WO2017086347A1 - Vulcanized composition of modified halogenated polyolefin composition - Google Patents

Vulcanized composition of modified halogenated polyolefin composition Download PDF

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WO2017086347A1
WO2017086347A1 PCT/JP2016/083966 JP2016083966W WO2017086347A1 WO 2017086347 A1 WO2017086347 A1 WO 2017086347A1 JP 2016083966 W JP2016083966 W JP 2016083966W WO 2017086347 A1 WO2017086347 A1 WO 2017086347A1
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halogenated polyolefin
acrylonitrile
copolymer
polyolefin composition
weight
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PCT/JP2016/083966
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French (fr)
Japanese (ja)
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宮川泰道
山本典正
鶴田貴志
永谷直人
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東ソー株式会社
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Priority to DE112016005267.7T priority Critical patent/DE112016005267T5/en
Priority to CN201680067357.9A priority patent/CN108291073A/en
Publication of WO2017086347A1 publication Critical patent/WO2017086347A1/en

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    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/023—On to modified polymers, e.g. chlorinated polymers
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C08F8/38—Sulfohalogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters

Definitions

  • the present invention relates to a vulcanized composition of a modified halogenated polyolefin composition. More specifically, the present invention relates to a graft copolymer in which a copolymer of acrylonitrile and an acrylic compound is bonded to a halogenated polyolefin, and a bond to a halogenated polyolefin. The present invention relates to a vulcanized composition of a composition containing a copolymer of acrylonitrile and an acrylic compound.
  • the inventor has intensively studied to solve the above problems, and as a result, has completed the present invention.
  • a modified halogenated polyolefin composition containing a graft copolymer in which a copolymer of acrylonitrile and an acrylic compound is bonded to a halogenated polyolefin, and a copolymer of acrylonitrile and an acrylic compound not bonded to the halogenated polyolefin A vulcanized composition obtained by vulcanizing a product.
  • the vulcanized composition according to [1] or [2], wherein [4] The total content of the copolymer of acrylonitrile and the acrylic compound not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition and the copolymer of the acrylonitrile and the acrylic compound in the graft copolymer is The vulcanized composition according to any one of [1] to [3], which is in the range of 20% to 75% by weight.
  • the weight ratio of the components derived from the acrylonitrile and the acrylic compound contained in the copolymer of acrylonitrile and the acrylic compound not bonded to the halogenated polyolefin and the graft copolymer is in the range of 3/97 to 70/30.
  • the vulcanized composition according to any one of [1] to [4], wherein [6] The vulcanized composition according to any one of [1] to [5], wherein the acrylic compound is 2-methoxyethyl acrylate.
  • the weight ratio of the epoxy group-containing copolymer in the graft copolymer to the epoxy group-containing copolymer not bonded to the halogenated polyolefin is in the range of 3/97 to 70/30.
  • the modified halogenated polyolefin composition of the second embodiment of the present invention is obtained by co-grafting an unsaturated monomer containing acrylonitrile, an epoxy group-containing compound and an acrylic compound to the halogenated polyolefin. Can do.
  • the graft copolymer can be obtained by fractionation from the resulting modified halogenated polyolefin composition.
  • the solvents include aromatic organic solvents such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodi Chlorinated organic solvents such as fluorobenzene, carbon tetrachloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetrachloroethane, trichlorofluoroethane, etc. These may be used alone or in combination of two or more, but it is preferable to use only a chlorinated organic solvent that is inert to the chlorination reaction.
  • aromatic organic solvents such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodi Chlorinated organic solvents such as fluoro
  • an amino compound such as pyridine or quinoline is added as a co-catalyst as necessary.
  • the amount of chlorine in the halogenated polyolefin used in the production of the modified halogenated polyolefin composition is not particularly limited, but it is preferably in the range of 15.0 to 45.0% by weight in consideration of oil resistance and mechanical properties, and further low temperature properties. In view of the above, it is preferably in the range of 20.0 wt% to 40.0 wt%.
  • the amount of sulfur when the halogenated polyolefin is chlorosulfonated polyethylene obtained by chlorinating and chlorosulfonated polyolefin is not particularly limited, but is preferably in the range of 0.1 to 3.0% by weight.
  • the acrylic compound co-grafted to the halogenated polyolefin is not limited as long as it is a compound containing an acryloyl group or a methacryloyl group.
  • alkyl vinyl ketone compounds such as methyl vinyl ketone
  • alkyl vinyl ether compounds such as vinyl ethyl ether
  • allyl ether compounds such as allyl methyl ether
  • vinyl aromatic compounds such as styrene, ⁇ -methyl styrene, chlorostyrene, vinyl toluene, vinyl naphthalene, etc.
  • the weight ratio (graft selectivity) of the copolymer of acrylonitrile and acrylic compound in the graft copolymer and the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin,
  • the weight ratio is preferably in the range of 3/97 to 70/30.
  • an epoxy group-containing compound and an acrylic compound an epoxy group-containing copolymer bonded to the halogenated polyolefin in the graft copolymer and an epoxy group-containing copolymer not bonded to the halogenated polyolefin.
  • the weight ratio (graft selectivity) between the epoxy group-containing copolymer in the graft copolymer and the epoxy group-containing copolymer that is not bonded to the halogenated polyolefin is not particularly limited, but the resulting modified halogenated polyolefin In order to achieve both the mechanical properties and oil resistance of the composition, the weight ratio is preferably in the range of 3/97 to 70/30.
  • a copolymer of acrylonitrile and an acrylic compound that is not bonded to a halogenated polyolefin and a copolymer of acrylonitrile and an acrylic compound in a graft copolymer are used.
  • the total content of the polymer is preferably in the range of 20% by weight to 75% by weight in order to achieve both excellent physical properties and oil resistance while maintaining the properties as the halogenated polyolefin composition. More preferably, it is in the range of 40% to 65% by weight.
  • the remaining components are components derived from the halogenated polyolefin in the graft copolymer.
  • the polymerization ratio of components derived from acrylonitrile and the acrylic compound contained in the coalescence is preferably in the range of 3/97 to 70/30, more preferably in the range of 10/90 to 70/30, and 15/85 to 60/40. It is preferable to be in the range.
  • the weight ratio of acrylonitrile in the copolymer is 3% or more, the tensile strength of the resulting modified halogenated polyolefin vulcanizate is maintained.
  • the weight ratio of acrylonitrile is 70% or less, the viscosity of the resulting modified halogenated polyolefin composition does not increase and the moldability is good.
  • the weight ratio of acrylonitrile is preferably as low as possible without impairing the oil resistance, and is in the range of 3/97 to 50/50.
  • the acrylonitrile contained in the epoxy group-containing copolymer in the graft copolymer and the epoxy group-containing copolymer not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition of the second embodiment of the present invention is preferably in the range of 3/97 to 70/30, more preferably in the range of 10/90 to 70/30, particularly in the range of 15/85 to 60/40. Is preferred. When the weight ratio of acrylonitrile in the copolymer is 3% or more, the tensile strength of the resulting modified halogenated polyolefin vulcanizate is maintained.
  • the weight ratio of acrylonitrile is 70% or less, the viscosity of the resulting modified halogenated polyolefin composition does not increase and the moldability is good.
  • the weight ratio of acrylonitrile is preferably as low as possible without impairing the oil resistance, and is in the range of 3/97 to 50/50.
  • the content of the epoxy group-containing compound-derived component in the modified halogenated polyolefin composition of the second embodiment of the present invention is preferably in the range of 1% by weight to 12% by weight.
  • the epoxy group-containing compound is an epoxy group-containing acrylic compound
  • the epoxy group-containing copolymer not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition and the epoxy group in the graft copolymer It is preferable to add an acrylic compound that does not contain an epoxy group in such a range that the weight ratio of the component derived from acrylonitrile and the acrylic compound contained in the containing copolymer is 10/90 to 70/30.
  • the epoxy group-containing compound acts as a crosslinking point in the modified halogenated polyolefin composition, and if the weight ratio of the epoxy group-containing compound in the modified halogenated polyolefin composition is 1% by weight or more, A sufficient crosslinked structure can be formed, and the resulting modified halogenated polyolefin vulcanizate is excellent in oil resistance and tensile strength.
  • the weight ratio of the component derived from the epoxy group-containing compound in the modified halogenated polyolefin composition is 12% by weight or less, the resulting modified halogenated polyolefin vulcanizate is hardened by forming an excessive cross-linked structure. The problem that the elongation at break is reduced does not occur without increasing the thickness.
  • the weight ratio of the epoxy group-containing compound in the modified halogenated polyolefin composition is preferably in the range of 2 to 10% by weight.
  • a copolymer containing acrylonitrile, an epoxy group-containing compound and an acrylic compound that are not bonded to the halogenated polyolefin is bonded to the halogenated polyolefin. Some are not bonded to halogenated polyolefins.
  • the method for adding the unsaturated monomer and the radical initiator described above is not particularly limited, and is a method in which the unsaturated monomer and / or the radical initiator are added together at the initial stage of the co-grafting reaction. Examples thereof include a method of adding at the initial stage of the grafting reaction and continuously injecting the remaining unsaturated monomers and / or radical initiators, and a method of continuously injecting all unsaturated monomers and / or radical initiators.
  • a molecular weight modifier may be added during the co-grafting reaction.
  • the molecular weight regulator include diisopropyl xanthogen disulfide, diethyl xanthogen disulfide, diethyl thiuram disulfide, 2,2′-dithiopropionic acid, 3,3′-dithiopropionic acid, 4,4′-dithiodibranic acid, 2,2 ′.
  • Disulfides such as dithiobisbenzoic acid, n-dodecyl mercaptan, octyl mercaptan, t-butyl mercaptan, thioglycolic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, 3-mercaptobenzoic acid, Mercaptans such as thiomaleic anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homocysteine, 6-mercaptotetrazoleacetic acid, 3-mercapto-1-propanesulfonic acid, diphenylethylene p- chloro diphenylethylene, p- cyano-diphenyl ethylene, alpha-methyl styrene dimer, benzyl dithio benzoate, organic tellurium compounds, sulfur and the like, can be used alone or in combination.
  • the antioxidant is not particularly limited, and is generally used as an antioxidant for polymers.
  • reaction temperature and reaction pressure of the co-grafting reaction are not particularly limited, but the reaction temperature is preferably 50 to 150 ° C. and the reaction pressure is preferably 0 to 1.0 MPa.
  • the desired modified halogenated polyolefin composition is obtained by precipitation with an insoluble solvent such as methanol, concentration and drying using a drum dryer, an extruder with a vent, or the like.
  • the graft copolymer is fractionated by adding the solution after completion of the reaction to a solvent in which the graft copolymer such as acetone is insoluble and the epoxy group-containing copolymer is soluble, and this is dried.
  • a solvent in which the graft copolymer such as acetone is insoluble and the epoxy group-containing copolymer is soluble is dried.
  • the vulcanized composition of the modified halogenated polyolefin composition of the present invention has both good flame retardancy, physical properties and oil resistance, especially various hoses, various seal materials, packing, etc. that require oil resistance. Can be used.
  • the total content of the epoxy group-containing copolymer not bonded to the halogenated polyolefin and the epoxy group-containing copolymer in the graft copolymer in the modified halogenated polyolefin composition is the halogenated raw material. It calculated from the weight of the reacted unsaturated monomer calculated
  • the modified halogenated polyolefin composition the total content of the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin and the copolymer of acrylonitrile and acrylic compound in the graft copolymer is The weight was calculated from the weight of the halogenated polyolefin as a raw material, the amount of unsaturated monomers (acrylonitrile and acrylic compound) charged, and the weight of reacted unsaturated monomers determined from the conversion rate of each unsaturated monomer.
  • Acetone extract weight [A] Acetone extraction residue weight [B] 3
  • the chlorine content in the acetone extract and the acetone extract residue is measured.
  • the sulfur content is measured by first using an acetone extract of the raw halogenated polyolefin or modified halogenated polyolefin composition in a combustion flask containing 10.0 ml of 3.0% by weight hydrogen peroxide as an absorbent. 30.0 mg of acetone extraction residue was burned according to the oxygen combustion method and allowed to stand for 30 minutes. Next, this absorbing solution was washed out with about 40.0 ml of pure water, and then 1 ml of acetic acid, 100.0 ml of 2-propyl alcohol, and 0.47 ml of arsenazo III were added. This was determined by quantifying sulfate ion by a photometric titration method with a 0.01N concentration barium acetate solution.
  • Example 1 After adding 21.6 kg of 1,1,2-trichloroethane, density of 960 kg / cm 3 , and melt flow rate (MFR) of 5.0 g / 10 min to 3 kg of 40 liter glass-lined autoclave, Steam was passed through the reactor jacket to uniformly dissolve the polyethylene at 110 ° C. During this time, nitrogen gas was introduced into the reactor at a flow rate of 10.0 liters / minute to remove air in the reactor. As a radical generator, a solution of 5.0 g of ⁇ , ⁇ -azobisisobutyronitrile dissolved in 1.0 liter of 1,1,2-trichloroethane at a flow rate of 4.0 ml / min, 6.5 kg of chloride.
  • MFR melt flow rate
  • the obtained chlorosulfonated polyethylene contained 35.3% by weight of chlorine and 0.22% by weight of sulfur.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-n-butyl acrylate copolymer content of 31.7% by weight, and the acrylonitrile / n-butyl acrylate acrylonitrile / n-butyl acrylate ratio. was 26/74.
  • the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
  • Example 2 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1, except that the amount of the unsaturated monomer charged was changed to 59.7 g of acrylonitrile and 48.1 g of n-butyl acrylate.
  • the resulting modified halogenated polyolefin composition has an acrylonitrile-n-butyl acrylate copolymer content of 27.4% by weight, and the acrylonitrile / n-butyl acrylate copolymer has an acrylonitrile / n-butyl acrylate ratio.
  • the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
  • Example 3 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 39.8 g of acrylonitrile and 75.1 g of ethyl acrylate.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 28.0% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 31/69. It was.
  • the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 26.1% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 59/41. It was.
  • the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
  • Example 5 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 39.8 g of acrylonitrile and 97.6 g of 2-methoxyethyl acrylate.
  • Example 6 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 59.7 g of acrylonitrile and 48.8 g of 2-methoxyethyl acrylate.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 24.4% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 45/55.
  • the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
  • Example 7 Modified halogenated polyolefin composition in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 180 g, and the unsaturated monomer was changed to 53.4 g of acrylonitrile and 100.8 g of ethyl acrylate. Got.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 29.9% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 32/68. It was.
  • the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
  • Example 8 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 103.9 g of acrylonitrile and 196.1 g of ethyl acrylate.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 54.0% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 33/67. It was.
  • the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
  • Example 9 Modified halogenated polyolefin composition in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 180 g, and the unsaturated monomer was changed to 79.4 g of acrylonitrile and 74.9 g of ethyl acrylate. Got.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 28.5% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 53/47. It was.
  • the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 3.
  • Example 10 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 154.4 g of acrylonitrile and 145.6 g of ethyl acrylate.
  • Example 11 Modified halogenation in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 200 g, and the unsaturated monomer was changed to 49.7 g of acrylonitrile and 121.8 g of 2-methoxyethyl acrylate. A polyolefin composition was obtained.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 55.4% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 30/70.
  • the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 3.
  • Example 13 Modified halogenation in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 180 g, and the unsaturated monomer was changed to 69.3 g of acrylonitrile and 85.0 g of 2-methoxyethyl acrylate. A polyolefin composition was obtained.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 50.2% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 49/51.
  • the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 3.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 42.8% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 40/60.
  • the physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 3.
  • Example 16 Co-grafting reaction was carried out using the chlorosulfonated polyethylene described in Example 15 as the halogenated polyolefin.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 32.1% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 49/51.
  • the physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 4.
  • Example 17 Co-grafting reaction was carried out using the chlorosulfonated polyethylene described in Example 15 as the halogenated polyolefin.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 45.1% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl acrylate copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 39/61.
  • the physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 4.
  • Example 18 Co-grafting reaction was carried out using the chlorosulfonated polyethylene described in Example 15 as the halogenated polyolefin.
  • Example 19 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 100.0 g of acrylonitrile, 268.4 g of 2-methoxyethyl acrylate, and 10.9 g of glycidyl methacrylate.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 56.6% by weight, and acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer.
  • the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate ratio was 31/64/5.
  • the physical properties were evaluated according to the formulation of formulation 3. The evaluation results are shown in Table 4.
  • Example 20 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the amount of the unsaturated monomer charged was changed to 39.8 g of acrylonitrile, 11.0 g of glycidyl methacrylate, and 96.1 g of n-butyl acrylate. It was.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-n-butyl acrylate copolymer (epoxy group-containing copolymer) content of 32.5% by weight, and acrylonitrile-glycidyl methacrylate-acrylic.
  • the acrylonitrile / n-butyl acrylate ratio of the acid n-butyl copolymer was 29/71.
  • the physical properties were evaluated according to the formulation of formulation 4. The evaluation results are shown in Table 4.
  • Example 21 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the amount of the unsaturated monomer charged was changed to 103.9 g of acrylonitrile, 11.0 g of glycidyl methacrylate, and 196.1 g of ethyl acrylate.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-ethyl acrylate copolymer content of 54.4% by weight and an acrylonitrile / acrylic acid acrylonitrile-glycidyl methacrylate-ethyl acrylate copolymer.
  • the ethyl ratio was 35/65.
  • the physical properties were evaluated according to the formulation of formulation 4. The evaluation results are shown in Table 4.
  • Example 22 A modified halogenated polyolefin composition was obtained in the same manner as in Example 20 except that the unsaturated monomer was changed to 100.0 g of acrylonitrile, 11.0 g of glycidyl methacrylate, and 268.4 g of 2-methoxyethyl acrylate.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 56.3% by weight, and the acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer.
  • the combined acrylonitrile / 2-methoxyethyl acrylate ratio was 33/67.
  • the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 58.8% by weight, and acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer.
  • the combined acrylonitrile / 2-methoxyethyl acrylate ratio was 31/69.
  • the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 63.4% by weight, and an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer.
  • the combined acrylonitrile / 2-methoxyethyl acrylate ratio was 29/71.
  • the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 55.1% by weight, and the acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer.
  • the combined acrylonitrile / 2-methoxyethyl acrylate ratio was 32/68.
  • the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
  • Example 26 Using TOSO-CSM TS-830 (manufactured by Tosoh Corporation) as the halogenated polyolefin, the unsaturated monomer was changed to 100.7 g of acrylonitrile, 317.3 g of 2-methoxyethyl acrylate, and 22.2 g of glycidyl methacrylate.
  • a modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 61.0% by weight, and acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer.
  • the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate ratio was 28/63/9.
  • the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
  • Example 27 A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 56.0 g of acrylonitrile, 314.6 g of 2-methoxyethyl acrylate, and 21.9 g of glycidyl methacrylate.
