Classifications

• • 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
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L23/32—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
  • C08L23/34—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur by chlorosulfonation

Definitions

• This disclosure relates to a chlorosulfonated polyolefin latex and its uses. More specifically, this disclosure relates to a coagulable chlorosulfonated polyolefin latex and a dip molding composition using the latex, as well as a dip molded article.
• Chlorosulfonated polyolefins are excellent in heat resistance, weather resistance, ozone resistance, chemical resistance, abrasion resistance, etc., and are used in the form of latex as coating materials and adhesive materials.
• Patent Document 1 discloses that in a transmission belt in which an ethylene-propylene-diene rubber matrix and polyester fibers are composited, a resorcinol-formalin-latex adhesive (RFL adhesive) using chlorosulfonated polyethylene latex as a latex component is used to bond the matrix rubber and the fibers.
• RTL adhesive resorcinol-formalin-latex adhesive
• chlorosulfonated polyolefin since chlorosulfonated polyolefin has excellent resistance to strong acids and strong alkalis, it is also used as a material for protective gloves for work in which highly hazardous chemicals are used frequently, such as in plating processes, semiconductor manufacturing processes, and dyeing processes.
• Gloves made of chlorosulfonated polyolefin are generally manufactured by immersing a hand mold corresponding to the three-dimensional shape of the glove in an organic solvent solution of rubber, drying, and vulcanizing the glove (for example, Patent Document 2).
• organic solvent solutions are not preferable from the viewpoint of environmental protection, and therefore a method for manufacturing gloves using chlorosulfonated polyolefin latex, which does not require the use of organic solvents during glove manufacturing, is desired.
• Patent Document 3 discloses a method for manufacturing gloves by preparing a hand mold that corresponds to the three-dimensional shape of the glove, treating the surface of the mold with a coagulant such as an aqueous calcium nitrate solution, and then immersing the treated hand mold in a dip liquid containing nitrile rubber latex to adhere rubber particles to the surface of the mold, followed by drying and crosslinking.
• Patent Document 4 discloses a method for manufacturing gloves by heat-sensitive coagulation of chlorosulfonated polyethylene latex.
• JP 2001-003991 A Japanese Patent Application Publication No. 05-230702 International Publication No. 2015/146974 JP 2011-032590 A
• the inventors therefore conducted research to provide a method that would enable coagulation of even chlorosulfonated polyolefin latex using a common coagulant.
• ⁇ Item 1> An aqueous dispersion medium; chlorosulfonated polyolefin; At least one compound (first agent) selected from the group consisting of alkylbenzene sulfonate, polyoxyalkylene disulfonate, and taurine salt; A fatty acid salt (second agent), 2.
• a chlorosulfonated polyolefin latex comprising: ⁇ Item 2-1>
• the taurine salt has the formula: RN( CH3 )-( CH2 ) 2 - SO3M (wherein R represents a cocoyl group or an acyl group having 8 to 18 carbon atoms, and M represents an alkali metal (preferably sodium or potassium), ammonium (NH4), or triethanolammonium (NH( CH2CH2OH ) 3 ).
• Item 2 The latex according to item 1.
• ⁇ Item 2-2> The alkylbenzene sulfonate is a C8-18 alkylbenzene sulfonate; Item 1 or 2-1.
• the polyoxyalkylene disulfonate is a salt of an ester in which hydroxy groups at both ends of a polyalkylene glycol are sulfated, the polyalkylene glycol being a polymer of C2-4 alkylene glycol;
• Item 1 The latex according to any one of Items 1 and 2-1 to 2-3, wherein a mass ratio of the first agent to the second agent is 0.5 to 5.
• first agent selected from the group consisting of alkylbenzene sulfonates, polyoxyalkylene disulfonates, and taurine salts
• second agent a fatty acid salt
• a method for producing a chlorosulfonated polyolefin latex At least one compound selected from the group consisting of alkylbenzene sulfonates, polyoxyalkylene disulfonates, and taurine salts; and a fatty acid salt, Chlorosulfonated polyolefin emulsion composition.
• a chlorosulfonated polyolefin latex is obtained that is highly stable and can be applied to the general coagulation dipping method. Furthermore, by using this latex, dip-molded bodies can be efficiently produced.
• the present disclosure preferably includes, but is not limited to, a chlorosulfonated polyolefin latex containing a specific emulsifier, its uses, and a manufacturing method, etc., and the present disclosure includes everything disclosed in this specification that can be recognized by a person skilled in the art.
• the chlorosulfonated polyolefin latex included in the present disclosure contains an aqueous dispersion medium, a chlorosulfonated polyolefin, at least one compound selected from the group consisting of alkylbenzene sulfonates, polyoxyalkylene disulfonates, and taurine salts, and a fatty acid salt.
• the chlorosulfonated polyolefin latex included in the present disclosure may be referred to as the "latex of the present disclosure.”
• the at least one compound selected from the group consisting of alkylbenzene sulfonates, polyoxyalkylene disulfonates, and taurine salts may be referred to as the "first agent,” and the fatty acid salt may be referred to as the "second agent.”
• Both the first agent and the second agent are compounds that can act as emulsifiers, and a good chlorosulfonated polyolefin latex can be prepared by using them in combination.
• Chlorosulfonated polyolefins can be obtained by chlorinating and chlorosulfonating polyolefins.
• polyolefins include polymers or copolymers of ⁇ -olefins, and copolymers of ⁇ -olefins and other polymerizable components.
• ⁇ -olefins examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.
• Other polymerizable components include linear dienes such as isoprene, 1,3-butadiene, 1,4-hexadiene, 1,6-octadiene, and 2-methyl-1,5-hexadiene; cyclic dienes such as 1,4-cyclohexadiene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, and 6-chloromethyl-5-isopropenyl-2-norbornene; and vinyl compounds such as vinyl acetate, vinyl chloride, acrylonitrile, styrene, methyl acrylate, and methyl meth
• Chlorosulfonated polyolefins are preferably chlorosulfonated ⁇ -olefin polymers.
• one type of ⁇ -olefin may be used alone or two or more types may be used.
• two or more types of ⁇ -olefins it is preferable that one type is ethylene.
• chlorosulfonated polyolefins include chlorosulfonated polyethylene, chlorosulfonated ethylene- ⁇ -olefin copolymers, and chlorosulfonated ⁇ -olefin polymers.
