Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
  • C08L11/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F136/02—Homopolymers 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
  • C08F136/04—Homopolymers 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
  • C08F136/14—Homopolymers 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
  • C08F136/16—Homopolymers 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
  • C08F136/18—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen containing chlorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
  • C08F236/16—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
  • C08F236/18—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen containing chlorine
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
  • C09J111/02—Latex

Definitions

• the present invention relates to a chloroprene-based polymer latex, a chloroprene-based polymer, an adhesive composition, a compound composition, a vulcanized molding, and a method for producing the same.
• Chloroprene-based rubbers are used in various applications because of their excellent heat resistance, weather resistance, ozone resistance, chemical resistance, flame retardancy, and the like.
• Solvent-type adhesives are also one of the representative examples, and are used in various applications due to their broad applicability to adherends and good balance of adhesive properties.
• layer separation in which the solvent-type adhesive separates into a component soluble in an organic solvent and a component insoluble in the organic solvent, tends to occur during storage.
• Patent Document 1 discloses that a specific ethylenically unsaturated sulfonic acid or a salt thereof is copolymerized in a specific range when chloroprene is polymerized. technology is known. Further, Patent Document 2 discloses a chloroprene rubber composition containing 0.005 to 10 parts by mass of at least one sulfonic acid compound having a specific structure with respect to 100 parts by mass of chloroprene rubber.
• chloroprene-based polymer latexes have the problem that they generate less aggregates during and after the polymerization reaction, and it is impossible to obtain an adhesive composition that does not cause layer separation for a long period of time.
• the present invention has been made in view of such circumstances, and it is possible to obtain an adhesive composition that generates less aggregates during and after the polymerization reaction and does not cause layer separation for a long period of time.
• a chloroprene-based polymer latex a chloroprene-based polymer
• an adhesive composition a compound composition, and a vulcanized molding containing such a chloroprene-based polymer latex or a chloroprene-based polymer, and methods for producing these It is something to do.
• a chloroprene-based polymer latex containing a chloroprene-based polymer wherein the amount of alkali metal cation substance in the chloroprene-based polymer latex per unit mass is 0.05 to 0.25 mmol/g.
• the ethanol-toluene azeotropic mixture soluble content specified in JIS K 6229 is refluxed and extracted.
• the amount of rosin acid measured by gas chromatography after acid-treating the extract with hydrochloric acid is 1.4 to 4.2% by mass with respect to 100% by mass of the chloroprene-based polymer contained in the solid content.
• a chloroprene-based polymer latex is provided.
• the present inventor found that by setting the amount of alkali metal cations and the amount of rosin acid contained in the chloroprene-based polymer latex within a specific numerical range, The present inventors have found that a chloroprene-based polymer latex can be obtained, which gives an adhesive composition that generates less aggregates and does not cause layer separation for a long period of time, and has completed the present invention.
• the chloroprene-based polymer has no peak at 4.15 to 4.20 ppm or a peak at 4.15 to 4.20 ppm in the 1 H-NMR spectrum measured in a deuterated chloroform solvent.
• the peak area of 4.15 to 4.20 ppm is C and the peak area of 4.05 to 6.10 ppm is B, C/B is less than 0.10/100.
• the above-described method for producing a chloroprene-based polymer latex comprising an emulsion polymerization step of emulsion-polymerizing a monomer containing a chloroprene monomer, wherein, in the emulsion polymerization step, Using 1.2 to 3.0 parts by mass of rosinate with respect to a total of 100 parts by mass of the chloroprene monomer and the chloroprene and the copolymerizable monomer, and hydroxylating with respect to 100 parts by mass of the aqueous medium
• a method for producing a chloroprene-based polymer latex using a total amount of sodium and potassium hydroxide of 0.1 to 1.1 parts by mass Provided is a method for producing a chloroprene-based polymer latex using a total amount of sodium and potassium hydroxide of 0.1 to 1.1 parts by mass.
• a chloroprene-based polymer obtained by drying up the chloroprene-based polymer latex described above.
• an adhesive composition containing the chloroprene-based polymer latex or chloroprene-based polymer described above.
• a compound composition containing the chloroprene-based polymer described above.
• a vulcanized molding comprising the compound composition described above.
• chloroprene-based polymer latex According to the chloroprene-based polymer latex according to the present invention, it is possible to obtain an adhesive composition that generates less aggregates during and after the polymerization reaction and that does not cause layer separation for a long period of time.
• Chloroprene-Based Polymer Latex contains a chloroprene-based polymer, and the amount of alkali metal cation substances in the chloroprene-based polymer latex and the amount of rosin acid contained in the chloroprene-based polymer are specified. is within the numerical range of
• the amount of alkali metal cation substance in the chloroprene-based polymer latex per unit mass is 0.05 to 0.25 mmol/g.