  • Example 28 A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 36.4 g of acrylonitrile, 282.2 g of 2-methoxyethyl acrylate, and 21.5 g of glycidyl methacrylate.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 61.9% by weight, and an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer.
  • the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate ratio was 12/81/9.
  • the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
  • Example 29 A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 20.8 g of acrylonitrile, 298.6 g of 2-methoxyethyl acrylate, and 21.5 g of glycidyl methacrylate.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 65.5% by weight, and acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer.
  • the ratio of the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate was 6/87/7.
  • the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
  • Example 30 A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 16.7 g of acrylonitrile, 328.6 g of 2-methoxyethyl acrylate, and 20.1 g of glycidyl methacrylate.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 67.7% by weight, and the acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer
  • the ratio of the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate was 4/90/6.
  • the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 6.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile polymer content of 15.2% by weight.
  • the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 6.
  • the Mooney viscosity of the blend is high and has problems with moldability.
  • Comparative Example 3 A modified halogenated polyolefin composition was obtained in the same manner as in Comparative Example 1 except that the graft reaction was changed to 100 g of chlorosulfonated polyethylene, 106.1 g of acrylonitrile, and 5.9 g of radical initiator.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 56.9% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 32/68.
  • the obtained modified halogenated polyolefin composition had a low viscosity and was difficult to knead for physical property evaluation, so physical property evaluation could not be performed.
  • the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 55.8% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 30/70. Although kneading was carried out with the formulation of Formula 4 and Formula 5, the physical property evaluation was difficult because the crosslinking reaction did not proceed.

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Abstract

Provided is a vulcanized composition formed by vulcanizing a modified halogenated polyolefin composition in which oil resistance has been greatly improved while the superior thermal resistance possessed by halogenated polyolefins has been maintained. Provided is a vulcanized composition formed by vulcanizing a modified halogenated polyolefin composition containing a graft copolymer in which a copolymer containing acrylonitryl and an acrylic compound is bound to a halogenated polyolefin, and a copolymer containing acrylonitryl and an acrylic compound.

Description

変性ハロゲン化ポリオレフィン組成物の加硫組成物Vulcanized composition of modified halogenated polyolefin composition
　本発明は、変性ハロゲン化ポリオレフィン組成物の加硫組成物に関するものであり、より詳しくは、ハロゲン化ポリオレフィンにアクリロニトリルとアクリル系化合物の共重合体が結合したグラフト共重合体及びハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル化合物の共重合体を含有する組成物の加硫組成物に関するものである。 The present invention relates to a vulcanized composition of a modified halogenated polyolefin composition. More specifically, the present invention relates to a graft copolymer in which a copolymer of acrylonitrile and an acrylic compound is bonded to a halogenated polyolefin, and a bond to a halogenated polyolefin. The present invention relates to a vulcanized composition of a composition containing a copolymer of acrylonitrile and an acrylic compound.
　また、本発明は、グラフト共重合体及びこれを含有する変性ハロゲン化ポリオレフィン組成物に関するものであり、より詳しくは、ハロゲン化ポリオレフィンに、アクリロニトリル、エポキシ基含有化合物及びアクリル系化合物を含有する不飽和単量体の共重合体が結合したグラフト共重合体並びに該グラフト共重合体及びハロゲン化ポリオレフィンに結合していないエポキシ基含有共重合体を含有する変性ハロゲン化ポリオレフィン組成物に関するものである。 The present invention also relates to a graft copolymer and a modified halogenated polyolefin composition containing the same. More specifically, the halogenated polyolefin contains an unsaturated compound containing acrylonitrile, an epoxy group-containing compound and an acrylic compound. The present invention relates to a modified halogenated polyolefin composition containing a graft copolymer to which a copolymer of monomers is bonded and an epoxy group-containing copolymer not bonded to the graft copolymer and the halogenated polyolefin.
　ハロゲン化ポリオレフィンは、クロロスルホン化ポリエチレンや塩素化ポリエチレン等の総称であり、優れた耐熱性、耐候性、耐オゾン性、耐薬品性及び明色性を有することから、各種ホースやホースのカバー材、電線被覆材、パッキン、ガスケット、ロール及びエスカレーターの手摺等の各種用途に使用されている。また、クロロスルホン化ポリエチレンや塩素化ポリエチレン等は塩素基を含有することから、天然ゴム、スチレン・ブタジエンゴム及びエチレン・プロピレン系ゴム等の汎用ゴムと比べて耐油性が良好であり、耐油性が要求されるホースやチューブ等にも多く使用されている。 Halogenated polyolefin is a general term for chlorosulfonated polyethylene, chlorinated polyethylene, etc., and has excellent heat resistance, weather resistance, ozone resistance, chemical resistance and light color, so various hoses and hose cover materials , Wire covering materials, packing, gaskets, rolls and escalator handrails. In addition, since chlorosulfonated polyethylene and chlorinated polyethylene contain chlorine groups, they have better oil resistance than natural rubber, styrene / butadiene rubber, and general-purpose rubber such as ethylene / propylene rubber. It is often used for required hoses and tubes.
　ハロゲン化ポリオレフィンの耐油性を向上する方法としては、ハロゲン量を増大させることが知られているが、この方法で耐油性を向上した場合、得られるハロゲン化ポリオレフィンのガラス転移温度が高くなり、室温付近での硬さが増大し、ゴム材料としての特性を失ってしまう問題が生じる。そのため、各種ホース用途分野に於いてはハロゲン量増大による耐油性の向上には限界があり、高度な耐油性が要求される用途に対しては好ましい方法とは言えない。 As a method for improving the oil resistance of the halogenated polyolefin, it is known to increase the halogen content. However, when the oil resistance is improved by this method, the glass transition temperature of the obtained halogenated polyolefin is increased, and the room temperature is increased. There is a problem that the hardness in the vicinity increases and the characteristics as a rubber material are lost. Therefore, in various hose application fields, there is a limit to improvement in oil resistance by increasing the halogen content, and it cannot be said that it is a preferable method for applications that require high oil resistance.
　自動車向けの燃料系ホースや、建設機械用の特殊な油圧ホース等の高度な耐油性が要求される用途に於いては、ハロゲン化ポリオレフィン単層での適用は困難であり、燃料等が直接接触する内層部分には、耐油性が特に優れたアクリロニトリル・ブタジエンゴム、水素添加アクリロニトリル・ブタジエンゴム、アクリルゴム、或いはフッ素系材料が使用されており、多層構造とせざるを得ない状況が生じている（例えば特許文献１～６参照。）。 In applications where high oil resistance is required, such as fuel hoses for automobiles and special hydraulic hoses for construction machinery, it is difficult to apply a single layer of halogenated polyolefin. The inner layer portion is made of acrylonitrile / butadiene rubber, hydrogenated acrylonitrile / butadiene rubber, acrylic rubber, or fluorine-based material with particularly excellent oil resistance, resulting in a situation where a multilayer structure must be formed ( For example, see Patent Documents 1 to 6.)
　しかし、昨今の自動車では、エンジンルームの省スペース化やターボ化によってエンジンルーム内の温度が上昇しており、内層材料としてのアクリロニトリル・ブタジエンゴムの耐熱性では限界を超える場合が生じている。このような場合には、アクリロニトリル・ブタジエンゴムより耐熱性に優れた水素添加アクリロニトリル・ブタジエンゴムやアクリルゴム、或いはフッ素系材料が使用されることとなるが、これらの材料はアクリロニトリル・ブタジエンゴムに比べて高価格であり、ホース製品の材料コストを大幅に増大させることとなるため、比較的低価格で、耐油性と耐熱性のバランスに優れたゴム材料が望まれている。 However, in recent automobiles, the temperature in the engine room has risen due to space saving and turbo conversion of the engine room, and the heat resistance of acrylonitrile butadiene rubber as the inner layer material may exceed the limit. In such a case, hydrogenated acrylonitrile / butadiene rubber, acrylic rubber, or fluorine-based material, which has better heat resistance than acrylonitrile / butadiene rubber, will be used, but these materials are compared to acrylonitrile / butadiene rubber. Therefore, a rubber material having a relatively low price and excellent balance between oil resistance and heat resistance is desired.
日本国特開平５－１９３０５３号公報Japanese Patent Laid-Open No. 5-193053 日本国特開平７－２４９６１号公報Japanese Unexamined Patent Publication No. 7-24961 日本国特開２００１－２０６９８７号公報Japanese Unexamined Patent Publication No. 2001-206987 日本国特開２００２－１０３４１２号公報Japanese Laid-Open Patent Publication No. 2002-10312 日本国特開２００７－２６９８６２号公報Japanese Laid-Open Patent Publication No. 2007-269862 日本国特開２０１４－２３１１５９号公報Japanese Unexamined Patent Publication No. 2014-231159
　本発明は、上記の課題に鑑みてなされたものであり、その目的はハロゲン化ポリオレフィンの持つ優れた耐熱性を維持したままに、耐油性が大きく改良された変性ハロゲン化ポリオレフィン組成物の加硫組成物を提供するものであり、また、グラフト共重合体及びこれを含有する変性ハロゲン化ポリオレフィン組成物を提供するものである。 The present invention has been made in view of the above problems, and its purpose is to vulcanize a modified halogenated polyolefin composition with greatly improved oil resistance while maintaining the excellent heat resistance of the halogenated polyolefin. The present invention provides a composition, and also provides a graft copolymer and a modified halogenated polyolefin composition containing the same.
　本発明者は、上記課題を解決するために鋭意検討した結果、本発明を完成するに至ったものである。 The inventor has intensively studied to solve the above problems, and as a result, has completed the present invention.
　すなわち、本発明は以下の［１］乃至［１５］に存する。
［１］　ハロゲン化ポリオレフィンにアクリロニトリルとアクリル系化合物の共重合体が結合したグラフト共重合体と、ハロゲン化ポリオレフィンに結合していないアクリロニトリルとアクリル系化合物の共重合体を含有する変性ハロゲン化ポリオレフィン組成物を加硫して成る加硫組成物。
［２］　ハロゲン化ポリオレフィンがクロロスルホン化ポリオレフィンであることを特徴とする［１］記載の加硫組成物。
［３］　グラフト共重合体中のアクリロニトリルとアクリル系化合物の共重合体と、ハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル系化合物の共重合体の重量比率が３／９７～７０／３０の範囲であることを特徴とする［１］又は［２］に記載の加硫組成物。
［４］　変性ハロゲン化ポリオレフィン組成物中のハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル系化合物の共重合体及びグラフト共重合体中のアクリロニトリルとアクリル系化合物の共重合体の合計の含有率が２０重量％から７５重量％の範囲であることを特徴とする［１］乃至［３］のいずれかに記載の加硫組成物。
［５］　ハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル系化合物の共重合体及びグラフト共重合体に含まれるアクリロニトリルとアクリル系化合物由来の成分の重量比率が、３／９７～７０／３０の範囲であることを特徴とする［１］乃至［４］のいずれかに記載の加硫組成物。
［６］　アクリル系化合物がアクリル酸２－メトキシエチルであることを特徴とする［１］乃至［５］のいずれかに記載の加硫組成物。
［７］　ハロゲン化ポリオレフィンに、アクリロニトリル、エポキシ基含有化合物及びアクリル系化合物を含有する不飽和単量体の共重合体（以下、エポキシ基含有共重合体という）が結合したグラフト共重合体。
［８］　［７］記載のグラフト共重合体及びハロゲン化ポリオレフィンに結合していないエポキシ基含有共重合体を含有することを特徴とする変性ハロゲン化ポリオレフィン組成物。
［９］　変性ハロゲン化ポリオレフィン組成物中のグラフト共重合体中のエポキシ基含有共重合体と、ハロゲン化ポリオレフィンと結合していないエポキシ基含有共重合体の合計の含有率が２０重量％から７５重量％の範囲であり、そのエポキシ基含有共重合体中のアクリロニトリルとアクリル系化合物由来の成分の重量比率が３／９７～７０／３０の範囲であることを特徴とする［８］に記載の変性ハロゲン化ポリオレフィン組成物。
［１０］　エポキシ基含有化合物由来の成分の含有率が１重量％から１２重量％の範囲であることを特徴とする［８］又は［９］に記載の変性ハロゲン化ポリオレフィン組成物。
［１１］　グラフト共重合体中のエポキシ基含有共重合体と、ハロゲン化ポリオレフィンに結合していないエポキシ基含有共重合体の重量比率が３／９７から７０／３０の範囲であることを特徴とする［８］又は［１０］に記載の変性ハロゲン化ポリオレフィン組成物。
［１２］　ハロゲン化ポリオレフィンがクロロスルホン化ポリエチレンであることを特徴とする［８］乃至［１１］のいずれかに記載の変性ハロゲン化ポリオレフィン組成物。
［１３］　アクリル系化合物がアクリル酸２－メトキシエチルであることを特徴とする［８］乃至［１２］のいずれかに記載の変性ハロゲン化ポリオレフィン組成物。
［１４］　エポキシ基含有化合物がアクリル酸グリシジル及び／又はメタクリル酸グリシジルであることを特徴とする［８］乃至［１３］のいずれかに記載の変性ハロゲン化ポリオレフィン組成物。
［１５］　特徴とする［８］乃至［１４］のいずれかに記載の変性ハロゲン化ポリオレフィン組成物を加硫して成る加硫組成物。 That is, the present invention resides in the following [1] to [15].
[1] A modified halogenated polyolefin composition containing a graft copolymer in which a copolymer of acrylonitrile and an acrylic compound is bonded to a halogenated polyolefin, and a copolymer of acrylonitrile and an acrylic compound not bonded to the halogenated polyolefin A vulcanized composition obtained by vulcanizing a product.
[2] The vulcanized composition according to [1], wherein the halogenated polyolefin is a chlorosulfonated polyolefin.
[3] The weight ratio of the copolymer of acrylonitrile and acrylic compound in the graft copolymer to the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin is in the range of 3/97 to 70/30. The vulcanized composition according to [1] or [2], wherein
[4] The total content of the copolymer of acrylonitrile and the acrylic compound not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition and the copolymer of the acrylonitrile and the acrylic compound in the graft copolymer is The vulcanized composition according to any one of [1] to [3], which is in the range of 20% to 75% by weight.
[5] The weight ratio of the components derived from the acrylonitrile and the acrylic compound contained in the copolymer of acrylonitrile and the acrylic compound not bonded to the halogenated polyolefin and the graft copolymer is in the range of 3/97 to 70/30. The vulcanized composition according to any one of [1] to [4], wherein
[6] The vulcanized composition according to any one of [1] to [5], wherein the acrylic compound is 2-methoxyethyl acrylate.
[7] A graft copolymer in which a copolymer of an unsaturated monomer containing acrylonitrile, an epoxy group-containing compound, and an acrylic compound (hereinafter referred to as an epoxy group-containing copolymer) is bonded to a halogenated polyolefin.
[8] A modified halogenated polyolefin composition comprising the graft copolymer according to [7] and an epoxy group-containing copolymer which is not bonded to the halogenated polyolefin.
[9] The total content of the epoxy group-containing copolymer in the graft copolymer in the modified halogenated polyolefin composition and the epoxy group-containing copolymer not bonded to the halogenated polyolefin is from 20% by weight to 75%. [8], wherein the weight ratio of the component derived from acrylonitrile and the acrylic compound in the epoxy group-containing copolymer is in the range of 3/97 to 70/30. Modified halogenated polyolefin composition.
[10] The modified halogenated polyolefin composition according to [8] or [9], wherein the content of the component derived from the epoxy group-containing compound is in the range of 1 to 12% by weight.
[11] The weight ratio of the epoxy group-containing copolymer in the graft copolymer to the epoxy group-containing copolymer not bonded to the halogenated polyolefin is in the range of 3/97 to 70/30. The modified halogenated polyolefin composition according to [8] or [10].
[12] The modified halogenated polyolefin composition according to any one of [8] to [11], wherein the halogenated polyolefin is chlorosulfonated polyethylene.
[13] The modified halogenated polyolefin composition according to any one of [8] to [12], wherein the acrylic compound is 2-methoxyethyl acrylate.
[14] The modified halogenated polyolefin composition according to any one of [8] to [13], wherein the epoxy group-containing compound is glycidyl acrylate and / or glycidyl methacrylate.
[15] A vulcanized composition obtained by vulcanizing the modified halogenated polyolefin composition according to any one of [8] to [14].
　以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
　本発明の第１の実施形態は、ハロゲン化ポリオレフィンにアクリロニトリルとアクリル系化合物の共重合体が結合したグラフト共重合体、及びハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル系化合物の共重合体を含有する変性ハロゲン化ポリオレフィン組成物の加硫組成物である。 In the first embodiment of the present invention, a graft copolymer in which a copolymer of acrylonitrile and an acrylic compound is bonded to a halogenated polyolefin, and a copolymer of acrylonitrile and an acrylic compound that are not bonded to the halogenated polyolefin are used. It is a vulcanized composition of the modified halogenated polyolefin composition contained.
　また、本発明の第２の実施形態は、ハロゲン化ポリオレフィンに、エポキシ基含共重合体が結合したグラフト共重合体、並びに当該グラフト共重合体及びハロゲン化ポリオレフィンに結合していないエポキシ基含有共重合体を含有する変性ハロゲン化ポリオレフィン組成物である。また、この変性ハロゲン化ポリオレフィン組成物の加硫組成物である。 The second embodiment of the present invention also includes a graft copolymer in which an epoxy group-containing copolymer is bonded to a halogenated polyolefin, and an epoxy group-containing copolymer that is not bonded to the graft copolymer and the halogenated polyolefin. A modified halogenated polyolefin composition containing a polymer. Moreover, it is a vulcanized composition of this modified halogenated polyolefin composition.
　本発明の第１の実施形態で用いる変性ハロゲン化ポリオレフィン組成物は、ハロゲン化ポリオレフィンにアクリロニトリルとアクリル系化合物を共グラフトすることにより得ることができる。 The modified halogenated polyolefin composition used in the first embodiment of the present invention can be obtained by co-grafting acrylonitrile and an acrylic compound to the halogenated polyolefin.
　また、本発明の第２の実施形態の変性ハロゲン化ポリオレフィン組成物は、ハロゲン化ポリオレフィンに、アクリロニトリル、エポキシ基含有化合物及びアクリル系化合物を含有する不飽和単量体を共グラフトすることにより得ることができる。また、グラフト共重合体は、得られた変性ハロゲン化ポリオレフィン組成物から分別により得ることができる。 Further, the modified halogenated polyolefin composition of the second embodiment of the present invention is obtained by co-grafting an unsaturated monomer containing acrylonitrile, an epoxy group-containing compound and an acrylic compound to the halogenated polyolefin. Can do. The graft copolymer can be obtained by fractionation from the resulting modified halogenated polyolefin composition.