• the " ⁇ -olefin" in chlorosulfonated ethylene- ⁇ -olefin copolymers and chlorosulfonated ⁇ -olefin polymers refers to ⁇ -olefins other than ethylene.
• propylene is preferred.
• chlorosulfonated ethylene- ⁇ -olefin copolymer is chlorosulfonated ethylene propylene copolymer
• a preferred example of a chlorosulfonated ⁇ -olefin polymer is chlorosulfonated propylene polymer
• Chlorosulfonated polyolefins may be used alone or in combination of two or more types.
• the sulfur content in the chlorosulfonated polyolefin is preferably 0.5% by mass or more, and more preferably 0.8% by mass or more. It is also preferably 2.0% by mass or less, and more preferably 1.5% by mass or less. It is also preferably 0.5 to 2.0% by mass, and more preferably 0.8 to 1.5% by mass.
• the chlorine content in the chlorosulfonated polyolefin of the present disclosure is not particularly limited, but is preferably 10% by mass or more, and more preferably 20% by mass or more. It is also preferably 50% by mass or less, and more preferably 40% by mass or less. It is also preferably 10 to 50% by mass, and more preferably 20 to 40% by mass.
• the sulfur content and chlorine content of chlorosulfonated polyolefin are the contents of sulfur atoms and chlorine atoms contained in the chlorosulfonated polyolefin, respectively, and can be measured by the oxygen flask combustion method.
• Methods for chlorinating and chlorosulfonating polyolefins include the solution method, in which the polyolefin is dissolved in an organic solvent and the reaction is carried out in a homogeneous system, the suspension method, in which the polyolefin is suspended in a solvent and the reaction is carried out, the melt method, in which the polyolefin is molten and the reaction is carried out, and the gas phase method, in which the polyolefin is suspended in the gas phase and the reaction is carried out.
• the solution method is preferred from the viewpoint of uniform chlorination and chlorosulfonation.
• chlorinating and chlorosulfonating agents examples include a combination of chlorine gas and sulfurous acid gas, a combination of chlorine gas and sulfuryl chloride, and sulfuryl chloride alone.
• the chlorosulfonation reaction can be carried out by using a chlorinating agent, a chlorosulfonating agent, a radical generator, and, if necessary, a co-catalyst such as pyridine.
• Chlorosulfonated polyolefins that are commercially available may be used. Examples of commercially available products include those sold by Tosoh Corporation under the trade names "TOSO-CSM” and "extos” (chlorosulfonated polyethylene).
• the content of chlorosulfonated polyolefin in the latex of the present disclosure is not particularly limited, but is preferably, for example, about 20 to 60% by mass, more preferably about 25 to 55% by mass or about 30 to 50% by mass, and even more preferably about 35 to 45% by mass.
• the latex of the present disclosure contains at least one compound (first agent) selected from the group consisting of alkylbenzene sulfonates, polyoxyalkylene disulfonates, and taurine salts.
• first agent selected from the group consisting of alkylbenzene sulfonates, polyoxyalkylene disulfonates, and taurine salts.
• the alkylbenzene sulfonate is preferably a C8-18 alkylbenzene sulfonate.
• the alkyl group of the alkylbenzene sulfonate is preferably a C8-18 (C8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18) alkyl group.
• the alkyl group may be linear or branched, and is preferably linear.
• the salt of the alkylbenzene sulfonate is preferably an alkali metal salt (more specifically, for example, sodium salt or potassium salt), ammonium salt, triethanolammonium salt, etc., and particularly preferably a sodium salt.
• the alkylbenzene sulfonate is preferably, for example, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, triethanolammonium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, sodium tetradecylbenzene sulfonate, sodium hexadecylbenzene sulfonate, sodium octadecylbenzene sulfonate, etc.
• sodium dodecylbenzenesulfonate is preferred from the viewpoint of ease of producing latex with a small particle size.
• Alkylbenzenesulfonates can be prepared by sulfonating alkylbenzene and neutralizing the resulting alkylbenzenesulfonic acid with a basic compound.
• the alkylbenzene used as the raw material can be prepared by the Friedel-Crafts reaction of alkyl halides and benzene, or by reacting olefins and benzene with hydrogen fluoride or zeolite.
• the resulting alkylbenzene can be reacted with a sulfonating agent to prepare alkylbenzenesulfonic acid.
• Examples of sulfonating agents include concentrated sulfuric acid, fuming sulfuric acid, chlorosulfuric acid, sulfur trioxide, and sulfur trioxide-Lewis base complexes.
• the resulting alkylbenzenesulfonic acid is neutralized with a basic compound.
• Examples of basic compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, and sodium carbonate, as well as ammonia and triethanolamine.
• alkylbenzene sulfonates may be used, such as those sold under the trade name "Neoperex G-25" by Kao Corporation, “Lipon LS-250” by Lion Specialty Chemical Co., Ltd., “Lunox S-40TD” by Toho Chemical Industry Co., Ltd., "Newcoal 210" and “Newcoal 220-L” by Nippon Nyukazai Co., Ltd., “Newrex R” by NOF Corporation, “Neogen RK” and “Neogen S-20F” by Daiichi Kogyo Seiyaku Co., Ltd., and "Takesurf A-41-B” and "Takesurf A-41-S” by Takemoto Oil Co., Ltd.
• Polyoxyalkylene disulfonates are salts of esters in which the hydroxyl groups at both ends of a polyalkylene glycol are sulfated.
• the polyalkylene glycol is preferably a polymer of C2-4 alkylene glycol, more specifically, polypropylene glycol, poly-1,2-butylene glycol, poly-1,3-butylene glycol, poly-1,4-butylene glycol, polyethylene glycol-propylene glycol copolymer, polyethylene glycol-1,2-butylene glycol copolymer, polypropylene glycol-1,2-butylene glycol copolymer, etc.
• the molar ratio E/A of the ethylene glycol unit (E) to the other glycol unit (A) is smaller than 1, that is, the amount of ethylene glycol units is less than the amount of other glycol units.
• the copolymer may be a random copolymer or a block copolymer.
• the number of repeating units of the polyalkylene glycol is preferably 1 to 50, more preferably 5 to 40, and particularly preferably 10 to 30.
