EP0000288B1 - Prépolymères reticulables de polyurethane, compositions adhésives les contenant, une méthode de liaison utilisant ces compositions et les articles liés ainsi obtenues - Google Patents

Prépolymères reticulables de polyurethane, compositions adhésives les contenant, une méthode de liaison utilisant ces compositions et les articles liés ainsi obtenues Download PDF

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Publication number
EP0000288B1
EP0000288B1 EP78300107A EP78300107A EP0000288B1 EP 0000288 B1 EP0000288 B1 EP 0000288B1 EP 78300107 A EP78300107 A EP 78300107A EP 78300107 A EP78300107 A EP 78300107A EP 0000288 B1 EP0000288 B1 EP 0000288B1
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EP
European Patent Office
Prior art keywords
poly
ethyleneoxy
glycol
prepolymer
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78300107A
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German (de)
English (en)
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EP0000288A1 (fr
Inventor
Judith Weisensee Becker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Priority claimed from US05/872,664 external-priority patent/US4125522A/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0000288A1 publication Critical patent/EP0000288A1/fr
Application granted granted Critical
Publication of EP0000288B1 publication Critical patent/EP0000288B1/fr
Expired legal-status Critical Current

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Classifications

    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/28—Soles; Sole-and-heel integral units characterised by their attachment, also attachment of combined soles and heels
    • A43B13/32—Soles; Sole-and-heel integral units characterised by their attachment, also attachment of combined soles and heels by adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/284—Compounds containing ester groups, e.g. oxyalkylated monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/90—Compositions for adhesives used in footwear

