WO1995013307A1 - Urethanne thermoplatique s'appliquant a une temperature et avec une viscosite polymere basses - Google Patents

Urethanne thermoplatique s'appliquant a une temperature et avec une viscosite polymere basses Download PDF

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Publication number
WO1995013307A1
WO1995013307A1 PCT/US1994/007228 US9407228W WO9513307A1 WO 1995013307 A1 WO1995013307 A1 WO 1995013307A1 US 9407228 W US9407228 W US 9407228W WO 9513307 A1 WO9513307 A1 WO 9513307A1
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WO
WIPO (PCT)
Prior art keywords
composition according
composition
polyurethane
functionality
isocyanate
Prior art date
Application number
PCT/US1994/007228
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English (en)
Inventor
William H. Mann
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Refac International, Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Refac International, Ltd. filed Critical Refac International, Ltd.
Priority to AU73565/94A priority Critical patent/AU7356594A/en
Publication of WO1995013307A1 publication Critical patent/WO1995013307A1/fr

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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
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C08G2170/20—Compositions for hot melt adhesives
    • 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

Definitions

  • hot melt urethane compositions formed from a mixture of one or more polyisocyanates, one or more hydroxyl terminated polyols, one or more chain extenders and one or more plasticizers.
  • a hot melt composition generally is one applied in the molten state, at temperatures of about 250°- 450°F (121.1°-232.2°C) , and having a viscosity in that condition (Brookfield viscometer) of less than about 50,000 cps, preferably less than about 25,000 cps. When cooled to room temperature, such compositions are solids that are.elastomeric in nature.
  • compositions are formed by heating the reactants at temperatures of at least about 330"F (165.6°C), preferably at about 350° to about 450°F (176.7°-232.2°C) for 2 or 3 hours.
  • the compositions of this patent have been found to be excellent starting materials for use in the present invention.
  • the disclosure of the 4,608,418 patent is hereby incorporated by reference.
  • compositions that have at the same time the properties of excellent adhesion, lower application temperature, lower viscositiy, and a thinner coating film. Another object is to provide methods for the preparation and application of these compositions.
  • the present invention is directed to multi-component compositions comprising from about 5% to about 95% of
  • compositions made in accordance with the teachings of US 4,608,418 can be used as the first component (la) of the compositions of the present invention.
  • the first component of the urethane compositions of the present invention is, as indicated in US 4,608,418, a thermoplastic hot melt composition comprising a polyurethane having at least one plasticizer reacted therein formed by heating a reaction mixture comprising at least one isocyanate having a functionality less than about 2.2, at least one hydroxyl terminated long chain polyol, at least one chain extender and at least one plasticizer at a temperature of at least about 330°F, wherein said components are present in amounts that are within the values of the following formula:
  • A+B+C 0.5 to about 7.0 D
  • A represents the equivalent weight of the long chain polyol x the moles thereof used
  • B represents the equivalent weight of the chain extender x the moles thereof used
  • C represents the equivalent weight of the isocyanate used
  • D represents the grams of plasticizer
  • the process for preparing the first component of the urethane compositions of the present invention generally is, as disclosed in US 4,608,418, to heat a polyurethane formed from a mixture of at least one isocyanate having a f nctionality less than about 2.2, at least one long chain polyol, at least one chain extender and at least one plasticizer at a temperature of at least about 330°F, wherein said components are present in an amount to meet the foregoing formula.
  • the urethane material of the first component is based on essentially stoichiometric amounts of a diisocyanate (which insures that a thermoplastic material results) having a functionality of 2.2 or less, preferably 2.15 or less and most preferably in the range of 2.0-2.1.
  • thermosetting material which is excluded from the first component, results.
  • the NCO/OH ratio in the reaction system is about 0.95 to about 1.05 as at values substantially in excess of 1.05 the reaction product tends to be non-thermoplastic.