• the polyoxyalkylene disulfonate is preferably a polyoxy C2-4 alkylene disulfonate, and the number of polyoxyalkylene repeats is preferably 1 to 50, more preferably 5 to 40, and particularly preferably 10 to 30.
• alkali metal salts e.g., sodium salts, potassium salts
• ammonium salts are preferred.
• polyoxyalkylene disulfonates include sodium polypropylene glycol disulfonate, potassium polypropylene glycol disulfonate, ammonium polypropylene glycol disulfonate, sodium polyethylene glycol-propylene glycol disulfonate, and sodium poly 1,2-butylene glycol disulfonate.
• sodium polypropylene glycol disulfonate is preferred from the viewpoint of the ease with which a latex having a small particle size can be obtained.
• Polyoxyalkylene disulfonates can be prepared by, for example, converting the hydroxyl groups at both ends of a polyalkylene glycol into sulfate esters, neutralizing the resulting sulfate ester with a basic compound, and forming a salt.
• Methods for preparing the polyalkylene glycol used as a raw material include ring-opening polymerization of a cyclic ether compound and dehydration condensation polymerization of glycols.
• examples of polyalkylene glycols include polypropylene glycol, poly-1,2-butylene glycol, poly-1,3-butylene glycol, poly-1,4-butylene glycol, polyethylene glycol-propylene glycol copolymer, polyethylene glycol-1,2-butylene glycol copolymer, and polypropylene glycol-1,2-butylene glycol copolymer.
• the molar ratio E/A of the ethylene glycol unit (E) to the other glycol unit (A) is smaller than 1, that is, the amount of ethylene glycol units is less than the amount of the other glycol units.
• the copolymer may be a random copolymer or a block copolymer.
• the number of repeating units of the polyalkylene glycol is preferably 1 to 50, more preferably 5 to 40, and particularly preferably 10 to 30.
• the method of sulfurization involves dissolving the polyalkylene glycol in an organic solvent and reacting under conditions where the amount of sulfating agent used is at least twice the molar amount of the polyalkylene glycol.
• sulfating agents include concentrated sulfuric acid, fuming sulfuric acid, chlorosulfuric acid, sulfur trioxide, and sulfur trioxide-Lewis base complex.
• the solution is neutralized with a suitable basic compound.
• basic compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, and sodium carbonate, as well as ammonia and triethanolamine.
• polyoxyalkylene disulfonates may be used, for example, "Newcol 240" manufactured by Nippon Nyukazai Co., Ltd.
• the taurine salt is preferably one obtained by amidating an N-alkyl taurine salt.
• Other examples of the salt include alkali metal salts (e.g., sodium salt, potassium salt), ammonium salt, and triethanolammonium salt.
• Such taurine salts include those of the formula: RN(CH 3 )-(CH 2 ) 2 -SO 3 M
• R represents a cocoyl group or an acyl group having 8 to 18 carbon atoms
• M represents an alkali metal (preferably sodium or potassium), ammonium (NH 4 ), or triethanolammonium (NH(CH 2 CH 2 OH) 3 ).
• acyl groups having 8 to 18 carbon atoms include lauroyl, myristoyl, palmitoyl, stearoyl, and oleoyl groups.
• taurine salts include sodium N-acyl methyl taurine salts such as sodium N-cocoyl methyl taurine, sodium N-lauroyl methyl taurine, sodium N-myristoyl methyl taurine, sodium N-palmitoyl methyl taurine, sodium N-stearoyl methyl taurine, and sodium N-oleoyl methyl taurine, as well as potassium N-cocoyl methyl taurine, ammonium N-cocoyl methyl taurine, ammonium N-cocoyl methyl taurine triethanolate, and sodium N-cocoyl ethyl taurine.
• sodium N-acyl methyl taurine is preferred from the viewpoint of easily obtaining a latex with a small particle size.
• Such taurine salts can be prepared, for example, by amidating N-alkyl taurine salts.
• N-alkyl taurine salts can be prepared by reacting chloroethyl sulfate, bromoethyl sulfate, isethionate, vinyl sulfonate, or the like with an alkylamine.
• Examples of methods for amidating N-alkyl taurine salts include reacting the resulting N-alkyl taurine salt with acyl chloride in the presence of a base, dehydrating and condensing N-alkyl taurine salts with fatty acids, and reacting N-alkyl taurine salts with fatty acid isopropenyl esters.
• Taurine salts may be commercially available products, such as those sold under the trade names "NIKKOL CMT-30”, “NIKKOL LMT-30”, “NIKKOL MMT”, “NIKKOL PMT” and “NIKKOL SMT” by Nikko Chemicals Co., Ltd., those sold under the trade names “NEOSCOPE CN-30” and “NEOSCOPE CTS-25” by Toho Chemical Industry Co., Ltd., and those sold under the trade names "DIAPONS S”, “DIAPONS LM” and “DIAPONS K” by NOF Corporation.
• the latex of the present disclosure includes a fatty acid salt (second agent).
• the fatty acid constituting the fatty acid salt may be either a saturated fatty acid or an unsaturated fatty acid.
• unsaturated fatty acid for example, those having 1, 2, 3, or 4 carbon double bonds are preferable, and those having 1 bond are more preferable.
• it may be either a straight chain or a branched chain.
• Fatty acids having 8 to 24 carbon atoms (8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24) are preferable, and fatty acids having 12 to 22 carbon atoms are more preferable.
• examples of the unsaturated fatty acids include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, and unsaturated fatty acids such as myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, ricinoleic acid, linoleic acid, linolenic acid, gadoleic acid, arachidonic acid, cetoleic acid, erucic acid, and brassidic acid.
• saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid
• unsaturated fatty acids such as myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, ricinoleic acid, linoleic acid, linolenic acid, gadoleic acid,
• fatty acid salts examples include alkali metal salts (for example, sodium salts and potassium salts), ammonium salts, and amine salts (for example, triethanolamine salts). Of these, the salts of the specific fatty acids mentioned above are preferred.
• laurate, myristate, or oleate from the viewpoint of superior latex stability, it is preferable to use laurate, myristate, or oleate, more preferably laurate or oleate, and even more preferably potassium laurate or potassium oleate.
• the fatty acid salts can be used alone or in combination of two or more.
