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WO2022107693A1 - Latex de polymère de chloroprène et procédé de production correspondant et adhésif aqueux utilisant ledit latex de polymère de chloroprène - Google Patents

Latex de polymère de chloroprène et procédé de production correspondant et adhésif aqueux utilisant ledit latex de polymère de chloroprène Download PDF

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Publication number
WO2022107693A1
WO2022107693A1 PCT/JP2021/041700 JP2021041700W WO2022107693A1 WO 2022107693 A1 WO2022107693 A1 WO 2022107693A1 JP 2021041700 W JP2021041700 W JP 2021041700W WO 2022107693 A1 WO2022107693 A1 WO 2022107693A1
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WO
WIPO (PCT)
Prior art keywords
polymer latex
chloroprene polymer
mass
chloroprene
parts
Prior art date
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PCT/JP2021/041700
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English (en)
Japanese (ja)
Inventor
駿広 佐藤
遼太郎 安藤
夢実 上野
Original Assignee
デンカ株式会社
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Priority to JP2022563725A priority Critical patent/JPWO2022107693A1/ja
Publication of WO2022107693A1 publication Critical patent/WO2022107693A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • C08L11/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin
    • 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
    • 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
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C09J193/04—Rosin

Definitions

  • the present invention relates to a chloroprene polymer latex effective as an adhesive, a method for producing the same, and an aqueous adhesive using the chloroprene polymer latex. More specifically, the present invention relates to a chloroprene polymer latex having excellent initial adhesive strength, particularly adhesive strength in a wet state, a method for producing the same, and an aqueous adhesive using the chloroprene polymer latex.
  • the chloroprene polymer is suitably used in adhesive applications such as solvent-based contact adhesives and graft adhesives because it can obtain a high degree of adhesive strength with low pressure bonding to a wide range of adherends.
  • solvent-based adhesives are regulated by volatile organic compounds (VOCs) due to environmental pollution and consideration for human health, in addition to the danger of ignition in the work environment and the cost of special exhaust and recovery equipment to prevent it.
  • VOCs volatile organic compounds
  • solvent regulations are becoming stricter year by year.
  • the development of water-based adhesives using chloroprene polymer latex is active in order to eliminate solvents, but water-based adhesives have stronger adhesive strength than conventional solvent-based adhesives. There is a problem that it is low.
  • a two-component adhesive has been studied as one of the techniques for improving the adhesive strength of the adhesive, particularly the initial adhesive strength.
  • a specific chloroprene polymer latex composition as a main agent has been studied.
  • Two-component adhesives (see Patent Documents 1 and 2) using a composition containing a specific amount of an acrylic latex or an SBR-based latex and an anionic surfactant and using a polyvalent metal salt as a curing agent are known. Adjust the balance between pot life and initial adhesion before use.
  • Japanese Unexamined Patent Publication No. 2007-332207 discloses an aqueous adhesive containing a chloroprene polymer latex composition, a polyoxyalkylene alkyl ether sulfate, and a pH adjuster.
  • International Publication No. 2016/133190, International Publication No. 2016/133191 (see Patent Documents 4 and 5) and the like contain a chloroprene homopolymer latex and a chloroprene copolymer latex containing a chloroprene copolymer or an acrylic polymer.
  • a one-component water-based adhesive comprising a blend of acrylic polymer latex is disclosed. Further, International Publication No.
  • Patent Document 6 discloses an aqueous adhesive characterized by containing a specific acid receiving agent and a specific antioxidant in a specific chloroprene polymer latex composition. There is.
  • the water-based adhesive produced according to the examples of these publications develops adhesive strength by being dried after being applied and then bonded. It cannot be said that the initial adhesive strength, especially the adhesive performance in a wet state, is sufficient, and this improvement has been an issue.
  • the present invention provides a chloroprene polymer latex suitable for water-based adhesive applications, which is a water-based adhesive having excellent initial adhesive strength, particularly excellent adhesive strength in a wet state, and an aqueous adhesive using the same. Is the subject.
