air-dried. Specifically, it was calculated by the following formula (I).
  • the solid content concentration means the concentration of solid content obtained by heating 2 g of sampled chloroprene-acrylonitrile copolymer latex at 130 ° C. and removing volatile components such as solvent (water), volatile chemicals and raw materials [mass %].
  • the total amount charged is the total amount of raw materials, reagents and solvent (water) charged in a polymerization vessel from the start of polymerization to a certain time.
  • the evaporation residue is the mass of the chemicals and raw materials charged from the start of the polymerization to a certain time and remaining as a solid content together with the polymer without being volatilized under the condition of 130 ° C.
  • the monomer charging amount is the total of the amount of the monomer initially charged in the polymerization vessel and the amount of the monomer added by a certain time from the start of polymerization.
  • the "monomer” referred to here is the total amount of the chloroprene monomer and the acrylonitrile monomer.
  • Polymerization rate [%] ⁇ (total charged amount [g] ⁇ solid content concentration [mass%] / 100) ⁇ (evaporation residue [g]) ⁇ / monomer charged amount [g] ⁇ 100 ( I)
  • a sheet was obtained by adjusting the pH of the above-mentioned chloroprene-acrylonitrile copolymer latex to pH 7.0 and freeze-coagulating it on a metal plate cooled to -20 ° C to break the emulsion. The sheet was washed with water and then dried at 130 ° C. for 15 minutes to obtain a solid chloroprene-acrylonitrile copolymer rubber.
  • the number-average molecular weight (Mn), weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the chloroprene-acrylonitrile copolymer rubber are the same as those of the chloroprene-acrylonitrile copolymer rubber in a sample adjusted concentration of 0.1 mass% with THF. After that, it was measured by a high-speed GPC device (TOSOH HLC-8320GPC: manufactured by Tosoh Corporation) (standard polystyrene conversion).
  • the TSK guard column HHR-H was used as a pre-column, three HSKgel GMHHR-H were used as an analytical column, and the sample pump pressure was 8.0 to 9.5 MPa, the flow rate was 1 ml / min, and the flow rate was 40 ° C. It was detected by the total.
  • the amount of structural units derived from the unsaturated nitrile monomer contained in the chloroprene-acrylonitrile copolymer rubber was calculated from the content of nitrogen atoms in the chloroprene-acrylonitrile copolymer rubber. Specifically, the nitrogen atom content of 100 mg of chloroprene-acrylonitrile copolymer rubber was measured using an elemental analyzer (Sumigraph 220F: manufactured by Sumika Analytical Center Co., Ltd.), and the structural unit derived from the acrylonitrile monomer was measured. Calculated. The elemental analysis was performed under the following conditions. The electric furnace temperature was set to 900 ° C. for the reaction furnace, 600 ° C. for the reduction furnace, 70 ° C. for the column temperature, and 100 ° C. for the detector temperature. .. The calibration curve was prepared using aspartic acid (10.52%) with a known nitrogen content as a standard substance.
  • the chloroprene-acrylonitrile copolymer rubber had a number average molecular weight (Mn) of 138 ⁇ 10 3 / mol, a weight average molecular weight (Mw) of 473 ⁇ 10 3 g / mol, and a molecular weight distribution (Mw / Mn) of 3.4. ..
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mn molecular weight distribution
  • Sulfur-based compound A 3-methylthiazolidine-2-thione, manufactured by LANXESS, Renoglan MTT-80
  • Sulfur-based compound B 4-methylthiazolidine-2-thione (commercially available product)
  • Sulfur-based compound C 4-isopropyl-3-methylthiazolidine-2-thione (commercially available product)
  • Organic peroxide B Perbutyl (registered trademark) C-40 manufactured by NOF CORPORATION
  • Organic peroxide C Perhexa (registered trademark) 25B manufactured by NOF CORPORATION
  • A represents the elongation value at break (average value of 5 sheets) of the measurement sample before heat treatment
  • B represents the elongation value at break (average value of 5 sheets) of the measurement sample after heat treatment.
  • the case where the rate of change was between -15% and 0% was evaluated as acceptable.
  • Change rate of elongation at break after heat aging (%) (BA) / A ⁇ 100 (II)
  • vulcanized molded articles were obtained using the chloroprene rubber compositions of Examples, vulcanization was performed while maintaining compression set and suppressing the decrease in elongation at break after heat aging. It turns out that the speed is improving. Since the vulcanized molded product has these properties, it is excellent in productivity and can be suitably used as a molded product such as a rubber member for automobile (sealing material), a hose (hose material), a rubber mold, a gasket and the like.

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  • Polymers & Plastics (AREA)
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  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

L'invention concerne une composition de caoutchouc chloroprène qui comprend 100 parties en masse d'un caoutchouc à base de chloroprène, 0,5 à 5,0 parties en masse d'un composé à base de soufre représenté par la formule générale (1), et plus de 0 partie en masse à 4,0 parties en masse ou moins d'un peroxyde organique. [Dans la formule, Ｒ１ représente un atome d'hydrogène, un groupe hydroxyle ou un groupe alkyle de 1 à 8 atomes de carbone, et Ｒ２ et Ｒ３ représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle de 1 à 8 atomes de carbone.]
PCT/JP2019/043550 2018-11-09 2019-11-06 Composition de caoutchouc chloroprène, et corps moulé par vulcanisation WO2020095961A1 (fr)

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WO2024101276A1 (fr) * 2022-11-09 2024-05-16 デンカ株式会社 Composition de caoutchouc, produit vulcanisé et objet moulé vulcanisé

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JPH07145269A (ja) * 1993-11-25 1995-06-06 Kureha Elastomer- Kk クロロプレンゴム組成物
JP2002020538A (ja) * 2000-07-13 2002-01-23 Denki Kagaku Kogyo Kk 粉末加硫ゴム組成物
JP2002060550A (ja) * 2000-08-16 2002-02-26 Denki Kagaku Kogyo Kk ハロゲン含有ゴム組成物
JP2011504846A (ja) * 2007-11-28 2011-02-17 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング ウィンドワイパ用ワイパゴム
JP2011038101A (ja) * 2009-08-07 2011-02-24 Rhein Chemie Rheinau Gmbh 加硫促進混合物

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JPH07145269A (ja) * 1993-11-25 1995-06-06 Kureha Elastomer- Kk クロロプレンゴム組成物
JP2002020538A (ja) * 2000-07-13 2002-01-23 Denki Kagaku Kogyo Kk 粉末加硫ゴム組成物
JP2002060550A (ja) * 2000-08-16 2002-02-26 Denki Kagaku Kogyo Kk ハロゲン含有ゴム組成物
JP2011504846A (ja) * 2007-11-28 2011-02-17 ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツング ウィンドワイパ用ワイパゴム
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ARIYOSHI, TAKASHI ET AL.: "Vulcanization of chloroprene rubber with peroxide (part I)", vol. 20, no. 1, 1976, pages 21 - 29, XP055707460, Retrieved from the Internet <URL:https://www.tosoh.co.jp/technology/assets/76-021.pdf> [retrieved on 20191127] *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024101276A1 (fr) * 2022-11-09 2024-05-16 デンカ株式会社 Composition de caoutchouc, produit vulcanisé et objet moulé vulcanisé

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