Classifications

• • 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
• • 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
  • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F36/02—Homopolymers and 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
  • C08F36/04—Homopolymers and 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
  • C08F36/14—Homopolymers and 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
  • C08F36/16—Homopolymers and 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
  • C08F36/18—Homopolymers and 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • 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]

Definitions

• the present invention relates to chloroprene-based block copolymers, latex, latex compositions and rubber compositions.
• a copolymer in which an aromatic vinyl monomer is polymerized with polychloroprene see, for example, Patent Document 2
• a copolymer in which a hydrophilic oligomer or a hydrophilic polymer is linked to a chloroprene-based polymer see, for example, Patent Document 3
• a copolymer having a block of an aromatic vinyl compound polymer and a block of a chloroprene polymer and specifying the total number average molecular weight and the number average molecular weight of the blocks of the chloroprene polymer see, for example, Patent Document 4
• acrylic acid ester weight A copolymer having a block of coalescence and a block of chloroprene polymer (see, for example, Patent Document 5) is known.
• Patent Document 6 The technique described in Patent Document 6 is known as a method for chemically bonding molecules between molecules without vulcanization.
• Japanese Unexamined Patent Publication No. 3-207710 Japanese Unexamined Patent Publication No. 3-212414 JP-A-2007-297502 International Publication No. 2018/181801 International Publication No. 2019/026914 Japanese Unexamined Patent Publication No. 2014-221901
• polychloroprene-based rubber compositions have been vulcanized with sulfur, zinc oxide, magnesium oxide and the like, and thiuram-based, dithiocarbamate-based, thiourea-based, guanidine-based, and xanthate acid in order to obtain the desired mechanical strength.
• the use of salt-based and thiazole-based vulcanization accelerators was indispensable. Since the vulcanization accelerator is a causative substance of type IV allergy that causes skin diseases such as dermatitis, reduction or non-use of the vulcanization accelerator has become an important theme. Further, since the elimination of the use of the vulcanization accelerator leads not only to the reduction of allergies but also to the cost reduction, a rubber composition that exhibits sufficient mechanical strength without using the vulcanization accelerator is desired. There is.
• the present invention presents a chloroprene-based block copolymer, latex, latex composition, and rubber composition that can obtain a product having excellent tensile properties and good flexibility without using a vulcanizing agent or a vulcanization accelerator.
• the challenge is to provide.
• the gist of the present invention is as follows.
• a molded product of a latex composition containing the chloroprene-based block copolymer is heat-treated at 130 ° C. for 30 minutes, and then the tensile strength at cutting measured in accordance with JIS K6251 is 17 MPa or more (1).
• R 1 and R 2 independently represent hydrogen, chlorine, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a mercapto group, or a heterocyclyl group, respectively.
• W 1 is saturated. Alternatively, it represents any of an unsaturated hydrocarbon group, a cyclic hydrocarbon group, a saturated or unsaturated hydrocarbon group containing a hetero atom, and a cyclic hydrocarbon group.
• Z 1 is represented by oxygen, sulfur or -NR 0-.
• R 0 represents any of hydrogen, chlorine, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a mercapto group, and a heterocyclyl group.
• a chloroprene-based block copolymer, latex, latex composition and rubber can be obtained without using a vulcanizing agent or a vulcanization accelerator to obtain a product having excellent tensile properties and good flexibility.
• the composition is provided.
• the chloroprene-based block copolymer comprises a monomer-derived polymer block (A) from which a polymer having a glass transition temperature of 80 ° C. or higher can be obtained during homopolymerization, 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 unit contained in the chloroprene-based polymer block (B).
• the polymer block (A) is a monomer-derived polymer block from which a polymer having a glass transition temperature of 80 ° C. or higher can be obtained during homopolymerization. By using such a monomer, the tensile strength of the obtained chloroprene-based block copolymer at the time of cutting is improved. It is preferable to use a monomer that can obtain a polymer having a glass transition temperature of 85 ° C. or higher. From the viewpoint of moldability, a monomer capable of obtaining a polymer having a glass transition temperature of 150 ° C. or lower is preferable, and a monomer capable of obtaining a polymer having a glass transition temperature of 120 ° C.