• the substance amount of the alkali metal cation is, for example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14 , 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25 mmol/g It can be within a range between any two of the numerical values recited herein.
• the amount of alkali metal cations in the chloroprene-based polymer latex is analyzed by an inductively coupled plasma atomic emission spectrometer after the chloroprene-based polymer latex is acid-decomposed with sulfuric acid and the like, acidified with hydrochloric acid. Specifically, it can be determined by the method described in Examples.
• the alkali metal cations according to one embodiment of the present invention are preferably potassium ions and/or sodium ions.
• the chloroprene-based polymer latex according to the present invention is obtained by freeze-drying the chloroprene-based polymer latex, and the ethanol-toluene The azeotropic mixture-soluble content is extracted under reflux, the resulting extract is acid-treated with hydrochloric acid, and the amount of rosin acid measured by gas chromatography is 100% by mass of the chloroprene-based polymer contained in the solid is 1.4 to 4.2% by mass.
• the amount of rosin acid in the solid content containing the chloroprene polymer is, for example, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2 .2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4 , 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2% by mass, and any two of the values exemplified here It may be in the range between.
• the amount of rosin acid in the solid content containing the chloroprene-based polymer is an ethanol-toluene azeotrope (ethanol/toluene volume ratio 7 /3(ETA)), the rosin acids can be determined by gas chromatography, and specifically can be evaluated by the method described in Examples.
• the rosin acid according to one embodiment of the present invention is, for example, a single component of resin acids such as abietic acid, dehydroabietic acid, dihydroabietic acid, pimaric acid, dihydropimaric acid, isopimaric acid, secodehydroabietic acid, or these It preferably contains a mixture.
• the chloroprene-based polymer latex according to the present invention by setting the amount of alkali metal cation and the amount of rosin acid within the above-mentioned specific numerical ranges, there is little generation of aggregates during and after the polymerization reaction,
• the chloroprene-based polymer latex can provide an adhesive composition that does not cause layer separation for a long period of time.
• the chloroprene-based polymer latex according to one embodiment of the present invention preferably satisfies the following condition 1 or 2.
• Condition 1 The substance amount of the alkali metal cation is 0.12 to 0.25 mmol/g, and the rosin acid amount is 1.4 to 3.2% by mass.
• the substance amount of the alkali metal cation is 0.05 to 0.25 mmol/g, and the rosin acid amount is 3.2 to 4.2% by mass.
• the chloroprene-based polymer latex according to one embodiment of the present invention satisfies the above condition 1 or 2, and by highly controlling the amount of alkali metal cation and the amount of rosin acid, The resulting chloroprene-based polymer latex can provide an adhesive composition that causes little subsequent generation of agglomerates, does not cause layer separation for a long period of time, and provides an adhesive composition that has a long pot life.
• the amount of the alkali metal cation substance is more preferably 0.13 mmol/g or more, and even more preferably 0.14 mmol/g or more.
• Substance amounts of alkali metal cations are, for example, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21 , 0.22, 0.23, 0.24, 0.25 mmol/g, and may be within a range between any two of the values exemplified herein.
• the amount of rosin acid is, for example, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3 , 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2% by mass, and the numerical values illustrated here It may be in the range between any two.
• the amount of alkali metal cation substance is, for example, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13 , 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25mmol/g and may be within a range between any two of the numerical values exemplified herein.
• the amount of rosin acid is, for example, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1 , 4.2% by weight, and may be in the range between any two of the values exemplified herein.
• chloroprene-based polymer is a homopolymer of 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene), or a chloroprene monomer and other copolymerizable with it. It is a copolymer with a monomer.
• Examples of monomers copolymerizable with chloroprene monomers include 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, acrylic acid or Esters thereof, methacrylic acid, esters thereof, and the like can be mentioned. These may be used alone or in combination of two or more.
• the chloroprene-based polymer according to one embodiment of the present invention has a chloroprene monomer when the chloroprene-based polymer is 100% by mass. It preferably contains 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more of the monomer units derived from the body.
• a chloroprene-based polymer according to an embodiment of the present invention can have no peak at 4.15 to 4.20 ppm in a 1 H-NMR spectrum measured in a deuterated chloroform solvent.
• the chloroprene-based polymer according to one embodiment of the present invention can have a peak at 4.15 to 4.20 ppm in a 1 H-NMR spectrum measured in a deuterated chloroform solvent.
