WO2010012400A2 - Adhésifs à dispersion de polyuréthanne cationique - Google Patents

Adhésifs à dispersion de polyuréthanne cationique Download PDF

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Publication number
WO2010012400A2
WO2010012400A2 PCT/EP2009/005268 EP2009005268W WO2010012400A2 WO 2010012400 A2 WO2010012400 A2 WO 2010012400A2 EP 2009005268 W EP2009005268 W EP 2009005268W WO 2010012400 A2 WO2010012400 A2 WO 2010012400A2
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WIPO (PCT)
Prior art keywords
sheet
adhesive composition
article
adhesive
temperature
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PCT/EP2009/005268
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German (de)
English (en)
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WO2010012400A3 (fr
Inventor
Jörg Büchner
Wolfgang Henning
Harald Kraus
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Bayer Materialscience Ag
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Publication of WO2010012400A2 publication Critical patent/WO2010012400A2/fr
Publication of WO2010012400A3 publication Critical patent/WO2010012400A3/fr

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    • 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
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
    • C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G2170/80—Compositions for aqueous 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
    • C08G2250/00—Compositions for preparing crystalline polymers

Definitions

  • the invention relates to an adhesive composition based on aqueous semicrystalline polyurethane or polyurea dispersions, which have a cationic hydrophilization, a sheet containing adhesive layers based on the adhesive composition and their use for the production of release paper-free labels.
  • Labels are coated on one side with a PSA (Pressure Sensitive Adhesive).
  • Pressure sensitive adhesives are by definition tacky at room temperature. They can be applied to the carrier film as an aqueous dispersion, as a solvent-containing preparation or as a hotmelt.
  • the labels are used for industrial applications as roll goods (large rolls). Because of the permanent stickiness of the adhesive layer, the roll goods must be protected against blocking by the insertion of a release paper (e.g., silicone paper) or release film.
  • a release paper or a release film causes both costs for the use of raw materials and additional costs for the disposal of the release paper or the release film.
  • US Pat. No. 5,354,588 describes a primer which improves the bonding of the pressure-sensitive adhesive to the carrier layer. In this way, when transferring the label material, the transfer of the pressure-sensitive adhesive to the adhesive-free side should be prevented.
  • the said PSAs are based on acrylate.
  • DE-A 197 24 648 discloses the application of the adhesive coating in a raster application in combination with an anti-adhesive coating which has a roughness of at least 1 ⁇ m. In this way, the easy rolling of the labels should be ensured without the use of a release paper. Screening can be done with dispersion adhesives, but preferably with hot melt adhesives, listing the typical formulations used with pressure sensitive adhesive applications with natural and synthetic rubbers as well as acrylates.
  • a release roll-free large roll label material is disclosed by using a release lacquer on the side opposite the adhesive layer side of the label structure. The use of the release coating prevents the blocking of the roll material.
  • the adhesives used are the acrylate pressure-sensitive adhesives described therein.
  • the US-A 2007/0054117 discloses heat-sealable adhesive papers, which are coated with heat-activatable dispersion polymers and inter alia for use "linerless label" are suitable.
  • polymers having a melting temperature> 220 0 F (104.4 0 C) and a glass transition temperature Tg> 50 0 F (+ 10 ° C.)
  • Tg glass transition temperature
  • Object of the present invention thus was to provide an adhesive composition that is applied as an adhesive layer on a substrate in the roll product under comparable pulls a release paper, even at high winding tensions and to 4O 0 C, does not lead to blocking of the label layers and the same time can be activated at temperatures below 90 0 C.
  • the present invention is an adhesive composition based on an aqueous, semicrystalline polyurethane or polyurea dispersion, which has a cationic hydrophilization and a melting temperature between 42 ° C and 80 0 C, preferably from 42 ° C to 60 0 C, especially preferably from 45 ° C to 52 ° C, a glass transition temperature between - 100 0 C and -1O 0 C, preferably from -60 0 C to -40 0 C, particularly preferably from -59 ° C to -45 ° C and a molecular weight M w from 20,000 to 80,000 g / mol, preferably from 25,000 to 60,000 g / mol, particularly preferably from 30,000 to 45,000 g / mol.