• 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 exemplified here. good.
• the glass transition temperature is the extrapolation glass transition end temperature (Teg) measured in accordance with JIS K 7121.
• Teg extrapolation glass transition end temperature
• Examples of the monomer unit constituting the polymer block (A) include an aromatic vinyl monomer unit, a methyl methacrylate monomer unit, and an acrylonitrile monomer unit.
• 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 copolymerizing these monomers or a weight composed of a monomer unit copolymerizable with these monomers, as long as the object of the present invention is not impaired. It may be a coalesced block.
• the number average molecular weight of the polymer block (A) is preferably 10,000 or more from the viewpoint of the tensile properties and moldability of the obtained chloroprene-based block copolymer.
• the number average molecular weight of the polymer block (A) can be, for example, 10000, 15000, 20000, 25000, 30,000, and may be within the range between any two of the numerical values exemplified here. Further, 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 It can be 9.9 or 2.0, and may be within the range between any two of the numerical values exemplified here.
• the number average molecular weight and the weight average molecular weight are polystyrene-equivalent values measured by gel permeation chromatography (GPC), and are measured values under the following measurement conditions.
• HLC-8320 manufactured by Tosoh Corporation
• the chloroprene-based polymer block (B) is a polymer block having a chloroprene monomer (2-chloro-1,3-butadiene) unit and a polyfunctional monomer unit.
• the chloroprene-based polymer block (B) is a chloroprene monomer unit, a polyfunctional monomer unit, and a monomer unit copolymerizable with these monomers as long as the object of the present invention is not impaired. It may be a polymer block composed of.
• each structural unit in the chloroprene-based polymer block (B) is not particularly limited, but is preferably 90 to 99.95% by mass of the chloroprene monomer unit and 0. It is 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. It is 00, 6.00, 7.00, 8.00, 9.00, 10.00 mass%, and may be within the range between any two of the numerical values exemplified here.
• the polyfunctional monomer is a compound having two or more radical polymerization groups in the molecule. From the viewpoints of the flexibility of the obtained chloroprene-based block copolymer, the tensile strength at the time of cutting, and the moldability, the monomer represented by the chemical formula (1) and the aromatic polyene monomer are preferably used. .. Examples of the monomer represented by the 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 10 or more and 30 or less carbon atoms, having a plurality of double bonds (vinyl groups) and a single or a plurality of aromatic groups, and is, for example, o-divinyl.
• R 1 and R 2 independently represent hydrogen, chlorine, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a mercapto group, or a heterocyclyl group, respectively.
• W 1 is saturated. Alternatively, it represents any of an unsaturated hydrocarbon group, a cyclic hydrocarbon group, a saturated or unsaturated hydrocarbon group containing a hetero atom, and a cyclic hydrocarbon group.
• Z 1 is represented by oxygen, sulfur or -NR 0-.
• R 0 represents any of hydrogen, chlorine, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a mercapto group, and a heterocyclyl group.
• the content of each structural unit of the chloroprene-based block copolymer is 5 to 30% by mass of the polymer block (A) and 70 to 95% by mass of the chloroprene-based polymer block (B), preferably the polymer block (A). ) 5 to 15% by mass, and 85 to 95% by mass of the chloroprene-based polymer block (B).
• the polymer block (A) is 5% by mass or more, the tensile strength at the time of cutting of the obtained chloroprene-based block copolymer is improved.
• the polymer block (A) is 30% by mass or less, the flexibility of the obtained chloroprene-based block copolymer is improved.
• the polymer block (A) is preferably 15% by mass or less.
• the chloroprene-based polymer block (B) is 70% by mass or more, the flexibility of the obtained chloroprene-based block copolymer is improved.