• the chloroprene-based polymer according to one embodiment of the present invention has a peak area of 4.15 to 4.20 ppm as C, and a peak area of 4.05 to 6.10 ppm as B.
• C/B is preferably less than 0.10/100, more preferably less than 0.09/100, and even more preferably 0.08/100 or less.
• C/B can be, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09/100, It may be in a range between any two of the numerical values exemplified here.
• the 1 H-NMR spectrum is measured by dissolving a chloroprene-based polymer purified with benzene and methanol and freeze-dried in deuterated chloroform. Peak positions are based on the peak of chloroform in deuterated chloroform (7.24 ppm).
• C/B can be controlled by adjusting the production conditions of the chloroprene-based polymer, for example, adjusting the charging amounts of rosinate and sodium hydroxide and potassium hydroxide during polymerization of the chloroprene-based polymer.
• the amount of alkali metal cations contained in the chloroprene-based polymer latex and the amount of rosin acid contained in the chloroprene-based polymer are within a specific numerical range.
• the 1 H-NMR spectrum measured in a deuterated chloroform solvent does not have a peak at 4.15 to 4.20 ppm, or the C/B is less than the upper limit, so that during the polymerization reaction
• the chloroprene-based polymer latex that generates less aggregates after the completion of the polymerization reaction does not cause layer separation for a long period of time, and becomes an adhesive composition having a long pot life.
• the peak appearing at 4.15 to 4.20 ppm in the 1 H-NMR spectrum is presumed to be related to the 1,2-OH rearrangement structure represented by the following formula.
• the chloroprene-based polymer latex according to one embodiment of the present invention since the peak area ratio related to the structure is less than the above upper limit, the cross-linking reaction of the chloroprene-based polymer is suppressed, and layer separation does not occur for a long period of time. Furthermore, the chloroprene-based polymer latex is considered to be an adhesive composition having a long pot life.
• a chloroprene-based polymer according to an embodiment of the present invention preferably has a peak at 5.80 to 6.00 ppm in a 1 H-NMR spectrum measured in a deuterated chloroform solvent. Further, in the chloroprene-based polymer according to one embodiment of the present invention, when A is the peak area of 5.80 to 6.00 ppm and B is the peak area of 4.05 to 6.10 ppm, A / B is It is preferably 1.18/100 or more, more preferably 1.20/100 or more.
• A/B is, for example, 1.18, 1.19, 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.28 , 1.29, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35/100, and within the range between any two of the values exemplified herein. may be
• the chloroprene-based polymer according to one embodiment of the present invention preferably has a peak at 5.40 to 5.60 ppm in 1 H-NMR spectrum measured in a deuterated chloroform solvent. Further, in the chloroprene-based polymer according to one embodiment of the present invention, when the peak area of 5.40 to 5.60 ppm is D and the peak area of 4.05 to 6.10 ppm is B, D / B is It is preferably 97.20/100 or less, more preferably 97.18/100 or less, and even more preferably 97.15/100 or less.
• D/B is, for example, 97.00, 97.01, 97.02, 97.03, 97.04, 97.05, 97.06, 97.07, 97.08, 97.09, 97.10 , 97.11, 97.12, 97.13, 97.14, 97.15, 97.16, 97.17, 97.18, 97.19, 97.20/100, where It may be in a range between any two of the numerical values given.
• the peak area ratio related to the above structure in the chloroprene-based polymer is within the above numerical range, so that layer separation does not occur for a longer period of time.
• the chloroprene-based polymer latex becomes an adhesive composition having a long pot life.
• chloroprene-based polymer latex may contain a freeze stabilizer, an emulsion stabilizer, a viscosity modifier, an antioxidant, a preservative, etc. within a range that does not impair the effects of the present invention. can.
• the content of the emulsifier other than the emulsifier containing rosin acid is 1 mass. % or less, and can be 0.5 mass % or less.
• emulsifiers other than rosin acid-containing emulsifiers include metal salt of aromatic sulfonic acid formalin condensate, sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, sodium alkyldiphenylethersulfonate, potassium alkyldiphenylethersulfonate, poly Sodium oxyethylene alkyl ether sulfonate, sodium polyoxypropylene alkyl ether sulfonate, potassium polyoxyethylene alkyl ether sulfonate, potassium polyoxypropylene alkyl ether sulfonate and the like.
• the content of the metal salt of the aromatic sulfonic acid formalin condensate for example, the content of the naphthalene sulfonic acid formalin condensate can be 1% by mass or less. .5% by mass or less.
• the amount of aggregates generated from the start to the end of the polymerization reaction is the chloroprene-based polymer. It is preferably less than 1% by mass with respect to 100% by mass.
