Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
  • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
  • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
  • C08F36/14—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
  • C08F36/16—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
  • C08F36/18—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen containing chlorine
• • C—CHEMISTRY; METALLURGY
  • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2852—Adhesive compositions
  • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
  • Y10T428/2883—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer of diene monomer [e.g., SBR, SIS, etc.]

Definitions

• the invention relates to adhesive compositions based on polychloroprene dispersions with improved pressure sensitive adhesive properties, a process for their production and their use as contact pressure sensitive adhesives for inorganic or organic substrates.
• all compounds and their mixtures which sufficiently stabilize the emulsion such as e.g. the water-soluble salts, in particular the sodium, potassium and ammonium salts of long-chain fatty acids, rosin and rosin derivatives, higher molecular weight alcohol sulfates, aryl sulfonic acids, formaldehyde condensates of aryl sulfonic acids, nonionic
• water-soluble salts in particular the sodium, potassium and ammonium salts of long-chain fatty acids, rosin and rosin derivatives, higher molecular weight alcohol sulfates, aryl sulfonic acids, formaldehyde condensates of aryl sulfonic acids, nonionic
• Polychloroprene is used either after appropriate compounding and vulcanization for the production of technical rubber articles, or it is used as a contact adhesive raw material ("Handbook of adhesives", Chapter 21, VanNostrand Reinhold, New York, 2nd edition 1977).
• Contact adhesives based on polychloroprene are predominantly solvent-based adhesives that are applied to both parts to be joined and allowed to dry. Subsequent joining of both parts under pressure results in a connection with high strength. With these solvent-based contact adhesives, the long period within which bonding at room temperature is possible (“open
• Time is considered to be particularly advantageous.
• Open time is defined in the present application as the time interval between the point in time at which the applied adhesive is sufficiently dry to allow the substrates to be bonded and the point in time at which it is no longer possible to apply one alone by applying pressure at room temperature to achieve a satisfactory bond.
• aqueous adhesive composition based on an aqueous polychloroprene dispersion which, after the water had evaporated, had a long "open time” during which it was possible to bond at room temperature without thermal activation.
• an improvement in the heat resistance of the contact adhesive can also be achieved.
• the object was achieved by the production of an aqueous adhesive composition based on polychloroprene dispersions, obtainable by continuous polymerization of chloroprene in an aqueous emulsion in the presence of unmodified resin acids as an emulsifier.
• This aqueous adhesive raw material dispersion can then be processed with the adhesive auxiliaries and additives known in the prior art to form an adhesive composition which has a sufficiently long "open time” in which adhesive bonding is possible at room temperature without thermal activation.
• the invention thus relates to an adhesive composition based on a
• Polychloroprene dispersion containing a tricyclic diterpene carboxylic acid with at least two conjugated C C double bonds per molecule.
• Adhesive compositions containing 100 parts by weight of a polychloroprene dispersion which contains, as emulsifier, a tricyclic diterpene carboxylic acid with at least two conjugated C alsC double bonds per molecule, 15 to 75 parts by weight of an adhesive resin, 1 to 10 parts of a metal oxide, are preferred. selected from the group consisting of zinc oxide and magnesium oxide and optionally further auxiliaries and additives, all of which are in the form of a dispersion.
• the polychloroprene dispersion contained in the adhesive composition according to the invention has an “open time” in the range from 4 to 15 days after the water has evaporated.
• the polychloroprene dispersion to be used in the process according to the invention is prepared by emulsion polymerization at 0 to 70 ° C., preferably at 5 to 50 ° C., and at pH values from 10 to 14, preferably 11 to 13.
• the activation takes place through the usual activators or activator systems.
• Examples include: formamidine sulfonic acid, potassium peroxodisulfate, redox systems based on potassium peroxodisulfate and optionally silver salt (sodium salt of anthraquinone- ⁇ -sulfonic acid), for example compounds such as formamide sulfinic acid, sodium salt of hydroxymethanesulfinic acid, sodium sulfite and sodium dithionite serve as redox partners , Redox systems based on peroxides and hydroperoxides are also suitable.
• the polychloroprene according to the invention can be prepared either continuously or batchwise.