Definitions

  • This invention relates to curable polyurethane prepolymers and adhesive compositions based thereon.
  • adhesive compositions are particularly well suited for bonding shoe soles to shoe uppers in footwear manufacturing.
  • the sole can be made of a variety of natural or synthetic plastic or elastomeric materials, such as polyvinyl chloride, thermoplastic rubber, styrene/butadiene copolymers, and thermoset polyurethanes.
  • the adhesive currently most widely used are solvent solutions of synthetic elastomers, such as polychloroprene or polyurethane.
  • the bonding process involves coating the substrates with an adhesive solution, evaporating the solvent, then "reactivating" the adhesive film by the application of mild heat before assembly. Activation temperatures above about 70°C must be avoided because they cause distortion of many heat-sensitive shoe materials.
  • Solvent-free adhesives are known and are used in other bonding operations. They comprise fluid isocyanate-terminated prepolymers that can be chain-extended or "cured" by admixture with diamine curing agents such as methylenedianiline. The combination of curing agent and an isocyanate-terminated prepolymer should have adequate potlife after mixing but sufficiently high reaction rate for continuous line applications. Unmodified methylenedianiline, when used with typical urethane prepolymers, gives adhesives having too short a potlife to be applicable in sole attaching operations.
  • a complex of methylenedianiline with sodium chloride in a mole ratio of 3:1 is a known curing agent for urethane prepolymers.
  • a typical dispersion of this complex is available from E.I. du Pont de Nemours 8 Co., Wilmington, Delaware, United States of America, under the name "Caytur 21".
  • Mixtures of "Caytur 21 with urethane prepolymers have a very long potlike but are slow to cure unless activated at temperatures above 120°C, that would destroy many typical shoe materials.
  • the activation temperature of methylenedianiline/sodium chloride complexes can be reduced to about 90°C by addition of certain active hydrogen compounds including urea, according to the teachings of U.S. 3,891,606 but this is still too high a temperature for most shoe materials. Therefore, a polyurethane- based adhesive capable of producing in a short time and at a moderate temperature bonds having good strength is greatly needed.
  • Such adhesive compositions may be formulated solvent free and, moreover, can be cured at a temperature of about 70°C which is a sufficiently low temperature as not to give rise to damage to shoe materials when the adhesive is used in footwear manufacturing operations.
  • the essence of our invention lies in the formation of the polyurethane prepolymer by reaction of tolylene diisocyanate with a mixture of a poly(tetramethyleneoxy) glycol and a poly(ethyleneoxy) compound.
  • the invention provides a curable polyurethane prepolymer formed by reaction of tolylene diisocyanate and a polyalkylene oxide characterised in that from 1.2-2.0 moles of tolylene diisocyanate containing at least 65% of the 2,4-isomer are reacted with 1 mole of poly(tetramethylene- oxy) glycol having a number average molecular weight of about 400-3000, and with a poly(ethyleneoxy) compound having a number average molecular weight of about 310-4000 and containing 7-30 (-CH 2- CH 2 0-) groups and 1 or 2 hydroxyl groups, its (-CH2 CH20-) groups providing 0.5-4.0% of the combined weight of the poly(ethyleneoxy) compound and poly(tetra- methyleneoxy) glycol, while the poly(tetramethyleneoxy) glycol provides no less than 80% of said combined weight.
  • a mixture of a methylenedianiline/sodium chloride complex with finely ground urea can be used as the curing agent for the isocyanate-terminated prepolymer in accordance with the invention to form an adhesive suitable for shoe sole attaching operatings.
  • the adhesive bond forms fast and has high strength.
  • a curing temperature of about 70°C does not damage the usual shoe sole materials or deform the molded shoe bottoms.
  • the isocyanate-terminated prepolymer can be readily made by those skilled in the art. Preparation of prepolymers of the present invention will suitably follow the teachings of U.S. Patents 2,929,800 (to Hill) and U.S. 3,755,261 (to Van Gulick) modified by the incorporation of the poly(ethyleneoxy) compound.
  • the order of addition of the ingredients is not critical.
  • the preferred proportion of the poly(ethyleneoxy) compound is such that its (-CH 2- CH,O-) groups provide 1.0 to 3.0% of the combined weight of poly(ethyleneoxy) compound and poly(tetramethyleneoxy) glycol. It is critical for the success of this invention that the prepolymers be based on a poly(tetramethyleneoxy) glycol, which must constitute at least 80% of the combined weight of poly(ethyleneoxy) compound and poly(tetra- methyleneoxy) glycol. Poly(ethyleneoxy) glycols and polyester glycols, for example, have been found to produce inferior results.
  • the poly(ethyleneoxy) compound is the product of addition of ethylene oxide to a suitable compound having one or two active hydrogens.
  • Representative starting materials from which the poly(ethyleneoxy) compounds of this invention are prepared include, for example, the following.
  • the preferred poly(ethyleneoxy) compounds are the readily available and highly effective oxyethylated alcohols, phenols, and diols; for example, octylphenoxy-poly(ethyleneoxy) ethanols, nonyl- phenoxypoly(ethyleneoxy) ethanols, poly(ethyleneoxy) glycol, and oxyethylated poly(propyleneoxy) glycols. Because of their basic character, which may adversely affect the stability of the adhesive compositions of the present invention, amines are not suitable starting materials.
  • the ethylene oxide reaction products will have repeating units ( ⁇ CH 2 ⁇ CH 2 ⁇ O ⁇ ).
  • Some commercial products suitable in the practice of the present invention are made by adding both ethylene oxide and propylene oxide to the base compound having one or two active hydrogens.
  • these alkylene oxide adducts contain both poly(ethyleneoxy) and poly(propyleneoxy) blocks.
  • the number of propyleneoxy units is not critical, so long as the total number of ethyleneoxy groups (-CH I- CH 2- 0-) in the molecule is within the 7-30 range, the total molecular weight is no more than 4000, and the mole ratio of ethyleneoxy units to propyleneoxy units is not less than 0.2.
  • the methylenedianiline/sodium chloride complex usually is sold as a dispersion in an inert liquid.
  • Such dispersions can be prepared following the general procedure of U.S. 3,876,604 (to Caruso et al). Finely powdered urea is best added to methylenedianiline/sodium chloride complex as a dispersion.