• the term "aggregate” refers to the dry weight of the residue when the polymerization solution is filtered through a wire mesh of 80 mesh, and the dry weight of deposits collected from the wall surface of the reactor when the chloroprene-based polymer is 100% by mass. can be evaluated as the sum of
• Method for producing chloroprene-based polymer latex is not particularly limited. can.
• a chloroprene monomer, or a chloroprene monomer and other monomers copolymerizable therewith are appropriately added with an emulsifier, a dispersant, a catalyst, a chain transfer agent, or the like.
• an emulsifier emulsifier, a dispersant, a catalyst, a chain transfer agent, or the like.
• a polymerization terminator can be added to obtain a chloroprene-based polymer latex.
• unreacted monomers can be removed from the chloroprene-based polymer latex thus obtained by a steam flash method, a concentration method, or the like.
• Monomers containing chloroprene monomers include chloroprene monomers and other monomers copolymerizable with the chloroprene monomers described above.
• ⁇ Rosinate> In the emulsion polymerization step according to one embodiment of the present invention, 1.2 to 3.0 parts by mass of rosinate is added to a total of 100 parts by mass of the chloroprene monomer and the chloroprene and copolymerizable monomer. It is preferable to use The amount of rosinate used is, for example, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0 parts by mass, any of the numerical values exemplified here or within a range between the two.
• rosinate examples include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium, and ammonium salts. Sodium salts and potassium salts are preferably used from the viewpoint of ease of handling.
• the rosin acid contained in the rosinate preferably includes the rosin acids exemplified above. Rosin acid may be used in combination in the emulsion polymerization step according to one embodiment of the present invention. When using rosin acid, the amount of rosin acid used can be, for example, 0.1, 0.2, 0.3, 0.4, 0.5 parts by mass, and any of the numerical values exemplified here It may be in a range between the two.
• emulsifiers/dispersants if necessary, other emulsifiers may be used in combination for the purpose of stabilizing the control of the polymerization reaction.
• other emulsifiers/dispersants for example, the compounds listed above as emulsifiers other than emulsifiers containing rosin acid can be used.
• the amount of the emulsifier other than the rosin acid-containing emulsifier used is 1 per 100 parts by mass in total of the chloroprene monomer and the chloroprene and the copolymerizable monomer. % by mass or less, and can be 0.5% by mass or less.
• sodium hydroxide and potassium hydroxide in a total amount of 0.1 to 1.1 parts by mass with respect to 100 parts by mass of the aqueous medium.
• the total amount of sodium hydroxide and potassium hydroxide is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 .0, 1.1 parts by weight, and may be in the range between any two of the values exemplified herein.
• the aqueous medium it is preferable to use water, particularly pure water.
• the manufacturing method according to one embodiment of the present invention preferably satisfies condition 3 or 4 below.
• Condition 3 In the emulsion polymerization step, 1.2 to 2.2 parts by mass of rosinate is used with respect to a total of 100 parts by mass of the chloroprene monomer and the chloroprene and copolymerizable monomer, and an aqueous medium A total of 0.5 to 1.1 parts by mass of sodium hydroxide and potassium hydroxide is used with respect to 100 parts by mass.
• Condition 4 In the emulsion polymerization step, 2.2 to 3.0 parts by mass of rosinate is used with respect to a total of 100 parts by mass of chloroprene monomer and chloroprene and copolymerizable monomer, and an aqueous medium A total of 0.1 to 1.1 parts by mass of sodium hydroxide and potassium hydroxide is used with respect to 100 parts by mass.
• the chloroprene-based polymer latex according to one embodiment of the present invention satisfies the above condition 3 or 4, and by highly controlling the amount of alkali metal cation and the amount of rosinate during polymerization, and a chloroprene-based polymer latex capable of obtaining an adhesive composition that generates less aggregates after the completion of the polymerization reaction, does not cause layer separation for a long period of time, and can obtain an adhesive composition with a long pot life. becomes.
• the rosinate is, for example, 1.2, 1.3, 1.4, 1.5 parts per 100 parts by mass of the chloroprene monomer and the chloroprene-copolymerizable monomer. , 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2 parts by weight within a range between any two of the values exemplified herein.
• the total amount of sodium hydroxide and potassium hydroxide is more preferably more than 0.5 parts by mass with respect to 100 parts by mass of the aqueous medium, for example, 0.5, 0.6, 0.7, 0 0.8, 0.9, 1.0, 1.1 parts by weight, and may be in the range between any two of the values exemplified herein.