　ハロゲン化ポリオレフィンとしては、原料であるポリオレフィンを塩素化、または塩素化及びクロロスルホン化して得られるハロゲン化ポリオレフィンが例示できる。また、必要に応じて臭素やフッ素を含有したハロゲン化ポリオレフィンも使用可能である。原料であるポリオレフィンには、例えば、ポリエチレン、ポリプロピレン等が挙げられ、ポリエチレンとしては、高密度ポリエチレン（ＨＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、線状低密度ポリエチレン（ＬＬＤＰＥ）、超低密度ポリエチレン（ＶＬＤＰＥ）、フッ素含有ポリエチレン等が挙げられる。これらを単独または併用して用いることができるが、良好な物理特性と耐油性を両立させるためには、高密度ポリエチレン（ＨＤＰＥ）が好ましい。 Examples of the halogenated polyolefin include halogenated polyolefins obtained by chlorinating, or chlorinating and chlorosulfonating a raw material polyolefin. In addition, halogenated polyolefins containing bromine or fluorine can be used as necessary. Examples of the raw material polyolefin include polyethylene, polypropylene, and the like. As the polyethylene, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE). ), Fluorine-containing polyethylene and the like. These can be used alone or in combination, but high-density polyethylene (HDPE) is preferred in order to achieve both good physical properties and oil resistance.
　原料であるポリオレフィンを塩素化、または塩素化及びクロロスルホン化する反応を行う際、溶剤としては、ベンゼン、トルエン、キシレン等の芳香族系有機溶剤や、モノクロロベンゼン、ジクロロベンゼン、フロロベンゼン、ジクロロジフロロベンゼン、四塩化炭素、クロロホルム、１，１－ジクロロエタン、１，２－ジクロロエタン、１，１，１－トリクロロエタン、１，１，２－トリクロロエタン、テトラクロロエタン、トリクロロフロロエタン等の塩素系有機溶剤が挙げられ、これらを単独または２種類以上を併用して用いることができるが、塩素化反応に対し不活性な塩素系有機溶剤のみの使用が好ましい。 When conducting the reaction of chlorinating the raw material polyolefin, or chlorinating and chlorosulfonating, the solvents include aromatic organic solvents such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodi Chlorinated organic solvents such as fluorobenzene, carbon tetrachloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetrachloroethane, trichlorofluoroethane, etc. These may be used alone or in combination of two or more, but it is preferable to use only a chlorinated organic solvent that is inert to the chlorination reaction.
　ポリオレフィンの塩素化、または塩素化及びクロロスルホン化を行う反応工程はラジカル発生剤を触媒として、塩素、または塩素と亜硫酸ガス、塩素と塩化スルフリル、塩化スルフリル単独、塩素と亜硫酸ガスと塩化スルフリルを、溶剤に溶解または懸濁したポリオレフィンと反応させる。また、臭素化のために塩素の一部又は全部を臭素に変更することも可能である。クロロスルホン化反応を行う場合には必要に応じて助触媒としてピリジン、キノリン等のアミノ化合物が添加させる。反応温度は塩素化反応、または塩素化反応及びクロロスルホン化反応が進行する範囲であれば特に限定するものではなく、例えば４０～１５０℃であり、適度な塩素化反応、または塩素化反応及びクロロスルホン化反応が進行するためには好ましくは６０～１３０℃の範囲である。反応圧力は塩素化反応、または塩素化反応及びクロロスルホン化反応が進行する範囲であれば特に限定するものではなく、例えば、０～１．０ＭＰａであり、適度な塩素化反応、または塩素化反応及びクロロスルホン化反応が進行するためには好ましくは０～０．７ＭＰａである。 The reaction step of chlorination of polyolefin, or chlorination and chlorosulfonation, using a radical generator as a catalyst, chlorine, chlorine and sulfurous acid gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine, sulfurous acid gas and sulfuryl chloride, React with polyolefin dissolved or suspended in solvent. It is also possible to change some or all of the chlorine to bromine for bromination. When the chlorosulfonation reaction is performed, an amino compound such as pyridine or quinoline is added as a co-catalyst as necessary. The reaction temperature is not particularly limited as long as the chlorination reaction, or the chlorination reaction and the chlorosulfonation reaction proceed, and is, for example, 40 to 150 ° C. In order for the sulfonation reaction to proceed, the temperature is preferably in the range of 60 to 130 ° C. The reaction pressure is not particularly limited as long as the chlorination reaction, or the chlorination reaction and the chlorosulfonation reaction proceed, and is, for example, 0 to 1.0 MPa, and is an appropriate chlorination reaction or chlorination reaction. For the chlorosulfonation reaction to proceed, the pressure is preferably 0 to 0.7 MPa.
　原料であるポリオレフィンを塩素化、または塩素化及びクロロスルホン化する反応を行う際に使用するラジカル発生剤は、塩素化反応、または塩素化反応及びクロロスルホン化反応が進行するものであれば特に限定するものではなく、例えば、アゾ系化合物、有機過酸化物等が挙げられる。アゾ系化合物としては、例えば、α，α’－アゾビスイソブチロニトリル、アゾビスシクロヘキサンカルボニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）等が挙げられ、有機過酸化物としては、例えば、過酸化ベンゾイル、過酸化アセチル、過酸化ｔ－ブチル、過安息香酸ｔ－ブチル等が挙げられる。取り扱い上安定性が高いため、好ましくはアゾ系化合物であり、適度な塩素化反応、または塩素化反応及びクロロスルホン化反応が進行するためには、特に好ましくはα，α’－アゾビスイソブチロニトリルである。 The radical generator used in the reaction of chlorinating or chlorinating and chlorosulfonating the polyolefin as a raw material is particularly limited as long as the chlorination reaction or the chlorination reaction and chlorosulfonation reaction proceed. For example, an azo compound, an organic peroxide, etc. are mentioned. Examples of the azo compound include α, α′-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and organic peroxides. Examples thereof include benzoyl peroxide, acetyl peroxide, t-butyl peroxide, t-butyl perbenzoate and the like. An azo compound is preferred because of its high handling stability, and α, α'-azobisisobutyrate is particularly preferred for the appropriate chlorination reaction or chlorination reaction and chlorosulfonation reaction to proceed. Ronitrile.
　塩素化、または塩素化及びクロロスルホン化を行う反応工程における、塩素、または塩素と亜硫酸ガス、塩素と塩化スルフリル、塩化スルフリル単独、塩素と亜硫酸ガスと塩化スルフリルとラジカル発生剤を添加する際の添加方法は、塩素化反応、または塩素化及びクロロスルホン化反応が進行すれば特に限定されないが、明色性のためにはラジカル発生剤を加える前に、塩素、または塩素と亜硫酸ガス、塩素と塩化スルフリル、塩化スルフリル単独、塩素と亜硫酸ガスと塩化スルフリル等を先に添加するのが好ましい。反応工程終了時にはラジカル発生剤の添加停止後、塩素、または塩素と亜硫酸ガス、塩素と塩化スルフリル、塩化スルフリル単独、塩素と亜硫酸ガスと塩化スルフリル等の添加を停止するのが好ましく、これらの添加方法は単独または併用しても良い。 Addition when adding chlorine, or chlorine and sulfurous acid gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine, sulfurous acid gas, sulfuryl chloride, and radical generators in the reaction process of chlorination or chlorination and chlorosulfonation The method is not particularly limited as long as the chlorination reaction, or the chlorination and chlorosulfonation reactions proceed, but for light color, before adding the radical generator, chlorine, chlorine and sulfurous acid gas, chlorine and chloride. It is preferable to add sulfuryl, sulfuryl chloride alone, chlorine, sulfurous acid gas and sulfuryl chloride first. At the end of the reaction process, after the addition of the radical generator is stopped, it is preferable to stop adding chlorine, chlorine and sulfurous acid gas, chlorine and sulfuryl chloride, sulfuryl chloride alone, chlorine, sulfurous acid gas and sulfuryl chloride, etc. May be used alone or in combination.
　変性ハロゲン化ポリオレフィン組成物の製造に用いられるハロゲン化ポリオレフィンの塩素量は特に制限はないが、耐油性や機械特性を考慮し、１５．０～４５．０重量％の範囲が好ましく、更に低温性を考慮した場合、２０．０重量％～４０．０重量％の範囲であることが好ましい。ハロゲン化ポリオレフィンが、ポリオレフィンを塩素化及びクロロスルホン化によって得られるクロロスルホン化ポリエチレンである場合の硫黄量は特に制限はないが、０．１～３．０重量％の範囲が好ましい。 The amount of chlorine in the halogenated polyolefin used in the production of the modified halogenated polyolefin composition is not particularly limited, but it is preferably in the range of 15.0 to 45.0% by weight in consideration of oil resistance and mechanical properties, and further low temperature properties. In view of the above, it is preferably in the range of 20.0 wt% to 40.0 wt%. The amount of sulfur when the halogenated polyolefin is chlorosulfonated polyethylene obtained by chlorinating and chlorosulfonated polyolefin is not particularly limited, but is preferably in the range of 0.1 to 3.0% by weight.
　ハロゲン化ポリオレフィンに共グラフトするアクリル系化合物は、アクリロイル基、又はメタクリロイル基を含有する化合物であれば制限されず、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ｎ－ペンチル、（メタ）アクリル酸ｎ－デシル、（メタ）アクリル酸ｎ－ドデシル、（メタ）アクリル酸ｎ－オクタデシル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－エトキシエチル等の（メタ）アクリル酸エステル、（メタ）アクリル酸２，２，２－トリフルオロエチル等のフッ素含有（メタ）アクリル酸系化合物等を例示することができ、これらは単独あるいは２種類以上併用しても良いが、良好な物理特性及び耐油性を維持するためには、アクリル酸メチル、アクリル酸エチル、アクリル酸２－メトキシエチル、アクリル酸ｎ－ブチルをそれぞれ単独あるいは併用することが望ましい。 The acrylic compound co-grafted to the halogenated polyolefin is not limited as long as it is a compound containing an acryloyl group or a methacryloyl group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n-butyl, 2-ethylhexyl (meth) acrylate, n-pentyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, ( Fluorine-containing (meth) acrylic acid such as (meth) acrylic acid ester such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and 2,2,2-trifluoroethyl (meth) acrylic acid Examples of these compounds may be used, and these may be used alone or in combination of two or more, To maintain the properties and oil resistance, methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, it is desirable to either alone or in combination of acrylic acid n- butyl.
　エポキシ基含有化合物としては、エポキシ基を含有する化合物であれば制限されず、例えば、アクリル酸グリシジル、４－ヒドロキシブチルアクリル酸グリシジルエーテル、メタクリル酸グリシジル、アリルグリシジルエーテル等を例示することができ、これらは単独あるいは２種類以上併用しても良いが、良好な物理特性及び耐油性を維持するためには、メタクリル酸グリシジルを使用することが望ましい。 The epoxy group-containing compound is not limited as long as it contains an epoxy group, and examples thereof include glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, glycidyl methacrylate, allyl glycidyl ether, and the like. These may be used alone or in combination of two or more. However, in order to maintain good physical properties and oil resistance, it is desirable to use glycidyl methacrylate.
　また、アクリロニトリル、アクリル系化合物、エポキシ基含有化合物以外に、変性ハロゲン化ポリオレフィンとしての特性を損なわない範囲で、その他の単量体をグラフト重合していても良い。例えばメチルビニルケトン等のアルキルビニルケトン化合物、ビニルエチルエーテル等のアルキルビニルエーテル化合物、アリルメチルエーテル等のアリルエーテル化合物、スチレン、α－メチルスチレン、クロロスチレン、ビニルトルエン、ビニルナフタレン等のビニル芳香族化合物、メタクリロニトリル等のビニルニトリル化合物、酢酸ビニル、クロロ酢酸ビニル、アクリルアミド、プロピレン、ブタジエン、イソプレン、ペンタジエン、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、プロピオン酸ビニル、無水マレイン酸、無水シトラコン酸、無水イタコン酸等を例示することができる。これらの上記単量体としては、グラフト重合に用いる総不飽和単量体中の２０重量％以下の割合で加えることが好ましい。 In addition to acrylonitrile, acrylic compounds, and epoxy group-containing compounds, other monomers may be graft-polymerized as long as the properties of the modified halogenated polyolefin are not impaired. For example, alkyl vinyl ketone compounds such as methyl vinyl ketone, alkyl vinyl ether compounds such as vinyl ethyl ether, allyl ether compounds such as allyl methyl ether, vinyl aromatic compounds such as styrene, α-methyl styrene, chlorostyrene, vinyl toluene, vinyl naphthalene, etc. , Vinyl nitrile compounds such as methacrylonitrile, vinyl acetate, vinyl chloroacetate, acrylamide, propylene, butadiene, isoprene, pentadiene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl propionate, maleic anhydride, anhydrous Examples thereof include citraconic acid and itaconic anhydride. These monomers are preferably added at a ratio of 20% by weight or less in the total unsaturated monomers used for graft polymerization.
　本発明の第１の実施形態の特徴は、アクリロニトリル及びアクリル系化合物を共グラフト反応によりハロゲン化ポリオレフィンに導入させることで、物理特性と耐油性に優れる変性ハロゲン化ポリオレフィン組成物を得ることができる点である。 A feature of the first embodiment of the present invention is that a modified halogenated polyolefin composition excellent in physical properties and oil resistance can be obtained by introducing acrylonitrile and an acrylic compound into a halogenated polyolefin by a co-graft reaction. It is.
　また、本発明の第２の実施形態の特徴は、アクリロニトリル、エポキシ基含有化合物及びアクリル系化合物を含有する不飽和単量体を共グラフト反応によりハロゲン化ポリオレフィンに導入させることで、物理特性と耐油性に優れるグラフト重合体および変性ハロゲン化ポリオレフィン組成物を得ることができる点である。 In addition, the second embodiment of the present invention is characterized in that an unsaturated monomer containing acrylonitrile, an epoxy group-containing compound and an acrylic compound is introduced into a halogenated polyolefin by a co-graft reaction, so that physical properties and oil resistance are improved. It is the point which can obtain the graft polymer and modified | denatured halogenated polyolefin composition which are excellent in property.
　本発明で用いる変性ハロゲン化ポリオレフィン組成物には、アクリロニトリルとアクリル系化合物に由来するものとして、グラフト共重合体中のハロゲン化ポリオレフィンと結合したアクリロニトリルとアクリル系化合物の共重合体及びハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル系化合物の共重合体が存在する。グラフト共重合体中のアクリロニトリル及びアクリル系化合物の共重合体と、ハロゲン化ポリオレフィンと結合していないアクリロニトリル及びアクリル系化合物の共重合体の重量比率（グラフト選択率）については特に制限はないが、得られる変性ハロゲン化ポリオレフィン組成物の力学物性と耐油性を両立させるためには、その重量比率が３／９７～７０／３０の範囲であることが好ましい。 The modified halogenated polyolefin composition used in the present invention is derived from acrylonitrile and an acrylic compound, and includes a copolymer of acrylonitrile and an acrylic compound bonded to the halogenated polyolefin in the graft copolymer, and a halogenated polyolefin; There are unbound copolymers of acrylonitrile and acrylic compounds. There is no particular limitation on the weight ratio (graft selectivity) of the copolymer of acrylonitrile and acrylic compound in the graft copolymer and the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin, In order to achieve both the mechanical properties and oil resistance of the resulting modified halogenated polyolefin composition, the weight ratio is preferably in the range of 3/97 to 70/30.
　また、アクリロニトリル、エポキシ基含有化合物及びアクリル系化合物に由来するものとして、グラフト共重合体中のハロゲン化ポリオレフィンと結合したエポキシ基含有共重合体及びハロゲン化ポリオレフィンと結合していないエポキシ基含有共重合体が存在する。グラフト共重合体中のエポキシ基含有共重合体と、ハロゲン化ポリオレフィンと結合していないエポキシ基含有共重合体の重量比率（グラフト選択率）については特に制限はないが、得られる変性ハロゲン化ポリオレフィン組成物の力学物性と耐油性を両立させるためには、その重量比率が３／９７～７０／３０の範囲であることが好ましい。 In addition, as derived from acrylonitrile, an epoxy group-containing compound and an acrylic compound, an epoxy group-containing copolymer bonded to the halogenated polyolefin in the graft copolymer and an epoxy group-containing copolymer not bonded to the halogenated polyolefin. Coalescence exists. The weight ratio (graft selectivity) between the epoxy group-containing copolymer in the graft copolymer and the epoxy group-containing copolymer that is not bonded to the halogenated polyolefin is not particularly limited, but the resulting modified halogenated polyolefin In order to achieve both the mechanical properties and oil resistance of the composition, the weight ratio is preferably in the range of 3/97 to 70/30.
　本発明の第１の実施形態で用いる変性ハロゲン化ポリオレフィン組成物中の、ハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル系化合物の共重合体及びグラフト共重合体中のアクリロニトリルとアクリル系化合物の共重合体の合計の含有率は、ハロゲン化ポリオレフィン組成物としての特性を維持しつつ、優れた物理特性と耐油性を両立させるためには２０重量％から７５重量％の範囲であることが好ましい。さらに好ましくは、４０重量％から６５重量％の範囲である。残りの成分は、グラフト共重合体中のハロゲン化ポリオレフィンに由来する成分である。 In the modified halogenated polyolefin composition used in the first embodiment of the present invention, a copolymer of acrylonitrile and an acrylic compound that is not bonded to a halogenated polyolefin and a copolymer of acrylonitrile and an acrylic compound in a graft copolymer are used. The total content of the polymer is preferably in the range of 20% by weight to 75% by weight in order to achieve both excellent physical properties and oil resistance while maintaining the properties as the halogenated polyolefin composition. More preferably, it is in the range of 40% to 65% by weight. The remaining components are components derived from the halogenated polyolefin in the graft copolymer.
　また、本発明の第２の実施形態のハロゲン化ポリオレフィンと結合していないエポキシ基含有共重合体及びグラフト共重合体中のエポキシ基含有共重合体の合計の含有率は、ハロゲン化ポリオレフィン組成物としての特性を維持しつつ、優れた物理特性と耐油性を両立させるためには２０重量％から７５重量％の範囲であることが好ましい。さらに好ましくは、４０重量％から６５重量％の範囲である。残りの成分は、グラフト共重合体中のハロゲン化ポリオレフィンに由来する成分である。 Further, the total content of the epoxy group-containing copolymer in the epoxy group-containing copolymer and graft copolymer not bonded to the halogenated polyolefin of the second embodiment of the present invention is the halogenated polyolefin composition. In order to achieve both excellent physical properties and oil resistance while maintaining the above properties, it is preferably in the range of 20 wt% to 75 wt%. More preferably, it is in the range of 40% to 65% by weight. The remaining components are components derived from the halogenated polyolefin in the graft copolymer.