  • the ingredients thereof are blended at the lowest possible temperature, the system is permitted to exotherm and, after the peak exotherm has been reached, the system is heated at about 330°F to about 450°F while agitating to complete the reaction.
  • the reaction of the one or more plasticizers into the system is substantially completed simultaneously with attainment of the requisite temperature of at least about 330°F (165.6°C). Based on experience to date, the plasticizer cannot be extracted therefrom or is only partially extractable by common organic solvents, e.g., hexane, gasoline, motor oil, and the like, at normal end use conditions for the first component absent the second component.
  • the polyisocyanate reactants useful in preparing the compositions of the present invention are aromatic, aliphatic, cycloaliphatic or aralkyl polyisocyanates containing from about 6 to 100 carbon atoms. Although the preferred isocyanate-containing reactants contain two isocyanate groups, reactants containing more than two such groups are operative so long as the average functionality does not exceed 2.2 and the resulting urethane is thermoplastic. Blends or mixtures also are included in the foregoing definition of polyisocyanate reactants. Isocyanate terminated prepolymers which perform as diisocyanates under the processing conditions of the present invention and have an average functionality of 2.2 or less also are useful and are considered equivalent to the preferred diisocyantes. The following list is an example of polyisocyanates useful in the present invention:
  • Isocyanate-terminated polyurethane prepolymers useful herein include blocked isocyanate prepolymers, such as, for example, a polyalkylene glycol or polyalkylene ether polyester, polyacetal, polyamide, polyester polyamide, or polythioether polyol, which can be reacted with an excess of a diisocyanate, such as those mentioned above, to form a suitable prepolymer with residual isocyanate groups.
  • the prepolymers are formed in conventional manner and are generally produced by reaction materials such as mentioned above and diisocyanates at temperatures of from about 50°F to about 130°F, the reaction time being matched to the predetermined temperature, for example two hours at about 120°F.
  • the substantially linear polyhydroxyl compounds with terminal hydroxyl groups include compounds of the formula HO-D-OH having a functionality of 2.2 or below wherein D is polyester, polyester amide, polyether, polyacetal, polycarbonate, or poly-N-alkylurethane. Other groups such as ester, ether, amide, urethane, or N-aIkylurethane groups optionally may be present in D.
  • the average molecular weight of the substantially linear polyhydroxyl compounds preferably from above 500 to 5000, most preferably from about 800 to about 3000. These compounds preferably have a melting point below 150°F, in particular below 110°F. It is also within the scope of the present invention to use mixtures of these compounds.
  • Useful compounds of formula HO-D-OH include polyesters of dibasic acids, for example adipic acid, and dialcohols, for example, ethylene glycol, propylene glycol, 1,4- butanediol; 2,5-hexanediol; 2,2-dimethyl-l,3-propanediol; 1, 6-hexanediol; 2-ethyl-l, 6-hexanediol; 2,2-dimethyl-l,3- hexanediol; p-bis-hydroxymethyl cyclohexane; 3-methyl-l,4- pentanediol; and 2,2-diethyl-l,3-propanediol.
  • dialcohols for example, ethylene glycol, propylene glycol, 1,4- butanediol; 2,5-hexanediol; 2,2-dimethyl-l,3-propanediol; 1, 6-hex
  • Chain extending agents compounds which carry at least two active hydrogen atoms per molecule and preferably have a molecular weight of from about 52 to below 500, most preferably from about 62 to about 250, are included in the reaction mixture. These compounds react with the isocyanate groups of the prepolymer to produce high molecular weight polyurethanes and polyurethane ureas by linking several isocyanate prepolymer.