• the rosinate is, for example, 2.2, 2.3, 2.4, 2.5 parts per 100 parts by mass of the chloroprene monomer and the chloroprene-copolymerizable monomer. , 2.6, 2.7, 2.8, 2.9, 3.0 parts by weight, and may be within a range between any two of the numerical values exemplified herein.
• the total amount of sodium hydroxide and potassium hydroxide is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.4, 0.4, 0.5, 0.6, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.4, 0.3, 0.4, 0.5, 0.6, 0.4, 0.4, 0.5, 0.6, 0.4, 0.4, 0.4, 0.5, 0.6, 0.4, 0.4, 0.4, 0.5, 0.6, 0.4, 0.4, 0.4, 0.5, 0.6, 0.4, 0.4, 0.5, 0.6, 0.4, 0.4, 0.5, 0.6, 0.4, 0.4, 0.5, 0.6, 0.4, 0.4, 0.5, 0.6 It can be 7, 0.8, 0.9, 1.0, 1.1 parts by weight, and can be in the range between any two of the values exemplified herein.
• polymerization initiator potassium persulfate, benzoyl peroxide, ammonium persulfate, hydrogen peroxide, and the like, which are commonly used in radical polymerization, can be used.
• the chain transfer agent is not particularly limited as long as it is commonly used in the production of chloroprene-based polymers.
• Examples include long-chain alkylmercaptans such as n-dodecylmercaptan, tert-dodecylmercaptan, and n-octylmercaptan.
• dialkyl xanthogen disulfides such as diisopropyl xanthogen disulfide and diethyl xanthogen disulfide
• chain transfer agents such as iodoform.
• the polymerization temperature is desirably in the range of 0 to 55° C. from the viewpoint of easy control of the reaction. From the viewpoint of conducting the polymerization reaction more smoothly and safely, it is desirable to set the lower limit of the polymerization temperature to 10° C. or higher and the upper limit to 45° C. or lower.
• Polymerization conversion can range from 60 to 95%.
• the polymerization reaction can be terminated by adding a polymerization terminator.
• ⁇ Polymerization terminator> for example, thiodiphenylamine, 4-tert-butylcatechol, 2,2'-methylenebis-4-methyl-6-tert-butylphenol and the like can be used. Unreacted monomers after completion of the emulsion polymerization can be removed by a conventional method such as distillation under reduced pressure.
• the method for producing a chloroprene-based polymer latex according to an embodiment of the present invention preferably does not include the step of heating at 140° C. or higher for 1 hour or longer, and more preferably does not include the step of heating at 140° C. or higher. Further, the method for producing a chloroprene-based polymer latex according to one embodiment of the present invention preferably does not include the step of heating at 55° C. or higher for 3 hours or longer, and does not include the step of heating at 55° C. or higher for 1 hour or longer. is more preferred.
• the production conditions of the chloroprene-based polymer for example, the charged amounts of rosinate and sodium hydroxide and potassium hydroxide during polymerization of the chloroprene-based polymer are highly adjusted.
• the microstructure of the chloroprene-based polymer can be controlled to a higher degree even without the heating step, or even if the temperature of the heating step is lower or the time is shorter than before. , resulting in a chloroprene-based polymer in which layer separation does not occur for a longer period of time than conventionally.
• the 1,2-OH rearrangement structure is It is considered that the chloroprene-based polymer latex can suppress an excessive increase in the amount of the chloroprene-based polymer latex, prevents the occurrence of layer separation for a longer period of time, and provides an adhesive composition having a long pot life.
• Chloroprene-Based Polymer The chloroprene-based polymer according to the present invention can be obtained by drying the above-described chloroprene-based polymer latex. Drying up is performed by a well-known method.
• Adhesive Composition contains the chloroprene-based polymer latex or chloroprene-based polymer described above.
• the adhesive composition according to one embodiment of the present invention can contain an organic solvent in addition to the chloroprene-based polymer latex or chloroprene-based polymer described above.
• the type of organic solvent is not limited, and organic solvents such as toluene, xylene, acetone, methyl ethyl ketone, n-hexane, cyclohexane, methyl cyclohexane, cyclopentane, isopropyl acetate and ethyl acetate can be used.
• Organic solvents are non-aromatic solvents such as n-hexane, cyclohexane, methylcyclohexane, acetone, methyl ethyl ketone, ethyl acetate, and butyl acetate, not aromatic solvents such as toluene, xylene, and ethylbenzene that cause sick house syndrome.
• non-aromatic solvents such as n-hexane, cyclohexane, methylcyclohexane, acetone, methyl ethyl ketone, ethyl acetate, and butyl acetate
• aromatic solvents such as toluene, xylene, and ethylbenzene that cause sick house syndrome.