　本発明の第１の実施形態で用いる変性ハロゲン化ポリオレフィン組成物中のハロゲン化ポリオレフィンと結合していないアクリロニトリル及びアクリル系化合物の共重合体及びグラフト共重合体中のアクリロニトリルとアクリル系化合物の共重合体に含まれる、アクリロニトリルとアクリル系化合物由来の成分の重合比率は３／９７～７０／３０の範囲であることが好ましく、更に１０／９０～７０／３０の範囲、１５／８５～６０／４０の範囲であることが好ましい。当該の共重合体中におけるアクリロニトリルの重量比率が３％以上の場合、得られる変性ハロゲン化ポリオレフィン加硫物の引張強さが維持される。一方、アクリロニトリルの重量比率が７０％以下の場合、得られる変性ハロゲン化ポリオレフィン組成物の粘度が上昇せず、成形加工性が良好である。また、変性ハロゲン化ポリオレフィンの耐寒性改善の観点からは、アクリロニトリルの重量比率は耐油性を損なわない範囲で低い方が好ましく、３／９７～５０／５０の範囲である。 Copolymer of acrylonitrile and acrylic compound not bonded to halogenated polyolefin in modified halogenated polyolefin composition used in the first embodiment of the present invention, and copolymer of acrylonitrile and acrylic compound in graft copolymer The polymerization ratio of components derived from acrylonitrile and the acrylic compound contained in the coalescence is preferably in the range of 3/97 to 70/30, more preferably in the range of 10/90 to 70/30, and 15/85 to 60/40. It is preferable to be in the range. When the weight ratio of acrylonitrile in the copolymer is 3% or more, the tensile strength of the resulting modified halogenated polyolefin vulcanizate is maintained. On the other hand, when the weight ratio of acrylonitrile is 70% or less, the viscosity of the resulting modified halogenated polyolefin composition does not increase and the moldability is good. From the viewpoint of improving the cold resistance of the modified halogenated polyolefin, the weight ratio of acrylonitrile is preferably as low as possible without impairing the oil resistance, and is in the range of 3/97 to 50/50.
　また、本発明の第２の実施形態の変性ハロゲン化ポリオレフィン組成物中のハロゲン化ポリオレフィンと結合していないエポキシ基含有共重合体及びグラフト共重合体中のエポキシ基含有共重合体に含まれるアクリロニトリルとアクリル系化合物由来の成分の重合比率は３／９７～７０／３０の範囲であることが好ましく、更に１０／９０～７０／３０の範囲、特に１５／８５～６０／４０の範囲であることが好ましい。当該の共重合体中におけるアクリロニトリルの重量比率が３％以上の場合、得られる変性ハロゲン化ポリオレフィン加硫物の引張強さが維持される。一方、アクリロニトリルの重量比率が７０％以下の場合、得られる変性ハロゲン化ポリオレフィン組成物の粘度が上昇せず、成形加工性が良好である。また、変性ハロゲン化ポリオレフィンの耐寒性改善の観点から、アクリロニトリルの重量比率は耐油性を損なわない範囲で低い方が好ましく、３／９７～５０／５０の範囲である。 In addition, the acrylonitrile contained in the epoxy group-containing copolymer in the graft copolymer and the epoxy group-containing copolymer not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition of the second embodiment of the present invention The polymerization ratio of the component derived from the acrylic compound is preferably in the range of 3/97 to 70/30, more preferably in the range of 10/90 to 70/30, particularly in the range of 15/85 to 60/40. Is preferred. When the weight ratio of acrylonitrile in the copolymer is 3% or more, the tensile strength of the resulting modified halogenated polyolefin vulcanizate is maintained. On the other hand, when the weight ratio of acrylonitrile is 70% or less, the viscosity of the resulting modified halogenated polyolefin composition does not increase and the moldability is good. From the viewpoint of improving the cold resistance of the modified halogenated polyolefin, the weight ratio of acrylonitrile is preferably as low as possible without impairing the oil resistance, and is in the range of 3/97 to 50/50.
　本発明の第２の実施形態の変性ハロゲン化ポリオレフィン組成物中のエポキシ基含有化合物由来成分の含有率は１重量％から１２重量％以下の範囲であることが好ましい。 The content of the epoxy group-containing compound-derived component in the modified halogenated polyolefin composition of the second embodiment of the present invention is preferably in the range of 1% by weight to 12% by weight.
　尚、エポキシ基含有化合物がエポキシ基含有アクリル系化合物である場合には、変性ハロゲン化ポリオレフィン組成物中のハロゲン化ポリオレフィンと結合していないエポキシ基含有共重合体及びグラフト共重合体中のエポキシ基含有共重合体に含まれるアクリロニトリルとアクリル系化合物由来の成分の重量比率が１０／９０～７０／３０となる範囲で、エポキシ基を含有しないアクリル系化合物を添加することが好ましい。 In the case where the epoxy group-containing compound is an epoxy group-containing acrylic compound, the epoxy group-containing copolymer not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition and the epoxy group in the graft copolymer It is preferable to add an acrylic compound that does not contain an epoxy group in such a range that the weight ratio of the component derived from acrylonitrile and the acrylic compound contained in the containing copolymer is 10/90 to 70/30.
　エポキシ基含有化合物は、当該の変性ハロゲン化ポリオレフィン組成物に於いて架橋点として作用するものであり、変性ハロゲン化ポリオレフィン組成物中のエポキシ基含有化合物の重量比率が１重量％以上であれば、十分な架橋構造を形成することでき、得られる変性ハロゲン化ポリオレフィン加硫物は耐油性、引張強さに優れる。 The epoxy group-containing compound acts as a crosslinking point in the modified halogenated polyolefin composition, and if the weight ratio of the epoxy group-containing compound in the modified halogenated polyolefin composition is 1% by weight or more, A sufficient crosslinked structure can be formed, and the resulting modified halogenated polyolefin vulcanizate is excellent in oil resistance and tensile strength.
　一方、変性ハロゲン化ポリオレフィン組成物中のエポキシ基含有化合物由来の成分の重量比率が１２重量％以下であれば、過度な架橋構造を形成することによる、得られる変性ハロゲン化ポリオレフィン加硫物の硬さが高くなることなく、破断伸びが低下する問題が発生しない。優れた耐油性と加硫物特性が要求される場合には、変性ハロゲン化ポリオレフィン組成物中のエポキシ基含有化合物の重量比率は２重量％から１０重量％以下の範囲が好ましい。 On the other hand, if the weight ratio of the component derived from the epoxy group-containing compound in the modified halogenated polyolefin composition is 12% by weight or less, the resulting modified halogenated polyolefin vulcanizate is hardened by forming an excessive cross-linked structure. The problem that the elongation at break is reduced does not occur without increasing the thickness. When excellent oil resistance and vulcanizate properties are required, the weight ratio of the epoxy group-containing compound in the modified halogenated polyolefin composition is preferably in the range of 2 to 10% by weight.
　本発明の第２の実施形態の変性ハロゲン化ポリオレフィン組成物中のハロゲン化ポリオレフィンと結合していないアクリロニトリル及びエポキシ基含有化合物及びアクリル系化合物を含有する共重合体には、ハロゲン化ポリオレフィンと結合したものとハロゲン化ポリオレフィンと結合していないものがある。ハロゲン化ポリオレフィンと結合したアクリロニトリル及びエポキシ基含有化合物及びアクリル系化合物を含有する共重合体と、ハロゲン化ポリオレフィンと結合していないアクリロニトリル及びエポキシ基含有化合物及びアクリル系化合物を含有する共重合体の重量比率（グラフト選択率）については特に制限はないが、得られる変性ハロゲン化ポリオレフィン組成物の力学物性と耐油性を両立させるためには、その重量比率が３／９７～７０／３０の範囲であることが好ましい。 In the modified halogenated polyolefin composition of the second embodiment of the present invention, a copolymer containing acrylonitrile, an epoxy group-containing compound and an acrylic compound that are not bonded to the halogenated polyolefin is bonded to the halogenated polyolefin. Some are not bonded to halogenated polyolefins. Weight of copolymer containing acrylonitrile and epoxy group-containing compound and acrylic compound bonded to halogenated polyolefin, and copolymer containing acrylonitrile, epoxy group-containing compound and acrylic compound not bonded to halogenated polyolefin The ratio (graft selectivity) is not particularly limited, but the weight ratio is in the range of 3/97 to 70/30 in order to achieve both the mechanical properties and oil resistance of the resulting modified halogenated polyolefin composition. It is preferable.
　本発明で用いる変性ハロゲン化ポリオレフィン組成物の製造法としては、本発明の変性ハロゲン化ポリオレフィン組成物が得られる方法であれば特に制限はない。例えば、ハロゲン化ポリオレフィンを溶剤に溶解、または押出し機などを用いて撹拌しながら、一括または連続でアクリロニトリル及びアクリル系化合物及びエポキシ基含有化合物を含有する不飽和単量体を添加して、ラジカル開始剤によりグラフト重合し、所定の重合転化率に達したところで、酸化防止剤を添加し、必要により溶剤または未反応の不飽和単量体を洗浄、減圧除去し、乾燥すること等によって、本発明の変性ハロゲン化ポリオレフィン組成物を得ることができる。 The production method of the modified halogenated polyolefin composition used in the present invention is not particularly limited as long as it is a method by which the modified halogenated polyolefin composition of the present invention can be obtained. For example, radical polymerization is initiated by adding unsaturated monomers containing acrylonitrile, an acrylic compound and an epoxy group-containing compound in a batch or continuously while dissolving a halogenated polyolefin in a solvent or stirring with an extruder. The graft polymerization is carried out with an agent, and when a predetermined polymerization conversion rate is reached, an antioxidant is added, and if necessary, the solvent or unreacted unsaturated monomer is washed, removed under reduced pressure, dried, etc. The modified halogenated polyolefin composition can be obtained.
　共グラフト反応工程を均一な溶液状態で行うためには、原料であるハロゲン化ポリオレフィンと単量体、及び得られる変性ハロゲン化ポリオレフィン組成物が可溶な溶剤を用いることが好ましい。溶剤としては、ベンゼン、トルエン、キシレン等の芳香族系有機溶剤や、モノクロロベンゼン、ジクロロベンゼン、フロロベンゼン、ジクロロジフロロベンゼン、四塩化炭素、クロロホルム、１，１－ジクロロエタン、１，２－ジクロロエタン、１，１，１－トリクロロエタン、１，１，２－トリクロロエタン、テトラクロロエタン、トリクロロフロロエタン等の塩素系有機溶剤が挙げられ、これらを単独または２種類以上を併用して用いることができる。 In order to perform the co-grafting reaction step in a uniform solution state, it is preferable to use a solvent in which the raw material halogenated polyolefin and monomer and the resulting modified halogenated polyolefin composition are soluble. Solvents include aromatic organic solvents such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodifluorobenzene, carbon tetrachloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, Examples include chlorinated organic solvents such as 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetrachloroethane, and trichlorofluoroethane. These may be used alone or in combination of two or more.
　ラジカル開始剤としては、パーオキサイド類やアゾ化合物等を用いることができる。パーオキサイド類としては、メチル―エチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、アセチルアセトンパーオキサイド等のケトンパーオキサイド類、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン、１，１－ジ（ｔ－ブチルパーオキシ）シクロヘキサン、２，２－ジ（ｔ－ブチルパーオキシ）ブタン、ｎ－ブチル－４，４－ジ（ｔ－ブチルパーオキシ）吉草酸等のパーオキシケタール類、ｐ－メンタン－ハイドロパーオキサイド、ジイソプロピルベンゼン－ハイドロパーオキサイド、１，１，３，３－テトラメチルブチル－ハイドロパーオキサイド、クメン－ハイドロパーオキサイド、ｔ－ブチル－ハイドロパーオキサイド等のハイドロパーオキサイド類、ジ（２－ｔ－ブチルパーオキシイソプロピル）ベンゼン、ジクミル－パーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、ｔ－ブチル－クミル－パーオキサイド、ジ－ｔ－ヘキシル－パーオキサイド、ジ－ｔ－ブチル－パーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキシン－３等のジアルキルパーオキサイド類、ジイソブチリル－パーオキサイド、ジ（３，５，５－トリメチルヘキサノイル）パーオキサイド、ジラウロイル－パーオキサイド、ジコハク酸－パーオキサイド、ジベンゾイル－パーオキサイド、ジ（４－メチルベンゾイル）パーオキサイド等のジアジルパーオキサイド類、ジ－ｎ－プロピル－パーオキシジカーボネート、ジイソプロピル－パーオキシジカーボネート、ジ（４－ｔ－ブチルシクロヘキシル）パーオキシジカーボネート、ジ（２－エチルヘキシル）パーオキシジカーボネート、ジ－ｓｅｃ－ブチル－パーオキシジカーボネート等のパーオキシジカーボネート類、クミル－パーオキシネオデカン酸、１，１，３，３－テトラメチルブチル－パーオキシネオデカン酸、ｔ－ヘキシル－パーオキシネオデカン酸、ｔ－ブチル－パーオキシネオデカン酸、ｔ－ブチル－パーオキシネオヘプタン酸、ｔ－ヘキシル－パーオキシピバル酸、ｔ－ブチル－パーオキシピバル酸、１，１，３，３－テトラメチルブチル－パーオキシ－２－エチルヘキサン酸、２，５－ジメチル－２，５－ジ（２－エチルヘキサノイルパーオキシ）ヘキサン、ｔ－ヘキシル－パーオキシ－２－エチルヘキサン酸、ｔ－ブチル－パーオキシ－２－エチルヘキサン酸、ｔ－ヘキシル－パーオキシ－イソプロピル－モノカーボネート、ｔ－ブチル－パーオキシ－マレイン酸、ｔ－ブチル－パーオキシ－３，５，５－トリメチルヘキサン酸、ｔ－ブチル－パーオキシラウリン酸、ｔ－ブチルーパーオキシイソプロピルーモノカーボネート、ｔ－ブチル－パーオキシ－２－エチルヘキシル－モノカーボネート、ｔ－ヘキシル－パーオキシベンゾエート、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、ｔ－ブチルパーオキシアセテート、ｔ－ブチル－パーオキシベンゾエート等のパーオキシエステル類が挙げられる。アゾ化合物としては、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）、１－［（１－シアノ－１－メチルエチル）アゾ］ホルムアミド、ジメチル－２，２’－アゾビス（２－メチルプロピオネート）、４，４’－アゾビス（４－シアノバレリン酸）、２，２’－アゾビス（２，４，４－トリメチルペンタン）、２，２’－アゾビス｛２－メチル－ｎ－［１，１’－ビス（ヒドロキシメチル）－２－ヒドロキシエチル］プロピオンアミド｝、２，２’－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］ジハイドロクロライド、２，２’－アゾビス［２－（イミダゾリン－２－イル）プロパン］ジサルフェートジハイドレート、２，２’－アゾビス｛２－［１－（２－ヒドロキシエチル）－２－イミダゾリン－２－イル］プロパン｝ジハイドロクロライド、２，２’－アゾビス（１－イミノ－１－ピロリジノ－２－メチルプロパン）ジハイドロクロライド、２，２’－アゾビス（２－メチルプロピオンアミジン）ジハイドロクロライド、２，２’－アゾビス［ｎ－（２－カルボキシエチル）－２－メチルプロピオンアミジン］テトラハイドレート等が挙げられる。これらのラジカル開始剤は、単独または併用して用いることができ、場合によっては、硫酸第一鉄等の第一鉄塩、ハイドロサルファイトナトリウム、アスコルビン酸、エリソルビン酸、アニリン、ｎ－ブチルアルデヒドアミン、三級アミン等の還元剤を添加してグラフト重合を行うこともできる。 As the radical initiator, peroxides, azo compounds and the like can be used. Examples of peroxides include ketone peroxides such as methyl-ethyl ketone peroxide, cyclohexanone peroxide, and acetylacetone peroxide, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butyl). Peroxyketals such as peroxy) cyclohexane, 2,2-di (t-butylperoxy) butane, n-butyl-4,4-di (t-butylperoxy) valeric acid, p-menthane-hydroper Hydroperoxides such as oxide, diisopropylbenzene-hydroperoxide, 1,1,3,3-tetramethylbutyl-hydroperoxide, cumene-hydroperoxide, t-butyl-hydroperoxide, di (2-t -Butylperoxyisopropyl) benzene Dicumyl-peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butyl-cumyl-peroxide, di-t-hexyl-peroxide, di-t-butyl-peroxide Oxides, dialkyl peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisobutyryl-peroxide, di (3,5,5-trimethylhexanoyl) peroxide, Diazyl peroxides such as dilauroyl-peroxide, disuccinic acid-peroxide, dibenzoyl-peroxide, di (4-methylbenzoyl) peroxide, di-n-propyl-peroxydicarbonate, diisopropyl-peroxydicarbonate Di (4-tert-butylcyclohexyl) peroxydi -Peroxydicarbonates such as sulfonate, di (2-ethylhexyl) peroxydicarbonate, di-sec-butyl-peroxydicarbonate, cumyl-peroxyneodecanoic acid, 1,1,3,3-tetramethylbutyl- Peroxyneodecanoic acid, t-hexyl-peroxyneodecanoic acid, t-butyl-peroxyneodecanoic acid, t-butyl-peroxyneoheptanoic acid, t-hexyl-peroxypivalic acid, t-butyl-peroxypivalic acid, 1,1 , 3,3-tetramethylbutyl-peroxy-2-ethylhexanoic acid, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexyl-peroxy-2-ethylhexanoic acid , T-butyl-peroxy-2-ethylhexanoic acid, t-hexyl-pero X-isopropyl-monocarbonate, t-butyl-peroxy-maleic acid, t-butyl-peroxy-3,5,5-trimethylhexanoic acid, t-butyl-peroxylauric acid, t-butyl-peroxyisopropyl monocarbonate , T-butyl-peroxy-2-ethylhexyl-monocarbonate, t-hexyl-peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butyl -Peroxyesters such as peroxybenzoate. Examples of the azo compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2- Methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, dimethyl-2,2′-azobis (2-methyl) Propionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis {2-methyl-n- [1 , 1′-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2'-azobis [2- (imidazolin-2-yl) propane] disulfate dihydrate, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane } Dihydrochloride, 2,2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2 ' -Azobis [n- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate and the like. These radical initiators can be used alone or in combination. In some cases, ferrous salts such as ferrous sulfate, hydrosulfite sodium, ascorbic acid, erythorbic acid, aniline, n-butyraldehyde amine Graft polymerization can also be carried out by adding a reducing agent such as a tertiary amine.
　上述の不飽和単量体及びラジカル開始剤の添加方法としては特に制限はなく、共グラフト反応の初期段階に一括で添加する方法、一部の不飽和単量体及び／またはラジカル開始剤を共グラフト反応の初期段階で添加し、残りの不飽和単量体及び／またはラジカル開始剤を連続注入する方法、すべての不飽和単量体及び／またはラジカル開始剤を連続注入する方法が挙げられる。 The method for adding the unsaturated monomer and the radical initiator described above is not particularly limited, and is a method in which the unsaturated monomer and / or the radical initiator are added together at the initial stage of the co-grafting reaction. Examples thereof include a method of adding at the initial stage of the grafting reaction and continuously injecting the remaining unsaturated monomers and / or radical initiators, and a method of continuously injecting all unsaturated monomers and / or radical initiators.