• the fatty acid salt may be added as a fatty acid salt, or may be prepared by neutralizing the fatty acid with an alkali in the system in which the latex is produced. When prepared in the system, it is not necessary to completely neutralize the fatty acid, and unreacted fatty acid may also be contained in the system, or an equivalent amount of alkali or more may be added to the fatty acid, so that excess alkali is contained in the system.
• the neutralization rate of the fatty acid is not particularly limited, but is preferably, for example, 60 to 400 mol%, more preferably 90 to 300 mol%, and even more preferably 100 to 200 mol%.
• a "neutralization rate of 400 mol%" means that the fatty acid is neutralized with 4 equivalents of alkali.
• Fatty acid salts may be commercially available products, such as those sold under the trade names “NnS Soap,” “SS-40N,” “OS Soap,” and “KS Soap” by Kao Corporation, those sold under the trade names “NIKKOL Potassium Laurate LK-120,” “NIKKOL Potassium Myristate MK-140,” and “THAISOAP MNK-40” by Nikko Chemicals Co., Ltd., and those sold under the trade names “Non-Sal PK-1,” “Non-Sal SK-1,” and “Non-Sal MK-1” by NOF Corporation.
• the fatty acids may be commercially available products, such as NOF Corporation's product names "NAA-142”, “NAA-160”, “NAA-35” and “Extra Olein", Miyoshi Oil & Fats Co., Ltd.'s product names "Palmitic Acid 60", “Stearic Acid 65” and “PM200”, Kao Corporation's product names "Lunac L-55A”, “Lunac BA” and “Lunac O-V”.
• the latex of the present disclosure may contain emulsifiers other than the first and second agents, so long as the effects of the invention of the present disclosure are not impaired.
• emulsifiers include anionic emulsifiers such as alkyl sulfate salts and alkyl phosphate salts; nonionic emulsifiers such as polyoxyethylene alkyl ethers and glycerin fatty acid esters; and amphoteric emulsifiers such as alkyl betaine salts, sulfobetaine salts, and N-acylamino acid salts.
• the latex of the present disclosure does not contain any emulsifiers other than the first and second agents. (In other words, it is preferable that the emulsifiers contained in the latex of the present disclosure are only the first and second agents.)
• the first agent is preferably contained in an amount of 1 to 15 parts by mass per 100 parts by mass of the chlorosulfonated polyolefin latex.
• the upper or lower limit of this range may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 parts by mass.
• the range is more preferably 1 to 10 parts by mass, and even more preferably 2 to 5 parts by mass. If the amount of the first agent used is within this range, a latex with a small particle size is more easily obtained, which is preferable.
• the second agent is preferably contained in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the chlorosulfonated polyolefin latex.
• the upper or lower limit of this range may be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, or 9 parts by mass.
• the range is more preferably 0.2 to 7 parts by mass, and even more preferably 0.5 to 5 parts by mass.
• the ratio of the first agent to the second agent is not particularly limited, but it is preferable that the mass ratio of the first agent to the second agent is 0.5 to 5.
• the upper or lower limit of this range may be, for example, 1, 1.5, 2, 2.5, 3, 3.5, 4, or 4.5.
• the range is 2 to 4. It is even more preferable that the above content ratio of the first agent to 100 parts by mass of the chlorosulfonated polyolefin latex and/or the above content ratio of the second agent to 100 parts by mass of the chlorosulfonated polyolefin latex are satisfied, and that the usage ratio of the first agent to the second agent is also satisfied.
• the above-mentioned conditions for the content ratio of the first agent and the second agent are satisfied, and it is particularly preferable that the total amount of the first agent and the second agent is 3 to 8 parts by mass, and especially preferable that it is 4 to 6 parts by mass, per 100 parts by mass of chlorosulfonated polyolefin.
• the aqueous dispersion medium is preferably one that is commonly used for latex, such as water.
• water There are no particular limitations on the water, and examples include tap water, deionized water, and distilled water.
• the content of the aqueous dispersion medium in the latex of the present disclosure is not particularly limited, and can be adjusted appropriately depending on the amount of other components contained.
• the latex of the present disclosure may contain preferably 60% by mass or more, more preferably 65% by mass or more or 70% by mass or more. It can also be used as the balance of the components other than the aqueous dispersion medium, and the content ratio of each component can be adjusted while making the entire latex 100% by mass.
• the average particle size of the chlorosulfonated polyolefin is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 5.0 ⁇ m, and even more preferably 0.5 to 2.0 ⁇ m.
• the average particle size of the chlorosulfonated polyolefin is 10 ⁇ m or less, the particles do not settle too quickly, and static stability is more preferable.
• the average particle size is 0.1 ⁇ m or more, the viscosity of the latex can be prevented from becoming too high, making it easier to handle.
• the average particle size in the present disclosure is the volume-based median particle size measured by a laser diffraction particle size distribution system.
• the latex of the present disclosure can be produced, for example, through an emulsification step in which chlorosulfonated polyolefin dissolved in an organic solvent is dispersed in an aqueous dispersion medium in the presence of the first and second agents to prepare an emulsion, and a desolvation step in which the organic solvent is removed from the emulsion.
• the organic solvent for dissolving the chlorosulfonated polyolefin is not particularly limited as long as it is capable of dissolving the chlorosulfonated polyolefin, and examples of the organic solvent include aliphatic hydrocarbon organic solvents such as hexane, heptane, and octane; alicyclic hydrocarbon organic solvents such as cyclohexane, methylcyclohexane, and decalin; aromatic hydrocarbon organic solvents such as benzene, toluene, and xylene; and halogenated hydrocarbon organic solvents such as chloroform, 1,2-dichloroethane, and chlorobenzene. These organic solvents may be used alone or in combination of two or more.
• the amount of organic solvent used is preferably set so that the concentration of chlorosulfonated polyolefin is, for example, 3 to 20% by mass, and more preferably 10 to 16% by mass. If the concentration of chlorosulfonated polyolefin is within this range, the solution is easy to handle and a latex with a small particle size is easily obtained, which is preferable.
• the temperature at which the chlorosulfonated polyolefin is dissolved in the organic solvent is preferably, for example, about 20 to 100°C. From the viewpoint of suppressing hydrolysis of the chlorosulfonated polyolefin (hydrolysis of the chlorosulfonic acid group), 40 to 80°C is more preferable.