  • the present inventors have a specific amount of gel content in the solid content, and the weight average molecular weight of the sol content of the solid content is a specific numerical value. It has been found that the above problems can be solved by using the chloroprene polymer latex in the range.
  • the present invention is a chloroprene polymer latex containing one or more emulsifiers selected from rosinic acid or an alkali metal salt thereof and a chloroprene polymer, and is insoluble in toluene in the solid content of the chloroprene polymer latex. It is characterized in that the content of the gel content, which is a component, is 20% by mass or less, and the weight average molecular weight of the sol component, which is a toluene-soluble component in the solid content of the chloroprene polymer latex, is 1 million or more. It is a chloroprene polymer latex.
  • the chloroprene polymer latex has a dropping amount of 1/3 mol / L hydrochloric acid required to adjust the pH to 10.5 with respect to 100 parts by mass of the chloroprene polymer latex. It is characterized by being a mass part.
  • an aqueous adhesive containing the above-mentioned chloroprene polymer latex.
  • the aqueous adhesive contains 1 to 20 parts by mass of amino acids with respect to 100 parts by mass of the chloroprene polymer latex.
  • the aqueous adhesive contains 0.1 to 30 parts by mass of the plasticizer with respect to 100 parts by mass of the chloroprene polymer latex.
  • the aqueous adhesive has a thickness of 20 mm ⁇ a length of 50 mm ⁇ a width of 50 mm, and the adhesive is spray-coated on the surface of the urethane foam having a density of 30 kg / m 3 so as to be 70 g / m 2 for 10 seconds.
  • the urethane foams are bonded together, the total thickness of the urethane foams bonded to each other is compressed to 10 mm, held for 5 seconds, released, left for 10 seconds, and then pulled in the direction perpendicular to the adhesive surface.
  • the initial adhesive strength at the time of the test is 5.5 N / cm 2 or more.
  • the adherend is a foam.
  • 0.005 to 0.1 parts by mass of the chain transfer agent is used with respect to a total of 100 parts by mass of the chloroprene monomer and the monomer copolymerizable with the chloroprene monomer.
  • a method for producing the chloroprene polymer latex which is added and polymerized at a temperature lower than 20 ° C. to a polymerization conversion rate of the chloroprene monomer of 50 to 90%.
  • the chloroprene polymer latex of the present invention maintains the high crystallization rate inherent in the chloroprene polymer and improves the initial adhesive strength, especially the adhesive strength in a wet state, so that it is suitable for applications requiring excellent initial adhesive strength. It can be widely used as a suitable adhesive. In particular, it is suitably used as a spray-type adhesive used for adhering polyurethane foam.
  • the chloroprene polymer latex according to an embodiment of the present invention contains one or more emulsifiers selected from rosin acid or an alkali metal salt thereof, and a chloroprene polymer.
  • a chloroprene monomer or a monomer copolymerizable with the chloroprene monomer and a chloroprene monomer are emulsion-polymerized in the presence of an emulsifier.
  • the chloroprene polymer latex according to the embodiment of the present invention is a total of one or more emulsifiers and chloroprene polymers selected from logonic acid or an alkali metal salt thereof when the solid content thereof is 100% by mass. Can be contained in an amount of 90% by mass or more, preferably 92% by mass or more, preferably 95% by mass or more, and preferably 98% by mass or more.
  • the chloroprene polymer according to the embodiment of the present invention is obtained by emulsion-polymerizing a chloroprene monomer or a monomer copolymerizable with the chloroprene monomer and a chloroprene monomer in the presence of an emulsifier. Can be obtained at.
  • the chloroprene polymer in the present invention is a homopolymer of 2-chloro-1,3-butadiene (hereinafter referred to as chloroprene monomer), or chloroprene alone with another monomer copolymerizable with the chloroprene monomer.
  • copolymer with a polymer
  • other monomers include 1-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, butadiene, isoprene, styrene, acrylonitrile, and sulfur.