　また、共重合体の分子量を調整するため、及び分子間架橋を抑制するため、共グラフト反応時に分子量調節剤を添加しても良い。分子量調節剤としては、例えば、ジイソプロピルキサントゲンジスルフィド、ジエチルキサントゲンジスルフィド、ジエチルチウラムジスルフィド、２，２’－ジチオプロピオン酸、３，３’－ジチオプロピオン酸、４，４’－ジチオジブラン酸、２，２’－ジチオビス安息香酸などのジスルフィド類、ｎ－ドデシルメルカプタン、オクチルメルカプタン、ｔ－ブチルメルカプタン、チオグリコール酸、チオリンゴ酸、２－メルカプトプロピオン酸、３－メルカプトプロピオン酸、チオサリチル酸、３－メルカプト安息香酸、チオマレイン酸無水物、ジチオマレイン酸、チオグルタール酸、システイン、ホモシステイン、６－メルカプトテトラゾール酢酸、３－メルカプト－１－プロパンスルホン酸等のメルカプタン類、ジフェニルエチレン、ｐ－クロロジフェニルエチレン、ｐ－シアノジフェニルエチレン、α－メチルスチレンダイマー、ベンジルジチオベンゾエート、有機テルル化合物、硫黄等が挙げられ、これらを単独または併用して用いることができる。 In order to adjust the molecular weight of the copolymer and to suppress intermolecular crosslinking, a molecular weight modifier may be added during the co-grafting reaction. Examples of the molecular weight regulator include diisopropyl xanthogen disulfide, diethyl xanthogen disulfide, diethyl thiuram disulfide, 2,2′-dithiopropionic acid, 3,3′-dithiopropionic acid, 4,4′-dithiodibranic acid, 2,2 ′. Disulfides such as dithiobisbenzoic acid, n-dodecyl mercaptan, octyl mercaptan, t-butyl mercaptan, thioglycolic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, 3-mercaptobenzoic acid, Mercaptans such as thiomaleic anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homocysteine, 6-mercaptotetrazoleacetic acid, 3-mercapto-1-propanesulfonic acid, diphenylethylene p- chloro diphenylethylene, p- cyano-diphenyl ethylene, alpha-methyl styrene dimer, benzyl dithio benzoate, organic tellurium compounds, sulfur and the like, can be used alone or in combination.
　酸化防止剤としては特に限定するものではなく、ポリマーの酸化防止剤として一般に利用されているもので、例えば２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、２，２－ビス〔｛［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオニル］オキシ｝メチル］プロパン－１，３－ジオール、１，３－ビス［３－（ｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、トリエチレングリコール－ビス［３－（３－ｔ－ブチル－５－メチル－ヒドロキシフェニル）プロピオネート］、１，６－ヘキサンジオール－ビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２，４－ビス－（ｎ－オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルアニリン）－１，３，５－トリアジン、ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２，２－チオ－ジエチレンビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、Ｎ，Ｎ’－ヘキサメチレンビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ヒドロシンナマイド）、３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ベンジルホスホネート－ジエチルエステル、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、トリス－（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）－イソシアヌレート、２，４－ビス［（オクチルチオ）メチル］－オルト－クレゾール、イソオクチル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、テトラキス［メチレン－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン、３，９－ビス〔２－［３－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）－プロピオニオキシ］－１，１－ジメチルエチル〕－２，４，８，１０－テトラオキサスピロ［５・５］ウンデカン等のフェノール系酸化防止剤、２，２－ヒドロキシ－５－メチルフェニル－ベンゾトリアゾール、４，４’－ビス－（２，２－ジメチルベンジル）ジフェニルアミン、ビス（１，２，２，５，６－ペンタメチル－４－ピペリジル）デカンジオナート等のアミン系酸化防止剤、ジラウリルー３，３’－チオジプロピオネート、ジミリスチル－３，３’－チオジプロピオネート、ジステアリルー３，３’－ジチオプロピオネート、ペンタエリスリチル－テトラキス（３－ラウリルチオプロピオネート）ジトリデシル－３，３’－チオジプロピオネート、２－メルカプトベンズイミダゾール等の硫黄系酸化防止剤、トリスノニルフェニルホスファイト、トリフェニルホスファイト、トリス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト等のリン系酸化防止剤、２，２，６，６－テトラメチルピペリジン－１－オキシル等の安定ラジカル系酸化防止剤等が挙げられる。 The antioxidant is not particularly limited, and is generally used as an antioxidant for polymers. For example, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′- Methylenebis (4-ethyl-6-tert-butylphenol), 2,2-bis [{[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] oxy} methyl] propane-1,3 -Diol, 1,3-bis [3- (t-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4- Droxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylaniline) -1,3,5-triazine, pentaerythrityl- Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinna Mido), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5 Di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,4-bis [(octylthio) methyl] -ortho-cresol Isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, , 9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionoxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxa Phenolic antioxidants such as spiro [5 · 5] undecane, 2,2-hydroxy-5-methylphenyl-benzotriazole, 4,4′-bis- (2,2 -Dimethylbenzyl) diphenylamine, amine-based antioxidants such as bis (1,2,2,5,6-pentamethyl-4-piperidyl) decanedionate, dilauryl 3,3′-thiodipropionate, dimyristyl-3, 3'-thiodipropionate, distearyl-3,3'-dithiopropionate, pentaerythrityl-tetrakis (3-laurylthiopropionate) ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole Sulfur-based antioxidants such as trisnonylphenyl phosphite, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, etc., 2,2,6,6- And stable radical antioxidants such as tetramethylpiperidine-1-oxyl.
　共グラフト反応の反応温度及び反応圧力は特に限定するものではないが、反応温度は５０～１５０℃、反応圧力は０～１．０ＭＰａの範囲が好ましい。 The reaction temperature and reaction pressure of the co-grafting reaction are not particularly limited, but the reaction temperature is preferably 50 to 150 ° C. and the reaction pressure is preferably 0 to 1.0 MPa.
　反応終了後、メタノール等の不溶性溶剤による析出、ドラムドライヤー、ベント付押出し機等を用いた濃縮、乾燥により、目的とする変性ハロゲン化ポリオレフィン組成物が得られる。 After completion of the reaction, the desired modified halogenated polyolefin composition is obtained by precipitation with an insoluble solvent such as methanol, concentration and drying using a drum dryer, an extruder with a vent, or the like.
　また、反応終了後の溶液を、アセトン等のグラフト共重合体が不溶で、アクリロニトリルとアクリル系化合物が可溶な溶剤に添加することによって、ハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル系化合物の共重合体を低減した変性ハロゲン化ポリオレフィン組成物を得ることが可能である。 In addition, by adding a solution after completion of the reaction to a solvent in which the graft copolymer such as acetone is insoluble and acrylonitrile and the acrylic compound are soluble, the acrylonitrile and the acrylic compound that are not bonded to the halogenated polyolefin are added. It is possible to obtain a modified halogenated polyolefin composition having a reduced copolymer.
　また、反応終了後の溶液を、アセトン等のグラフト共重合体が不溶で、エポキシ基含有共重合体が可溶な溶剤に添加することによって、グラフト共重合体を分別し、これを乾燥することにより、エポキシ基含有共重合体を含有しないグラフト共重合体を得ることが可能である。 Moreover, the graft copolymer is fractionated by adding the solution after completion of the reaction to a solvent in which the graft copolymer such as acetone is insoluble and the epoxy group-containing copolymer is soluble, and this is dried. Thus, it is possible to obtain a graft copolymer that does not contain an epoxy group-containing copolymer.
　本発明において、変性ハロゲン化ポリオレフィン組成物は加硫物として使用される。本発明の変性ハロゲン化ポリオレフィン組成物の加硫物を得る方法としては、変性ハロゲン化ポリオレフィン組成物と各種配合剤をロール又はバンバリーミキサー等で配合又は混練した後、プレス加硫、蒸気加硫、高周波（ＵＨＦ）加硫あるいは電子線加硫等が行われる。加硫温度は特に制限はないが、１３０～２００℃であり、好ましくは１５０～１８０℃である。また、必要に応じて二次加硫を行うことも可能である。二次加硫の条件は、加熱オーブン中１４０～１８０℃の範囲で、２時間～６時間行う。各種配合剤としては加硫剤、加硫促進剤、受酸剤、可塑剤、補強剤、充填剤、加工助剤、老化防止剤等が挙げられ、必要に応じて用いられる。 In the present invention, the modified halogenated polyolefin composition is used as a vulcanizate. As a method of obtaining a vulcanized product of the modified halogenated polyolefin composition of the present invention, the modified halogenated polyolefin composition and various compounding agents are blended or kneaded with a roll or a Banbury mixer, and then press vulcanized, steam vulcanized, High frequency (UHF) vulcanization or electron beam vulcanization is performed. The vulcanization temperature is not particularly limited, but is 130 to 200 ° C, preferably 150 to 180 ° C. Moreover, it is also possible to perform secondary vulcanization as needed. The secondary vulcanization is performed in a heating oven in the range of 140 to 180 ° C. for 2 to 6 hours. Examples of various compounding agents include vulcanizing agents, vulcanization accelerators, acid acceptors, plasticizers, reinforcing agents, fillers, processing aids, anti-aging agents, and the like, and they are used as necessary.
　加硫剤としては、硫黄等の無機系加硫剤、チウラムポリスルフィド類、ジチオカルバミン酸塩類、オキシム類、ニトロソ化合物、有機過酸化物等の有機系加硫剤が挙げられる。加硫促進剤としては、チオウレア類、グアニジン類、チアゾール類、スルフェンアミド類、チウラム類、ジチオカルバミン酸塩類、キサントゲン酸塩類等が挙げられる。受酸剤としては酸化マグネシウム、酸化亜鉛、ハイドロタルサイト、リサージ等が挙げられる。可塑剤としては、鉱物油系軟化剤、植物油系軟化剤、合成軟化剤、合成可塑剤等が挙げられる。補強材としては、カーボンブラック、ホワイトカーボン等が挙げられる。充填剤としては、炭酸カルシウム類、塩基性炭酸マグネシウム類、珪酸及び珪酸塩類等が挙げられる。加工助剤としては脂肪酸類、脂肪酸エステル類、脂肪酸金属塩類、炭化水素系ワックス等が挙げられる。老化防止剤としては、アミン系老化防止剤、フェノール系老化防止剤、硫黄系老化防止剤、リン系老化防止剤、ワックス類等が挙げられる。 Examples of the vulcanizing agent include inorganic vulcanizing agents such as sulfur, organic vulcanizing agents such as thiuram polysulfides, dithiocarbamates, oximes, nitroso compounds, and organic peroxides. Examples of the vulcanization accelerator include thioureas, guanidines, thiazoles, sulfenamides, thiurams, dithiocarbamates, xanthates, and the like. Examples of the acid acceptor include magnesium oxide, zinc oxide, hydrotalcite, and resurge. Examples of the plasticizer include mineral oil softeners, vegetable oil softeners, synthetic softeners, and synthetic plasticizers. Examples of the reinforcing material include carbon black and white carbon. Examples of the filler include calcium carbonates, basic magnesium carbonates, silicic acid and silicates. Processing aids include fatty acids, fatty acid esters, fatty acid metal salts, hydrocarbon waxes, and the like. Examples of the anti-aging agent include amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based anti-aging agents, phosphorus-based anti-aging agents, and waxes.
　本発明の変性ハロゲン化ポリオレフィン組成物を加硫して成る加硫組成物は、特に耐油性が必要とされる各種ホースや各種シール材、パッキン等に用いることができる。 The vulcanized composition obtained by vulcanizing the modified halogenated polyolefin composition of the present invention can be used for various hoses, various sealing materials, packing and the like that particularly require oil resistance.
　本発明の変性ハロゲン化ポリオレフィン組成物の加硫組成物は、良好な難燃性、物理特性と耐油性を両立しており、特に耐油性が必要とされる各種ホースや各種シール材、パッキン等に用いることができる。 The vulcanized composition of the modified halogenated polyolefin composition of the present invention has both good flame retardancy, physical properties and oil resistance, especially various hoses, various seal materials, packing, etc. that require oil resistance. Can be used.
　以下に実施例を用いて本発明を更に詳しく説明するが、本発明はこれら実施例のみに制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
　尚、以下の実施例等で用いた値は、以下の測定法で行ったものである。 In addition, the values used in the following examples and the like are those obtained by the following measurement methods.
　＜不飽和単量体の転化率＞
　不飽和単量体の転化率は、反応終了後の溶液を少量採取し、未反応の不飽和単量体量をガスクロマトグラフィー（ＧＣ－２０２５、島津製作所製）を用いて測定することにより求めた。 <Conversion rate of unsaturated monomer>
The conversion rate of the unsaturated monomer is obtained by collecting a small amount of the solution after completion of the reaction and measuring the amount of the unreacted unsaturated monomer using gas chromatography (GC-2025, manufactured by Shimadzu Corporation). It was.
　＜エポキシ基含有共重合体の含有率＞
　変性ハロゲン化ポリオレフィン組成物中に於ける、ハロゲン化ポリオレフィンと結合していないエポキシ基含有共重合体及びグラフト共重合体中のエポキシ基含有共重合体の合計の含有率は、原料であるハロゲン化ポリオレフィン重量と、不飽和単量体の仕込み量と各不飽和単量体の転化率から求めた反応した不飽和単量体重量から算出した。 <Content of epoxy group-containing copolymer>
The total content of the epoxy group-containing copolymer not bonded to the halogenated polyolefin and the epoxy group-containing copolymer in the graft copolymer in the modified halogenated polyolefin composition is the halogenated raw material. It calculated from the weight of the reacted unsaturated monomer calculated | required from the polyolefin weight, the preparation amount of the unsaturated monomer, and the conversion rate of each unsaturated monomer.
　含有率＝｛反応した不飽和単量体重量／（ハロゲン化ポリオレフィン重量＋反応した不飽和単量体重量）｝×１００
　＜共重合体の含有率＞
　変性ハロゲン化ポリオレフィン組成物中に於ける、ハロゲン化ポリオレフィンと結合していないアクリロニトリル及びアクリル系化合物の共重合体及びグラフト共重合体中のアクリロニトリルとアクリル系化合物の共重合体の合計の含有率は、原料であるハロゲン化ポリオレフィン重量と、不飽和単量体（アクリロニトリル及びアクリル系化合物）の仕込み量と各不飽和単量体の転化率から求めた反応した不飽和単量体重量から算出した。 Content = {weight of unsaturated monomer reacted / (weight of halogenated polyolefin + weight of unsaturated monomer reacted)} × 100
<Content of copolymer>
In the modified halogenated polyolefin composition, the total content of the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin and the copolymer of acrylonitrile and acrylic compound in the graft copolymer is The weight was calculated from the weight of the halogenated polyolefin as a raw material, the amount of unsaturated monomers (acrylonitrile and acrylic compound) charged, and the weight of reacted unsaturated monomers determined from the conversion rate of each unsaturated monomer.
　含有率＝｛反応した不飽和単量体重量／（ハロゲン化ポリオレフィン重量＋反応した不飽和単量体重量）｝×１００
　＜エポキシ基含有共重合体の含有率＞
　変性ハロゲン化ポリオレフィン組成物中に於ける、ハロゲン化ポリオレフィンと結合していないエポキシ基含有共重合体及びグラフト共重合体中のエポキシ基含有共重合体の合計の含有率は、原料であるハロゲン化ポリオレフィン重量と、不飽和単量体の仕込み量と各不飽和単量体の転化率から求めた反応した不飽和単量体重量から算出した。 Content = {weight of unsaturated monomer reacted / (weight of halogenated polyolefin + weight of unsaturated monomer reacted)} × 100
<Content of epoxy group-containing copolymer>
The total content of the epoxy group-containing copolymer not bonded to the halogenated polyolefin and the epoxy group-containing copolymer in the graft copolymer in the modified halogenated polyolefin composition is the halogenated raw material. It calculated from the weight of the reacted unsaturated monomer calculated | required from the polyolefin weight, the preparation amount of the unsaturated monomer, and the conversion rate of each unsaturated monomer.
　含有率＝｛反応した不飽和単量体重量／（ハロゲン化ポリオレフィン重量＋反応した不飽和単量体重量）｝×１００
　＜共重合体中のアクリロニトリルとアクリル系化合物の重量比率＞
　変性ハロゲン化ポリオレフィン組成物中に於ける、ハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル系化合物の共重合体及びグラフト共重合体中のアクリロニトリルとアクリル系化合物の共重合体に含まれるアクリロニトリルとアクリル系化合物由来の成分の重量比率は、不飽和単量体の重合率より算出した。 Content = {weight of unsaturated monomer reacted / (weight of halogenated polyolefin + weight of unsaturated monomer reacted)} × 100
<Weight ratio of acrylonitrile and acrylic compound in copolymer>
Acrylonitrile and acrylic contained in a copolymer of acrylonitrile and an acrylic compound not bonded to the halogenated polyolefin and a copolymer of acrylonitrile and an acrylic compound in a graft copolymer in the modified halogenated polyolefin composition The weight ratio of the component derived from the system compound was calculated from the polymerization rate of the unsaturated monomer.
　アクリロニトリル重量比率
　＝（反応したアクリロニトリル重量／反応した不飽和単量体重量）×１００
　アクリル系化合物重量比率
　＝（反応したアクリル系化合物重量／反応した不飽和単量体重量）×１００
　＜共重合体中のアクリロニトリルとエポキシ基含有化合物とアクリル系化合物の重量比率＞
　変性ハロゲン化ポリオレフィン組成物中に於ける、ハロゲン化ポリオレフィンと結合していないエポキシ基含有共重合体及びグラフト共重合体中のエポキシ基含有共重合体に含まれるアクリロニトリル、エポキシ基含有化合物、アクリル系化合物由来の成分の重量比率は、不飽和単量体の重合率より算出した
　アクリロニトリル重量比率
　＝（反応したアクリロニトリル重量／反応した不飽和単量体重量）×１００
　エポキシ基含有化合物重量比率
　＝（反応したエポキシ基含有化合物重量／反応した不飽和単量体重量）×１００
　アクリル系化合物重量比率
　＝（反応したアクリル系化合物重量／反応した不飽和単量体重量）×１００
　＜グラフト選択率＞
　変性ハロゲン化ポリオレフィン組成物中に於けるハロゲン化ポリオレフィンに結合したアクリロニトリル及びアクリル系化合物の共重合体と、ハロゲン化ポリオレフィンに結合していないアクリロニトリルとアクリル系化合物の共重合体の重量比率（グラフト選択率）、及び変性ハロゲン化ポリオレフィン組成物中に於ける、ハロゲン化ポリオレフィンに結合したエポキシ基含有共重合体と、ハロゲン化ポリオレフィンに結合していないエポキシ基含有共重合体の重量比率は、以下の方法によって求めた。
１）得られた変性ハロゲン化ポリオレフィン組成物をアセトンで抽出し、アセトン抽出物及びアセトン抽出残渣の夫々を乾燥し、精秤する。 Acrylonitrile weight ratio = (reacted acrylonitrile weight / reacted unsaturated monomer weight) × 100
Acrylic compound weight ratio = (reacted acrylic compound weight / reacted unsaturated monomer weight) × 100
<Weight ratio of acrylonitrile, epoxy group-containing compound and acrylic compound in copolymer>
Acrylonitrile, epoxy group-containing compound, acrylic type contained in the epoxy group-containing copolymer in the modified halogenated polyolefin composition and the epoxy group-containing copolymer in the graft copolymer not bonded to the halogenated polyolefin The weight ratio of the component derived from the compound is the acrylonitrile weight ratio calculated from the polymerization rate of the unsaturated monomer = (reacted acrylonitrile weight / reacted unsaturated monomer weight) × 100
Weight ratio of epoxy group-containing compound = (weight of reacted epoxy group-containing compound / weight of reacted unsaturated monomer) × 100
Acrylic compound weight ratio = (reacted acrylic compound weight / reacted unsaturated monomer weight) × 100
<Graft selectivity>
Weight ratio of copolymer of acrylonitrile and acrylic compound bonded to halogenated polyolefin and copolymer of acrylonitrile and acrylic compound not bonded to halogenated polyolefin in the modified halogenated polyolefin composition (graft selection) The weight ratio of the epoxy group-containing copolymer bonded to the halogenated polyolefin and the epoxy group-containing copolymer not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition is as follows: Determined by the method.