• the chloroprene-based polymer block (B) is preferably 85% by mass or more.
• the chloroprene-based polymer block (B) is 95% by mass or less, the tensile strength of the obtained chloroprene-based block copolymer at the time of cutting is improved.
• the chloroprene-based block copolymer is 100% by mass, the content of the polymer block (A) contained in the chloroprene-based block copolymer is, for example, 5, 10, 15, 20, 25, 30% by mass.
• the chloroprene-based block copolymer according to one embodiment of the present invention may consist of a polymer block (A) and a polymer block (B), and shall not contain other polymer blocks. Can be done.
• the chloroprene-based block copolymer can be a diblock copolymer of the 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 molding processability.
• the chloroprene-based block copolymer of the present embodiment has a tensile strength at the time of cutting measured in accordance with JIS K6251 after heat-treating a molded product of a latex composition containing the chloroprene-based block copolymer at 130 ° C. for 30 minutes.
• the value is preferably 17 MPa or more.
• the tensile strength at the time of cutting is more preferably 18 MPa or more, further preferably 19 MPa or more, and even more preferably 20 MPa or more.
• the upper limit is not particularly limited, but is, for example, 30 MPa or less.
• the chloroprene-based block copolymer of the present embodiment is obtained when the molded product of the latex composition containing the chloroprene-based block copolymer is heat-treated at 130 ° C. for 30 minutes and then measured according to JIS K6251.
• the elongation is preferably 900% or more, more preferably 905% or more, and even more preferably 910% or more.
• the upper limit is not particularly limited, but is, for example, 1300% or less.
• the chloroprene-based block copolymer of the present embodiment is obtained by heat-treating a molded product of a latex composition containing the chloroprene-based block copolymer at 130 ° C. for 30 minutes and then measuring at 500% elongation according to JIS K 6251.
• the modulus is preferably 3.0 MPa or less, more preferably 2.9 MPa or less, and even more preferably 2.8 MPa or less.
• the lower limit is not particularly limited, but is, for example, 1.0 MPa or more.
• the chloroprene-based block copolymer of the present embodiment has the above-mentioned tensile strength after a molded product composed of a latex composition containing a latex containing the chloroprene-based block copolymer and a rubber composition is heat-treated at 130 ° C. for 30 minutes. It can have stretch on cutting and a modulus on stretch of 500%.
• the molded product may not use a vulcanization agent and a vulcanization accelerator during molding.
• a molded body can be obtained by the method described in Examples for measuring tensile strength.
• the polyfunctionality contained in the chloroprene-based polymer block (B) can be adjusted.
• the content of the sex 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 can be produced by known methods such as solution polymerization, emulsion polymerization and bulk polymerization, but emulsion polymerization is suitable for obtaining a desired chloroprene block copolymer.
• the polymerization method is not particularly limited as long as a desired chloroprene-based block copolymer can be obtained, but the polymerization step 1 for synthesizing the polymer block (A) is followed by the polymerization step 2 for synthesizing the chloroprene-based block (B). It is preferably produced by a production method that goes through a two-step polymerization step 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 above-mentioned glass transition temperature.
• the emulsifier used in the polymerization is not particularly limited, but an anion-based or nonionic-based emulsifier is preferable from the viewpoint of emulsion stability. In particular, it is preferable to use an alkali metal rosinate because the obtained chloroprene-based block copolymer can be provided with 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 efficiently performing the polymerization reaction.
• the radical polymerization initiator a known radical polymerization initiator can be used, and examples thereof include potassium persulfate, benzoyl peroxide, hydrogen peroxide, and azo compounds.
• the polymerization temperature may be appropriately determined depending on the type of the monomer, but is preferably 10 to 100 ° C, particularly preferably 20 to 80 ° C.
• Polymerization step 2 In the polymerization step 2, the chloroprene monomer and the polyfunctional monomer are added to the latex containing the polymer block (A) obtained in the polymerization step 1 and polymerized to form the target chloroprene block. Obtain a latex containing a polymer.
• the chloroprene monomer and the polyfunctional monomer may be added all at once or added.
• 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 stopped by adding a polymerization inhibitor.
• polymerization terminator examples include thiodiphenylamine, 4-thir-butylcatechol, 2,2'-methylenebis-4-methyl-6-thylbutylphenol and the like.
• the unreacted monomer after completion of the polymerization can be removed by a method such as conventional vacuum distillation.
• the latex containing the chloroprene-based block copolymer obtained in the polymerization step 2 includes a freeze stabilizer, an emulsion stabilizer, a viscosity modifier, an antioxidant, a preservative, etc. after polymerization as long as the object of the present invention is not impaired. 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 such as a method of recovering by immersing in a coagulating liquid and a method of precipitating with a poor solvent such as methanol are known. 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 represents any of hydrogen, chlorine, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a mercapto group, and a heterocyclyl group.
• the terminal structure represented by the above chemical formula (2) or chemical formula (3) is introduced into a chloroprene-based block copolymer by polymerizing in the presence of a known RAFT agent.
• the compound that derives the structure represented by the chemical formula (2) is not particularly limited, and general compounds can be used, and examples thereof include dithiocarbamates and dithioesters.
• benzyl1-pyrrolecarbodithioate (common name: benzyl1-pyrroldithiocarbamate), benzylphenylcarbodithioate, 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), benzylphthalimidylcarbodithioate, (common name: benzylphthalimidyldithiocarbamate), 2-cyanoprop-2-yl-1-pyrrolecarbodithioate, (common name: 2-cyanoprop-2- (Il-1
• the compound that derives 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 and dibenzyl.
• the latex according to the present embodiment is a latex containing the above-mentioned chloroprene-based block copolymer.
• This latex can be obtained by immersing it in a coagulating liquid and molding it to obtain a dip-molded article.
• the immersion molded product can be suitably used for gloves, balloons, catheters, boots and the like.
• the latex of the present embodiment is a method in which the liquid at the end of polymerization obtained by the polymerization method described in the method for producing a chloroprene-based block copolymer is used as it is as a latex, or a recovered chloroprene-based block copolymer is used as an emulsifier. It can be obtained by forcibly emulsifying with 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-mentioned chloroprene-based block copolymer.
• the raw materials other than the chloroprene-based block copolymer are not particularly limited, and can be appropriately selected depending on the purpose and application. Examples of raw materials that can be contained in latex compositions and rubber compositions containing chloroprene-based block copolymers include vulcanizing agents, vulcanization accelerators, fillers or reinforcing agents, plasticizers, processing aids and lubricants, and aging. Examples include an inhibitor and a silane coupling agent.
• 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 / or the vulcanization accelerator and The total content of the vulcanization accelerator 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 exhibits sufficient mechanical strength without vulcanization. Therefore, from the viewpoint of reducing allergies and reducing costs, those containing no vulcanizing agent and vulcanization accelerator are preferable.
• Anti-aging agents are used to improve the heat resistance of rubber compositions, and include primary anti-aging agents that capture radicals to prevent autoxidation and secondary anti-aging agents that detoxify hydroperoxides. be. These antioxidants can be added at a ratio of 0.1 part by mass or more and 10 parts by mass or less to 100 parts by mass of the latex component in the latex composition / rubber composition, preferably 2 parts by mass or more. The range is 5 parts by mass or less. These anti-aging agents can be used alone or in combination of two or more. Examples of the primary anti-aging agent include phenol-based anti-aging agents, amine-based anti-aging agents, acrylate-based anti-aging agents, imidazole-based anti-aging agents, carbamic acid metal salts, and waxes.
• examples of the secondary anti-aging agent include phosphorus-based anti-aging agents, sulfur-based anti-aging agents, and imidazole-based anti-aging agents.
• examples of anti-aging agents are not particularly limited, but are N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, p- (p).
• -Toluenesulfonylamide 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-N'-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, 1,1,3- Tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 4,4'-butylidenebis- (3-methyl-6-t-butylphenol), 2,2-thiobis (4-methyl-6) -T-butylphenol), 7-octadecyl-3- (4'-hydroxy-3', 5'-di-
• the rubber composition can be produced according to a conventional method using a known machine or device.
• Example 1 Polymerization Step 1 Synthesis of Polymer Block (A-1) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium loginate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalene sulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 18.7 g, 350 g of styrene monomer, and 6.07 g of butylbenzyl trithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Demor N Demor N
• the sampled latex was mixed with a large amount of methanol to precipitate a resin component, which was then filtered and dried to obtain a sample of polymer block (A-1). From the obtained sample, the number average molecular weight, molecular weight distribution, and glass transition temperature of the polymer block (A) were determined by analysis. The analysis results are shown in Table 1. The methods for measuring the "number average molecular weight”, “molecular weight distribution”, and “glass transition temperature” will be described later.
• 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. From the obtained sample, the content (mass%) of the polymer block (A-1) and the chloroprene-based polymer block (B-1) of the chloroprene-based block copolymer was determined by analysis. The analysis results are shown in Table 1. The measurement method will be described later.
• Example 2 Polymerization Step 1 Synthesis of Polymer Block (A-2) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. 3333 g of pure water, 160 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 26.0 g of potassium hydroxide, sodium salt of ⁇ -naphthalene sulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 13.3 g, 250 g of styrene monomer, and 4.33 g of butylbenzyl trithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Demor N Demor N
• Example 3 Polymerization Step 1 Synthesis of Polymer Block (A-3) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. 5733 g of pure water, 275 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 44.7 g of potassium hydroxide, sodium salt of ⁇ -naphthalene sulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 22.9 g, 430 g of styrene monomer, and 7.45 g of butylbenzyl trithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Demor N Demor N
• Example 4 (Polymerization Step 1) Synthesis of Polymer Block (A-4) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium loginate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalene sulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 18.7 g, 350 g of styrene monomer, and 6.07 g of butylbenzyl trithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Demor N Demor N
• the polymerization rate of the chloroprene monomer reaches 80%, the polymerization is stopped by adding a 10 wt% aqueous solution of N, N-diethylhydroxylamine, which is a polymerization inhibitor, and unreacted chloroprene single amount by vacuum distillation. The body was removed. For the measurement of physical properties, 20 ml of the obtained latex was sampled, and the remaining latex was used to prepare a film for evaluation. The content (mass%) of the polymer block (A-4) and the chloroprene-based polymer block (B-4) 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.
• Example 5 (Polymerization Step 1) Synthesis of Polymer Block (A-5) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium loginate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalene sulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 18.7 g, 350 g of styrene monomer, and 6.07 g of butylbenzyl trithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Demor N Demor N
• the body was removed.
• 20 ml of the obtained latex was sampled, and the remaining latex was used to prepare a film for evaluation.
• the content (mass%) of the polymer block (A-5) and the chloroprene-based polymer block (B-5) 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.
• Example 6 Polymerization Step 1 Synthesis of Polymer Block (A-6) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium loginate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalene sulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 18.7 g, 350 g of styrene monomer, and 6.07 g of butylbenzyl trithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Demor N Demor N
• Example 7 (Polymerization Step 1) Synthesis of Polymer Block (A-7) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium loginate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalene sulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 18.7 g, 350 g of styrene monomer, and 6.07 g of butylbenzyl trithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Demor N Demor N
• Example 8 (Polymerization Step 1) Synthesis of Polymer Block (A-8) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium loginate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalene sulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 18.7 g, 350 g of styrene monomer, and 6.07 g of butylbenzyl trithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Demor N Demor N
• the polymerization rate of the chloroprene monomer reaches 80%, the polymerization is stopped by adding a 10 wt% aqueous solution of N, N-diethylhydroxylamine, which is a polymerization inhibitor, and unreacted chloroprene single amount by vacuum distillation. The body was removed. For the measurement of physical properties, 20 ml of the obtained latex was sampled, and the remaining latex was used to prepare a film for evaluation. The content (mass%) of the polymer block (A-8) and the chloroprene-based polymer block (B-8) 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.
• Example 9 Polymerization Step 1 Synthesis of Polymer Block (A-9) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium loginate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalene sulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 18.7 g, 350 g of styrene monomer, and 6.07 g of butylbenzyl trithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Demor N Demor N
• Example 10 Polymerization Step 1 Synthesis of Polymer Block (A-10) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. 6667 g of pure water, 320 g of disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.), 52.0 g of potassium hydroxide, sodium salt of ⁇ -naphthalene sulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 26.7 g, 500 g of styrene monomer, and 6.50 g of butylbenzyl trithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Demor N Demor N
• Example 11 (Polymerization Step 1) Synthesis of Polymer Block (A-11) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. Pure water 4666 g, disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.) 224 g, potassium hydroxide 36.4 g, sodium salt of ⁇ -naphthalene sulfonic acid formalin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 18.7 g, 350 g of methyl methacrylate monomer, and 4.14 g of butyl-2-cyanoisopropyltrithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Pure water 4666 g disproportionated potassium rosinate (manufactured by Harima Kasei Group Co., Ltd.) 224 g
• Example 12 (Polymerization Step 1) Synthesis of Polymer Block (A-12) Polymerization was carried out using an autoclave having a capacity of 10 L and a stirrer and a jacket for heating and cooling. 4666 g of pure water, 224 g of disproportionated potassium loginate (manufactured by Harima Kasei Group Co., Ltd.), 36.4 g of potassium hydroxide, sodium salt of ⁇ -naphthalene sulfonic acid formarin condensate (manufactured by Kao Co., Ltd., trade name: Demor N) 18.7 g, 350 g of styrene monomer, and 6.07 g of butylbenzyl trithiocarbonate were charged, and the mixture was stirred at 200 rpm under a nitrogen stream at an internal temperature of 80 ° C.
• Demor N Demor N
• the content (mass%) of the polymer block (A-16) and the chloroprene-based polymer block (B-16) 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.
• the content (% by mass) of the polymer block (A-17) and the chloroprene-based polymer block (B-17) 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.
• the content (mass%) of the homopolymer of the polymer block (A) and the homopolymer of the chloroprene-based polymer block (B) in the polymer obtained by mixing was determined by analysis in the same manner as in Example 1. The analysis results are shown in Table 3.
• Glass transition temperature of polymer block (A) The glass transition temperature was measured by the following method using a differential scanning calorimeter according to JIS K 7121. Device name: DSC1 (manufactured by Mettler Toledo) Procedure: Under a nitrogen stream of 50 ml / min, the temperature is raised to 120 ° C. at a temperature rise rate of 10 ° C./min, kept at 120 ° C. for 10 minutes, then cooled to -60 ° C., and the temperature rise rate is 10 ° C./min.
• a calibration line was prepared from the content of (B).
• a sample of the chloroprene-based block copolymer precipitated by mixing the sampled latex with methanol was measured by a pyrolysis gas chromatogram, and the peak derived from the polymer block (A) and the peak derived from the chloroprene-based polymer block (B) were measured. From the area ratio, the contents of the polymer block (A) and the chloroprene-based polymer block (B) in the chloroprene-based block copolymer were determined using the calibration line prepared above.
• a ceramic cylinder having an outer diameter of 50 mm was immersed in a coagulating solution 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 immersed in the latex prepared above for 2 minutes. Then, it was washed with running water at 45 ° C. for 1 minute and heat-treated at 130 ° C. for 30 minutes to remove water, and a film for a tensile test (140 ⁇ 150 mm, thickness: 0.2 mm) was prepared.

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