  • Acrylic acid and its esters, methacrylic acid and its esters and the like can be mentioned, and two or more of these may be used in combination as other monomers.
  • the chloroprene polymer is a copolymer of another monomer copolymerizable with the chloroprene monomer and the chloroprene monomer
  • the chloroprene polymer is used when the total amount of the chloroprene polymer is 100 parts by mass. It is preferable that the structural unit derived from the chloroprene monomer is contained in an amount of 50% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
  • the chloroprene polymer can also be a homopolymer of the chloroprene monomer.
  • the chloroprene polymer latex according to the embodiment of the present invention has a gel content of 20% by mass or less in the solid content when the solid content contained in the entire chloroprene polymer latex is 100% by mass. Moreover, the weight average molecular weight of the sol content in the solid content is 1 million or more.
  • the gel content of the solid content of the chloroprene polymer latex in the present invention refers to a component of the solid content of the chloroprene polymer latex that is insoluble in the toluene solvent, and the sol content is the toluene solvent in the solid content of the chloroprene polymer latex.
  • the gel content can be calculated as follows. First, the chloroprene polymer latex is freeze-dried and then precisely weighed to obtain A (g). This is dissolved in toluene (prepared to 0.6%) at 23 ° C. for 20 hours, and the gel is separated using a centrifuge and a 200 mesh wire mesh.
  • the gel After air-drying the gel, the gel is dried in an atmosphere of 110 ° C. for 1 hour, and finely weighed to obtain B.
  • the gel content can be calculated according to the following formula.
  • Gel content B / A x 100 (%)
  • the weight average molecular weight of the sol content can be obtained by performing GPC measurement on the sol content obtained by the above separation.
  • the molecular weight can be obtained in terms of polystyrene.
  • the manifestation of the excellent initial adhesive force in the present invention is due to the fact that the chloroprene polymer latex contains a large amount of a sol component having excellent molecular mobility. Therefore, the fusion of the chloroprene polymer molecular chains at the adhesive interface occurs rapidly, the adhesive strength is instantly developed, and excellent initial adhesive strength can be exhibited. If the gel content of the chloroprene polymer latex exceeds 20% by mass, this initial adhesive strength is lowered, which is not preferable.
  • the chloroprene polymer latex in the present invention has a solid gel content of 20% by mass or less. More preferably, it is 10% by mass or less.
  • the gel content of the solid content of the chloroprene polymer latex is, for example, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4 It can be 3, 2, 1, 0% by mass, and may be within the range between any two of the numerical values exemplified here.
  • the chloroprene polymer latex may also be gel-free.
  • the weight average molecular weight of the sol content that is, the weight average molecular weight of the toluene solvent-soluble component of the solid content of the chloroprene polymer latex plays an important role, and the weight average molecular weight of the solid content of the chloroprene polymer latex in the present invention. Is over 1 million. When the weight average molecular weight of the sol content is 1 million or more, the molecular chains of the chloroprene polymer are likely to be entangled and the adhesive strength is improved. Further, from the viewpoint of productivity, it is preferable that the weight average molecular weight of the sol content is 2.5 million or less.
  • the more preferable range of the weight average molecular weight of the sol content is more than 1.1 million and 2.5 million or less, preferably 1.2 million or more and 2 million or less, and even more preferably more than 1.25 million and 2 million. It is as follows.
  • the weight average molecular weight of the sol is, for example, 1 million, 1.05 million, 1.1 million, 1.15 million, 1.2 million, 1.25 million, 1.3 million, 1.35 million, 1.4 million, 1.45 million, 1.5 million, 1.6 million, 1.7 million, 1.8 million. , 1.9 million, 2 million, 2.1 million, 2.2 million, 2.3 million, 2.4 million, 2.5 million, and may be within the range between any two of the numerical values exemplified here.