• the amount of the organic solvent used may be appropriately adjusted depending on the application and type of the adhesive, and is not particularly limited. It is preferable because the balance between the heat resistant adhesive strength and the initial adhesive strength as is good.
• the adhesive composition may contain, in addition to the solvent, metal oxides, tackifying resins and anti-aging agents. By adding these additives to the adhesive, the initial adhesive strength, normal adhesive strength, spray coatability, etc. of the obtained adhesive can be improved.
• metal oxides examples include zinc oxide (zinc white), aluminum oxide, titanium oxide, and magnesium oxide.
• tackifying resin for example, a phenolic resin, a rosin resin, a coumarone resin, a petroleum resin, or the like can be used.
• anti-aging agents examples include 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,6-di- t-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N′-hexane-1,6-diylbis-3-(3,5 -di-t-butyl-4-hydroxyphenylpropionamide), 3,5-bis(1,1-dimethylethyl)-4-hydroxyalkyl ester, diethyl [ ⁇ 3,5-bis(1,
• the adhesive composition may further contain formaldehyde catchers, fillers, and the like, depending on desired physical properties.
• formaldehyde catchers examples include pyrrolidine, piperidine, piperazine, morpholine, melamine, dicyandiamide, urea, ethyleneurea, 4,5-dimethoxyethyleneurea, propyleneurea, 5-methylpropyleneurea, 5-hydroxypropyleneurea, 5- Methoxypropylene urea, oxalyl urea (parabanic acid), hydrazobenzothiazole, semicarbazide, thiosemicarbazide can be used.
• a formaldehyde catcher agent can trap formaldehyde, a harmful volatile substance.
• Talc calcium carbonate, clay, smectite, silica, hydrotalcite, mica, and the like can be used as fillers.
• an ultraviolet absorber such as benzotriazole or a light stabilizer such as hindered amine may be added to the adhesive composition.
• the adhesive composition of the present embodiment also contains at least one crude rubber (uncrosslinked or unvulcanized rubber).
• the method for producing the adhesive composition is not particularly limited, and known machines and devices may be used.
• a method for producing an adhesive composition in general, an alkylphenol resin or magnesium oxide is dissolved in an organic solvent, for example, after standing at 25° C. for 20 hours, a chloroprene-based polymer (latex containing), a metal A method of dissolving a mixture obtained by kneading an oxide, an antioxidant, etc. with a roll is known.
• the chloroprene-based polymer or chloroprene-based polymer latex can be directly dissolved and dispersed in an organic solvent together with metal oxides, antioxidants, etc. without kneading with a roll to form an adhesive composition.
• An adhesive composition according to one embodiment of the present invention is used as a raw material for an adhesive.
• an adhesive can be obtained by adding other additives to the adhesive composition or mixing the adhesive composition with another adhesive composition.
• Adhesives are suitable for joining and adhering the same or different types of paper, wood, cloth, leather, jersey, leather, rubber, plastic, foam, pottery, glass, mortar, cement-based materials, ceramics, metals, etc. be able to.
• the adhesive composition according to one embodiment of the present invention it is preferable that layer separation is not observed even after 20 days after preparation, and it is preferable that layer separation is not observed even after 30 days. more preferred.
• the adhesive composition according to one embodiment of the present invention preferably has a pot life of 1000 minutes or longer, more preferably exceeding 1500 minutes. The pot life is measured by adding 4 parts by mass of an isocyanate curing agent to 100 parts by mass of the adhesive composition, and taking the viscosity after 10 minutes as the initial viscosity. Means the time required to increase the viscosity to 0.5 times.
• the compound composition according to the present invention contains a chloroprene-based polymer.
• a vulcanized molded article according to the present invention is obtained by vulcanizing the compound composition described above.
• the compound composition according to one embodiment of the present invention includes, for example, vulcanizing agents, vulcanization accelerators, fillers or reinforcing agents, plasticizers, processing aids and lubricants, anti-aging agents, It can also contain a silane coupling agent and the like.
• the type of vulcanizing agent is not particularly limited as long as it does not impair the effects of the present invention, and one or more of the usual vulcanizing agents that can be used for chloroprene rubber can be freely selected and used. can.
• vulcanizing agents include zinc oxide, magnesium oxide, lead oxide, trilead tetroxide, iron trioxide, titanium dioxide, calcium oxide, and hydrotalcite.
• the compounding amount of the vulcanizing agent is also not particularly limited.
• the compound composition according to one embodiment of the present invention preferably contains 3 to 15 parts by mass of the vulcanizing agent with respect to 100 parts by mass of the chloroprene-based polymer. Addition within this range ensures the safety of processing and provides a good vulcanizate.