• Chain transfer agents such as mercaptans, e.g. in DE-A 3 002 711, GB-PS
• FR-PS 2 073 106 are described, or as xanthogen disulfides, as described, for example, in DE-A 1 186 215, in DE-A 2 156 453, 2 306 610 and 3 044 811, in which EP-A 53 319, described in GB-PS 512 458 and 952 156 and in US-A 2 321 693 and 2 567 117 can be used.
• Particularly preferred chain transfer agents are n-dodecyl mercaptan and the xanthogen disulfides used in DE-A 3 044 811, DE-A 2 306 610 and DE-A 2 156 453.
• the tricyclic diterpene carboxylic acids to be used according to the invention can be obtained in the form of the crude, unmodified resin acids (SW Barendrecht, LT Lees in Ullmanns Encyclopadie der Technischen Chemie, 4th edition vol. 12, 528-538, Verlag Chemie, Weinheim - New York 1976)
• Tall oil, pine balm or root resin can be used, provided that they are free from distillable components of turpentine oil.
• tricyclic diterpene carboxylic acids themselves are easily accessible, they can also be used in pure form. Suitable tricyclic diterpene carboxylic acids include, for example, abietic acid, palustric acid, neoabietic acid and levopimaric acid.
• the tricyclic, conjugated unsaturated diterpene carboxylic acids can be determined from a mixture of resin acids by type and amount by gas chromatography; for example according to or analogous to J. Amer. Oil Chem. Soc. 54, 289 (1977).
• composition of an unmodified resin acid obtained from pine balm is the composition of an unmodified resin acid obtained from pine balm:
• emulsifying substances can also be used, e.g. the water-soluble salt of the condensation product of naphthalenesulfonic acid and formaldehyde.
• the adhesive composition according to the invention is free of, or low in organic solvents.
• “poor” means a content of less than 30% by weight (organic solvent), based on the finished adhesive.
• the adhesive composition according to the invention optionally contains further adhesive auxiliaries and additives.
• fillers such as quartz powder, quartz sand, highly disperse silica,
• Heavy spar, calcium carbonate, chalk, dolomite or talc optionally together with wetting agents, for example polyphosphates (such as sodium hexametaphosphate), naphthalenesulfonic acid, ammonium or sodium polyacrylic acid salts, are added, the fillers generally in amounts of 10 to 60%, preferably 20 to 50 wt .-%, based on adhesive, and the wetting agents are generally added in amounts of 0.2 to 0.6 wt .-%, based on filler.
• Zinc oxide is of particular importance as an additive as an acceptor for small amounts of hydrogen chloride which can be split off from the polymers.
• auxiliaries are, for example, in amounts of 0.01 to 1% by weight, based on adhesive, organic thickeners to be used, such as cellulose derivatives, alginates, starch, starch derivatives or polyacrylic acid or in amounts of 0.05 to 5% by weight. %, based on adhesive, inorganic thickeners to be used, such as bentonites.
• the adhesive composition according to the invention can also be used for preservation
• Fungicides can be added. These are generally used in amounts of 0.02 to 1.0% by weight, based on the adhesive. Suitable fungicides are, for example, phenol and cresol derivatives or organotin compounds.
• tackifying resins e.g. unmodified or modified natural resins such as rosin esters, hydrocarbon resins or synthetic resins such as phthalate resins can optionally be added to the adhesive composition in dispersed form, cf. "Adhesive Resins" R. Jordan, R. Schuwaldner, pp. 75-115, Hinterwaldner Verlag Kunststoff 1994. Alkylphenol resin dispersions with softening points greater than 110 ° C. are preferred, and a terpene phenol resin with a softening point above 110 ° C. is particularly preferred.
• Organic solvents such as toluene, xylene, butyl acetate, methyl ethyl ketone, ethyl acetate, dioxane or their mixtures or plasticizers such as, for example, those based on adipate, phthalate or phosphate can optionally be added to the polychloroprene dispersions.
• the adhesives according to the invention can be used to bond any substrates of the same or different types, for example wood, paper, plastics, textiles, leather, rubber and inorganic materials such as ceramic, earthenware or asbestos cement.
• the aqueous adhesive composition according to the invention also makes it possible to bond substrates which are difficult to bond, such as thermoplastic olefins (TPO), or ethylene-vinyl acetate copolymers (EVA) with a high ethylene content, which otherwise would not be pretreated by a surface
• TPO thermoplastic olefins
• EVA ethylene-vinyl acetate copolymers
• the polymerization is carried out by a continuous process as described in EP-A 0 032 977.
• the aqueous phase (W) and the monomer phase (M) are fed in at a constant ratio and the activator phase (A) using a measuring and control apparatus.
• the average residence time per boiler is 25 minutes.
• the reactors correspond to those described in DE-A 2 650 714 (data in parts by weight per 100 g parts by weight of monomers used).
• Demineralized water 115.0 parts by weight of sodium salt of a disproportionated abietic acid 2.6 parts by weight of sodium salt of a condensation product of naphthalenesulfonic acid and formaldehyde 0.7 part by weight
• the reaction starts slightly at an internal temperature of 40 ° C.
• the heat of polymerization released is dissipated and the polymerization temperature is kept at 45 ° C.
• the reaction is stopped by adding phenothiazine.
• the remaining monomer is removed from the polymer by steam distillation and the polymer latex is creamed by adding alginate, as described in "Neoprene Latices, John C. Carl,
• the viscosity of the latex is 100 mPas, the solids content is 58%.
• Example 2 (example according to the invention)
• the viscosity of the latex is 104 mPas, the solids content is 58%.
• the polymerization is carried out as described in Example 1, but at 10 ° C. and without 2,3-dichlorobutadiene.
• the reaction starts in the 1st boiler of the cascade.
• the heat of polymerization released is removed by external cooling and the polymerization temperature is reduced to 10 ° C.
• the reaction is stopped by adding phenothiazine.
• the remaining monomer is removed from the polymer by steam distillation and the polymer latex is creamed. After a polymerization time of 4 days, the polymerization slat is extended.
• a dispersion with a solids content of 56% and a viscosity of 98 mPas is obtained.
• the dispersion is applied to a glass plate and dried for 3 days at room temperature under a nitrogen atmosphere to a film.
• 250 mg of sample are dissolved or swollen in 25 ml of THF (mixed with 1 g of polymerization inhibitor per liter of THF) in a closed vessel at room temperature for 24 hours.
• the mixture is ultracentrifuged at 20,000 rpm for 1 hour and the weight fraction of the material centrifuged off after drying is determined.
• the test is carried out in accordance with EN 1392.
• a 100 ⁇ m thick wet film of the dispersion is applied to two test specimens (Nora rubber, roughened, 100 x 30 mm) and aired for 1 hour at room temperature. The test specimens are then put together at 4 bar for 10 seconds. A tear test is carried out on a commercially available tensile testing machine at room temperature. The strength values are shown immediately after bonding, after 1 and 9
• Polyester film (Hostaphan RN 75/0, thickness: 0.075 mm.) Is presented and the
• Dispersions with a film puller with a doctor blade gap of 0.2 mm applied in a width of 5 mm The polyester strips with the adhesive dispersion are stored in an air-conditioned room at 23 ° C and 50% relative humidity. At intervals of 12 hours, two cardboard strips are crossed and loaded with a 50 g weight for 10 seconds. The end of the contact adhesive time is exceeded when the films can no longer be contacted by hand in the separation test.
• the polychloroprene dispersion is placed in a beaker.
• the stabilizer, the anti-aging agent, ZnO and the resin are added with stirring.
• the material was dried for 24 hours at RT and the adhesion of the adhesive film to the TPO substrate (DOW Engage type) was checked.
• the dry adhesive film can be removed from the TPO substrate without any problems (no adhesion to TPO).
• the dry adhesive film shows a slight adhesion to the TPO substrate. Only with the adhesive composition according to the invention were adhesive films produced which have excellent adhesion. When trying to pull the dry adhesive film off the TPO, the adhesive film tears because the adhesion to TPO is too strong.

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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)
• Adhesives Or Adhesive Processes (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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