  • Examples of useful chain extending agents are the following: ethylene glycol; propane-l,2-diol; hexane-1,6-diol; 2- ethyl-1,6-hexanediol; dihydroxyethylurea; terephthalic acid-bis-( -hydroxyethylamide) ; hydroquinone-bis- hydroxyethy1 ether; naphthylene-1,5-k:s-hydroxyethy1 ether; 1,l-dimethyl-4-(bis-/3-hydroxy /l)- se icarbazide; succinic acid; adipic acid; isophthalic acid; 1,4-cyclohexane dicarboxylic acid; ethylene diamine; hexamethylene diamine; 1,4- cyclohexane diamine; hexahydro- -xylene diamine; - xylylene diamine; p-xylylene diamine; bis(j ⁇ - aminoeth
  • Plasticizers are also included in the reaction mixture.
  • the plasticizer must be capable of being reacted into the polyurethane at temperatures of about 330°F (165.6°C) .
  • compositions manufactured by Advanced Resin Technology, Inc. include the following compositions manufactured by Advanced Resin Technology, Inc. :
  • C101-35 is a thermoplastic MDI- based, polyester urethane elastomer formed with a long chain ethylene adipate polyester diol having an average molecular weight (m.w.) of 1000 and hydroxyl number of 55.
  • C100-55, C103-46, C200-65, C201-57, C210-50D and C301-75 are MDI- based polycaprolactone urethane elastomers
  • L104-40 is an HMDI-based long chain polycaprolactone diol with an average m.w. of 3000 and hydroxyl number of 37.4.
  • L3300-80, L3300-85 and L3300-90 are HMDI-based polyether urethane elastomers.
  • C100-55, C101-35, C103-46, C200-65, C201-57 and C301-75 are preferred.
  • compositions made in accordance with the teachings of US 4,870,142 also can be used as the first component (lb) of the compositions of the present invention.
  • Compositions according to this patent comprise the reaction product of at least one polyisocyanate, at least one hydroxyl terminated polyol and/or at least one chain extender, and at least one epoxy resin.
  • the •• urethane" materials of this patent are based on essentially stoichiometric amounts of a polyisocyanate, which insures an initially thermoplastic material, having a functionality of 2.2 or less, preferably 2.15 or less, and most preferably in the range of 2.0-2.1.
  • polyisocyanate 4,4- diphenylmethane disiocyanate (MDI) is preferred.
  • MDI 4,4- diphenylmethane disiocyanate
  • An example of a commercially available suitable polyisocyanate is ISONATE 143L (Dow) .
  • Isocyanate-terminated polyurethane prepolymers may be used wherein the isocyanate group is blocked with such groups as epsilon-caprolactam, methyl ethyl ketoxime, phenol, and branched alcohols such as t- butyl alcohol and isopropanol.
  • a polyalkylene glycol or polyalkylene ether polyester, polyacetal, polyamide, polyester polyamide, or polythiolether polyol may be reacted with an excess of a polyisocyanate to form a suitable prepolymer with residual isocyanate groups.
  • Such prepolymers are formed in conventional manner.
  • suitable relatively high molecular weight compounds are substantially linear polyhydroxyl compounds with terminal hydroxyl groups of the formula HO-D-OH include polyesters, polyester amides, polyethers, polyacetals, polycarbonates or poly-N-alkylurethanes, other groups such as ester, ether, amide, urethane or N-alkylurethane groups optionally being present in the foregoing compounds.
  • the average functionality of these polyols is 2.2 or below.
  • the molecular weight thereof preferably is from about 500 to about 5000, preferably from about 800 to about 3000 (number average) .
  • These compounds preferably have a melting point below 150°C, in particular, below 110°C. It is also possible to use mixtures of these relatively high molecular weight compounds.
  • the substantially linear polyhydroxyl compound can be in a preformed polyisocyanate or a polyurethane prepolymer.
  • polyhydroxyl compounds are polyesters of dibasic acids, for example, adipic acid, and diols, or mixtures of diols, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 2,5-hexanediol, 2,2- dimethyl-1, 3-propanediol, 1,6-hexanediol, 2-ethyl-l,6- hexanediol, 2,2-dimethyl-l,3-hexanediol, p_-bis- hydroxy ethylcyclohexane, 3-methyl-l,4-pentanediol, and 2,2- diethyl-1,3-propanediol.