• the emulsification process can be carried out in the following two forms, for example:
• an emulsion can be prepared by dissolving or dispersing the first and second agents in an aqueous dispersion medium, and then adding and dispersing a chlorosulfonated polyolefin solution to the aqueous dispersion medium (this emulsification process is sometimes referred to as the first form).
• the first and second agents used in this form act as emulsifiers.
• the first and second agents may be added separately to the aqueous dispersion medium, or the first and second agents may be mixed and then added to the aqueous dispersion medium.
• an emulsion can be prepared by adding a fatty acid to a chlorosulfonated polyolefin solution, mixing, dissolving or dispersing, and adding this mixed solution to an aqueous dispersion medium in which the first agent and a neutralizer for the fatty acid have been dissolved, and dispersing the mixture (this emulsification process is sometimes referred to as the second form).
• the fatty acid used is the same as described above, and is used as a precursor for the second agent.
• the neutralizer used may be any agent that can act on the fatty acid to form a fatty acid salt, and preferred examples include sodium hydroxide, sodium methoxide, potassium hydroxide, potassium tert-butoxide, ammonia, triethanolamine, etc.
• the amount of aqueous dispersion medium used in the emulsification process is preferably set so that, for example, in the first form, the total concentration of the first agent and the second agent relative to the aqueous dispersion medium is 0.1 to 50% by mass.
• the second form it is preferably set so that the total concentration of the first agent contained in the aqueous dispersion medium, the fatty acid salt formed by the fatty acid in the organic solvent solution and the neutralizing agent for the aqueous dispersion medium is 0.1 to 50% by mass relative to the aqueous dispersion medium.
• the amounts of the first agent and the second agent used are preferably set to 2 to 5 parts by mass and 0.5 to 4 parts by mass, respectively, per 100 parts by mass of chlorosulfonated polyolefin dissolved in an organic solvent.
• the amount of the first agent used is preferably set to the same as in the first form.
• the amounts of the fatty acid and neutralizing agent used are preferably set so that the amount of fatty acid salt formed by adding the organic solvent solution to the aqueous dispersion medium is the same as in the first form.
• a method of stirring and mixing using an emulsifier having an appropriate shear force for example, a batch type emulsifier such as a homomixer, homodisper, homogenizer, or colloid mill, a method of stirring and mixing using a continuous type emulsifier such as an in-line homomixer or in-line homogenizer, or a method of dispersing using an ultrasonic disperser, etc. can be used. These methods may be used alone or in combination of two or more.
• the temperature in the emulsification process is not particularly limited, but is preferably set to 5 to 70°C, and more preferably to 25 to 60°C.
• the average particle size of the chlorosulfonated polyolefin in the target chlorosulfonated polyolefin latex can also be adjusted by controlling the intensity of stirring and mixing, the frequency of ultrasonic waves, the processing time, the processing temperature, etc., during the preparation of the emulsion.
• methods for removing the organic solvent from the emulsion obtained in the emulsification step include, for example, a method of distilling the emulsion under normal pressure, reduced pressure or increased pressure, a method of blowing steam or the like into the emulsion to volatilize and remove the organic solvent, and a method of removing the organic solvent using a membrane that selectively allows only the organic solvent to pass through. These methods may be carried out alone or in combination of two or more types.
• a defoaming agent may be used to suppress foaming of the emulsion.
• defoaming agents include mineral oil-based defoaming agents, silicone-based defoaming agents, acetylene-based defoaming agents, metal soap-based defoaming agents, acrylic defoaming agents, and fluorine-based defoaming agents.
• acetylene-based defoaming agents are preferred. These may be used alone or in combination of two or more types.
• the amount of defoaming agent used depends on the amount of emulsifier used, but is preferably 100 to 2000 ppmwt per 100 parts by mass of chlorosulfonated polyolefin.
• the defoaming agent may be added to the emulsion before the desolvation step, or may be added appropriately during the desolvation step.
• the method of addition may be a method of adding all at once, a method of dropping, a method of spraying, etc.
• the emulsion after removing the organic solvent can be concentrated to the desired solids concentration, if necessary.
• Concentration methods include, for example, heat concentration, centrifugation, filtration, and wet separation.
• the method of concentration using a filtration membrane is preferred, since it does not require much heat or stress to be applied to the emulsion and is less likely to impair the stability of the emulsion, and the method of concentration using an ultrafiltration membrane is more preferred.
• the solids concentration of the desired chlorosulfonated polyolefin latex obtained through the solvent removal process is preferably 20 to 60% by mass.
• a neutralizing agent may be added to the obtained chlorosulfonated polyolefin latex to adjust the pH.
• a neutralizing agent for example, a common neutralizing agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, monoethanolamine, etc. may be used.
• the neutralizing agent may be added before the desolvation step, may be added during the desolvation step, or may be added after the desolvation step.
• additives such as dispersion stabilizers such as polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethyl cellulose, and stabilizers such as dibutylhydroxytoluene, 2,5-di-tert-butylhydroquinone, and bisphenol A type epoxy resin may be added within a range that does not impair the effects of the invention of the present disclosure.
• Such additives may be added to the chlorosulfonated polyolefin latex after preparation, or, depending on the type of additive, may be added to the organic solvent solution or aqueous dispersion medium used in the emulsification process when preparing the chlorosulfonated polyolefin latex.
• these additives are added as an aqueous solution or aqueous dispersion liquid individually or as a mixture.
• the total amount is about 0.1 to 10 parts by mass per 100 parts by mass of chlorosulfonated polyolefin.
• the present disclosure also includes a chlorosulfonated polyolefin emulsion composition that includes a first agent and a second agent.
• the chlorosulfonated polyolefin emulsion composition may be referred to as the emulsion composition of the present disclosure. Since the emulsion composition of the present disclosure includes a first agent and a second agent, a coagulable chlorosulfonated polyolefin latex that has excellent stability can be produced by emulsifying a chlorosulfonated polyolefin with the emulsion composition of the present disclosure.
• the emulsion composition of the present disclosure can be preferably used to produce the chlorosulfonated polyolefin latex of the present disclosure.
• the latex disclosed herein can be particularly preferably used as a dip molding composition.
• the latex of the present disclosure may further contain known additives such as rheology adjusters, antioxidants, defoamers, pH adjusters, chelating agents, vulcanizing agents, vulcanization accelerators, vulcanization accelerator assistants, acid acceptors, film-forming assistants, plasticizers, fillers, and pigments, within the scope of not impairing the effects of the invention of the present disclosure.