  • the chloroprene polymer latex according to one embodiment of the present invention contains one or more emulsifiers selected from rosin acid or an alkali metal salt thereof. That is, in one embodiment of the present invention, the emulsifier used for emulsion polymerization is preferably one or more selected from rosin acid or an alkali metal salt thereof. When rosin acid or an alkali metal salt thereof is used as an emulsifier, the emulsion stability of the chloroprene polymer latex composition is easily lowered when a mechanical stimulus is applied. Therefore, when the chloroprene polymer latex composition is used as an adhesive, excellent initial adhesive strength can be exhibited.
  • the most preferable emulsifier used in emulsifying polymerization is rosin acid, and the rosin acid is wood rosin acid, gum rosin acid, tall oil rosin acid, disproportionated rosin acid obtained by disproportionating them, or an alkali metal salt thereof. Any of the above can be used, and it is particularly preferable to use disproportionate rosin acid.
  • the chloroprene polymer latex according to one embodiment of the present invention may contain two or more kinds of rosin acid or an alkali metal salt thereof.
  • the chloroprene polymer latex according to the embodiment of the present invention contains 1.0 to 4.5% by mass of logonic acid or an alkali metal salt thereof in the chloroprene polymer latex when the chloroprene polymer latex is 100% by mass. It is preferably contained, more preferably 1.5 to 4.0% by mass, and even more preferably 2.0 to 3.5% by mass.
  • the chloroprene polymer latex according to the embodiment of the present invention is, in addition to logonic acid or an alkali metal salt thereof, an alkyl sulfonate having 8 to 20 carbon atoms, an alkylaryl sulphate, a condensate of sodium naphthalin sulfonate and formaldehyde, and an alkyl. It can also further contain anionic emulsifiers and dispersants such as diphenyl ether sodium disulfonate.
  • the chloroprene polymer latex according to the embodiment of the present invention has an anionic emulsifier or dispersion in the chloroprene polymer latex in addition to rosinic acid or an alkali metal salt thereof when the chloroprene polymer latex is 100 parts by mass.
  • the agent can be contained in an amount of 0.05 to 5 parts by mass, preferably 0.1 to 2 parts by mass.
  • a nonionic emulsifier or a dispersant may be used in combination.
  • a nonionic emulsifier in combination, the low temperature stability of the chloroprene polymer latex composition and the adhesive characteristics when used as an adhesive can be improved.
  • the chloroprene polymer latex according to the embodiment of the present invention may further contain these nonionic emulsifiers and dispersants.
  • the chloroprene polymer latex according to the embodiment of the present invention preferably contains an alkali metal salt from the viewpoint of polymerization control surface and initial adhesive strength, particularly adhesive performance in a wet state.
  • alkali metal salt examples include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate and the like.
  • Sodium hydroxide and potassium hydroxide are preferable because of cost and water solubility. Two or more of these metal alkali salts may be used in combination.
  • the amount of 1/3 mol / L hydrochloric acid added dropwise to adjust the pH to 10.5 is 0.1 with respect to 100 parts by mass of the chloroprene polymer latex. It is preferably about 10.0 parts by mass.
  • the dropping amount of 1/3 mol / L hydrochloric acid required to adjust the pH to 10.5 is 0.1 or less, the storage stability of the chloroprene polymer latex is lowered, and when it is 10.0 or more. If there is, the polymerization controllability and productivity of the chloroprene polymer will decrease.
  • the amount of 1/3 mol / L hydrochloric acid dropped to adjust the pH to 10.5 is 0.5 to 8.0 parts by mass.
  • the amount of 1/3 mol / L hydrochloric acid added dropwise to adjust the pH to 10.5 can be controlled by adjusting the amount of the alkali metal salt contained in the chloroprene polymer latex.
  • the chloroprene polymer latex according to the embodiment of the present invention preferably has a solid content concentration of 40 to 60% by mass, and can be, for example, 40, 45, 50, 55, 60% by mass. It may be in the range between any two of the exemplified values.
  • the solid content concentration can be expressed as D / C ⁇ 100 (%) when the chloroprene polymer latex is Cg and the mass after drying for 1 hour in an atmosphere of 125 ° C. is Dg.
  • the solid content concentration of the chloroprene polymer latex is within the above numerical range, when the chloroprene polymer is used as an adhesive, it can be dried sufficiently quickly and a uniform adhesive layer is formed. be able to.
  • the chloroprene polymer latex according to the embodiment of the present invention comprises a chloroprene monomer, a monomer copolymerizable with the chloroprene monomer, and a chloroprene monomer. It can be obtained by a production method including a step of emulsion polymerization in the presence of an emulsifier.
  • the types and amount ratios of the chloroprene polymer to be polymerized and the monomers copolymerizable with the chloroprene monomer are as described above.
  • the amount of one or more emulsifiers selected from logonic acid or an alkali metal salt thereof is 100 parts by mass in total of the chloroprene polymer to be polymerized and the monomer copolymerizable with the chloroprene monomer.
  • 0.5 to 10 parts by mass is preferable, and 2 to 6 parts by mass is more preferable.
  • alkyl sulfonates having 8 to 20 carbon atoms, alkylaryl sulfate, and naphthalin sulfonic acid are used during emulsification polymerization.
  • Anionic emulsifiers and dispersants such as a condensate of sodium and formaldehyde, and sodium alkyldiphenyl ether disulfonate can also be used in combination.
  • the amount of the anionic emulsifier or dispersant added can be copolymerized with the chloroprene polymer and the chloroprene monomer to be polymerized. It can be 0.05 to 5 parts by mass, preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total of the monomers.
  • an alkali metal salt at the time of emulsion polymerization.
  • the alkali metal salt include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, sodium hydrogencarbonate and the like.
  • the amount of the alkali metal salt added the amount of 1/3 mol / L hydrochloric acid required to adjust the pH to 10.5 in the finally obtained chloroprene polymer latex is 100 parts by mass of the chloroprene polymer latex. On the other hand, the amount is preferably 0.1 to 10.0 parts by mass, and more preferably 0.5 to 8.0 parts by mass.
  • the amount of the alkali metal salt added during emulsion polymerization is preferably 0.01 to 5 parts by mass, preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the total of the chloroprene polymer to be polymerized and the monomer copolymerizable with the chloroprene monomer. .1 to 3 parts by mass is more preferable.
  • a chain transfer agent in order to adjust the molecular weight and the molecular weight distribution of the chloroprene polymer. Further, the chain transfer agent may be added during the polymerization.
  • the chain transfer agent long-chain alkyl mercaptans such as n-dodecyl mercaptan and t-dodecyl mercaptan, and dialkylxanthogen disulfides such as diisopropylxanthogen disulfide and diethylxanthogen disulfide are preferable.
  • Long-chain alkyl mercaptans are more preferred from the viewpoint of easy control of molecular weight and gel content. Two or more of these chain transfer agents may be used in combination.
  • the total amount of the chain transfer agent added during emulsion polymerization is 0.005 to 0.1 parts by mass with respect to 100 parts by mass of the total of the chloroprene polymer to be polymerized and the monomer copolymerizable with the chloroprene monomer. Is preferable, for example, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1 part by mass. It may be within the range between any two of the numerical values exemplified here.
  • the polymerization conversion rate of the chloroprene monomer or the like at the time of emulsion polymerization of the chloroprene polymer or the like is preferably 50% by mass or more and less than 90% by mass, more preferably 60 to 85% by mass, for example, 50, 55. It can be 60, 65, 70, 75, 80, 85, 90% by mass, and may be within the range between any two of the numerical values exemplified here.
  • the polymerization conversion rate of the chloroprene monomer is less than 50%, the solid content concentration of the chloroprene polymer latex decreases, which imposes a load on the drying process after applying the adhesive and makes it difficult to make the adhesive layer uniform.
  • the polymerization conversion rate (% by mass) is determined by [(total of polymer mass / monomer mass) ⁇ 100].
  • the polymerization conversion rate may be simply referred to as a polymerization rate.
  • the chloroprene polymer can be polymerized in the range of 0 to 45 ° C., but it is particularly preferable to polymerize at a low temperature of 5 to 15 ° C., for example, 0, 5, 10, 15, 20, 25, 30, 35. , 40, 45 ° C., and may be within the range between any two of the numerical values exemplified here. It is known that the trans-1,4-bond occupies 85% or more of the chloroprene homopolymer, and its molecular structure is relatively rich in regularity. The chloroprene homopolymer has properties as a typical crystalline polymer due to the high degree of regularity of this molecular structure.
  • the polymerization temperature By setting the polymerization temperature to a low temperature of 5 to 15 ° C., the ratio of trans-1,4-bonds in the polychloroprene molecule is further increased, so that a chloroprene homopolymer having a higher crystallization rate can be obtained. Sufficient adhesive strength is achieved when this is used as a one-component water-based adhesive.
  • a normal radical polymerization initiator can be used, and specifically, an organic or inorganic peroxide such as benzoyl peroxide, potassium persulfate, and ammonium persulfate, and azobisisobutyi are used. Azo compounds such as ronitrile can be used. A co-catalyst such as anthraquinone sulfonate, potassium sulfite, and sodium sulfite may be used in combination as appropriate.
  • a polymerization inhibitor is added to terminate the reaction when a predetermined polymerization rate is reached for the purpose of obtaining a polymer having a desired molecular weight and distribution.
  • the polymerization inhibitor include phenothiazine, pt-butylcatechol, hydroquinone, hydroquinone monomethyl ether, and diethyl hydroxylamine.
  • the solid content concentration of the chloroprene polymer latex is not particularly limited, but is usually 40 to 65% by mass.
  • the solid content concentration of the chloroprene polymer latex is adjusted, for example, by adjusting the blending ratio containing a solvent such as water during the emulsion polymerization of the chloroprene polymer, or by evaporating the water contained in the chloroprene polymer latex under reduced pressure. Can be controlled.
  • the chloroprene polymer latex according to the embodiment of the present invention may be a chloroprene polymer latex composition containing the chloroprene polymer latex, and may be particularly an aqueous adhesive.
  • the aqueous adhesive according to one embodiment of the present invention may contain a pH adjuster.
  • the pH adjuster is added in order to improve the initial adhesive strength and storage stability when the chloroprene polymer latex composition is used as an aqueous adhesive.
  • a weak acid or a buffer solution can be used as the pH adjuster.
  • hydroxy acids such as citric acid and glycolic acid, and at least one compound selected from boric acid and amino acids are desirable, and among them, amino acids are preferable. More preferred.
  • Specific examples of the amino acid include glycine, alanine, threonine, and proline. It is more preferable to use glycine, which is a kind of amino acid, in terms of cost, adhesive performance, ease of handling, and the like.
  • the amount of the pH adjuster added is not particularly limited, but it is preferable to use an amount that can adjust the pH of the aqueous adhesive in the range of 7 to 10. More preferably, it is desirable to add an amount capable of adjusting the pH range to 8 to 10.
  • an amino acid particularly glycine
  • it is preferably 1 to 20 parts by mass, more preferably 2 to 16 parts by mass, and further preferably 3 to 3 parts by mass with respect to 100 parts by mass of the chloroprene polymer latex.
  • 13 parts by mass is used, sufficient adhesive force can be developed at a favorable cost.
  • the water-based adhesive according to one embodiment of the present invention may contain a plasticizer.
  • the amount of the plasticizer added is 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the chloroprene polymer latex.
  • the plasticizer preferably has good compatibility with the chloroprene polymer, and is not particularly limited.
  • dibutyl sebacate dibutyl phthalate, dioctyl adipate, dioctyl azelate, dioctyl sebacate, dioctyl phthalate, and bird.
  • cresyl phosphate cresyl diphenyl phosphate, etc.
  • Chloroprene polymer latex compositions are generally susceptible to deterioration by oxygen.
  • a stabilizer such as an antioxidant can be appropriately used as the aqueous adhesive as long as the effect of the present invention is not impaired.
  • the amount of the antioxidant added is 0.1 to 3 parts by mass of the antioxidant with respect to 100 parts by mass of the solid content of the chloroprene polymer latex. It is preferable to use a part. By setting this range, the stability of the flexibility of the obtained adhesive layer over time can be improved. If the antioxidant is insoluble in water or destabilizes the emulsified state of the chloroprene polymer latex composition, it may be added after preparing it into an aqueous dispersion in advance.
  • the chloroprene polymer latex composition of the present invention has, as an additive other than the above, a filler, a tackifier, a pigment, a colorant, a wetting agent, as long as the effect of the present invention is not impaired.
  • a defoaming agent, a thickener and the like can be appropriately used.
  • other resin emulsions (latex) may be supplementarily blended up to 30% by mass (solid content equivalent) of the total composition. Specific examples thereof include (modified) vinyl acetate, vinyl acetate / acrylic mixed, acrylic / styrene mixed, and resin emulsions such as urethane.
  • the water-based adhesive according to the embodiment of the present invention has a thickness of 20 mm ⁇ a length of 50 mm ⁇ a width of 50 mm, and sprays the adhesive on the surface of urethane foam having a density of 30 kg / m 3 so as to be 70 g / m 2 . After application and an open time of 10 seconds, the urethane foams are bonded together, the total thickness of the bonded urethane foams is 40 mm, compressed to 10 mm, held for 5 seconds, released, and left for 10 seconds before the adhesive surface.
  • the initial adhesive strength is preferably 5.5 N / cm 2 or more, more preferably 6.0 N / cm 2 or more, and 6.5 N / cm 2 or more. Is even more preferable.
  • an adhesive having high adhesive strength even when the open time is long and high adhesive strength even when the open time is short has been desired, but in the existing technology, for example, an open time of 10 seconds is short. High adhesive strength could not be obtained in the open time. According to the water-based adhesive according to the embodiment of the present invention, high adhesive strength can be obtained even with an open time of 10 seconds.
  • the water-based adhesive according to the embodiment of the present invention has a thickness of 20 mm ⁇ a length of 50 mm ⁇ a width of 50 mm, and sprays the adhesive on the surface of urethane foam having a density of 30 kg / m 3 so as to be 70 g / m 2 . After application and an open time of 1 minute, the urethane foams are bonded to each other, the total thickness of the urethane foams bonded to each other is compressed to 10 mm, held for 5 seconds, released, and left for 10 seconds before the adhesive surface.
  • the initial adhesive strength is preferably 6.0 N / cm 2 or more, more preferably 6.5 N / cm 2 or more, and 7.0 N / cm 2 or more. Is even more preferable.
  • the water-based adhesive according to the embodiment of the present invention high adhesive strength can be obtained in both an open time of 10 seconds and an open time of 1 minute, and the open time can be obtained at a work site where the water-based adhesive is used. Variations can be tolerated, and the advantage of increasing the degree of freedom in the process can be obtained.
  • the water-based adhesive according to one embodiment of the present invention can be a one-component water-based adhesive.
  • a suitable adherend of the water-based adhesive according to the embodiment of the present invention is a foam made of a material such as polyurethane, ethylene-vinyl acetate copolymer, polyethylene, or water absorption of wood, cloth, textile, or the like. It is a sexual adherend.
  • the chloroprene polymer latex composition containing the chloroprene polymer latex produced under the above various conditions is a water-based adhesive having excellent initial adhesive strength, contact property, water resistance, spray coating property, and storage stability.
  • it can be suitably used as a one-component water-based adhesive.
  • Example 1 Using a reactor with an internal volume of 10 liters, 90 parts by mass of water, 4.5 parts by mass of disproportionate logoic acid, 0.5 parts by mass of potassium hydroxide, and sodium salt of formaldehyde naphthalene sulfonic acid condensate 0 under a nitrogen stream. .3 parts by mass was charged, and after dissolution, 100 parts by mass of chloroprene monomer and 0.05 parts by mass of n-dodecyl mercaptan were added with stirring. Polymerization was carried out at 10 ° C.
  • the gel content of the solid content of the obtained chloroprene polymer latex and the weight average molecular weight of the sol content were measured according to the following methods.
  • [Gel content] The chloroprene polymer latex sample was freeze-dried and finely weighed to give A.
  • the gel was dissolved in toluene (prepared to 0.6%) at 23 ° C. for 20 hours, and the gel was separated using a centrifuge and a 200 mesh wire mesh.
  • the gel content was air-dried, dried in an atmosphere of 110 ° C. for 1 hour, and finely weighed to obtain B.
  • the gel content was calculated according to the following formula.
  • Gel content B / A x 100 (%)
  • Weight average molecular weight of sol GPC measurement was performed under the following conditions. The weight average molecular weight was calculated in terms of polystyrene. As a sample, the separated sol was prepared in a 0.1% THF solution. Measuring device for number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) and block copolymer formation rate by gel permeation chromatography (GPC): Gel permeation chromatograph (HLC) manufactured by Toso Co., Ltd.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • HLC Gel permeation chromatograph
  • a water-based adhesive was prepared by blending 5 parts by mass of dibutyl sebacate and 6 parts by mass of glycine with 100 parts by mass of the chloroprene polymer latex obtained above using a three-one motor.
  • Example 2 to 6 The test was carried out in the same manner as in Example 1 except that the amount of n-dodecyl mercaptan used in the test and the polymerization rate were changed. Examples 2 to 6 were used, and the adhesion test results were summarized in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un latex de polymère de chloroprène approprié pour être utilisé dans un adhésif aqueux et qui constitue un adhésif aqueux qui présente une excellente force de collage initiale et qui présente en particulier une excellente force de collage dans un état humide. Ce latex de polymère de chloroprène contient un polymère de chloroprène et un ou plusieurs émulsifiants choisis parmi l'acide de colophane et un sel de métal alcalin correspondant et est caractérisé en ce que le rapport de teneur en gel insoluble dans le toluène dans la teneur en solides du latex de polymère de chloroprène est inférieur ou égal à 20 % en masse et le poids moléculaire moyen en poids de la teneur en sol soluble dans le toluène dans la teneur en solides du latex de polymère de chloroprène est supérieur ou égal à 1 million.
PCT/JP2021/041700 2020-11-19 2021-11-12 Latex de polymère de chloroprène et procédé de production correspondant et adhésif aqueux utilisant ledit latex de polymère de chloroprène WO2022107693A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0827448A (ja) * 1994-05-09 1996-01-30 Tosoh Corp 接着剤用ラテックス及びそれを用いたクロロプレン系接着剤組成物
JP2000319452A (ja) * 1999-05-06 2000-11-21 Denki Kagaku Kogyo Kk クロロプレンラテックス組成物およびその製造方法
JP2001019923A (ja) * 1999-07-05 2001-01-23 Denki Kagaku Kogyo Kk クロロプレンラテックスを用いた接着剤組成物
WO2016133191A1 (fr) * 2015-02-19 2016-08-25 デンカ株式会社 Composition de latex et adhésif aqueux monocomposant
JP2019143002A (ja) * 2018-02-16 2019-08-29 東ソー株式会社 クロロプレン重合体ラテックスとその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0827448A (ja) * 1994-05-09 1996-01-30 Tosoh Corp 接着剤用ラテックス及びそれを用いたクロロプレン系接着剤組成物
JP2000319452A (ja) * 1999-05-06 2000-11-21 Denki Kagaku Kogyo Kk クロロプレンラテックス組成物およびその製造方法
JP2001019923A (ja) * 1999-07-05 2001-01-23 Denki Kagaku Kogyo Kk クロロプレンラテックスを用いた接着剤組成物
WO2016133191A1 (fr) * 2015-02-19 2016-08-25 デンカ株式会社 Composition de latex et adhésif aqueux monocomposant
JP2019143002A (ja) * 2018-02-16 2019-08-29 東ソー株式会社 クロロプレン重合体ラテックスとその製造方法

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