  • dibasic acids for example, adipic acid
  • diols or mixtures of diols, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 2,5-hex
  • polyesters of this kind show very high resistance to hydrolysis.
  • the polyesters contain branched alkyl radicals, the polyesters also show outstanding low temperature elasticity in the end products.
  • Polyesters obtained by polymerizing caprolactones with glycols are also suitable starting materials.
  • Other glycols such as hydrogenated bis- phenol A, cyclohexane dimethanol, caprolactone diol (i.e., the reaction product of caprolactone and ethylene glycol) , hydroxyalkylated bis-phenols, polyether glycols, e.g., poly(oxytetramethylene)glycol and the like also are useful.
  • polyesters such as polyethylene glycol adipates, polyethylene butylene adipates, polyethylene glycol azelates, polyethylene butylene azelates, polycaprolactones, polycarbonates, polyethers, polybutadienes, or copolymers with acrylonitrile, styrene and the like.
  • the chain extending component is a compound having, per molecule, at least two active hydrogen atoms and preferably a number average molecular weight of from about 52 to about 400, most preferably from about 62 to about 250 (number average) . These compounds react with the isocyanate groups of the prepolymer and build up high molecular weight polyurethane and polyurethane ureas by linking several isocyanate prepolymer molecules.
  • useful chain extending agents are, for instance, ethylene glycol, propane-l,2-diol, butane-l,4-diol, hexane-1,6-diol, 2(3)- methylhexane-1,6-diol, 3-methylhexane-l,6-diol, hydroquinone-bis-hydroxyethyl ether, and naphthylene-1,5- bis-hydroxyethyl ether.
  • the NCO/OH ratio in the reaction system be in the order of about 0.8 to about 1.1 as values substantially in excess of 1.1 tend to produce an initial reaction product that is non-thermoplastic.
  • the last mandatory component of the compositions of US 4,870,142 is an epoxy resin having hydroxyl function less than about 1.8, and preferably less than 1.5.
  • the precise nature of the epoxy resin is not overly important so long as it contains sufficient hydroxyl groups to react with isocyanate groups to provide a curable, non-gelled thermoplastic polymer alloy product.
  • the hydroxyl functionality of the epoxy resin typically is greater than about 0.1 and must be less than about 1.8, and most preferably less than about 1.5.
  • the equivalent weight of the epoxy resin can vary widely but most have an equivalent weight of about 100 to about 500.
  • the molecular weight of the epoxy resin is not overly important although, assuming a direct correlation between molecular weight and the number of hydroxyl groups, if the number of hydroxyl groups is too great, cross-linking or gelation could occur and this should be avoided.
  • the amount of epoxy resin used according to the present invention can be defined by the range of about 0.5 to about
  • a + B + C ca. 0.5 to 20 D
  • A equivalent weight of long chain polyol(s) x (number of equivalents thereof) , and can be zero (0) ;
  • B equivalent weight of chain extender(s), x (number of equivalents thereof) , and can be zero (0) ;
  • D epoxy resin(s) (number of grams thereof) ; but A and B cannot both be zero.
  • the epoxy resin will comprise from about 15% to about 75% of the total composition weight, more preferably, from about 20% to about 70% of the total composition weight, and most preferably from about 25% to about 65% of the total composition weight.
  • compositions of component (lb) are normally formed by first blending together the long chain linear polyol, the chain extender, and the epoxy resin and, if used, any additional ingredients such as an additional thermoplastic resin, filler, etc. Blending conditions are not important and any conventional blending means can be used, though it may be necessary to melt some materials to obtain a uniform liquid or to insure an homogeneous system. Sj * _, e a solvent is not used, this is preferably accomplished at the lowest possible temperature to avoid premature reaction until the system is well mixed.
  • the polyisocyanate is then generally added slowly with agitation.