• the compound composition according to one embodiment of the present invention can be vulcanized more effectively by using a vulcanization accelerator in combination with the vulcanizing agent.
• the type of vulcanization accelerator that can be blended in the compound composition according to the present invention is not particularly limited as long as it does not impair the effects of the present invention.
• a species or two or more species can be freely selected and used.
• Vulcanization accelerators include thiuram-based, dithiocarbamate-based, thiourea-based, guanidine-based, xanthate-based, and thiazole-based accelerators, which may be used alone or in combination of two or more as necessary.
• Thiuram-based vulcanization accelerators include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis(2-ethylhexyl)thiuram disulfide, tetramethylthiuram monosulfide, and dipentamethylenethiuram tetrasulfide.
• Dithiocarbamate-based vulcanization accelerators include sodium dibutyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, and copper dimethyldithiocarbamate.
• ferric dimethyldithiocarbamate, tellurium diethyldithiocarbamate, etc., and zinc dibutyldithiocarbamate is particularly preferably used.
• Thiourea-based vulcanization accelerators include ethylenethiourea, N,N'-diethylthiourea, trimethylthiourea, and N,N'-diphenylthiourea.
• Guanidine-based vulcanization accelerators include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, and dicatechol borate di-o-tolylguanidine salts.
• Examples of xanthate-based vulcanization accelerators include zinc butylxanthate and zinc isopropylxanthate.
• Thiazole-based vulcanization accelerators include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, 2-mercaptobenzothiazole zinc salt, cyclohexylamine salt of 2-mercaptobenzothiazole, 2-(4'- morpholinodithio)benzothiazole and the like.
• the amount of the vulcanization accelerator added is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the chloroprene-based polymer.
• Fillers or reinforcing agents are added to adjust the hardness of rubber or improve mechanical strength, and are not particularly limited, but examples include carbon black, silica, clay, talc, and calcium carbonate. be done. These fillers may be used individually by 1 type, and may use 2 or more types together. The blending amount of these fillers and reinforcing agents may be adjusted according to the physical properties required for the rubber composition and the crosslinked rubber or vulcanized rubber obtained from the rubber composition, and is not particularly limited. It can be added in a total amount of 15 parts by mass or more and 200 parts by mass or less based on 100 parts by mass of the chloroprene-based polymer in the compound composition.
• the primary anti-aging agent is mainly added to suppress the decrease in hardness, elongation at break, etc. when the vulcanized molded product to be obtained is heated, and to improve heat resistance.
• agents amine anti-aging agents, acrylate anti-aging agents, metal carbamates and waxes.
• These primary antioxidants can be used singly or in combination.
• these compounds 4,4'-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine, octylated diphenylamine, and N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylene, which are amine anti-aging agents.
• Diamine is preferable because it has a large effect of improving heat resistance.
• the blending amount of the primary anti-aging agent is 0.1 to 10 parts by mass, preferably 1 to 5 parts by mass, per 100 parts by mass of the chloroprene-based polymer contained in the compound composition.
• the secondary anti-aging agent is mainly added to prevent deterioration of hardness, elongation at break, and compression set when the vulcanized molded product and compound to be obtained are heated, and to improve heat resistance.
• phosphorus antioxidants, sulfur antioxidants, and imidazole antioxidants are mainly added to prevent deterioration of hardness, elongation at break, and compression set when the vulcanized molded product and compound to be obtained are heated, and to improve heat resistance.
• phosphorus antioxidants sulfur antioxidants, and imidazole antioxidants. These secondary antioxidants can be used singly or in combination.
• the phosphorus antioxidants tris(nonylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, the sulfur antioxidants dilarium thiodiopropionate, dimistyl- 3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, imidazole anti-aging agents 2-mercaptobenzimidazole, and 1-benzyl-2-ethylimidazole have the effect of improving heat resistance. Preferable because it is large.
• the content of the secondary antioxidant is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the chloroprene-based polymer in the compound composition. Heat resistance can be improved by setting the amount of the secondary anti-aging agent to be within this range.
• a compound composition according to an embodiment of the present invention may contain a plasticizer.
• the plasticizer is not particularly limited as long as it is compatible with the chloroprene-based polymer. Examples include vegetable oils such as rapeseed oil, phthalate-based plasticizers, DUP (diundecyl phthalate), and DOS (dioctyl sebacate). , DOA (dioctyl adipate), ester plasticizers, ether ester plasticizers, thioether plasticizers, aromatic oils, naphthenic oils, etc., and one or more of them can be used according to the properties required for the compound composition. can be used in combination.
• the blending amount of the plasticizer is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the chloroprene-based polymer.