  • the urea dispersion can be made by ball-milling urea with an inert liquid of U.S. 3,876,604 until proper particle size is obtained (usually, less than 20 microns).
  • the amount of urea used should be 2-5 parts per 100 parts by weight of complex.
  • the proportion of the methylenedianiline/sodium chloride complex to the prepolymer is such that the amine -NH!-NCO mole ratio is about 0.95:1 to 1.50:1, ratios of 1.00:1 to 1.30:1 being preferred. Below 0.95; the bond development is too slow for most industrial applications, while above 1.50 the ultimate bond strength is often too low.
  • the compositions of the present invention can be used not only as heat-activated adhesives but also as casting or liquid injection-molding compositions. Should the present system be used for casting or molding, rather than as an adhesive, the lower limit of the -NH 2/- NCO range can be as low as 0.70, the preferred range being 0.85-1.20. Within the preferred range, cured articles having best physical properties are obtained.
  • the adhesive is used as a two-part system.
  • the isocyanate-terminated prepolymer which contains the poly(ethyleneoxy) compound is mixed with the curing agent shortly before use.
  • the composition has at room temperature a potlife in excess of 8 hours; preferred compositions, in excess of 24 hours.
  • the adhesive is applied by suitable means such as brushing, doctoring or transfer coating onto one or both surfaces which are to be bonded; the adhesive surface or surfaces are heated to initiate reaction, and the parts joined in a press for at least 10 seconds.
  • the bonded assembly is sufficiently strong to be subjected to the remaining steps of footwear finishing. The strength of the bond increases with time, approaching its maximum within several hours after bonding.
  • the adhesive composition of the present invention can be also used, if desired, in other applications, including those where parts to be joined are coated with the adhesive composition, assembled together, and then heated to full cure. Such applications require, of course, heat-stable parts to be joined.
  • Prepolymer A containing 4.1% free isocyanate groups (prepared by a reaction of 1.0 mole poly(tetramethyleneoxy) glycol of molecular weight 1000 with 1.6 moles of 2,4-tolylene diisocyanate for 3 hours at 80°C) is added 3.25 g of octylphenoxypoly(ethyleneoxy) ethanol having an average molecular weight of about 756 and a poly(ethyleneoxy) block of 12-13 (-CH,--CH 2 0-) units.
  • Both Prepolymer A and Prepolymer B are made into adhesives by combining with either curing agent C consisting of a 1:1 dispersion of methylenedianiline/sodium chloride complex in di(2-ethylhexyl) phthalate or curing agent D which is prepared by adding 4.5 parts per 100 parts of curing agent C to a 50% dispersion of finely divided urea in di(2-ethylhexyl) azelate.
  • curing agent C consisting of a 1:1 dispersion of methylenedianiline/sodium chloride complex in di(2-ethylhexyl) phthalate
  • curing agent D which is prepared by adding 4.5 parts per 100 parts of curing agent C to a 50% dispersion of finely divided urea in di(2-ethylhexyl) azelate.
  • All four adhesive compositions are still workable 24 hours after preparation.
  • the four compositions are used as adhesives by coating 5 mils (0.13 mm) of the adhesive on roughed 0.3 mm thick slabs of cured styrene-butadiene copolymer.
  • the slabs are immediately heated by radiant heat using a Compo Industries, Inc. 220 volt adhesive activator so that the adhesive reaches a surface temperature of 73°C.
  • the adhesive coating is placed in contact with the vinyl surface of a vinyl-coated fabric containing about 30% dioctyl phthalate as a plasticizer in the vinyl coating and the combined assembly is pressed at 0.41 MPa for 20 sec.
  • the combined pieces are then peel tested as described in ASTM D2558-69 section 8.1 at a jaw separation rate of 5 cm/min. The results are shown in the following table:
  • Prepolymer A (used in Example 1) is added 6.05 g of an oxyethylated poly(propyleneoxy) glycol derived by end-capping poly(propyleneoxy) glycol with poly(ethyleneoxy) groups.
  • the glycol has an average molecular weight of 2750 and contains about 25% by weight of ethyleneoxy units, which corresponds to 16 ethyleneoxy units total.
  • the (-CH 2- CH 2 0-) fraction is 1.84% and the poly(tetramethyleneoxy) glycol content is 92.8% of the combined weight of both glycols.
  • the resulting Prepolymer E contains 3.6% free isocyanate groups.
  • Prepolymer F To 100 g of Prepolymer A (used in Example 1) is added 2.0 g of poly(ethyleneoxy) glycol of molecular weight 1000 (degree of polymerization 22-23) to form Prepolymer F with a free isocyanate content of 3.6%.
  • the proportion of (-CH 2- CH 2 0-) units is 2.49%, and the proportion of poly(tetra- methyleneoxy) glycol is 97.5% of the total weight of both glycols.
  • a series of prepolymers (B x ) was prepared, to show the effect of the number of ethyleneoxy groups, by mixing 4.3 millimoles of octylphenoxypoly(ethyleneoxy) ethanols of the general formula: with 100 g of Prepolymer A from Example 1.
  • a series of four modified prepolymers were prepared by the procedure of Example 1 by adding increasing amounts of an oxyethylated poly(propyleneoxy) glycol derived by end-capping poly(propyleneoxy) glycol with poly(ethyleneoxy) units to 100 g portions of Prepolymer A.
  • the oxyethylated poly(propyleneoxy) glycol had a molecular weight of about 2650 and contained about 30% by weight of ⁇ CH 2 ⁇ CH 2 O ⁇ units.
  • the modified prepolymers were made into adhesives by the addition of curing agent D.
  • the resulting adhesives were evaluated by bonding slabs of styrene- butadiene copolymer to vinyl-coated fabric as described in Example 1.
  • the pot-life of the adhesives was determined by measuring their viscosities 8 hours and 24 hours after preparation.
  • Prepolymers A and B were made into adhesive compositions by the addition of 27.9 parts of curing agent D per 100 parts of prepolymer. In less than 8 hours both of these adhesive compositions became too viscous for use.
  • Prepolymer C was modified by the addition of 3.25 g of octylphenoxypoly(ethyleneoxy)ethanol having an average molecular weight of 756 following the procedure of Example 1 to form a prepolymer designated as Prepolymer C'.
  • Prepolymers C and C' were converted to adhesives by the addition of 27.9 and 26.7 parts per 100 parts prepolymer, respectively, of curing agent D.
  • the resulting adhesives were tested by bonding styrene-butadiene copolymer and vinyi-coated fabric as in Example 1. Peel strengths 1 minute after release from the press were less than 0.02 kN/m which is inadequate for use as a shoe adhesive.