  • agitation There is no special criticality to the conditions used for polyisocyanate addition, but preferably, the lowest possible temperature to avoid premature reaction is used until the system is well mixed. Constant agitation is preferred to avoid localized pockets of materials which are not blended into an homogeneous system and, if reaction is occurring, one obviously wishes to avoid "hot spots" in the reaction system.
  • thermoplastic material as a second component of the compositions of the present invention, such as thermoplastic polyamide resins made from dimer acids, an ethyl vinyl acetate (EVA) polymer or copolymer resin, or a thermoplastic polyurethane, e . g. an ester or an ether, a polyester polycaprolactone, an ethylene glycol ether, an ethylene copolymer with acrylic or methacrylic acid, or a flexible or rigid polyvinyl chloride.
  • EVA ethyl vinyl acetate
  • thermoplastic polyurethane e g. an ester or an ether, a polyester polycaprolactone, an ethylene glycol ether, an ethylene copolymer with acrylic or methacrylic acid, or a flexible or rigid polyvinyl chloride.
  • thermoplastic materials are the following: a) thermoplastic polyamide resins: Versamid 930 [Henkel] and Macro elt 6238 (Henkel) , b) EVA resins: ELVAX resins (DuPont) , HL-4096-X (H.B.
  • thermoplastic polyurethane polyesters TEXIN (Miles) 480A, 591A, 688A, 345D, 355D, 455D, 458D and 5187
  • polyurethane polyethers TEXIN (Miles) 985A, 990A and 970D
  • polyester polycaprolactones PELLETHANE (Dow) 2102 and 2354
  • ethylene copolymers with acrylic or methylacrylic acids several of which are commerically available
  • polyvinyl chlorides several of which are commercially available both in flexible and original forms.
  • the materials are mixed and the resulting blend or dry blend is processed in an appropriate mixing equipment such as, for example, an extruder, a sigma mixer, a planetary mixer, and the like, under a process that controls heat, pressure and shear energy in the equipment to insure proper mixing without overheating the mixture.
  • an appropriate mixing equipment such as, for example, an extruder, a sigma mixer, a planetary mixer, and the like
  • the processing temperatures will vary with the materials in the blend and their percentages. In general, any combination of shear and temperature to melt the materials is satisfactory and will usually be a temperature of about 250-400°F (121.1-204.4°C) , usually not over 425°F (218.4°C), with minimal shear conditions.
  • the product from the mixer can be underwater pelletized, strand pelletized, crushed, granulated or otherwise particle reduced. It is then ready to be further processed in adhesive dispensing equipment, film extruder, hot melt dispenser closed pail unloader, or similar equipment for handling heated plastic materials.
  • the thinness of the films involved, as thin as 1 mil or less, and the heat sink effect of using the container as the mandrel in applying the label enhances the performance of the system in enabling the material to cool thereby improving adhesive properties.
  • compositions of the present invention have many advantageous properties among which can be mentioned: a) depressed viscosity thereby enabling the composition to be applied without using solvents at lower viscosity with easier processing conditions with the introduction of heat and shear, b) due to the lowering of viscosity with introduction of heat and shear, the composition can be cooled below the original melting temperatures but still be of sufficiently low viscosity to be applied as a coatable film, c) the ability to be cooled sufficiently to enable application to heat sensitive/heat shrink materials, either single films or laminates, tubing, polypropylene heat shrink labels and films, films of polystyrene or foam polystyrene, polyvinyl chloride and blends, polyethylene, and various other blends of olefinic polymers without distorting the film, d) sufficient temperature resistance to withstand the rigors of commercial pasteurization processes as normally found in the beer and beverage industries, e) sufficient thermal resistance to withstand for short periods of time higher process temperatures normally encountered in the beverage/
  • the materials are well and evenly dispersed, and protected from moisture during blending, they are extruded in a 0.75 inch (1.90 cm) Killion extruder using the following extruder heat profile starting at the feed zone, feed hopper water cooled throat, zone 1 - 385°F (196.1°C), zone 2 - 380°F (193.3°C), zone 3 - 370°F (187.8°C), die 350°F (176.7°C) .