• additives can be preferably used, particularly when the latex of the present disclosure is used as a dip molding composition.
• Rheology modifiers include polysaccharides such as cellulose, cellulose nanofiber, cellulose nanocrystal, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, chitin, chitosan, guar gum, and xanthan gum; water-soluble vinyl polymers such as polyacrylic acid, sodium polyacrylate, crosslinked polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinyl methyl ether, and polyvinylpyrrolidone; and clay minerals such as montmorillonite, nontronite, saponite, beidellite, and hectorite.
• polysaccharides such as cellulose, cellulose nanofiber, cellulose nanocrystal, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, chitin, chitosan, guar gum, and xanthan gum
• antioxidants examples include phenol-based antioxidants such as dibutylhydroxytoluene, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), and 2,5-di-tert-butylhydroquinone; amine-based antioxidants such as N-phenyl-1-naphthylamine and di(4-octylphenyl)amine; phosphorus-based antioxidants such as tris(nonylphenyl)phosphite; sulfur-based antioxidants such as dilauryl thiodipropionate, 2-mercaptobenzimidazole, and nickel dibutyldithiocarbamate; and bisphenol A epoxy resins.
• phenol-based antioxidants such as dibutylhydroxytoluene, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), and 2,5-di-tert-butylhydroquinone
• defoaming agents examples include oil-based defoaming agents, mineral oil-based defoaming agents, silicone-based defoaming agents, polyether-based defoaming agents, etc.
• pH adjusters include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, trimethylamine, triethanolamine, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, acetic acid, etc.
• Chelating agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, trans-1,2-diaminocyclohexanetetraacetic acid, diethylenetriaminepentaacetic acid, bis(aminoethyl)glycol ether-N,N,N',N'-tetraacetic acid, N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid, dihydroxyethylglycine, 1-hydroxyethane-1,1-diphosphonic acid, gluconic acid, citric acid, malic acid, and tartaric acid.
• vulcanizing agents include sulfur such as powdered sulfur, sulfur flowers, precipitated sulfur, and colloidal sulfur; organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide; maleimide compounds such as N,N'-m-phenylene bismaleimide; quinoid compounds such as p-quinone dioxime and p,p'-dibenzoylquinone dioxime; metal compounds such as magnesium oxide and lead oxide; and polyhydric alcohol compounds such as pentaerythritol, dipentaerythritol, sorbitol, and trimethylolpropane.
• sulfur such as powdered sulfur, sulfur flowers, precipitated sulfur, and colloidal sulfur
• organic peroxides such as di-tert-butyl peroxide and dicumyl peroxide
• maleimide compounds such as N,N'-m-phenylene bismaleimide
• quinoid compounds such as p-quinone dioxime and p,
• Vulcanization accelerators include diethyldithiocarbamic acid, dibutyldithiocarbamic acid, diphenyldithiocarbamic acid, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, sodium diphenyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc diphenyldithiocarbamate, 2-mercaptobenzothiazole, zinc 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, 2-(4'-morpholinyl) Nodithio)benzothiazole, trimethylthiourea, N,N'-diethylthiourea, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, N-cyclohexyl-2-benzothiazolylsulfenamide, N-oxyd
• vulcanization accelerators examples include metal oxides such as zinc oxide and magnesium oxide, and fatty acids such as stearic acid and palmitic acid.
• Acid acceptors include metal oxides such as lead oxide, magnesium oxide, zinc oxide, and calcium oxide; metal hydroxides such as magnesium hydroxide, calcium hydroxide, and aluminum hydroxide; clay minerals such as hydrotalcite; and epoxy compounds such as phenyl glycidyl ether, bisphenol A diglycidyl ether, epoxidized soybean oil, epoxidized linseed oil, epoxidized polybutadiene, and polyglycidyl methacrylate.
• metal oxides such as lead oxide, magnesium oxide, zinc oxide, and calcium oxide
• metal hydroxides such as magnesium hydroxide, calcium hydroxide, and aluminum hydroxide
• clay minerals such as hydrotalcite
• epoxy compounds such as phenyl glycidyl ether, bisphenol A diglycidyl ether, epoxidized soybean oil, epoxidized linseed oil, epoxidized polybutadiene, and polyglycidyl methacrylate.
• film-forming aids include propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol mono isobutyl ether, ethylene glycol mono tert-butyl ether, ethylene glycol monophenyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono n-butyl ether, diethylene glycol mono isobutyl ether, diethylene glycol mono tert-butyl ether, diethylene glycol monophenyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol mono
• Plasticizers include phthalates, adipic esters, glycerin fatty acid esters, polyether polyols, polyester polyols, etc.
• Fillers include carbon fiber, cellulose fiber, carbon black, silica, talc, clay, calcium carbonate, titanium oxide, barium sulfate, etc.
• Pigments include carbon black, titanium oxide, chromium oxide, iron blue, amber, nickel titanium yellow, viridian, cobalt blue, phthalocyanine blue, phthalocyanine green, molybdenum orange, chrome yellow, anthraquinone, quinacridone, etc.
• the amount of additives contained in the latex of the present disclosure is not particularly limited, but is preferably 5 to 30 parts by mass per 100 parts by mass of the solid content (i.e., chlorosulfonated polyolefin) in the latex composition.
• other rubber latexes may be included as long as the effect is not impaired.
• examples of such other latexes include natural rubber latex, isoprene rubber latex, butadiene rubber latex, chloroprene rubber latex, butyl rubber latex, styrene-butadiene rubber latex, acrylic rubber latex, acrylonitrile-butadiene rubber latex, silicone rubber latex, fluororubber latex, epichlorohydrin rubber latex, and olefin rubber latex.
• the content of the other rubbers is preferably less than the content of the chlorosulfonated polyolefin, and is preferably, for example, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less per 100 parts by mass of the chlorosulfonated polyolefin.
• the method for preparing such a dip molding composition is not particularly limited, and examples thereof include a method of mixing various additives with the chlorosulfonated polyolefin latex using a dispersing machine such as a ball mill, a bead mill, a kneader, or a disperser, a method of preparing an aqueous dispersion of desired additives in advance using a dispersing machine and then mixing the aqueous dispersion with the chlorosulfonated polyolefin latex, and a method of mixing some additives with the chlorosulfonated polyolefin latex and then mixing it with an aqueous dispersion of other additives.