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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)
  • Polyurethanes Or Polyureas (AREA)

Claims (8)

1. Un prépolymère de polyuréthane durcissable formé par réaction de diisocyanate de tolylene et d'un oxyde de polyalcoylène, caractérisé en ce qu'on fait réagir de 1,2 à 2,0 moles de diisocyanate de tolylène contenant au moins 65% de l'isomère 2,4 avec 1 mole de poly(oxytétraméthylène)glycol ayant un poids moléculaire moyen en nombre d'environ 400 à 3000, et avec un composé polyoxyéthylénique ayant un poids moléculaire moyen en nombre d'environ 310-4000 et contenant 7 à 30 groupes (―CH2―CH2O―) et 1 ou 2 groupes hydroxyle, ces groupes (―CH2―CH2O―) constituant de 0,5 à 4,0% du poids combiné du composé polyoxyéthylénique et du poly(oxytétraméthylène)glycol, et le poly(oxytétraméthylène)glycol ne constituant pas moins de 80% dudit poids combiné.
2. Un prépolymère selon la revendication 1, caractérisé en ce que la proportion de composé polyoxyéthylénique est telle que ses groupes (―CH2―CH2O―) constituent de 1,0 à 3,0% du poids combiné de composé polyoxyéthylénique et du poly(oxytétraméthylène)glycol.
3. Un prépolymère selon la revendication 1 ou 2, caractérisé en ce que le composé polyoxyéthylénique est un poly(oxyéthylène)glycol, un poly(oxypropylène)glycol oxyéthylé ou un alcoylphénoxy- poly(éthylèneoxy)éthanol.
4. Une composition adhésive comprenant, en mélange, un prépolymère de polyuréthane durcissable, un complexe de méthylène dianiline et de chlorure de sodium dans un rapport molaire de 3:1 et de l'urée, caractérisée en ce que le prépolymère est tel que défini à l'une quelconque des revendications 1 à 3, le rapport molaire des groupes amino-NH2 aux groupes -NCO est d'environ 0,95:1 à 1,50:1, et la proportion d'urée est de 2 à 5 parties par 100 parties en poids du complexe méthylènedianiline/chlorure de sodium.
5. Une composition selon la revendication 4, caractérisée en ce que les proportions sont telles que le rapport des groupes amino-NH2 aux groupes-NCO va de 1,00:1 à 1,30:1.
6. Un procédé pour coller deux ou plusieurs surfaces selon lequel on revêt au moins une des surfaces à coller d'une composition adhésive, on chauffe à environ 70°C la surface revêtue, et on joint les surfaces ensemble et on les maintient ensemble pendant au moins 10 secondes, caractérisé en ce que la composition adhésive est telle que définie à la revendication 4 ou 5.
7. Un article collé obtenu par le procédé de la revendication 6.
8. Une chaussure dont le dessus est collé à la semelle par le procédé de la revendication 6.
EP78300107A 1977-07-01 1978-06-29 Prépolymères reticulables de polyurethane, compositions adhésives les contenant, une méthode de liaison utilisant ces compositions et les articles liés ainsi obtenues Expired EP0000288B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US81236677A 1977-07-01 1977-07-01
US812366 1977-07-01
US05/872,664 US4125522A (en) 1977-07-01 1978-01-26 Adhesive composition
US872664 1978-01-26