  • the viscosity of the PTMEG Decreases.
  • the melt temperature is similarly reduced compared to the original melt temperature of the PTMEG. If the extruded product is re-extruded, its melt temperature will be similarly lowered, depending, of course, upon similar percentages and shear involved.
  • Example 1 The procedure of Example 1 is repeated using a mixture consisting of 25 g of LambdaTM C200-65 and 75 g of a polyester-based polyurethane, ESTANE 58144. A similar reduction in viscosity and melt temperature of the extrudate is obtained.
  • Example 1 The procedure of Example 1 is repeated using a mixture consisting of 75 g of LambdaTM C301-35 and 25 g of a polyamide resin (Versamid 930, Henkel) . A similar reduction in viscosity and melt temperature of the extrudate is obtained.
  • An adhesive composition for use in hot melt adhesive applications is prepared from equal parts by weight of C301- 75 and an ethylene vinyl acetate resin, 34-2771 (National Starch and Chemical Company) .
  • the composition is melted in standard hot melt equipment at a temperature of 250°F to 300°F (121.1°C to 148.9°C).
  • the material is cooled to a lower temperature of approximately 200°F (93.3°C) but still maintains a viscosity sufficiently low to permit delivery to the coating/application heads.
  • the material can still be applied as a thin continuous film and during application to the heat shrink polypropylene film/heat sensitive film, the film does not change or distort as the adhesive composition is being applied.
  • the adhesive composition develops enough "green strength" to hold the label securely during the heat shrinking operations. That is, the adhesive is strong enough and heat resistant enough to go through the heat shrinking station in which a stream of high heat forced air is directed at the top and bottom of the container for a short period of time to shrink the label without degrading the film itself.
  • the container After a period of time of from a few hours to about 12 hours, and in some cases up to as much as 48 hours, the container is filled via the commercial pasteurization process.
  • the adhesive maintained its integrity and prevented the label from moving during the commercial pasteurization process, and meets the performance requirements of commercial pasteurization as found in the beer/beverage industry. In addition, once cooled, the adhesive performs well as a standard label 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)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention se rapporte à des compositions à multicomposants comprenant d'environ 5 % à environ 95 % d'un polyuréthanne obtenu en chauffant un mélange de réaction comprenant au moins un isocyanate ayant une fonctionnalité inférieure à environ 2, au moins un polyol à longue chaîne, au moins un allongeur de chaîne et au moins un plastifiant, ou un alliage polymère thermoplastique comprenant le produit de réaction d'au moins un polyisocyanate ayant une fonctionnalité de 2,2 ou moins, au moins un composé de polyhydroxyle pratiquement linéaire et/ou au moins un allongeur de chaîne, et au moins une résine époxy ou une combinaison de celle-ci, et au moins un autre matériau thermoplastique sélectionné dans le groupe composé de polyamide, polyuréthanne, acétate de vinyle d'éthyle, ester de polyuréthanne et chlorure de polyvinyle.