1) The obtained modified halogenated polyolefin composition is extracted with acetone, and each of the acetone extract and the acetone extraction residue is dried and precisely weighed.
　　　　アセトン抽出物重量　［Ａ］
　　　　アセトン抽出残渣物重量　［Ｂ］
３）アセトン抽出物、及びアセトン抽出残渣物中の塩素含有率を測定する。 Acetone extract weight [A]
Acetone extraction residue weight [B]
3) The chlorine content in the acetone extract and the acetone extract residue is measured.
　　　　原料ハロゲン化ポリオレフィンの塩素含有率　［Ｃ］
　　　　アセトン抽出物の塩素含有率　［Ｄ］
　　　　アセトン抽出残渣物の塩素含有率　［Ｅ］
アセトン抽出物中の共重合体含有率［Ｆ］＝（［Ｃ］－［Ｄ］）×１００／［Ｃ］
アセトン抽出残渣物中の共重合体含有率［Ｇ］＝（［Ｃ］－［Ｅ］）×１００／［Ｃ］
グラフト選択率＝（［Ｂ］×［Ｇ］）×１００／（［Ａ］×［Ｆ］＋［Ｂ］×［Ｇ］）
　＜塩素含有率の測定＞
　塩素含有率の測定は、最初に、吸収液として１．７重量％硫酸ヒドラジニウム水溶液１５．０ｍｌを入れた燃焼フラスコ内で、原料ハロゲン化ポリオレフィンまたは変性ハロゲン化ポリオレフィン組成物のアセトン抽出物またはアセトン抽出残渣物３０．０ｍｇを酸素燃焼法に従い燃焼させ、３０分静置した。次に、この吸収液を純水１００．０ｍｌで洗い出し、濃度０．０５Ｎの硝酸銀水溶液で電位差滴定法により塩素イオンを定量することにより求めた。 Chlorine content of raw halogenated polyolefin [C]
Chlorine content of acetone extract [D]
Chlorine content of acetone extraction residue [E]
Copolymer content in acetone extract [F] = ([C] − [D]) × 100 / [C]
Copolymer content in acetone extraction residue [G] = ([C] − [E]) × 100 / [C]
Graft selectivity = ([B] × [G]) × 100 / ([A] × [F] + [B] × [G])
<Measurement of chlorine content>
Chlorine content is measured first by acetone extract or acetone extraction of raw halogenated polyolefin or modified halogenated polyolefin composition in a combustion flask containing 15.0 ml of 1.7% by weight hydrazinium sulfate aqueous solution as an absorbing solution. 30.0 mg of the residue was combusted according to the oxygen combustion method and left to stand for 30 minutes. Next, this absorption solution was washed out with 100.0 ml of pure water, and the chloride ion was determined by potentiometric titration with a 0.05N silver nitrate aqueous solution.
　＜硫黄含有率の測定＞
　硫黄含有率の測定は、最初に、吸収液として３．０重量％の過酸化水素水１０．０ｍｌを入れた燃焼フラスコ内で、原料ハロゲン化ポリオレフィンまたは変性ハロゲン化ポリオレフィン組成物のアセトン抽出物またはアセトン抽出残渣物３０．０ｍｇを酸素燃焼法に従い燃焼させ、３０分静置した。次に、この吸収液を純水約４０．０ｍｌで洗い出した後、酢酸１ｍｌ、２－プロピルアルコール１００．０ｍｌ、アルセナゾＩＩＩ０．４７ｍｌを加えた。これを濃度０．０１Ｎの酢酸バリウム溶液で光度滴定法により硫酸イオンを定量することにより求めた。 <Measurement of sulfur content>
The sulfur content is measured by first using an acetone extract of the raw halogenated polyolefin or modified halogenated polyolefin composition in a combustion flask containing 10.0 ml of 3.0% by weight hydrogen peroxide as an absorbent. 30.0 mg of acetone extraction residue was burned according to the oxygen combustion method and allowed to stand for 30 minutes. Next, this absorbing solution was washed out with about 40.0 ml of pure water, and then 1 ml of acetic acid, 100.0 ml of 2-propyl alcohol, and 0.47 ml of arsenazo III were added. This was determined by quantifying sulfate ion by a photometric titration method with a 0.01N concentration barium acetate solution.
　＜物理的特性評価＞
　変性ハロゲン化ポリオレフィン組成物を表１に記載した所定の配合処方にてＪＩＳ－Ｋ－６２９９（２０１２年度版）に従い混練を行い、得られたサンプルを厚み２ｍｍの金型にて加硫を行った。その後、引張強さ（ＴＢ）、破断時伸び（ＥＢ）、１００％引張応力（Ｍ１００）はＪＩＳ－Ｋ－６２５１（２０１２年度版）に従い、引張速度５００ｍｍ／分、２３℃の条件にて評価した。 <Physical property evaluation>
The modified halogenated polyolefin composition was kneaded in accordance with JIS-K-6299 (2012 edition) with the prescribed formulation described in Table 1, and the resulting sample was vulcanized with a 2 mm thick mold. . Thereafter, tensile strength (TB), elongation at break (EB), and 100% tensile stress (M100) were evaluated according to JIS-K-6251 (2012 edition) under conditions of a tensile speed of 500 mm / min and 23 ° C. .
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　＜耐油性評価＞
　得られた加硫物をＪＩＳ－Ｋ－６２５８（２０１２年度版）に従い、試験用潤滑油のＮｏ．３油を用い、１００℃で７２時間浸漬した後の体積変化率を測定することにより評価した。 <Oil resistance evaluation>
According to JIS-K-6258 (2012 edition), the obtained vulcanized product was tested for lubricating oil No. Three oils were used for evaluation by measuring the volume change rate after being immersed at 100 ° C. for 72 hours.
　実施例１
　４０リットルのグラスライニング製オートクレーブに１，１，２－トリクロロエタンを２１．６ｋｇ、密度が９６０ｋｇ／ｃｍ３、メルトフローレート（ＭＦＲ）が５．０ｇ／１０分の高密度ポリエチレン３ｋｇを添加した後、反応器のジャケットに蒸気を通し、１１０℃でポリエチレンを均一に溶解した。またこの間、反応器に１０．０リットル／分の流速で窒素ガスを導入し、反応器内の空気を除去した。ラジカル発生剤として、５．０ｇのα，α－アゾビスイソブチロニトリルを１，１，２－トリクロロエタン１．０リットルに溶解した溶液を４．０ｍｌ／分の流量で、６．５ｋｇの塩化スルフリルを２５．０ｍｌ／分の流量で、各々別の投入口より反応器へ連続的に添加した。反応中は反応器の圧力を０．２ＭＰａに保った。反応終了後、反応系の圧力を常圧まで低下し、その後常圧下で窒素を吹き込むことによって、溶液中に溶存する塩化水素、亜硫酸ガスを系外に排出した。その後ドラム乾燥機にて生成物を単離し、クロロスルホン化ポリエチレンを得た。 Example 1
After adding 21.6 kg of 1,1,2-trichloroethane, density of 960 kg / cm 3 , and melt flow rate (MFR) of 5.0 g / 10 min to 3 kg of 40 liter glass-lined autoclave, Steam was passed through the reactor jacket to uniformly dissolve the polyethylene at 110 ° C. During this time, nitrogen gas was introduced into the reactor at a flow rate of 10.0 liters / minute to remove air in the reactor. As a radical generator, a solution of 5.0 g of α, α-azobisisobutyronitrile dissolved in 1.0 liter of 1,1,2-trichloroethane at a flow rate of 4.0 ml / min, 6.5 kg of chloride. Sulfuryl was continuously added to the reactor through a separate inlet at a flow rate of 25.0 ml / min. During the reaction, the pressure of the reactor was kept at 0.2 MPa. After completion of the reaction, the pressure in the reaction system was reduced to normal pressure, and then nitrogen was blown under normal pressure to discharge hydrogen chloride and sulfurous acid gas dissolved in the solution out of the system. Thereafter, the product was isolated with a drum dryer to obtain chlorosulfonated polyethylene.
　得られたクロロスルホン化ポリエチレンは、３５．３重量％の塩素と、０．２２重量％の硫黄を含有していた。 The obtained chlorosulfonated polyethylene contained 35.3% by weight of chlorine and 0.22% by weight of sulfur.
　次に、得られたクロロスルホン化ポリエチレンを用いて、共グラフト反応を実施した。 Next, a co-grafting reaction was performed using the obtained chlorosulfonated polyethylene.
　窒素雰囲気下４リットルのガラスフラスコにクロロスルホン化ポリエチレン１５０ｇ、１，１，２－トリクロロエタン２．０ｋｇを仕込み、内部を窒素で置換し、１１０℃に加熱してクロロスルホン化ポリエチレンを溶解した。内温を６５℃まで冷却した後、アクリロニトリル３９．８ｇ、アクリル酸ｎ－ブチル９６．１ｇを添加し、１，１，２－トリクロロエタン１４４ｇに溶解したラジカル開始剤（日油（株）製　パーロイルＯＰＰ；ジ－２－エチルヘキシル－パーオキシジカーボネート）３．７ｇを溶解した溶液を５時間かけて滴下して反応を実施した。その後、１時間撹拌を継続し、得られた反応溶液をドラム乾燥機にて乾燥することにより、変性ハロゲン化ポリオレフィン組成物を得た。 In a 4 liter glass flask under nitrogen atmosphere, 150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 39.8 g of acrylonitrile and 96.1 g of n-butyl acrylate were added, and a radical initiator dissolved in 144 g of 1,1,2-trichloroethane (Perroyl OPP manufactured by NOF Corporation) A solution of 3.7 g of di-2-ethylhexyl-peroxydicarbonate) was added dropwise over 5 hours to carry out the reaction. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸ｎ－ブチル共重合体含有率は３１．７重量％であり、アクリロニトリル－アクリル酸ｎ－ブチル共重合体のアクリロニトリル／アクリル酸ｎ－ブチル比率は２６／７４であった。処方１の配合処方にて物性評価を実施した。評価結果を表２に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-n-butyl acrylate copolymer content of 31.7% by weight, and the acrylonitrile / n-butyl acrylate acrylonitrile / n-butyl acrylate ratio. Was 26/74. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
　実施例２
　不飽和単量体の仕込量を、アクリロニトリル５９．７ｇ、アクリル酸ｎ－ブチル４８．１ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 2
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1, except that the amount of the unsaturated monomer charged was changed to 59.7 g of acrylonitrile and 48.1 g of n-butyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸ｎ－ブチル共重合体含有率は２７．４重量％であり、アクリロニトリル－アクリル酸ｎ－ブチル共重合体のアクリロニトリル／アクリル酸ｎ－ブチル比率は５４／４６であった。処方１の配合処方にて物性評価を実施した。評価結果を表２に示す。 The resulting modified halogenated polyolefin composition has an acrylonitrile-n-butyl acrylate copolymer content of 27.4% by weight, and the acrylonitrile / n-butyl acrylate copolymer has an acrylonitrile / n-butyl acrylate ratio. Was 54/46. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
　実施例３
　不飽和単量体を、アクリロニトリル３９．８ｇ、アクリル酸エチル７５．１ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 3
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 39.8 g of acrylonitrile and 75.1 g of ethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸エチル共重合体含有率は２８．０重量％であり、アクリロニトリル－アクリル酸エチル共重合体のアクリロニトリル／アクリル酸エチル比率は３１／６９であった。処方１の配合処方にて物性評価を実施した。評価結果を表２に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 28.0% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 31/69. It was. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
　実施例４
　不飽和単量体を、アクリロニトリル５９．７ｇ、アクリル酸エチル２７．６ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 4
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 59.7 g of acrylonitrile and 27.6 g of ethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸エチル共重合体含有率は２６．１重量％であり、アクリロニトリル－アクリル酸エチル共重合体のアクリロニトリル／アクリル酸エチル比率は５９／４１であった。処方１の配合処方にて物性評価を実施した。評価結果を表２に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 26.1% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 59/41. It was. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
　実施例５
　不飽和単量体を、アクリロニトリル３９．８ｇ、アクリル酸２－メトキシエチル９７．６ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 5
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 39.8 g of acrylonitrile and 97.6 g of 2-methoxyethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は３１．０重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３１／６９であった。処方１の配合処方にて物性評価を実施した。評価結果を表２に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 31.0% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 31/69. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
　実施例６
　不飽和単量体を、アクリロニトリル５９．７ｇ、アクリル酸２－メトキシエチル４８．８ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 6
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 59.7 g of acrylonitrile and 48.8 g of 2-methoxyethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は２４．４重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は４５／５５であった。処方１の配合処方にて物性評価を実施した。評価結果を表２に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 24.4% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 45/55. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
　実施例７
　共グラフト反応におけるクロロスルホン化ポリエチレンの仕込量を１８０ｇ、不飽和単量体を、アクリロニトリル５３．４ｇ、アクリル酸エチル１００．８ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 7
Modified halogenated polyolefin composition in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 180 g, and the unsaturated monomer was changed to 53.4 g of acrylonitrile and 100.8 g of ethyl acrylate. Got.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸エチル共重合体含有率は２９．９重量％であり、アクリロニトリル－アクリル酸エチル共重合体のアクリロニトリル／アクリル酸エチル比率は３２／６８であった。処方１の配合処方にて物性評価を実施した。評価結果を表２に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 29.9% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 32/68. It was. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
　実施例８
　不飽和単量体を、アクリロニトリル１０３．９ｇ、アクリル酸エチル１９６．１ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 8
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 103.9 g of acrylonitrile and 196.1 g of ethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸エチル共重合体含有率は５４．０重量％であり、アクリロニトリル－アクリル酸エチル共重合体のアクリロニトリル／アクリル酸エチル比率は３３／６７であった。処方１の配合処方にて物性評価を実施した。評価結果を表２に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 54.0% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 33/67. It was. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
　実施例９
　共グラフト反応におけるクロロスルホン化ポリエチレンの仕込量を１８０ｇ、不飽和単量体を、アクリロニトリル７９．４ｇ、アクリル酸エチル７４．９ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 9
Modified halogenated polyolefin composition in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 180 g, and the unsaturated monomer was changed to 79.4 g of acrylonitrile and 74.9 g of ethyl acrylate. Got.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸エチル共重合体含有率は２８．５重量％であり、アクリロニトリル－アクリル酸エチル共重合体のアクリロニトリル／アクリル酸エチル比率は５３／４７であった。処方１の配合処方にて物性評価を実施した。評価結果を表３に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 28.5% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 53/47. It was. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 3.
　実施例１０
　不飽和単量体を、アクリロニトリル１５４．４ｇ、アクリル酸エチル１４５．６ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 10
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 154.4 g of acrylonitrile and 145.6 g of ethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸エチル共重合体含有率は５２．６重量％であり、アクリロニトリル－アクリル酸エチル共重合体のアクリロニトリル／アクリル酸エチル比率は５１／４９であった。処方１の配合処方にて物性評価を実施した。評価結果を表２に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 52.6% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 51/49. It was. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
　実施例１１
　共グラフト反応におけるクロロスルホン化ポリエチレンの仕込量を２００ｇ、不飽和単量体を、アクリロニトリル４９．７ｇ、アクリル酸２－メトキシエチル１２１．８ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 11
Modified halogenation in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 200 g, and the unsaturated monomer was changed to 49.7 g of acrylonitrile and 121.8 g of 2-methoxyethyl acrylate. A polyolefin composition was obtained.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は３０．２重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は２９／７１であった。処方１の配合処方にて物性評価を実施した。評価結果を表３に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 30.2% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 29/71. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 3.
　実施例１２
　不飽和単量体を、アクリロニトリル８６．９ｇ、アクリル酸２－メトキシエチル２１３．１ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 12
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 86.9 g of acrylonitrile and 213.1 g of 2-methoxyethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は５５．４重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３０／７０であった。処方１の配合処方にて物性評価を実施した。評価結果を表３に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 55.4% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 30/70. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 3.
　実施例１３
　共グラフト反応におけるクロロスルホン化ポリエチレンの仕込量を１８０ｇ、不飽和単量体を、アクリロニトリル６９．３ｇ、アクリル酸２－メトキシエチル８５．０ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 13
Modified halogenation in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 180 g, and the unsaturated monomer was changed to 69.3 g of acrylonitrile and 85.0 g of 2-methoxyethyl acrylate. A polyolefin composition was obtained.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は２８．８重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は４９／５１であった。処方１の配合処方にて物性評価を実施した。評価結果を表３に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 28.8% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 49/51. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 3.
　実施例１４
　不飽和単量体を、アクリロニトリル１３４．８ｇ、アクリル酸２－メトキシエチル１６５．３ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 14
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 134.8 g of acrylonitrile and 165.3 g of 2-methoxyethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は５０．２重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は４９／５１であった。処方１の配合処方にて物性評価を実施した。評価結果を表３に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 50.2% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 49/51. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 3.
　実施例１５
　ハロゲン化ポリオレフィンとして、ＴＯＳＯＨ－ＣＳＭ　ＴＳ－５３０（東ソー（株）製　クロロスルホン化ポリエチレン、塩素量３５．６重量％、硫黄量１．０３重量％、ムーニー粘度ＭＬ１＋４＝５６）を用いて、共グラフト反応を実施した。 Example 15
Co-grafting using TOSOH-CSM TS-530 (Chlorosulfonated polyethylene manufactured by Tosoh Corporation, chlorine content 35.6% by weight, sulfur content 1.03% by weight, Mooney viscosity ML1 + 4 = 56) as halogenated polyolefin The reaction was carried out.