• a compound composition according to an embodiment of the present invention may include processing aids.
• Processing aids are mainly added to improve processing characteristics such as making it easier for the compound composition to separate from rolls, molding dies, screws of extruders, and the like.
• processing aids include fatty acids such as stearic acid and paraffin-based processing aids such as polyethylene.
• a compound composition according to one embodiment of the present invention is obtained by kneading a chloroprene-based polymer or a chloroprene-based polymer latex and other necessary components at a vulcanization temperature or lower.
• a device for kneading the raw material components conventionally known kneading devices such as a mixer, a Banbury mixer, a kneader mixer, and an open roll can be used.
• a vulcanized molded article according to one embodiment of the present invention is a vulcanized molded article obtained by vulcanizing the above compound composition.
• the above compound composition may be vulcanized after being molded into various desired shapes, or the compound composition may be made into vulcanized rubber in advance and then molded into various shapes.
• Methods for molding compound compositions and vulcanized rubber include conventional methods such as press molding, extrusion molding and calender molding. For these, the methods commonly used in the rubber industry may be adopted.
• the method of vulcanization of the compound composition is not particularly limited, general steam vulcanization or UHF vulcanization can be used to form a vulcanized rubber.
• Steam vulcanization is a means of vulcanizing an unvulcanized compound composition by applying pressure and temperature with steam gas as a heating medium
• UHF vulcanization is a method of vulcanizing the compound composition by irradiating it with microwaves. It is a means of sulphurizing.
• the compound composition may be vulcanized by raising the mold temperature to the vulcanization temperature while holding the compound composition inside the mold.
• the vulcanization temperature can be appropriately set according to the formulation of the compound composition and the type of vulcanizing agent.
• Vulcanization time can be, for example, 10 to 30 minutes.
• the vulcanized rubber is particularly suitable for use in compounds, belts, parts for overhead vehicles, seismic isolation rubber, hoses, wipers, immersion products, sealing parts, boots, rubber-coated fabrics, rubber rolls or sponge products.
• Example 1 0.2 parts of n-dodecylmercaptan and potassium rosinate (disproportionated tall rosin potassium salt, manufacturer: manufactured by Harima Kasei Co., Ltd.) were added to a reactor having an internal volume of 5 liters per 100 parts by mass of chloroprene monomer. 4 parts by mass of sodium hydroxide, 0.64 parts by mass of sodium hydroxide, 0.4 parts by mass of sodium salt of formaldehyde naphthalenesulfonic acid condensate (trade name: Demoll NL, manufacturer: manufactured by Kao Corporation), and 100 parts by mass of pure water are added. did.
• Examples 2-5 Comparative Examples 1-4
• a chloroprene-based polymer latex was obtained by the method described in Examples except that the amount of rosin acid charged and the total amount of sodium hydroxide and potassium hydroxide charged were as shown in Table 1.
• the aggregates are the dry weight of the residue when the polymerization liquid after the completion of polymerization is filtered through a wire mesh of 80 mesh when the chloroprene-based polymer is 100% by mass, and the dry weight of the deposits collected from the wall surface of the reactor. Evaluated as a total of
• ⁇ Adhesive Composition Adjustment> 50 parts by mass of alkylphenol resin (Tamanol 526: manufactured by Arakawa Chemical Industries, Ltd.) and 3 parts by mass of magnesium oxide (Kyowamag #150: manufactured by Kyowa Chemical Industry Co., Ltd.) were dissolved in 120 parts by mass of a solvent of cyclohexane/ethyl acetate 1:1. , at room temperature for 16 hours.
• the adhesive was placed in a glass container and stored in a constant temperature water bath at 23°C under light shielding. A visual observation of the adhesive was performed and the date on which separation of the adhesive components was observed was recorded. The layer separation resistance was evaluated according to the following evaluation criteria. A: No separation of the adhesive component was observed even after 30 days. B: No separation of the adhesive component was observed even after 20 days, but separation of the adhesive component was observed before 30 days. C: Separation of the adhesive component was observed before more than 20 days.
• ⁇ Pot life test of adhesive composition 4 parts by mass of an isocyanate curing agent (Desmojur RFE: manufactured by Bayer) was added to 100 parts by mass of the adhesive composition, and the viscosity after 10 minutes was taken as the initial viscosity.
• the pot life was defined as the time from when the initial viscosity was measured until the viscosity increased to 1.5 times the initial viscosity. Pot life was evaluated according to the following criteria. A: The viscosity did not increase even after 1500 minutes. B: It did not thicken below 1000 minutes, but thickened before exceeding 1500 minutes. C: Thickened in less than 1000 minutes.

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