• a dispersing machine such as a ball mill, a bead mill, a kneader, or a disperser
• the pH of the latex of the present disclosure is preferably 5 or higher (particularly when used as a dip molding composition), and more preferably 7 to 12.
• the latex of the present disclosure When used as a dip molding composition, it may be aged (also called pre-vulcanization) before being subjected to dip molding.
• the aging time cannot be generally determined because it depends on the type of additives and the aging temperature, but it is preferably 1 to 7 days, more preferably 1 to 3 days.
• the aging temperature is preferably 10 to 50°C, more preferably 20 to 40°C. After aging, it is preferable to store the mixture at a temperature of 30° C. or lower until it is used for dip molding.
• the present disclosure also includes dip molded bodies obtained by using the latex of the present disclosure as a dip molded body composition.
• Dip molding is a method in which a mold (molding mold) is immersed in a dip molding composition, the composition is deposited on the surface of the mold, the mold is then lifted out of the composition, and the composition deposited on the surface of the mold is then dried.
• the mold used for dip molding can be a mold that corresponds to the desired three-dimensional shape and is integrally formed from ceramic, metal, glass, plastic, etc.
• the surface of the mold can be finished with a matte finish or equipped with other materials such as fibers or other types of rubber coatings.
• the mold can be preheated before being immersed in the dip molding composition.
• a coagulant to aggregate the solids (hereinafter sometimes simply referred to as rubber components) mainly composed of chlorosulfonated polyolefin.
• Methods for using the coagulant include a method in which the mold before immersing in the dip molding composition is immersed in a solution of the coagulant (hereinafter also referred to as the coagulating liquid) to adhere the coagulant to the mold, and a method in which the mold on which the dip molding composition has been deposited is immersed in the coagulating liquid. From the viewpoint of obtaining a dip molded body with little unevenness in thickness, a method in which the mold before immersing in the dip molding composition is immersed in a solution of the coagulant to adhere the coagulant to the mold is preferable.
• metal salts are preferred, and water-soluble metal salts are more preferred.
• metal salts polyvalent metal salts that generate polyvalent metal ions are preferred from the viewpoint of high coagulation power, and water-soluble polyvalent metal salts are more preferred.
• water-soluble metal salts include metal halides such as sodium chloride, potassium chloride, barium chloride, calcium chloride, magnesium chloride, zinc chloride, and aluminum chloride; metal nitrates such as sodium nitrate, potassium nitrate, barium nitrate, calcium nitrate, zinc nitrate, and aluminum nitrate; metal acetates such as sodium acetate, potassium acetate, barium acetate, calcium acetate, zinc acetate, and aluminum acetate; and metal sulfates such as sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, and aluminum sulfate.
• metal halides such as sodium chloride, potassium chloride, barium chloride, calcium chloride, magnesium chloride, zinc chloride, and aluminum chloride
• metal nitrates such as sodium nitrate, potassium nitrate, barium nitrate, calcium nitrate, zinc nitrate, and aluminum
• alkaline earth metals are preferred, and calcium, barium, and magnesium are more preferred, and calcium is particularly preferred.
• calcium chloride and calcium nitrate are particularly preferred from the viewpoint of high solubility in water. These coagulants may be used alone or in combination of two or more.
• the coagulant is preferably used in the form of an aqueous solution.
• This aqueous solution may further contain a water-soluble organic solvent such as methyl alcohol or ethyl alcohol, or a nonionic surfactant.
• the concentration of the coagulant is not particularly limited, but is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and particularly preferably 15 to 35 mass%.
• the immersion time of the mold in the coagulant is not particularly limited, but is usually preferably 5 to 300 seconds, and more preferably 10 to 100 seconds.
• the solvent of the coagulating liquid may be removed by drying.
• the drying temperature can be set appropriately depending on the type of solvent and salt used, and is preferably 60 to 150°C, and more preferably 80 to 120°C. There are no particular limitations on the drying time, but it is preferably 1 to 600 seconds, and more preferably 5 to 300 seconds.
• the time for which the mold is immersed in the latex (dip molding composition) of the present disclosure may be set appropriately depending on the desired thickness (film thickness), but is preferably 5 to 600 seconds, and more preferably 10 to 300 seconds.
• the mold After the mold is removed from the dip molding composition, it is usually heated to dry the solidified coating formed on the mold surface.
• drying method There are no particular limitations on the drying method, and drying can be performed using a hot air heater, infrared heater, microwave heater, high-frequency heater, etc.
• the drying temperature is not particularly limited, but is preferably 50 to 160°C, more preferably 60 to 140°C, and particularly preferably 70 to 120°C.
• the drying time is also not particularly limited, but is preferably 1 to 120 minutes, more preferably 10 to 100 minutes, and particularly preferably 20 to 60 minutes.
• the solidified film formed on the mold surface may be vulcanized by further heating.
• the heating conditions during vulcanization are not particularly limited, but 60 to 200°C is preferable, 80 to 180°C is more preferable, and 100 to 160°C is particularly preferable. By setting the heating temperature within this range, it is possible to achieve an appropriate vulcanization speed and suppress deterioration of the rubber components due to excessive heating.
• the heating time for vulcanization may be appropriately selected depending on the heating temperature, and is usually 5 to 120 minutes.
• the heating method may be, for example, the same heating method as described above.
• the mold onto which the dip molding composition has been deposited Before or after heating the mold onto which the dip molding composition has been deposited, it is preferable to wash the mold with water or hot water to remove water-soluble impurities (e.g., excess emulsifier, surfactant, coagulant, uncoagulated latex, etc.).
• water-soluble impurities e.g., excess emulsifier, surfactant, coagulant, uncoagulated latex, etc.
• the temperature of the water or hot water used is preferably 20 to 80°C, more preferably 30 to 70°C.
• the washing time is preferably about 0.5 to 60 minutes.