　窒素雰囲気下４リットルのガラスフラスコにクロロスルホン化ポリエチレン１５０ｇ、１，１，２－トリクロロエタン２．０ｋｇを仕込み、内部を窒素で置換し、１１０℃に加熱してクロロスルホン化ポリエチレンを溶解した。内温を６５℃まで冷却した後、アクリロニトリル３９．８ｇ、アクリル酸２－メトキシエチル２１３．１ｇ、ラジカル開始剤（日油（株）製　パーブチルＯ；ｔ－ブチル－パーオキシ－２－エチルヘキサノエート）７．０ｇを添加し、１，１，２－トリクロロエタン１４４ｇに溶解した還元剤（大内新興化学工業（株）製　ノクセラー８；ｎ－ブチルアルデヒドアミン）２．０ｇを溶解した溶液を５時間かけて滴下して反応を実施した。その後、１時間撹拌を継続し、得られた反応溶液をドラム乾燥機にて乾燥することにより、変性ハロゲン化ポリオレフィン組成物を得た。 In a 4 liter glass flask under nitrogen atmosphere, 150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 39.8 g of acrylonitrile, 213.1 g of 2-methoxyethyl acrylate, a radical initiator (Perbutyl O manufactured by NOF Corporation; t-butyl-peroxy-2-ethylhexanoate) ) 7.0 g was added, and a solution in which 2.0 g of a reducing agent dissolved in 144 g of 1,1,2-trichloroethane (Noxeller 8; n-butyraldehyde amine manufactured by Ouchi Shinsei Chemical Co., Ltd.) was dissolved for 5 hours. The reaction was carried out dropwise. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は４２．８重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は４０／６０であった。処方２の配合処方にて物性評価を実施した。評価結果を表３に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 42.8% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 40/60. The physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 3.
　実施例１６
　ハロゲン化ポリオレフィンとして、実施例１５記載のクロロスルホン化ポリエチレンを用いて、共グラフト反応を実施した。 Example 16
Co-grafting reaction was carried out using the chlorosulfonated polyethylene described in Example 15 as the halogenated polyolefin.
　窒素雰囲気下４リットルのガラスフラスコにクロロスルホン化ポリエチレン１５０ｇ、１，１，２－トリクロロエタン２．０ｋｇを仕込み、内部を窒素で置換し、１１０℃に加熱してクロロスルホン化ポリエチレンを溶解した。内温を６５℃まで冷却した後、アクリロニトリル３９．８ｇ、アクリル酸２－メトキシエチル２１３．１ｇ、還元剤（大内新興化学工業（株）製　ノクセラー８；ｎ－ブチルアルデヒドアミン）２．０ｇを添加し、１，１，２－トリクロロエタン１４４ｇに溶解した溶解したラジカル開始剤（日油（株）製　パーブチルＯ；ｔ－ブチル－パーオキシ－２－エチルヘキサノエート）７．０ｇ溶液を５時間かけて滴下して反応を実施した。その後、１時間撹拌を継続し、得られた反応溶液をドラム乾燥機にて乾燥することにより、変性ハロゲン化ポリオレフィン組成物を得た。 In a 4 liter glass flask under nitrogen atmosphere, 150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 39.8 g of acrylonitrile, 213.1 g of 2-methoxyethyl acrylate, and 2.0 g of a reducing agent (Noxeller 8; n-butyraldehyde amine manufactured by Ouchi Shinsei Chemical Co., Ltd.) A 7.0 g solution of dissolved radical initiator dissolved in 144 g of 1,1,2-trichloroethane (NOF Corporation, perbutyl O; t-butyl-peroxy-2-ethylhexanoate) was added over 5 hours. The reaction was carried out dropwise. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は３２．１重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は４９／５１であった。処方２の配合処方にて物性評価を実施した。評価結果を表４に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 32.1% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 49/51. The physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 4.
　実施例１７
　ハロゲン化ポリオレフィンとして、実施例１５記載のクロロスルホン化ポリエチレンを用いて、共グラフト反応を実施した。 Example 17
Co-grafting reaction was carried out using the chlorosulfonated polyethylene described in Example 15 as the halogenated polyolefin.
　窒素雰囲気下４リットルのガラスフラスコにクロロスルホン化ポリエチレン１５０ｇ、１，１，２－トリクロロエタン２．０ｋｇを仕込み、内部を窒素で置換し、１１０℃に加熱してクロロスルホン化ポリエチレンを溶解した。内温を６５℃まで冷却した後、アクリロニトリル３９．８ｇ、アクリル酸２－メトキシエチル２１３．１ｇ、還元剤（大内新興化学工業（株）製　ノクセラー８；ｎ－ブチルアルデヒドアミン）２．０ｇを添加し、１，１，２－トリクロロエタン２８８ｇに溶解した溶解したラジカル開始剤（日油（株）製　パーブチルＯ；ｔ－ブチル－パーオキシ－２－エチルヘキサノエート）７．０ｇ溶液を１０時間かけて滴下して反応を実施した。その後、１時間撹拌を継続し、得られた反応溶液をドラム乾燥機にて乾燥することにより、変性ハロゲン化ポリオレフィン組成物を得た。 In a 4 liter glass flask under nitrogen atmosphere, 150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 39.8 g of acrylonitrile, 213.1 g of 2-methoxyethyl acrylate, and 2.0 g of a reducing agent (Noxeller 8; n-butyraldehyde amine manufactured by Ouchi Shinsei Chemical Co., Ltd.) Add a 7.0 g solution of dissolved radical initiator dissolved in 288 g of 1,1,2-trichloroethane (Perbutyl O; t-butyl-peroxy-2-ethylhexanoate, manufactured by NOF Corporation) over 10 hours. The reaction was carried out dropwise. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は４５．１重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３９／６１であった。処方２の配合処方にて物性評価を実施した。評価結果を表４に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 45.1% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl acrylate copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 39/61. The physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 4.
　実施例１８
　ハロゲン化ポリオレフィンとして、実施例１５記載のクロロスルホン化ポリエチレンを用いて、共グラフト反応を実施した。 Example 18
Co-grafting reaction was carried out using the chlorosulfonated polyethylene described in Example 15 as the halogenated polyolefin.
　窒素雰囲気下４リットルのガラスフラスコにクロロスルホン化ポリエチレン１５０ｇ、１，１，２－トリクロロエタン２．０ｋｇを仕込み、内部を窒素で置換し、１１０℃に加熱してクロロスルホン化ポリエチレンを溶解した。内温を６５℃まで冷却した後、アクリロニトリル３９．８ｇ、アクリル酸２－メトキシエチル２１３．１ｇ、還元剤（大内新興化学工業（株）製　ノクセラー８；ｎ－ブチルアルデヒドアミン）２．０ｇを添加し、１，１，２－トリクロロエタン２８８ｇに溶解した溶解したラジカル開始剤（日油（株）製　パーブチルＯ；ｔ－ブチル－パーオキシ－２－エチルヘキサノエート）１４．０ｇ溶液を１０時間かけて滴下して反応を実施した。その後、１時間撹拌を継続し、得られた反応溶液をドラム乾燥機にて乾燥することにより、変性ハロゲン化ポリオレフィン組成物を得た。 In a 4 liter glass flask under nitrogen atmosphere, 150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 39.8 g of acrylonitrile, 213.1 g of 2-methoxyethyl acrylate, and 2.0 g of a reducing agent (Noxeller 8; n-butyraldehyde amine manufactured by Ouchi Shinsei Chemical Co., Ltd.) Add 14.0 g solution of dissolved radical initiator dissolved in 288 g of 1,1,2-trichloroethane (Perbutyl O; manufactured by NOF Corporation; t-butyl-peroxy-2-ethylhexanoate) over 10 hours. The reaction was carried out dropwise. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は５２．３重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３０／７０であった。処方２の配合処方にて物性評価を実施した。評価結果を表４に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 52.3% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl acrylate copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 30/70. The physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 4.
　実施例１９
　不飽和単量体を、アクリロニトリル１００．０ｇ、アクリル酸２－メトキシエチル２６８．４ｇ、メタクリル酸グリシジル１０．９ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 19
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 100.0 g of acrylonitrile, 268.4 g of 2-methoxyethyl acrylate, and 10.9 g of glycidyl methacrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体含有率は５６．６重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル／メタクリル酸グリシジル比率は３１／６４／５であった。処方３の配合処方にて物性評価を実施した。評価結果を表４に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 56.6% by weight, and acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer. The combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate ratio was 31/64/5. The physical properties were evaluated according to the formulation of formulation 3. The evaluation results are shown in Table 4.
　実施例２０
　不飽和単量体の仕込量を、アクリロニトリル３９．８ｇ、メタクリル酸グリシジル１１．０ｇ、アクリル酸ｎ－ブチル９６．１ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 20
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the amount of the unsaturated monomer charged was changed to 39.8 g of acrylonitrile, 11.0 g of glycidyl methacrylate, and 96.1 g of n-butyl acrylate. It was.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－メタクリル酸グリシジル－アクリル酸ｎ－ブチル共重合体（エポキシ基含有共重合体）含有率は３２．５重量％であり、アクリロニトリル－メタクリル酸グリシジル－アクリル酸ｎ－ブチル共重合体のアクリロニトリル／アクリル酸ｎ－ブチル比率は２９／７１であった。処方４の配合処方にて物性評価を実施した。評価結果を表４に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-n-butyl acrylate copolymer (epoxy group-containing copolymer) content of 32.5% by weight, and acrylonitrile-glycidyl methacrylate-acrylic. The acrylonitrile / n-butyl acrylate ratio of the acid n-butyl copolymer was 29/71. The physical properties were evaluated according to the formulation of formulation 4. The evaluation results are shown in Table 4.
　実施例２１
　不飽和単量体の仕込量を、アクリロニトリル１０３．９ｇ、メタクリル酸グリシジル１１．０ｇ、アクリル酸エチル１９６．１ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 21
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the amount of the unsaturated monomer charged was changed to 103.9 g of acrylonitrile, 11.0 g of glycidyl methacrylate, and 196.1 g of ethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－メタクリル酸グリシジル－アクリル酸エチル共重合体含有率は５４．４重量％であり、アクリロニトリル－メタクリル酸グリシジル－アクリル酸エチル共重合体のアクリロニトリル／アクリル酸エチル比率は３５／６５であった。処方４の配合処方にて物性評価を実施した。評価結果を表４に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-ethyl acrylate copolymer content of 54.4% by weight and an acrylonitrile / acrylic acid acrylonitrile-glycidyl methacrylate-ethyl acrylate copolymer. The ethyl ratio was 35/65. The physical properties were evaluated according to the formulation of formulation 4. The evaluation results are shown in Table 4.
　実施例２２
　不飽和単量体を、アクリロニトリル１００．０ｇ、メタクリル酸グリシジル１１．０ｇアクリル酸２－メトキシエチル２６８．４ｇに変更した以外は実施例２０と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 22
A modified halogenated polyolefin composition was obtained in the same manner as in Example 20 except that the unsaturated monomer was changed to 100.0 g of acrylonitrile, 11.0 g of glycidyl methacrylate, and 268.4 g of 2-methoxyethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－メタクリル酸グリシジル－アクリル酸２－メトキシエチル共重合体含有率は５６．３重量％であり、アクリロニトリル－メタクリル酸グリシジル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３３／６７であった。処方５の配合処方にて物性評価を実施した。評価結果を表５に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 56.3% by weight, and the acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer. The combined acrylonitrile / 2-methoxyethyl acrylate ratio was 33/67. The physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
　実施例２３
　ハロゲン化ポリオレフィンとして、ＴＯＳＯＨ－ＣＳＭ　ＴＳ－５３０（東ソー（株）製　クロロスルホン化ポリエチレン、塩素量３５．６重量％、硫黄量１．０３重量％、ムーニー粘度ＭＬ１＋４＝５６）を用いて、共グラフト反応を実施した。 Example 23
Co-grafting using TOSOH-CSM TS-530 (Chlorosulfonated polyethylene manufactured by Tosoh Corporation, chlorine content 35.6% by weight, sulfur content 1.03% by weight, Mooney viscosity ML1 + 4 = 56) as halogenated polyolefin The reaction was carried out.
　窒素雰囲気下４リットルのガラスフラスコにクロロスルホン化ポリエチレン１５０ｇ、１，１，２－トリクロロエタン２．０ｋｇを仕込み、内部を窒素で置換し、１１０℃に加熱してクロロスルホン化ポリエチレンを溶解した。内温を６５℃まで冷却した後、アクリロニトリル１００．０ｇ、メタクリル酸グリシジル２３．０ｇ、アクリル酸２－メトキシエチル３０８．０ｇを添加し、１，１，２－トリクロロエタン１４４ｇに溶解したラジカル開始剤（日油（株）製　パーロイルＯＰＰ；ジ－２－エチルヘキシル－パーオキシジカーボネート）３．７ｇを溶解した溶液を５時間かけて滴下して反応を実施した。その後、１時間撹拌を継続し、得られた反応溶液をドラム乾燥機にて乾燥することにより、変性ハロゲン化ポリオレフィン組成物を得た。 In a 4 liter glass flask under nitrogen atmosphere, 150 g of chlorosulfonated polyethylene and 2.0 kg of 1,1,2-trichloroethane were charged, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 100.0 g of acrylonitrile, 23.0 g of glycidyl methacrylate and 308.0 g of 2-methoxyethyl acrylate were added, and a radical initiator dissolved in 144 g of 1,1,2-trichloroethane ( A reaction in which 3.7 g of Perroyl OPP (di-2-ethylhexyl-peroxydicarbonate) manufactured by NOF Corporation was dissolved was dropped over 5 hours to carry out the reaction. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－メタクリル酸グリシジル－アクリル酸２－メトキシエチル共重合体含有率は５８．８重量％であり、アクリロニトリル－メタクリル酸グリシジル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３１／６９であった。処方５の配合処方にて物性評価を実施した。評価結果を表５に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 58.8% by weight, and acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer. The combined acrylonitrile / 2-methoxyethyl acrylate ratio was 31/69. The physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
　実施例２４
　不飽和単量体を、アクリロニトリル１０６．０ｇ、メタクリル酸グリシジル３６．０ｇ、アクリル酸２－メトキシエチル３６１．０ｇに変更した以外は実施例２３と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 24
A modified halogenated polyolefin composition was obtained in the same manner as in Example 23, except that the unsaturated monomer was changed to 106.0 g of acrylonitrile, 36.0 g of glycidyl methacrylate, and 361.0 g of 2-methoxyethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－メタクリル酸グリシジル－アクリル酸２－メトキシエチル共重合体含有率は６３．４重量％であり、アクリロニトリル－メタクリル酸グリシジル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は２９／７１であった。処方５の配合処方にて物性評価を実施した。評価結果を表５に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 63.4% by weight, and an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer. The combined acrylonitrile / 2-methoxyethyl acrylate ratio was 29/71. The physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
　実施例２５
　ハロゲン化ポリオレフィンとして、ＴＯＳＯＨ－ＣＳＭ　ＴＳ－５３０（東ソー（株）製　クロロスルホン化ポリエチレン、塩素量３５．６重量％、硫黄量１．０３重量％、ムーニー粘度ＭＬ１＋４＝５６）を用いて、共グラフト反応を実施した。 Example 25
Co-grafting using TOSOH-CSM TS-530 (Chlorosulfonated polyethylene manufactured by Tosoh Corporation, chlorine content 35.6% by weight, sulfur content 1.03% by weight, Mooney viscosity ML1 + 4 = 56) as halogenated polyolefin The reaction was carried out.
　窒素雰囲気下４リットルのガラスフラスコにクロロスルホン化ポリエチレン１５０ｇ、１，１，２－トリクロロエタン２．５ｋｇを仕込み、内部を窒素で置換し、１１０℃に加熱してクロロスルホン化ポリエチレンを溶解した。内温を６５℃まで冷却した後、アクリロニトリル８６．９ｇ、メタクリル酸グリシジル１１．０ｇ、アクリル酸２－メトキシエチル２１３．１ｇ、還元剤（大内新興化学工業（株）製　ノクセラー８；ｎ－ブチルアルデヒドアミン）２．０ｇを添加し、１，１，２－トリクロロエタン１４４ｇにラジカル開始剤（日油（株）製　パーブチルＯ；ｔ－ブチル－パーオキシ－２－エチルヘキサノエート）１４．０ｇを溶解した溶液を５時間かけて滴下して反応を実施した。その後、１時間撹拌を継続し、得られた反応溶液をドラム乾燥機にて乾燥することにより、変性ハロゲン化ポリオレフィン組成物を得た。 In a 4 liter glass flask under a nitrogen atmosphere, 150 g of chlorosulfonated polyethylene and 2.5 kg of 1,1,2-trichloroethane were charged, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 86.9 g of acrylonitrile, 11.0 g of glycidyl methacrylate, 213.1 g of 2-methoxyethyl acrylate, a reducing agent (Noxeller 8 manufactured by Ouchi Shinsei Chemical Co., Ltd .; n-butyl) 2.0 g of aldehyde amine) was added and 14.0 g of radical initiator (Perbutyl O; t-butyl-peroxy-2-ethylhexanoate) manufactured by NOF Corporation was dissolved in 144 g of 1,1,2-trichloroethane. The solution was added dropwise over 5 hours to carry out the reaction. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－メタクリル酸グリシジル－アクリル酸２－メトキシエチル共重合体含有率は５５．１重量％であり、アクリロニトリル－メタクリル酸グリシジル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３２／６８であった。処方５の配合処方にて物性評価を実施した。評価結果を表５に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 55.1% by weight, and the acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer. The combined acrylonitrile / 2-methoxyethyl acrylate ratio was 32/68. The physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
　実施例２６
　ハロゲン化ポリオレフィンとして、ＴＯＳＯ－ＣＳＭ　ＴＳ－８３０（東ソー株式会社製）を用い、不飽和単量体を、アクリロニトリル１００．７ｇ、アクリル酸２－メトキシエチル３１７．３ｇ、メタクリル酸グリシジル２２．２ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 26
Using TOSO-CSM TS-830 (manufactured by Tosoh Corporation) as the halogenated polyolefin, the unsaturated monomer was changed to 100.7 g of acrylonitrile, 317.3 g of 2-methoxyethyl acrylate, and 22.2 g of glycidyl methacrylate. A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体含有率は６１．０重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル／メタクリル酸グリシジル比率は２８／６３／９であった。処方５の配合処方にて物性評価を実施した。評価結果を表５に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 61.0% by weight, and acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer. The combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate ratio was 28/63/9. The physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
　実施例２７
　不飽和単量体を、アクリロニトリル５６．０ｇ、アクリル酸２－メトキシエチル３１４．６ｇ、メタクリル酸グリシジル２１．９ｇに変更した以外は実施例２６と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 27
A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 56.0 g of acrylonitrile, 314.6 g of 2-methoxyethyl acrylate, and 21.9 g of glycidyl methacrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体含有率は６２．１重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル／メタクリル酸グリシジル比率は１７／７４／９であった。処方５の配合処方にて物性評価を実施した。評価結果を表５に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 62.1% by weight, and an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer. The combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate ratio was 17/74/9. The physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
　実施例２８
　不飽和単量体を、アクリロニトリル３６．４ｇ、アクリル酸２－メトキシエチル２８２．２ｇ、メタクリル酸グリシジル２１．５ｇに変更した以外は実施例２６と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 28
A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 36.4 g of acrylonitrile, 282.2 g of 2-methoxyethyl acrylate, and 21.5 g of glycidyl methacrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体含有率は６１．９重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル／メタクリル酸グリシジル比率は１２／８１／９であった。処方５の配合処方にて物性評価を実施した。評価結果を表５に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 61.9% by weight, and an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer. The combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate ratio was 12/81/9. The physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
　実施例２９
　不飽和単量体を、アクリロニトリル２０．８ｇ、アクリル酸２－メトキシエチル２９８．６ｇ、メタクリル酸グリシジル２１．５ｇに変更した以外は実施例２６と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 29
A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 20.8 g of acrylonitrile, 298.6 g of 2-methoxyethyl acrylate, and 21.5 g of glycidyl methacrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体含有率は６５．５重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル／メタクリル酸グリシジル比率は６／８７／７であった。処方５の配合処方にて物性評価を実施した。評価結果を表５に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 65.5% by weight, and acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer. The ratio of the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate was 6/87/7. The physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
　実施例３０
　不飽和単量体を、アクリロニトリル１６．７ｇ、アクリル酸２－メトキシエチル３２８．６ｇ、メタクリル酸グリシジル２０．１ｇに変更した以外は実施例２６と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Example 30
A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 16.7 g of acrylonitrile, 328.6 g of 2-methoxyethyl acrylate, and 20.1 g of glycidyl methacrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体含有率は６７．７重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル－メタクリル酸グリシジル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル／メタクリル酸グリシジル比率は４／９０／６であった。処方５の配合処方にて物性評価を実施した。評価結果を表６に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 67.7% by weight, and the acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer The ratio of the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate was 4/90/6. The physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 6.