PCT/US1994/007228 1993-11-12 1994-06-21 Urethanne thermoplatique s'appliquant a une temperature et avec une viscosite polymere basses WO1995013307A1 (fr)

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AU73565/94A AU7356594A (en) 1993-11-12 1994-06-21 Polymer viscosity depressant/super cooling thermoplastic urethane

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US15096993A 1993-11-12 1993-11-12
US08/150,969 1993-11-12

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1273607A1 (fr) * 2000-04-04 2003-01-08 Battelle Memorial Institute Polyurethanne et fibre elastique en polyurethanne
WO2009019347A1 (fr) * 2007-08-07 2009-02-12 Setup Performance Procédé de modification des caractéristiques physiques, rhéologiques et thermomécaniques d'un polymère thermoplastique polaire
FR2988394A1 (fr) * 2012-03-26 2013-09-27 Rhodia Operations Agent fluidifiant et procede utilisant cet agent
CN104043570A (zh) * 2014-07-01 2014-09-17 国家电网公司 一种输电杆塔喷涂热熔高分子聚合物包覆保护方法
EP2944662A1 (fr) * 2014-05-16 2015-11-18 Henkel AG & Co. KGaA Adhésif thermofusible de polyuréthane thermoplastique
CN113272384A (zh) * 2019-01-09 2021-08-17 艾维恩股份有限公司 呈现出提高的抗污染性的热塑性聚氨酯配混物
EP3908631A4 (fr) * 2019-01-09 2022-09-14 Avient Corporation Composés de polyuréthane thermoplastique présentant une résistance améliorée aux taches
US11697733B2 (en) 2019-01-09 2023-07-11 Avient Corporation Thermoplastic polyurethane compounds exhibiting stain resistance and enhanced UV stability

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5248731A (en) * 1989-03-20 1993-09-28 Reeves Bros. Inc. Calenderable thermoplastic compositions containing millable linear polyurethanes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5248731A (en) * 1989-03-20 1993-09-28 Reeves Bros. Inc. Calenderable thermoplastic compositions containing millable linear polyurethanes

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1273607A1 (fr) * 2000-04-04 2003-01-08 Battelle Memorial Institute Polyurethanne et fibre elastique en polyurethanne
EP1273607A4 (fr) * 2000-04-04 2003-05-02 Battelle Memorial Institute Polyurethanne et fibre elastique en polyurethanne
WO2009019347A1 (fr) * 2007-08-07 2009-02-12 Setup Performance Procédé de modification des caractéristiques physiques, rhéologiques et thermomécaniques d'un polymère thermoplastique polaire
FR2919874A1 (fr) * 2007-08-07 2009-02-13 Setup Performance Soc Par Acti Procede de modification des caracteristiques physiques, rheologiques et thermomecaniques d'un polymere thermoplastique polaire
FR2988394A1 (fr) * 2012-03-26 2013-09-27 Rhodia Operations Agent fluidifiant et procede utilisant cet agent
WO2013144034A1 (fr) 2012-03-26 2013-10-03 Rhodia Operations Agent fluidifiant et procede utilisant cet agent
US9290657B2 (en) 2012-03-26 2016-03-22 Rhodia Operations Fluidizing agent and method using said agent
WO2015173338A1 (fr) * 2014-05-16 2015-11-19 Henkel Ag & Co. Kgaa Adhésif thermofusible à base de polyuréthane thermoplastique
EP2944662A1 (fr) * 2014-05-16 2015-11-18 Henkel AG & Co. KGaA Adhésif thermofusible de polyuréthane thermoplastique
CN106459723A (zh) * 2014-05-16 2017-02-22 汉高股份有限及两合公司 热塑性聚氨酯热熔性粘合剂
CN104043570A (zh) * 2014-07-01 2014-09-17 国家电网公司 一种输电杆塔喷涂热熔高分子聚合物包覆保护方法
CN113272384A (zh) * 2019-01-09 2021-08-17 艾维恩股份有限公司 呈现出提高的抗污染性的热塑性聚氨酯配混物
EP3908629A4 (fr) * 2019-01-09 2022-09-14 Avient Corporation Composés de polyurethane thermoplastique présentant une résistance améliorée aux taches
EP3908631A4 (fr) * 2019-01-09 2022-09-14 Avient Corporation Composés de polyuréthane thermoplastique présentant une résistance améliorée aux taches
US11697733B2 (en) 2019-01-09 2023-07-11 Avient Corporation Thermoplastic polyurethane compounds exhibiting stain resistance and enhanced UV stability
CN113272384B (zh) * 2019-01-09 2024-02-13 埃万特公司 呈现出提高的抗污染性的热塑性聚氨酯配混物

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