• the dip-molded article After drying (and further vulcanization if necessary), the dip-molded article is removed from the mold. Methods for removal include peeling from the mold by hand, peeling from the mold using a peeling roller, and peeling using water pressure or compressed air pressure. After being removed from the mold, the dip-molded article may be further washed with water. Furthermore, if necessary, in order to prevent adhesion at the contact surfaces between dip-molded articles and to improve slippage when attaching and removing them, inorganic fine particles such as talc or calcium carbonate or organic fine particles such as cornstarch may be applied to the surface, an elastomer layer containing fine particles may be further formed on the surface, or the surface layer may be chlorinated.
• inorganic fine particles such as talc or calcium carbonate or organic fine particles such as cornstarch
• the thickness of the dip-molded body thus obtained is preferably, for example, 0.1 to 2 mm, more preferably 0.2 to 1.5 mm, and particularly preferably 0.3 to 1.0 mm.
• the thickness of the film can be appropriately set by the immersion time, etc., as described above.
• chlorosulfonated polyolefin chlorosulfonated polyethylene (product name "TOSO-CSM” by Tosoh Corporation, product number: TS-320, TS-530, or CN-1500) was used.
• the chlorine content and sulfur content in these chlorosulfonated polyethylenes (CSM rubbers) are as follows: TS-320: Chlorine content 23% by mass, sulfur content 1.0% by mass TS-530: Chlorine content 35% by mass, sulfur content 1.0% by mass CN-1500: Chlorine content 30% by mass, sulfur content 1.4% by mass
• the emulsifiers (including fatty acid precursors) used in the examples and comparative examples are listed below.
• C Sodium polyoxyalkylene disulfonate (manufactured by Nippon Nyukazai Co., Ltd., product name "Newcol 240", solid content concentration 30% by mass)
• each emulsifier in the examples and comparative examples are values relative to 100 parts by mass of chlorosulfonated polyolefin (specifically, chlorosulfonated polyethylene) in the chlorosulfonated polyolefin latex.
• the number of parts added [phr] (per hundred rubber) in Table 1 indicates the corresponding value.
• the emulsifier concentration (solids concentration) contained in each of the above emulsifier products is different, and the value of parts by mass of each emulsifier in the examples is a value calculated from the amount of emulsifier converted based on the solids concentration.
• a sodium alkyl (C10-16) benzenesulfonate product (Newrex R) with a solids concentration of 50% by mass is used as the first agent for 37.8 g of chlorosulfonated polyethylene.
• the chlorosulfonated polyethylene latexes and coatings obtained in the respective Examples and Comparative Examples were evaluated by the following methods.
• the average particle diameters of the emulsion and latex were measured using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, product name "SALD-2300")
• SALD-2300 laser diffraction particle size distribution analyzer
• the average particle diameter here is the value of the volume-based median particle diameter calculated by assuming that the particle to be measured, which shows the same diffraction and scattered light pattern as a sphere with a diameter of 1 ⁇ m, has a particle diameter of 1 ⁇ m regardless of its shape.
• the dip-formed body was divided into approximately thirds in the longitudinal direction, and the thickness was measured near the center of gravity of three points (three rectangles) at the top, middle, and bottom, and the overall average was taken to determine the thickness of the dip-formed body.
• Example 1 (Latex manufacturing) 37.8 g of chlorosulfonated polyethylene (TOSO-CSM, product number TS-320, manufactured by Tosoh Corporation) and 232.2 g of toluene were charged into a 500 mL separable flask and dissolved by stirring at 70° C. for 6 hours. 0.39 g of oleic acid (NOF Corporation, product name Extra Olein) was added thereto to prepare an organic solvent solution.
• TOSO-CSM chlorosulfonated polyethylene
• TS-320 product number TS-320, manufactured by Tosoh Corporation
• the aqueous solution was added to the organic solvent solution, and the mixture was stirred and mixed for 12 minutes using a homomixer (TK homomixer M model, manufactured by Primix Corporation) to obtain an emulsion.
• the rotation speed during stirring and mixing was set to 12,000 rpm.
• the obtained emulsion was heated to 55°C under a reduced pressure of 20 kPa to remove the toluene, and then concentrated to a solids concentration of 40% using an ultrafilter (ultrafiltration membrane: flat membrane type, molecular weight cutoff 200,000, material polysulfone) to obtain chlorosulfonated polyethylene latex.
• the solids concentration was determined by drying a portion of the obtained latex at 130°C for 2 hours to remove the moisture, and then measuring the mass of the residue.
• a ceramic mold (boat-shaped, 10 cm long x 1.5 cm wide x 1 cm deep) was immersed in a 35% by mass calcium nitrate aqueous solution for 5 seconds and dried in a 120°C air dryer for 5 minutes. The ceramic mold was then immersed in the dip molding composition for 30 seconds to allow the rubber component to adhere to the ceramic mold, and then removed from the dip molding composition. The ceramic mold was dried in a 100°C air dryer for 20 minutes, and then further heated at 160°C for 20 minutes to perform vulcanization. After cooling to room temperature, the coating was peeled off from the ceramic mold, and the thickness of the resulting dip molded body was measured.
• Examples 2 to 11 and Comparative Examples 1 to 5> The same procedure as in Example 1 was repeated except that the types and amounts of rubbers and emulsifiers shown in Table 1 were used, and the obtained latexes and films were evaluated.
• the emulsifier used as the first agent was changed to the following components, but the conditions were the same as in Example 1. As a result, latex could be prepared (i.e., no rubber aggregation occurred), and there was no case in which the stability and coagulation properties were both rated as good.
• the emulsifiers used as the first agent are summarized below by results.
• the invention according to one aspect of the present disclosure provides a chlorosulfonated polyolefin latex that is highly stable and can be applied to a general coagulation dipping method. By using this latex, dip-molded articles can be efficiently manufactured. Furthermore, the invention according to the present disclosure is useful from the viewpoint of environmental protection, as it makes it possible to obtain dip-molded articles such as gloves without using organic solvents during dip molding.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=92905076

Family Applications (1)

Country Status (4)

Citations (6)

• 2024
  • 2024-03-25 JP JP2025510802A patent/JPWO2024203980A1/ja active Pending
  • 2024-03-25 CN CN202480021530.6A patent/CN120882801A/zh active Pending
  • 2024-03-25 WO PCT/JP2024/011543 patent/WO2024203980A1/ja not_active Ceased
  • 2024-03-26 TW TW113111162A patent/TW202500636A/zh unknown

Patent Citations (6)

Also Published As

Similar Documents

Legal Events