　比較例１
　ハロゲン化ポリオレフィンとして、実施例１記載のクロロスルホン化ポリエチレンを用いて、共グラフト反応を実施した。 Comparative Example 1
Co-grafting reaction was carried out using the chlorosulfonated polyethylene described in Example 1 as the halogenated polyolefin.
　窒素雰囲気下４リットルのガラスフラスコにクロロスルホン化ポリエチレン２５０ｇ、１，１，２－トリクロロエタン２．５ｋｇを仕込み、内部を窒素で置換し、１１０℃に加熱してクロロスルホン化ポリエチレンを溶解した。内温を６５℃まで冷却した後、アクリロニトリル６６．３ｇを添加し、１，１，２－トリクロロエタン１１５ｇに溶解した溶解したラジカル開始剤（日油（株）製　パーロイルＯＰＰ；ジ－２－エチルヘキシル－パーオキシジカーボネート）４．０ｇ溶液を４時間かけて滴下して反応を実施した。その後、１時間撹拌を継続し、得られた反応溶液をドラム乾燥機にて乾燥することにより、変性ハロゲン化ポリオレフィン組成物を得た。 In a 4 liter glass flask under a nitrogen atmosphere, 250 g of chlorosulfonated polyethylene and 2.5 kg of 1,1,2-trichloroethane were charged, the inside was replaced with nitrogen, and the mixture was heated to 110 ° C. to dissolve the chlorosulfonated polyethylene. After cooling the internal temperature to 65 ° C., 66.3 g of acrylonitrile was added, and the dissolved radical initiator dissolved in 115 g of 1,1,2-trichloroethane (Perroyl OPP manufactured by NOF Corporation; di-2-ethylhexyl- Peroxydicarbonate) 4.0 g solution was added dropwise over 4 hours to carry out the reaction. Thereafter, stirring was continued for 1 hour, and the resulting reaction solution was dried with a drum dryer to obtain a modified halogenated polyolefin composition.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル重合体含有率は９．７重量％であった。処方１の配合処方にて物性評価を実施した。評価結果を表６に示す。耐油性が不十分であった。 The resulting modified halogenated polyolefin composition had an acrylonitrile polymer content of 9.7% by weight. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 6. Oil resistance was insufficient.
　比較例２
　グラフト反応に於いて、クロロスルホン化ポリエチレン１５０ｇ、アクリロニトリル７９．６ｇに変更した以外は比較例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Comparative Example 2
A modified halogenated polyolefin composition was obtained in the same manner as in Comparative Example 1 except that the graft reaction was changed to 150 g of chlorosulfonated polyethylene and 79.6 g of acrylonitrile.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル重合体含有率は１５．２重量％であった。処方１の配合処方にて物性評価を実施した。評価結果を表６に示す。配合物のムーニー粘度が高く、成形性に問題を有する。 The resulting modified halogenated polyolefin composition had an acrylonitrile polymer content of 15.2% by weight. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 6. The Mooney viscosity of the blend is high and has problems with moldability.
　比較例３
　グラフト反応に於いて、クロロスルホン化ポリエチレン１００ｇ、アクリロニトリル１０６．１ｇ、ラジカル開始剤５．９ｇに変更した以外は比較例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Comparative Example 3
A modified halogenated polyolefin composition was obtained in the same manner as in Comparative Example 1 except that the graft reaction was changed to 100 g of chlorosulfonated polyethylene, 106.1 g of acrylonitrile, and 5.9 g of radical initiator.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル重合体含有率は３１．３重量％であった。処方１の配合処方にて物性評価を実施した。評価結果を表６に示す。配合物のムーニー粘度が高く、引張物性の破断伸びが劣ることから問題を有する。 The resulting modified halogenated polyolefin composition had an acrylonitrile polymer content of 31.3% by weight. The physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 6. There is a problem because the Mooney viscosity of the blend is high and the elongation at break of tensile properties is inferior.
　比較例４
　窒素雰囲気下４リットルのガラスフラスコに１，１，２－トリクロロエタン２．５ｋｇを仕込み、内部を窒素で置換し、内温を６５℃まで昇温した後、アクリロニトリル８３．３ｇ、アクリル酸２－メトキシエチル２３３．７ｇを添加し、１，１，２－トリクロロエタン１４４ｇに溶解したラジカル開始剤（日油（株）製　パーロイルＯＰＰ；ジ－２－エチルヘキシル－パーオキシジカーボネート）３．７ｇを溶解した溶液を５時間かけて滴下して反応を実施した。その後、１時間撹拌を継続した。その後、実施例１と同じクロロスルホン化ポリエチレン１２５ｇを添加し、完全に溶解するまで撹拌を継続した。得られた反応溶液をドラム乾燥機にて乾燥する際、フィルムの粘着性が高く、強度が弱いため、フィルムとして取り出すことが不可能であった。 Comparative Example 4
In a 4 liter glass flask under a nitrogen atmosphere, 2.5 kg of 1,1,2-trichloroethane was charged, the inside was replaced with nitrogen, the internal temperature was raised to 65 ° C., 83.3 g of acrylonitrile, 2-methoxyacrylate, A solution in which 3.73.7 g of ethyl was added and 3.7 g of a radical initiator dissolved in 144 g of 1,1,2-trichloroethane (paroyl OPP manufactured by NOF Corporation; di-2-ethylhexyl-peroxydicarbonate) was dissolved. Was added dropwise over 5 hours to carry out the reaction. Thereafter, stirring was continued for 1 hour. Thereafter, 125 g of the same chlorosulfonated polyethylene as in Example 1 was added, and stirring was continued until it was completely dissolved. When the obtained reaction solution was dried with a drum dryer, it was impossible to take out as a film because the film had high adhesiveness and low strength.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は５６．９重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３２／６８であった。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 56.9% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 32/68.
　得られた変性ハロゲン化ポリオレフィン組成物は、粘度が低く、物性評価のための混練作業が困難であったため、物性評価ができなかった。 The obtained modified halogenated polyolefin composition had a low viscosity and was difficult to knead for physical property evaluation, so physical property evaluation could not be performed.
　比較例５
　不飽和単量体を、アクリロニトリル１００．０ｇ、アクリル酸２－メトキシエチル２６８．４ｇに変更し、反応後に溶解するクロロスルホン化ポリエチレンをＴＯＳＯＨ－ＣＳＭ　ＴＳ－５３０（東ソー（株）製　クロロスルホン化ポリエチレン、塩素量３５．３重量％、硫黄量１．０１重量％、ムーニー粘度ＭＬ１＋４＝９０）に変更した以外は比較例４と同様にして変性ハロゲン化ポリオレフィン組成物の溶液を得た。得られた反応溶液をドラム乾燥機にて乾燥する際、フィルムの粘着性が高く、強度が弱いため、フィルムとして取り出すことが不可能であった。 Comparative Example 5
The unsaturated monomer was changed to 100.0 g of acrylonitrile and 268.4 g of 2-methoxyethyl acrylate, and chlorosulfonated polyethylene dissolved after the reaction was changed to TOSOH-CSM TS-530 (chloro-sulfonated polyethylene manufactured by Tosoh Corporation). A modified halogenated polyolefin composition solution was obtained in the same manner as in Comparative Example 4 except that the chlorine content was 35.3% by weight, the sulfur content was 1.01% by weight, and the Mooney viscosity ML1 + 4 = 90. When the obtained reaction solution was dried with a drum dryer, it was impossible to take out as a film because the film had high adhesiveness and low strength.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は６２．８重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３０／７０であった。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 62.8% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 30/70.
　得られた変性ハロゲン化ポリオレフィン組成物は、粘度が低く、物性評価のための混練作業が困難であったため、物性評価ができなかった。 The obtained modified halogenated polyolefin composition had a low viscosity and was difficult to knead for physical property evaluation, so physical property evaluation could not be performed.
　比較例６
　不飽和単量体を、アクリロニトリル１００．０ｇ、アクリル酸２－メトキシエチル２６８．４ｇに変更した以外は実施例１と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Comparative Example 6
A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 100.0 g of acrylonitrile and 268.4 g of 2-methoxyethyl acrylate.
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－アクリル酸２－メトキシエチル共重合体含有率は５５．８重量％であり、アクリロニトリル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３０／７０であった。処方４および処方５の配合処方にて混練したが、架橋反応が進行しなかったため物性評価は困難であった。 The resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 55.8% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 30/70. Although kneading was carried out with the formulation of Formula 4 and Formula 5, the physical property evaluation was difficult because the crosslinking reaction did not proceed.
　比較例７
　不飽和単量体を、アクリロニトリル１０６．０ｇ、メタクリル酸グリシジル、６７．０ｇ、アクリル酸２－メトキシエチル３６１．０ｇに変更した以外は実施例２４と同様にして変性ハロゲン化ポリオレフィン組成物を得た。 Comparative Example 7
A modified halogenated polyolefin composition was obtained in the same manner as in Example 24 except that the unsaturated monomer was changed to 106.0 g of acrylonitrile, glycidyl methacrylate, 67.0 g, and 361.0 g of 2-methoxyethyl acrylate. .
　得られた変性ハロゲン化ポリオレフィン組成物のアクリロニトリル－メタクリル酸グリシジル－アクリル酸２－メトキシエチル共重合体含有率は６５重量％であり、アクリロニトリル－メタクリル酸グリシジル－アクリル酸２－メトキシエチル共重合体のアクリロニトリル／アクリル酸２－メトキシエチル比率は３１／６９であった。処方２の配合処方にて物性評価を実施した。評価結果を表６に示す。 The resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 65% by weight, and the acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer The acrylonitrile / 2-methoxyethyl acrylate ratio was 31/69. The physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 6.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　本発明を詳細に、また特定の実施態様を参照して説明したが、本発明の本質と範囲を逸脱することなく、様々な変更や修正を加えることができることは当業者にとって明らかである。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
　なお、２０１５年１１月１７日に出願された日本特許出願２０１５－２２４８６２号及び２０１５年１２月２２日に出願された日本特許出願２０１５－２５０２７０号の明細書、特許請求の範囲及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 It should be noted that all of the specifications, claims and abstracts of Japanese Patent Application No. 2015-224862 filed on November 17, 2015 and Japanese Patent Application No. 2015-250270 filed on December 22, 2015. The contents of which are hereby incorporated herein by reference.

Claims (15)

  1. ハロゲン化ポリオレフィンにアクリロニトリルとアクリル系化合物の共重合体が結合したグラフト共重合体と、ハロゲン化ポリオレフィンに結合していないアクリロニトリルとアクリル系化合物の共重合体を含有する変性ハロゲン化ポリオレフィン組成物を加硫して成る加硫組成物。 A graft copolymer in which a copolymer of acrylonitrile and an acrylic compound is bonded to a halogenated polyolefin, and a modified halogenated polyolefin composition containing a copolymer of acrylonitrile and an acrylic compound not bonded to the halogenated polyolefin are added. A vulcanized composition obtained by vulcanization.
  2. ハロゲン化ポリオレフィンがクロロスルホン化ポリオレフィンであることを特徴とする請求項１記載の加硫組成物。 The vulcanized composition according to claim 1, wherein the halogenated polyolefin is a chlorosulfonated polyolefin.
  3. グラフト共重合体中のアクリロニトリルとアクリル系化合物の共重合体と、ハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル系化合物の共重合体の重量比率が３／９７～７０／３０の範囲であることを特徴とする請求項１又は請求項２に記載の加硫組成物。 The weight ratio of the copolymer of acrylonitrile and acrylic compound in the graft copolymer to the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin is in the range of 3/97 to 70/30. The vulcanized composition according to claim 1 or 2, wherein
  4. 変性ハロゲン化ポリオレフィン組成物中のハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル系化合物の共重合体及びグラフト共重合体中のアクリロニトリルとアクリル系化合物の共重合体の合計の含有率が２０重量％から７５重量％の範囲であることを特徴とする請求項１乃至請求項３のいずれかに記載の加硫組成物。 The total content of the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition and the copolymer of acrylonitrile and acrylic compound in the graft copolymer is 20% by weight. The vulcanized composition according to any one of claims 1 to 3, wherein the vulcanized composition is in the range of from 75 to 75% by weight.
  5. ハロゲン化ポリオレフィンと結合していないアクリロニトリルとアクリル系化合物の共重合体及びグラフト共重合体に含まれるアクリロニトリルとアクリル系化合物由来の成分の重量比率が、３／９７～７０／３０の範囲であることを特徴とする請求項１乃至４のいずれかに記載の加硫組成物。 The weight ratio of the components derived from acrylonitrile and the acrylic compound contained in the copolymer of acrylonitrile and the acrylic compound not bonded to the halogenated polyolefin and the graft copolymer is in the range of 3/97 to 70/30. The vulcanized composition according to any one of claims 1 to 4, wherein:
  6. アクリル系化合物がアクリル酸２－メトキシエチルであることを特徴とする請求項１乃至請求項５のいずれかに記載の加硫組成物。 The vulcanized composition according to any one of claims 1 to 5, wherein the acrylic compound is 2-methoxyethyl acrylate.
  7. ハロゲン化ポリオレフィンに、アクリロニトリル、エポキシ基含有化合物及びアクリル系化合物を含有する不飽和単量体の共重合体（以下、エポキシ基含有共重合体という）が結合したグラフト共重合体。 A graft copolymer in which a copolymer of an unsaturated monomer containing acrylonitrile, an epoxy group-containing compound and an acrylic compound (hereinafter referred to as an epoxy group-containing copolymer) is bonded to a halogenated polyolefin.
  8. 請求項７記載のグラフト共重合体及びハロゲン化ポリオレフィンに結合していないエポキシ基含有共重合体を含有することを特徴とする変性ハロゲン化ポリオレフィン組成物。 A modified halogenated polyolefin composition comprising the graft copolymer according to claim 7 and an epoxy group-containing copolymer which is not bonded to the halogenated polyolefin.
  9. 変性ハロゲン化ポリオレフィン組成物中のグラフト共重合体中のエポキシ基含有共重合体と、ハロゲン化ポリオレフィンと結合していないエポキシ基含有共重合体の合計の含有率が２０重量％から７５重量％の範囲であり、そのエポキシ基含有共重合体中のアクリロニトリルとアクリル系化合物由来の成分の重量比率が３／９７～７０／３０の範囲であることを特徴とする請求項８に記載の変性ハロゲン化ポリオレフィン組成物。 The total content of the epoxy group-containing copolymer in the graft copolymer in the modified halogenated polyolefin composition and the epoxy group-containing copolymer not bonded to the halogenated polyolefin is 20% by weight to 75% by weight. The modified halogenation according to claim 8, wherein the weight ratio of the component derived from acrylonitrile and the acrylic compound in the epoxy group-containing copolymer is in the range of 3/97 to 70/30. Polyolefin composition.
  10. エポキシ基含有化合物由来の成分の含有率が１重量％から１２重量％の範囲であることを特徴とする請求項８又は９に記載の変性ハロゲン化ポリオレフィン組成物。 The modified halogenated polyolefin composition according to claim 8 or 9, wherein the content of the component derived from the epoxy group-containing compound is in the range of 1 wt% to 12 wt%.
  11. グラフト共重合体中のエポキシ基含有共重合体と、ハロゲン化ポリオレフィンに結合していないエポキシ基含有共重合体の重量比率が３／９７から７０／３０の範囲であることを特徴とする請求項８又は１０に記載の変性ハロゲン化ポリオレフィン組成物。 The weight ratio of the epoxy group-containing copolymer in the graft copolymer to the epoxy group-containing copolymer not bonded to the halogenated polyolefin is in the range of 3/97 to 70/30. The modified halogenated polyolefin composition according to 8 or 10.
  12. ハロゲン化ポリオレフィンがクロロスルホン化ポリエチレンであることを特徴とする請求項８乃至請求項１１のいずれかに記載の変性ハロゲン化ポリオレフィン組成物。 The modified halogenated polyolefin composition according to any one of claims 8 to 11, wherein the halogenated polyolefin is chlorosulfonated polyethylene.
  13. アクリル系化合物がアクリル酸２－メトキシエチルであることを特徴とする請求項８乃至請求項１２のいずれかに記載の変性ハロゲン化ポリオレフィン組成物。 The modified halogenated polyolefin composition according to any one of claims 8 to 12, wherein the acrylic compound is 2-methoxyethyl acrylate.
  14. エポキシ基含有化合物がアクリル酸グリシジル及び／又はメタクリル酸グリシジルであることを特徴とする請求項８乃至請求項１３のいずれかに記載の変性ハロゲン化ポリオレフィン組成物。 The modified halogenated polyolefin composition according to any one of claims 8 to 13, wherein the epoxy group-containing compound is glycidyl acrylate and / or glycidyl methacrylate.
  15. 特徴とする請求項８乃至請求項１４のいずれかに記載の変性ハロゲン化ポリオレフィン組成物を加硫して成る加硫組成物。 A vulcanized composition obtained by vulcanizing the modified halogenated polyolefin composition according to any one of claims 8 to 14.
PCT/JP2016/083966 2015-11-17 2016-11-16 Vulcanized composition of modified halogenated polyolefin composition WO2017086347A1 (en)

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