  • Polyurethane urea dispersions contain as structural components A) one or more semicrystalline, di- or higher-functional polyester polyols having a number-average molecular weight of from 400 to 5000 daltons, preferably from 1000 to 3000 daltons, more preferably from 1500 to 2500 daltons,
  • Suitable semicrystalline di- or higher-functional polyester polyols A) are based on linear dicarboxylic acids and / or derivatives thereof, such as anhydrides, esters or acid chlorides and aliphatic or cycloaliphatic, linear or branched polyols.
  • Suitable dicarboxylic acids are adipic acid, succinic acid, sebacic acid or dodecanedioic acid, adipic acid is preferred. These are used in amounts of at least 85 mol%, preferably from 90 to 100.mol%, based on the total amount of all carboxylic acids.
  • dicarboxylic acids examples include glutaric acid, azelaic acid, 1,4-, 1,3- or 1,2-cyclohexanedicarboxylic acid, terephthalic acid or isophthalic acid. These are used in amounts of up to a maximum of 15 mol%, preferably from 0 to 10 mol%, based on the total amount of all carboxylic acids.
  • Suitable polyol components for the semicrystalline polyesters are monoethylene glycol, 1,4-butanediol, 1,6-hexanediol or neopentyl glycol, but preferably 1,4-butanediol. These are used in amounts of at least 80 mol%, preferably from 90 to 100 mol%, based on the total amount of all polyols.
  • polystyrene resin examples include diethylene glycol, hydroxypivalic acid neopentyl glycol, cyclohexanedimethanol, pentanediol-1,5, pentanediol-1,2, nonanediol-1,9, trimethylolpropane, glycerol or pentaerythritol. These are used in amounts of not more than 20 mol%, preferably from 0 to 10 mol%, based on the total amount of all polyols.
  • polyesters A are also suitable. Preference is given to using polyester A) based on adipic acid and butanediol or adipic acid and hexanediol or adipic acid and a mixture of hexanediol and neopentyl glycol.
  • Suitable as synthesis component B) are di- or higher-functional polyol components having a number-average molecular weight of from 62 to 399 daltons, for example polyethers, polyesters, polycarbonates, polylactones or polyamides.
  • suitable components B) are the aliphatic or cycloaliphatic, linear or branched polyols mentioned under A).
  • Preferred components B) are monoethylene glycol, 1,4-butanediol or 1,6-hexanediol. Particularly preferred is 1,4-butanediol.
  • Potentially cationic monomers C) having tertiary amino groups are, for example, tris (hydroxyalkyl) -amines, N, N'-bis (hydroxyalkyl) -alkylamines, N-hydroxyalkyl-dialkylamines, tris
  • aminoalkyl (aminoalkyl) -amines, N, N'-bis (aminoalkyl) -alkylamines, N-aminoalkyl-dialkylamines, wherein the
  • Alkyl radicals and alkanediyl units of these tertiary amines independently from 2 to 6
  • polyethers having tertiary nitrogen atoms preferably having two terminal hydroxyl groups such as those described in U.S. Pat. by the alkoxylation of two amine-containing hydrogen atoms, e.g. Methylamine, aniline, or
  • N, N 'dimethylhydrazine are accessible in a conventional manner into consideration.
  • Preferred potentially cationic monomers C) are N, N'-bis (hydroxyalkyl) alkylamines, such as N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-methyldipropanolamine, N-ethyldipropanolamine, N-propyldipropanolamine, particularly preferably N-methyldiethanolamine ,
  • tertiary amines are converted into the corresponding ammonium salts either with acids, for example mineral acids such as phosphoric acid, sulfuric acid or hydrohalic acids or organic acids such as lactic acid or by reaction with suitable quaternizing agents such as C 1 -C 6 -alkyl halides, for example bromides or chlorides.
  • acids for example mineral acids such as phosphoric acid, sulfuric acid or hydrohalic acids or organic acids such as lactic acid
  • suitable quaternizing agents such as C 1 -C 6 -alkyl halides, for example bromides or chlorides.
  • acids particularly preferably phosphoric acid or lactic acid, very particularly preferably phosphoric acid.
  • any organic compounds are suitable which have at least two free isocyanate groups per molecule.
  • Diisocyanates Y (NCO) 2 are preferably used, where Y is a divalent aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a divalent cycloaliphatic hydrocarbon radical having 6 to 15 carbon atoms, a bivalent aromatic hydrocarbon radical having 6 to 15 carbon atoms or a divalent araliphatic hydrocarbon radical containing from 7 to 15 carbon atoms atoms.
  • diisocyanates examples include tetramethylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanato-cyclohexane, 1-isocyanato-S ⁇ S-trimethyl-S-isocyanatomethyl cyclohexane, 4,4'-diisocyanato -dicyclohexylmethane, 4,4'-diisocyanato-dicyclohexylpropane- (2,2), 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanato-diphenylmethane , 2,2'- and 2,4'-diisocyanatodiphenylmethane, tetramethylxyl
  • polyfunctional polyisocyanates known per se in polyurethane chemistry or else modified polyisocyanates known per se, for example carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and / or biuret groups.
  • Preferred diisocyanates D) are aliphatic and araliphatic diisocyanates such as hexamethylene diisocyanate, 1,4-diisocyanato-cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methylcyclohexane, 4,4'-diisocyanato-dicyclohexylmethane or 4,4'-diisocyanato-dicyclohexylpropane- (2,2) as well as consisting of these compounds mixtures.
  • Particularly preferred structural components D) are mixtures of hexamethylene diisocyanate and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane.
  • structural component E are primary and / or secondary monoamino compounds and / or primary and / or secondary diamino compounds in question,
  • E examples are aliphatic and / or alicyclic primary and / or secondary monoamines such as ethylamine, diethylamine, the isomeric propyl and butylamines, higher linear aliphatic monoamines and cycloaliphatic monoamines such as cyclohexylamine.
  • Further examples are amino alcohols, i. Compounds which contain amino and hydroxyl groups in a molecule, such as, for example, Ethanolamine, N-methylethanolamine, diethanolamine and 2-propanolamine. Of course, mixtures of several monoamino compounds can be used.
  • Preferred monoamino compounds are diethylamine, ethanolamine or diethanolamine. Particularly preferred is diethanolamine.
  • diamino compounds examples include 1, 2-ethanediamine, 1, 6-hexamethylenediamine, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane (isophoronediamine), piperazine 1,4-diaminocyclohexane or bis (4-aminocyclohexyl )-methane.
  • Adipinsaeuredihydrazid, hydrazine or Hydrazine hydrate in question.
  • Polyamines such as diethylenetriamine can also be used instead of a diamino compound.
  • amino alcohols i. Compounds containing amino and hydroxyl groups in a molecule, e.g. 1, 3-diamino-2-propanol, N- (2-hydroxyethyl) ethylenediamine or N, N-bis (2-hydroxyethyl) ethylenediamine.
  • Preferred diamino components are 1,2-ethanediamine, 1,6-hexamethylenediamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane (isophoronediamine), piperazine, N- (2-hydroxyethyl) ethylenediamine or N, N-bis (2-hydroxyethyl) ethylenediamine.
  • diaminocomponents are 1,2-ethanediamine or N- (2-hydroxyethyl) ethylenediamine, very particularly preferred is N- (2-hydroxyethyl) ethylenediamine.
  • component E) are mixtures of monoamino alcohols and diamino alcohols, very particularly preferably a mixture of diethanolamine and N- (2-hydroxyethyl) ethylenediamine.
  • the content of cationic groups is between 10 and 600 mmol per kg of solid, preferably between 100 and 400 mmol, more preferably between 150 and 300 mmol per kg of solid.
  • the aqueous polyurethane-polyurethaneurea dispersions are prepared by reacting in a first step the components A), B), C) and D), if appropriate in the presence of a water-miscible but isocyanate-inert solvent, in a Rector in whole or in part initially charged and heated to temperatures in the range of 50 to 120 0 C, then optionally not added at the beginning of the reaction components A), B), C) or D) are added, in a second step, the chain extension with the mixture E.
  • aqueous polyurethane-polyurea dispersants can be carried out in one or more stages in homogeneous or in multistage reaction, in some cases in disperse phase. After complete or partial polyaddition, a dispersing, Emulsifying or dissolving step. This is followed, if appropriate, by a further polyaddition or modification in disperse phase.
  • a dispersing, Emulsifying or dissolving step is followed, if appropriate, by a further polyaddition or modification in disperse phase.
  • the acetone method is used for the preparation of all known from the prior art methods.
  • the acetone method is used for the preparation of all known from the prior art methods.
  • Suitable solvents are e.g. Acetone, butanone, tetrahydrofuran, dioxane, acetonitrile, dipropylenglykoldimethylether and l-methyl-2-pyrrolidone, preferably are butanone or acetone, particularly preferred is acetone.
  • the amounts used of the individual components A) to D) are such that an isocyanate index of 1.05 to 2.5, preferably from 1.1 to 1.5 results.
  • the isocyanate content of the prepolymers is between 0.3 and 3.0%, preferably between 0.7 and 2.5%, particularly preferably between 1.3 and 1.9%.
  • component A there are 50 to 96 parts by weight, preferably 75 to 90 parts by weight of component A), 0 to 10 parts by wt., Preferably 0 to 5 parts by weight of component B), 0.1 to 10 wt Parts, preferably 0.5 to 5 parts by weight, more preferably 0.8 to 3.5 parts by weight of component C) and 3 to 30 parts by weight, preferably 5 to 20 parts by weight of Component D) is used with the requirement that the sum of the components yields 100.
  • component B) may be included in the composition in amounts of 0.1 to 4 parts by weight.
  • the reaction of components A), B) and C) with D) takes place, based on the total amount of isocyanate-reactive groups, partially or completely, but preferably completely.
  • the degree of conversion is usually monitored by monitoring the NCO content of the reaction mixture.
  • both spectroscopic measurements e.g. Infrared or near-infrared spectra, determinations of the refractive index as well as chemical analyzes, such as titrations of samples taken.
  • the chain extension with component E) can be carried out before dispersing, during dispersion or after dispersion.
  • the chain extension preferably takes place before the dispersion.
  • the chain extension is carried out at temperatures of 15 to 60 ° C., preferably from 25 to 55 ° C., more preferably from 40 to 50 ° C.
  • chain extension in the context of the present invention also encompasses the reactions of the monoamino compounds which, as a result of their monofunctionality, function as chain terminators and thus do not lead to an increase in molecular weight but to a decrease in molecular weight. This is especially true for the amino alcohols, since their hydroxyl groups in the selected temperature range not or only to a very small extent react with the isocyanate groups.
  • Component E) can be added to the reaction mixture with organic solvents and / or diluted with water.
  • the addition of several aminic compounds E) can be carried out successively in any order or simultaneously by adding a mixture.
  • the conversion of the tertiary amino groups into cationic groups can take place before, during or after chain extension, preferably after chain extension. In addition, it can be done before or during the dispersion. It preferably takes place during the dispersion, wherein the acid is added to the dispersing water.
  • the prepolymer optionally under high shear, e.g. vigorous stirring, either added to the dispersing water or, conversely, the dispersing water is stirred into the prepolymer. Then, if not done in the homogeneous phase, the chain extension can then take place.
  • high shear e.g. vigorous stirring
  • the optionally used organic solvent for example acetone, is distilled off.
  • the dispersions have a solids content of 10 to 70 wt .-%, preferably 25 to 60% by weight and particularly preferably 35 to 55 wt .-%.
  • the adhesive compositions according to the invention can be used alone or with the binders, excipients and tension agents known in coating and adhesive technology, in particular emulsifiers or light stabilizers such as UV absorbers or sterically hindered amines (HALS), furthermore antioxidants, fillers or auxiliary agents, eg anti-settling agents - Ten l, defoaming and / or wetting agents, leveling agents, reactive thinners, plasticizers, catalysts, auxiliary solvents and / or thickeners and additives, such as pigments, dyes or matting agents are used. Also tackifying resins (“tackifiers”) can be added.
  • emulsifiers or light stabilizers such as UV absorbers or sterically hindered amines (HALS), furthermore antioxidants, fillers or auxiliary agents, eg anti-settling agents - Ten l, defoaming and / or wetting agents, leveling agents, reactive thinners, plasticizers, catalysts, auxiliary solvents and
  • Tackifying resins are understood as meaning all natural or synthetic resins or polymers which, as additives, are the tack, that is to say the property, after a short, light pressure to stick firmly on surfaces, increase. To achieve this, adhesive resins must, inter alia, have sufficient compatibility with the polymers. Tackifiers themselves need no tack. Widely used tackifiers include terpene oligomers, aliphatic petrochemical resins or rosins.
  • the additives may be added to the adhesive composition of the invention immediately prior to processing. However, it is also possible to add at least some of the additives before, during or after the dispersion of the binder.
  • the adhesive compositions according to the invention comprising the aqueous semicrystalline polyurethane or polyurea dispersions are suitable for bonding any desired substrates, such as e.g. Paper, cardboard, wood, textiles, metal, leather, glass or mineral materials.
  • the adhesive compositions of the invention are useful for bonding gum materials such as e.g. Natural and synthetic rubbers, various plastics such as polyurethanes, polyvinyl acetate or polyvinyl chloride.
  • the adhesive compositions of the present invention have after thermal activation at temperatures greater than the melting temperature of a long tack, which is particularly advantageous for use as a "linerless label adhesive layer". Furthermore show the adhesive layers produced from the inventive adhesive compositions to 40 0 C, even at high winding Press In this way, release paper or release film-free labels, in particular in the form of large-size rolls for industrial applications, are possible Moreover, the adhesive compositions according to the invention exhibit particularly high adhesion values and the tack is largely independent of the layer thickness of the adhesive layer Therefore, the adhesive compositions of the present invention are preferably used for the production of linerless labeis.
  • the adhesive layer containing the adhesive composition according to the invention is block-free at temperatures ⁇ 40 ° C.
  • a polymer is block-free if it does not flow onto a substrate surface under pressure and thus can not wet it. Block freedom can be demonstrated by determining the tack. In the case of a block-free polymer layer, the tack is ⁇ 0.11 N / mm 2 .
  • fabrics comprising a thermally activated adhesive layer and a substrate, wherein the adhesive layer contains the adhesive composition according to the invention.
  • Suitable substrates are paper or plastic films, such as polyester, polypropylene, polyethylene, polyacetate, polylactide or cellophane film. In this case, the substrate may be printed on one side or on both sides.
  • the fabrics are labels, more preferably labels without release paper or liner ("linerless label").
  • the present invention also provides a process for the production of the sheetlike structures according to the invention, wherein the adhesive layer is applied to the substrate in a layer thickness of 10 to 50 ⁇ m, preferably of 20 to 30 ⁇ m.
  • the adhesive application can be done, for example, by spraying, with smooth rollers, gravure rollers, anilox rollers, in screen printing and rotary screen printing and doctor blade applicators chamber doctor blade or rotary blade.
  • subject matter is a method for applying the fabric of the invention to an article, wherein the fabric is first heated to a temperature> 40 0 C and then applied to the article.
  • the article preferably its surface, is first heated to a temperature> 40 0 C and then the fabric is applied.
  • the fabric and the article are heated separately from each other first to a temperature> 40 0 C and then the fabric is applied to the article.
  • These items may be, for example, packaging containers such as cartons, cans, bottles or foil bags.
  • Preferred articles are bottles or foil bags, particularly preferred are glass bottles.
  • the dispersions were applied to aluminum plates with a 100 ⁇ m doctor blade.
  • the solids content of the dispersions was previously adjusted with deionized water in such a way that after drying the desired layer thickness of the polymer films was established (assumption: density of the dispersions and of the polymers Ig / cm 3 ).
  • the dispersion layers were dried for 24 hours under standard conditions (23 ° C./50% rh).
  • Tack measurements were taken with the Texture Analyzer from Stable Micro Systems Ltd., