Classifications

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  • 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
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
• • 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
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/014—Stabilisers against oxidation, heat, light or ozone
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
  • C08L11/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/08—Styrene
• • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
  • C08F212/36—Divinylbenzene
• • 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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • 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
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
  • C08F236/16—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
  • C08F236/18—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen containing chlorine
• • 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
  • C08F2438/00—Living radical polymerisation
  • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

• the present invention relates to a chloroprene-based block copolymer, latex, latex composition and rubber composition.
• Patent Document 6 As a method for chemically bonding molecules without vulcanization, the technique described in Patent Document 6 is known.
• polychloroprene-based rubber compositions have been treated with vulcanizing agents such as sulfur, zinc oxide, and magnesium oxide, and thiuram-based, dithiocarbamate-based, thiourea-based, guanidine-based, and xanthogenic acid.
• vulcanizing agents such as sulfur, zinc oxide, and magnesium oxide
• salt-based, thiazole-based vulcanization accelerators was essential. Since the vulcanization accelerator is a causative agent of type IV allergy that causes skin diseases such as dermatitis, the reduction or non-use of vulcanization accelerators has become an important theme. In addition, reducing or eliminating the use of vulcanization accelerators not only reduces allergies but also reduces costs, so a rubber composition that exhibits sufficient mechanical strength even with a reduced amount of vulcanization accelerator is desired.
• the present invention is to obtain a molded article having excellent tensile strength at break, tensile elongation at break, and 25% modulus even if the vulcanizing agent or vulcanization accelerator is reduced or not used.
• a chloroprene block copolymer latex, latex composition and rubber composition.
• a polymer block (A) derived from a monomer that provides a polymer having a glass transition temperature of 80° C. or higher when homopolymerized, chloroprene monomer units and polyfunctional monomers A chloroprene-based block copolymer containing 40 to 70% by mass of a chloroprene-based polymer block (B) having monomer units is provided.
• a latex containing the chloroprene-based block copolymer described above there is provided a latex containing the chloroprene-based block copolymer described above. Further, according to another aspect of the present invention, there is provided a latex composition comprising 100 parts by mass of the latex described above and 0.5 to 5.0 parts by mass of an antioxidant. According to another aspect of the present invention, there is provided a rubber composition containing the chloroprene-based block copolymer described above. Moreover, according to another aspect of the present invention, there is provided a rubber composition containing the latex described above.
• the molded product of the latex composition containing the chloroprene-based block copolymer has a 25% modulus of 2.5 MPa or more measured according to JIS K6251 after being heat-treated at 130° C.
• the described chloroprene-based block copolymer [3] The molded article of the latex composition containing the chloroprene-based block copolymer has a tensile strength at break of 20 MPa or more measured according to JIS K 6251 after being heat-treated at 130° C. for 30 minutes. ] The chloroprene-based block copolymer according to . [4] The chloroprene-based block copolymer according to any one of [1] to [3], wherein the polymer block (A) has a number average molecular weight of 10,000 or more.
• R 1 and R 2 are each independently hydrogen, chlorine, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted represents either a mercapto group or a substituted or unsubstituted heterocyclyl group
• W 1 is a saturated or unsaturated hydrocarbon group, a saturated or unsaturated cyclic hydrocarbon group, or a saturated or unsaturated hydrocarbon group containing a hetero atom
• , represents a saturated or unsaturated cyclic hydrocarbon group containing a hetero atom
• Z 1 represents a structure represented by oxygen, sulfur or —NR 0 —
• R 0 is hydrogen, chlorine, substituted or unsubstituted is an alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstitute
• R 3 is hydrogen, chlorine, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted mercapto group, substituted or unsubstituted represents any of the heterocyclyl groups of
• a molded article having excellent tensile strength at break, tensile elongation at break, and 25% modulus can be obtained even if vulcanizing agents and vulcanization accelerators are reduced or not used.
• Chloroprene-based block copolymers, latexes, latex compositions and rubber compositions are provided.
• the chloroprene-based block copolymer comprises a polymer block (A) derived from a monomer that gives a polymer having a glass transition temperature of 80° C. or higher when homopolymerized, and a chloroprene monomer and a polyfunctional monomer unit. It is a block copolymer containing a chloroprene-based polymer block (B) having The chloroprene-based block copolymer includes those having a structure in which the block copolymers are chemically bonded to each other via the polyfunctional monomer units contained in the chloroprene-based polymer block (B).
• the polymer block (A) is a polymer block derived from a monomer that gives a polymer having a glass transition temperature of 80° C. or higher upon homopolymerization. By using such a monomer, the tensile strength at break of the obtained chloroprene-based block copolymer is improved. It is preferable to use a monomer that gives a polymer having a glass transition temperature of 85° C. or higher. From the viewpoint of moldability, it is preferable that the monomer gives a polymer having a glass transition temperature of 150° C. or lower, and particularly preferably a monomer that gives a polymer having a glass transition temperature of 120° C. or lower. The glass transition temperature is, for example, 80, 85, 90, 95, 100, 105, 110, 120, 130, 140, 150 ° C., even if it is within the range between any two of the numerical values illustrated here good.
• the glass transition temperature is an extrapolated glass transition end temperature (Teg) measured in accordance with JIS K 7121.
• Teg extrapolated glass transition end temperature
• DSC1 manufactured by Mettler Toledo
• the polymer block (A) is a polymer block obtained by polymerizing the monomer (A)
• the monomer (A) homopolymerizes the monomer A and has a number average molecular weight of 10,000.
• the homopolymer (A) is preferably a monomer having the above glass transition temperature, and when a homopolymer (A) of a number average molecular weight of 30,000 to 700,000 is used, , the homopolymer (A) is more preferably a monomer having the above glass transition temperature.
• the monomer units constituting the polymer block (A) include aromatic vinyl monomer units, methyl methacrylate monomer units, and acrylonitrile monomer units.
• a unit derived from an aromatic vinyl monomer is preferably used, and a styrene unit is preferably used.
• the polymer block (A) is a polymer block obtained by copolymerization of these monomers, or a polymer block composed of monomer units copolymerizable with these monomers, as long as the object of the present invention is not impaired. It may be a coalescing block.
• the number average molecular weight of the polymer block (A) is preferably 10,000 or more from the viewpoint of tensile properties and moldability of the resulting chloroprene-based block copolymer.
• the number average molecular weight of the polymer block (A) is, for example, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, 55000, 60000, 65000, 70000, 75000, 80000, 85000, 90000, 95000, 100,000 and may be in the range between any two of the numbers exemplified here.
• the molecular weight distribution of the polymer block (A) is preferably 2.0 or less from the viewpoint of moldability.
• the molecular weight distribution of the polymer block (A) is, for example, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1 .9, 2.0, and may be in the range between any two of the numbers exemplified herein.
• the number average molecular weight and the weight average molecular weight are polystyrene equivalent values measured by gel permeation chromatography (GPC) under the measurement conditions described below.
• HLC-8320 manufactured by Tosoh Corporation
• Solvent Tetrahydrofuran
• Calibration curve Prepared using standard polystyrene (PS).
• the chloroprene-based polymer block (B) is a polymer block having chloroprene monomer (2-chloro-1,3-butadiene) units and polyfunctional monomer units.
• the chloroprene-based polymer block (B) includes chloroprene monomer units, polyfunctional monomer units, and monomer units copolymerizable with these monomers, as long as the object of the present invention is not impaired. It may be a polymer block consisting of.
• each structural unit in the chloroprene-based polymer block (B) is not particularly limited, but preferably 90 to 99.95% by mass of chloroprene monomer units and 0.95% by mass of polyfunctional monomer units. 05 to 10% by mass.
• the content of the polyfunctional monomer unit in the chloroprene-based polymer block (B) is, for example, 0.05, 0.50, 1.00, 2.00, 3.00, 4.00, 5.00. 00, 6.00, 7.00, 8.00, 9.00, 10.00% by mass, and may be within a range between any two of the numerical values exemplified here.
• the polyfunctional monomer according to the present invention is a compound having two or more radically polymerizable groups in its molecule.
• the polyfunctional monomer preferably has multiple independent polymerizable substituents.
• the polyfunctional monomer has at least one set of polymerizable substituents that are non-conjugated.
• at least one set of polymerizable substituents is preferably separated from each other by at least one atom, preferably by three or more atoms. It is preferable that at least one of them is sandwiched and spaced apart.
• the polymerizable substituents can be vinyl groups and can be carbon-carbon double bonds.
• Monomers represented by Chemical Formula (1) include 1.9-nonanediol dimethacrylate, 1.9-nonanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, and 1.6-hexanediol.
• the aromatic polyene monomer is an aromatic polyene having a carbon number of 10 or more and 30 or less and having a plurality of double bonds (vinyl groups) and one or more aromatic groups, such as o-divinyl Benzene, p-divinylbenzene, m-divinylbenzene, 1,4-divinylnaphthalene, 3,4-divinylnaphthalene, 2,6-divinylnaphthalene, 1,2-divinyl-3,4-dimethylbenzene, 1,3- units derived from aromatic polyene monomers such as divinyl-4,5,8-tributylnaphthalene, preferably one or two of orthodivinylbenzene units, paradivinylbenzene units and metadivinylbenzene units; A mixture of the above is preferably used.
• R 1 and R 2 are each independently hydrogen, chlorine, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted represents either a mercapto group or a substituted or unsubstituted heterocyclyl group
• W 1 is a saturated or unsaturated hydrocarbon group, a saturated or unsaturated cyclic hydrocarbon group, or a saturated or unsaturated hydrocarbon group containing a hetero atom
• , represents a saturated or unsaturated cyclic hydrocarbon group containing a hetero atom
• Z 1 represents a structure represented by oxygen, sulfur or —NR 0 —
• R 0 is hydrogen, chlorine, substituted or unsubstituted is an alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstitute
• Monomer units copolymerizable with chloroprene monomer units and polyfunctional monomer units include, for example, 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, styrene , acrylonitrile, methacrylonitrile, isoprene, butadiene.
• polyfunctional monomers shall not contain 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, styrene, acrylonitrile, methacrylonitrile, isoprene and butadiene.
• a chloroprene-based copolymer according to one embodiment of the present invention includes chloroprene monomer units and 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, styrene, acrylonitrile, and methacrylonitrile. , isoprene, and polyfunctional monomer units derived from polyfunctional monomers other than butadiene.
• the chloroprene-based copolymer according to one embodiment of the present invention is ⁇ Chloroprene monomer unit ⁇ Derived from polyfunctional monomers other than 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, styrene, acrylonitrile, methacrylonitrile, isoprene and butadiene It can have a polyfunctional monomer unit, a chloroprene monomer unit, and a monomer unit copolymerizable with the polyfunctional monomer unit.
• each structural unit of the chloroprene-based block copolymer is 30 to 60% by mass for the polymer block (A) and 40 to 70% by mass for the chloroprene-based polymer block (B), preferably the polymer block (A ) more than 30% by mass and 60% by mass or less, and 40% by mass or more and less than 70% by mass of the chloroprene-based polymer block (B).
• the polymer block (A) is at least the above lower limit, the obtained chloroprene-based block copolymer has improved tensile strength at break.
• the polymer block (A) is equal to or less than the above upper limit, the elongation at break is improved.
• the content of the polymer block (A) contained in the chloroprene-based block copolymer is, for example, 30, 31, 32, 33, 34, 35, 40, 45, 50, 55, 60% by weight, can be greater than 30% by weight, and can be within a range between any two of the values exemplified herein.
• a chloroprene-based block copolymer according to one embodiment of the present invention can be composed of a polymer block (A) and a polymer block (B), and should not contain other polymer blocks. can be done.
• the chloroprene-based block copolymer can be a diblock copolymer of polymer block (A)-polymer block (B).
• the weight average molecular weight of the chloroprene-based block copolymer is not particularly limited, but is preferably 50,000 to 600,000, particularly preferably 100,000 to 500,000, from the viewpoint of moldability.
• the chloroprene-based block copolymer of the present embodiment has a tensile strength at break measured in accordance with JIS K 6251 after heat-treating a molded article of a latex composition containing the chloroprene-based block copolymer at 130°C for 30 minutes. is preferably 20 MPa or more.
• the tensile strength at break is more preferably greater than 25 MPa, even more preferably 30 MPa or greater, and even more preferably 32 MPa or greater.
• the upper limit is not particularly limited, it is, for example, 50 MPa or less.
• the chloroprene-based block copolymer of the present embodiment has a cutting time measured in accordance with JIS K 6251 after heat-treating a molded body of a latex composition containing the chloroprene-based block copolymer at 130°C for 30 minutes.
• the elongation is preferably 450% or more, more preferably 600% or more, and even more preferably 800% or more.
• the upper limit is not particularly limited, it is, for example, 1300% or less.
• the chloroprene-based block copolymer of the present embodiment has a 25% elongation measured in accordance with JIS K 6251 after heat-treating a molded body of a latex composition containing the chloroprene-based block copolymer at 130°C for 30 minutes.
• the modulus is preferably 2.5 MPa or more, more preferably 3.0 MPa, and even more preferably greater than 5.0 MPa.
• the upper limit is not particularly limited, it is, for example, 9.0 MPa or less.
• the chloroprene-based block copolymer of the present embodiment has the tensile strength, It can have an elongation at break and a modulus at 25% elongation.
• the molded article can be molded without using a vulcanizing agent and a vulcanization accelerator.
• a molded body for measuring tensile strength can be obtained by the method described in Examples.
• a polyfunctional compound contained in the chloroprene-based polymer block (B) The content of the organic monomer unit may be adjusted, or the content of the polymer block (A) in the chloroprene-based block copolymer may be adjusted.
• the polymerization mode is not particularly limited, and it can be produced by known methods such as solution polymerization, emulsion polymerization, and bulk polymerization, but emulsion polymerization is suitable for obtaining the desired chloroprene-based block copolymer.
• the polymerization method is not particularly limited as long as the desired chloroprene-based block copolymer can be obtained.
• the polymerization step 2 for synthesizing the chloroprene-based polymer block (B) is performed. It is preferable to manufacture by a manufacturing method through a two-stage polymerization process consisting of.
• Polymerization step 1 In the polymerization step 1, the monomers constituting the polymer block (A) are subjected to living radical polymerization to synthesize the polymer block (A). As described above, the polymer block (A) obtained here preferably has the glass transition temperature described above.
• the emulsifier used in the polymerization is not particularly limited, but anionic or nonionic emulsifiers are preferred from the viewpoint of emulsion stability. In particular, it is preferable to use an alkali metal rosin acid salt because the chloroprene-based block copolymer to be obtained can be given appropriate strength to prevent excessive shrinkage and breakage.
• the concentration of the emulsifier is preferably 5 to 50% by mass with respect to 100% by mass of the monomers constituting the polymer block (A) from the viewpoint of efficient polymerization reaction.
• known radical polymerization initiators can be used, such as potassium persulfate, benzoyl peroxide, hydrogen peroxide, and azo compounds.
• the polymerization temperature may be appropriately determined according to the type of monomer, but is preferably 10 to 100°C, particularly preferably 20 to 80°C.
• Polymerization step 2 In the polymerization step 2, a chloroprene monomer and a polyfunctional monomer are added to the latex containing the polymer block (A) obtained in the polymerization step 1 and polymerized to obtain the desired chloroprene-based block copolymer. A latex containing a polymer is obtained. The chloroprene monomer and polyfunctional monomer may be added all at once or in portions.
• the polymerization temperature in the polymerization step 2 is preferably 10 to 50° C. from the viewpoint of ease of polymerization control.
• the polymerization reaction is terminated by adding a polymerization terminator.
• polymerization terminator examples include thiodiphenylamine, 4-tert-butylcatechol, 2,2'-methylenebis-4-methyl-6-tert-butylphenol and the like. Unreacted monomers after completion of polymerization can be removed by a conventional method such as distillation under reduced pressure.
• the latex containing the chloroprene-based block copolymer obtained in the polymerization step 2 may be added with a freeze stabilizer, an emulsion stabilizer, a viscosity modifier, an antioxidant, a preservative, etc. after polymerization within a range that does not impair the purpose of the present invention. can be optionally added.
• the method for recovering the chloroprene-based block copolymer from the latex containing the chloroprene-based block copolymer is not particularly limited, and known methods include a method of recovering by immersion in a coagulation liquid, a method of precipitating with a poor solvent such as methanol, and the like. method can be used.
• the chloroprene-based block copolymer preferably has a functional group having a structure represented by the following chemical formula (2) or chemical formula (3).
• R 3 is hydrogen, chlorine, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted mercapto group, substituted or unsubstituted represents any of the heterocyclyl groups of
• the terminal structure represented by the above chemical formula (2) or chemical formula (3) is introduced into the chloroprene-based block copolymer by polymerizing in the presence of a known RAFT agent.
• the compound leading to the structure represented by the above chemical formula (2) is not particularly limited, and general compounds can be used, such as dithiocarbamates and dithioesters.
• benzyl 1-pyrrole carbodithioate (common name: benzyl 1-pyrrole dithiocarbamate), benzylphenyl carbodithioate, 1-benzyl-N,N dimethyl-4-aminodithiobenzoate, 1-benzyl-4- Methoxydithiobenzoate, 1-phenylethylimidazole carbodithioate (common name: 1-phenylethylimidazole dithiocarbamate), benzyl-1-(2-pyrrolidinone) carbodithioate) (common name: benzyl-1-(2-pyrrolidinone) ) dithiocarbamate), benzyl phthalimidyl carbodithioate, (common name: benzyl phthalimidyl dithiocarbamate), 2-cyanoprop-2-yl-1-pyrrole carbodithioate, (common name: 2-cyanoprop-2- yl-1-pyrrol
• the compound leading to the structure represented by the above chemical formula (3) is not particularly limited, and general compounds can be used, for example, 2-cyano-2-propyldodecyltrithiocarbonate, dibenzyl Trithiocarbonate, butylbenzyltrithiocarbonate, 2-[[(butylthio)thioxomethyl]thio]propionic acid, 2-[[(dodecylthio)thioxomethyl]thio]propionic acid, 2-[[(butylthio)thioxomethyl]thio ] succinic acid, 2-[[(dodecylthio)thioxomethyl]thio]succinic acid, 2-[[(dodecylthio)thioxomethyl]thio]-2-methylpropionic acid, 2,2′-[carbonothioyl bis(thio)] Bis[2-methylpropionic acid], 2-amino-1-methyl-2-oxoethylbutyltrithiocarbonate
• the latex according to this embodiment is a latex containing the chloroprene-based block copolymer described above.
• the present latex can be immersed in a coagulating liquid and molded to obtain an immersion-molded article.
• the dip-molded article can be suitably used for gloves, balloons, catheters, boots, and the like.
• the latex of the present embodiment can be produced by using the liquid at the end of the polymerization obtained by the polymerization method described in the production method of the chloroprene-based block copolymer as a latex, or by using the recovered chloroprene-based block copolymer as an emulsifier. can be obtained by a method of forcibly emulsifying the latex by using be.
• the latex composition according to this embodiment contains a chloroprene-based block copolymer.
• the rubber composition according to the present embodiment is a rubber composition containing the above-described chloroprene-based block copolymer.
• Raw materials other than the chloroprene-based block copolymer are not particularly limited, and can be appropriately selected according to the purpose and application.
• Raw materials that can be contained in latex compositions and rubber compositions containing chloroprene-based block copolymers include, for example, vulcanizing agents, vulcanization accelerators, fillers or reinforcing agents, plasticizers, processing aids and lubricants, aging Examples include inhibitors and silane coupling agents.
• a rubber composition according to an embodiment of the present invention can also be made of the latex described above.
• the rubber composition according to one embodiment of the present invention can also be made of a latex composition.
• the latex composition/rubber composition of the present embodiment may contain a vulcanizing agent or a vulcanization accelerator.
• a vulcanizing agent and/or a vulcanization accelerator when the latex composition/rubber composition is 100% by mass, the vulcanizing agent and The total content of vulcanization accelerators can be 5% by mass or less, more preferably 1% by mass or less, and more preferably 0.1% by mass.
• the latex composition/rubber composition of the present embodiment develops sufficient mechanical strength without vulcanization. Therefore, from the viewpoint of allergenicity reduction and cost reduction, it is preferable to use one that does not contain a vulcanizing agent or a vulcanization accelerator.
• the anti-aging agent is used to improve the heat resistance of the rubber composition.
• These antioxidants can be added in a proportion of 0.1 parts by mass or more and 10 parts by mass or less, preferably 2 parts by mass or more, per 100 parts by mass of the latex component in the latex composition/rubber composition. The range is 5 parts by mass or less.
• These antioxidants can be used alone or in combination of two or more.
• Examples of primary anti-aging agents include phenol-based anti-aging agents, amine-based anti-aging agents, acrylate-based anti-aging agents, imidazole-based anti-aging agents, metal carbamates, and waxes.
• antioxidants include N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4′-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine, p-(p -toluenesulfonylamido)diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N -phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-
• undecane tris(nonylphenyl)phosphite, tris(mixed mono- and di-nonylphenyl)phosphite, diphenyl mono(2-ethylhexyl)phosphite, diphenyl monotridecyl phosphite, diphenyl isodecyl phosphite , diphenyl isooctyl phosphite, diphenyl nonylphenyl phosphite, triphenylphosphite, tris(tridecyl)phosphite, triisodecylphosphite, tris(2-ethylhexyl)phosphite, tris(2,4-di -t-butylphenyl)phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra(tride)
• the rubber composition can be produced according to conventional methods using known machines and devices.
• Example 1 Polymerization Step 1 Synthesis of Polymer Block (A-1) Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) 18.7 g of styrene monomer, 1119 g of styrene monomer, and 6.38 g of butylbenzyl trithiocarbonate were charged, the internal temperature was raised to 80° C., and the mixture was stirred at 200 rpm under a nitrogen stream.
• Demoll N Demoll N
• the sampled latex was mixed with a large amount of methanol to precipitate a resin component, filtered and dried to obtain a sample of polymer block (A-1).
• the number average molecular weight and molecular weight distribution of the polymer block (A-1) were determined by analysis. Table 1 shows the analysis results of the number average molecular weight. The molecular weight distribution was 1.43. It was also confirmed that the polymer block (A-1) had a glass transition temperature of 100.degree. In addition, the measuring method will be described later.
• Polymerization step 2 Synthesis of chloroprene-based polymer block (B-1) After polymerization step 1, when the internal temperature was lowered to 45°C, 3198 g of chloroprene monomer and 65 g of 1,9-nonanediol diacrylate were added. Polymerization was carried out by slowly adding 3 g over 2 hours. When the polymerization rate of the chloroprene monomer reaches 80%, the polymerization is stopped by adding a 10% by weight aqueous solution of N,N-diethylhydroxylamine as a polymerization terminator, and the unreacted chloroprene monomer is removed by distillation under reduced pressure. removed the body. For physical property measurement, 20 ml of the obtained latex was sampled, and the remaining latex was used to prepare a film for evaluation.
• the sampled latex was mixed with a large amount of methanol to precipitate a resin component, filtered and dried to obtain a sample of a chloroprene-based block copolymer.
• the content (% by mass) of the polymer block (A-1) of the chloroprene-based block copolymer and the chloroprene-based polymer block (B-1) was determined from the resulting sample by analysis. The analysis results are shown in Table 1. In addition, the measuring method will be described later.
• Example 2 Polymerization Step 1 Synthesis of Polymer Block (A-2) Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) 18.7 g of styrene monomer, 1733 g of styrene monomer, and 6.59 g of butylbenzyltrithiocarbonate were charged, the internal temperature was raised to 80° C., and the mixture was stirred at 200 rpm under a nitrogen stream.
• Demoll N Demoll N
• Polymerization step 2 Synthesis of chloroprene-based polymer block (B-2) After polymerization step 1, when the internal temperature was lowered to 45°C, 2595g of chloroprene monomer and 53.9-nonanediol diacrylate were added. Polymerization was carried out by slowly adding 0 g over 2 hours. When the polymerization rate of the chloroprene monomer reaches 80%, the polymerization is stopped by adding a 10% by weight aqueous solution of N,N-diethylhydroxylamine as a polymerization terminator, and the unreacted chloroprene monomer is removed by distillation under reduced pressure. removed the body.
• Example 3 Polymerization Step 1 Synthesis of Polymer Block (A-3) Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) 18.7 g of styrene monomer, 2390 g of styrene monomer and 6.81 g of butylbenzyltrithiocarbonate were charged, the internal temperature was raised to 80° C., and the mixture was stirred at 200 rpm under a nitrogen stream.
• Demoll N Demoll N
• Example 4 (Polymerization Step 1) Synthesis of Polymer Block (A-4) Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) 18.7 g of styrene monomer, 1119 g of styrene monomer, and 6.38 g of butylbenzyl trithiocarbonate were charged, the internal temperature was raised to 80° C., and the mixture was stirred at 200 rpm under a nitrogen stream.
• Demoll N Demoll N
• (Polymerization step 4) Synthesis of chloroprene-based polymer block (B-4) After polymerization step 1, when the internal temperature was lowered to 45°C, 3230 g of chloroprene monomer and 32.9-nonanediol diacrylate were added. Polymerization was carried out by slowly adding 6 g over 2 hours. When the polymerization rate of the chloroprene monomer reaches 80%, the polymerization is stopped by adding a 10% by weight aqueous solution of N,N-diethylhydroxylamine as a polymerization terminator, and the unreacted chloroprene monomer is removed by distillation under reduced pressure. removed the body.
• Example 5 (Polymerization Step 1) Synthesis of Polymer Block (A-5) Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) 18.7 g of styrene monomer, 1113 g of styrene monomer, and 28.5 g of butylbenzyltrithiocarbonate were charged, the internal temperature was raised to 80° C., and the mixture was stirred at 200 rpm under a nitrogen stream.
• Demoll N Demoll N
• (Polymerization step 5) Synthesis of chloroprene-based polymer block (B-5) After polymerization step 1, when the internal temperature was lowered to 45°C, 3182 g of chloroprene monomer and 64 g of 1,9-nonanediol diacrylate were added. Polymerization was carried out by slowly adding 9 g over 2 hours. When the polymerization rate of the chloroprene monomer reaches 80%, the polymerization is stopped by adding a 10% by weight aqueous solution of N,N-diethylhydroxylamine as a polymerization terminator, and the unreacted chloroprene monomer is removed by distillation under reduced pressure. removed the body.
• Example 6 Polymerization Step 1 Synthesis of Polymer Block (A-6) Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) 18.7 g of styrene monomer, 1120 g of styrene monomer, and 2.87 g of butylbenzyl trithiocarbonate were charged, the internal temperature was raised to 80° C., and the mixture was stirred at 200 rpm under a nitrogen stream.
• Demoll N Demoll N
• Example 7 (Polymerization Step 1) Synthesis of Polymer Block (A-7) Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) 18.7 g of styrene monomer, 1119 g of styrene monomer, and 6.38 g of butylbenzyl trithiocarbonate were charged, the internal temperature was raised to 80° C., and the mixture was stirred at 200 rpm under a nitrogen stream.
• Demoll N Demoll N
• Polymerization step 7 Synthesis of chloroprene-based polymer block (B-7) After polymerization step 1, when the internal temperature was lowered to 45°C, 3198 g of chloroprene monomer and 65 g of 1,9-nonanediol dimethacrylate were added. Polymerization was carried out by slowly adding 3 g over 2 hours. When the polymerization rate of the chloroprene monomer reaches 80%, the polymerization is stopped by adding a 10% by weight aqueous solution of N,N-diethylhydroxylamine as a polymerization terminator, and the unreacted chloroprene monomer is removed by distillation under reduced pressure. removed the body.
• Example 8 (Polymerization Step 1) Synthesis of Polymer Block (A-8) Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) 18.7 g of styrene monomer, 1119 g of styrene monomer, and 6.37 g of butylbenzyltrithiocarbonate were charged, the internal temperature was raised to 80° C., and the mixture was stirred at 200 rpm under a nitrogen stream.
• Demoll N Demoll N
• (Polymerization step 8) Synthesis of chloroprene-based polymer block (B-8) After polymerization step 1, when the internal temperature was lowered to 45°C, 3198 g of chloroprene monomer and 65.3 g of divinylbenzene were added over 2 hours. Polymerization was carried out by slow addition. When the polymerization rate of the chloroprene monomer reaches 80%, the polymerization is stopped by adding a 10% by weight aqueous solution of N,N-diethylhydroxylamine as a polymerization terminator, and the unreacted chloroprene monomer is removed by distillation under reduced pressure. removed the body.
• Example 9 Polymerization Step 1 Synthesis of Polymer Block (A-9) Polymerization was carried out using an autoclave with a capacity of 10 L, equipped with a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) 18.7 g, 1119 g of methyl methacrylate monomer, and 6.37 g of butylbenzyl trithiocarbonate were charged, the internal temperature was raised to 80° C., and the mixture was stirred at 200 rpm under a nitrogen stream.
• Demoll N Demoll N
• Example 10 Polymerization Step 1 Synthesis of Polymer Block (A-10) Polymerization was carried out using an autoclave with a capacity of 10 L, equipped with a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (manufactured by Kao Corporation, trade name: Demoll N) 18.7 g of styrene monomer, 1112 g of styrene monomer, and 31.7 g of butylbenzyltrithiocarbonate were charged, the internal temperature was raised to 80° C., and the mixture was stirred at 200 rpm under a nitrogen stream.
• Demoll N Demoll N
• (Polymerization step 12) Synthesis of chloroprene-based polymer block (B-12) After polymerization step 1, when the internal temperature was lowered to 45°C, 1498 g of chloroprene monomer and 30.9-nonanediol diacrylate were added. Polymerization was carried out by slowly adding 6 g over 2 hours. When the polymerization rate of the chloroprene monomer reaches 80%, the polymerization is stopped by adding a 10% by weight aqueous solution of N,N-diethylhydroxylamine as a polymerization terminator, and the unreacted chloroprene monomer is removed by distillation under reduced pressure. removed the body.
• the content (% by mass) of the polymer block (A-13) and the chloroprene polymer block (B-13) of the chloroprene-based block copolymer was determined by analysis in the same manner as in Example 1. The analysis results are shown in Table 1.
• Glass transition temperature of polymer block (A) The glass transition temperature was measured according to JIS K 7121 using a differential scanning calorimeter by the following method. Apparatus name: DSC1 (manufactured by Mettler Toledo) Procedure: Under a nitrogen stream of 50 ml/min, heat up to 120°C at a temperature increase rate of 10°C/min, keep at 120°C for 10 minutes, cool to -60°C, and heat at a temperature increase rate of 10°C/min.
• the area ratio of the peak derived from the chloroprene-based polymer block (B) and the peak derived from the chloroprene-based polymer block (B), and the polymer block (A) and the chloroprene-based polymer block in the chloroprene-based block copolymer obtained by measuring 1H-NMR A calibration curve was created from the content of (B).
• a sample of the chloroprene-based block copolymer precipitated by mixing the sampled latex with methanol was measured with a pyrolysis gas chromatogram to determine the difference between the peak derived from the polymer block (A) and the peak derived from the chloroprene-based polymer block (B). From the area ratio, the content of the polymer block (A) and the chloroprene-based polymer block (B) in the chloroprene-based block copolymer was determined using the calibration curve prepared above.
• a pottery cylinder having an outer diameter of 50 mm was immersed in a coagulating liquid containing 62 parts by mass of water, 35 parts by mass of potassium nitrate tetrahydrate, and 3 parts by mass of calcium carbonate for 1 second and taken out. After drying for 4 minutes, it was soaked in the latex prepared above for 2 minutes. After that, it was washed with running water at 45° C. for 1 minute, heat-treated at 130° C. for 30 minutes to remove moisture, and a film (140 ⁇ 150 mm, thickness: 0.2 mm) for tensile test was produced.

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