Publications (2)

Publication Number Publication Date
EP0000288A1 EP0000288A1 (fr) 1979-01-10
EP0000288B1 true EP0000288B1 (fr) 1981-03-11

Family

ID=27123597

Family Applications (1)

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EP78300107A Expired EP0000288B1 (fr) 1977-07-01 1978-06-29 Prépolymères reticulables de polyurethane, compositions adhésives les contenant, une méthode de liaison utilisant ces compositions et les articles liés ainsi obtenues

Country Status (7)

Country Link
EP (1) EP0000288B1 (fr)
JP (1) JPS5414497A (fr)
BR (1) BR7804199A (fr)
CA (1) CA1107437A (fr)
DE (1) DE2860517D1 (fr)
ES (1) ES471352A1 (fr)
IT (1) IT1098355B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IE51643B1 (en) * 1980-10-15 1987-01-21 Smith & Nephew Ass Coated articles and materials suitable for coating
US4330454A (en) * 1981-04-06 1982-05-18 The Goodyear Tire & Rubber Company Storable flowable polypropylene ether urethane composition
JPH0794523B2 (ja) * 1987-09-02 1995-10-11 東洋ゴム工業株式会社 高透湿性、低膨潤性、高モジュラス等のすぐれた特性を有するポリウレタン重合体の製造方法
US4772676A (en) * 1987-11-18 1988-09-20 The Firestone Tire & Rubber Company Ambient temperature quasi-polar catalysts of amine curable polymers
JPH02258883A (ja) * 1988-12-20 1990-10-19 Dow Chem Co:The ポリウレタン接着剤及びその製造方法
AU3966999A (en) * 1998-04-27 1999-11-16 Dow Chemical Company, The Cure on demand adhesives for assembling shoe soles

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1326963A (fr) * 1962-06-29 1963-05-10 Cie De Prod Chim Boston Adhésif pour la fixation de semelles à des empeignes de chaussures
US4010146A (en) * 1975-09-29 1977-03-01 Samuel Moore And Company Polyol blends and polyurethane prepared therefrom

Also Published As

Publication number Publication date
IT7825210A0 (it) 1978-06-30
DE2860517D1 (en) 1981-04-09
JPS5414497A (en) 1979-02-02
CA1107437A (fr) 1981-08-18
BR7804199A (pt) 1979-03-20
EP0000288A1 (fr) 1979-01-10
ES471352A1 (es) 1979-10-01
IT1098355B (it) 1985-09-07
JPS6237650B2 (fr) 1987-08-13

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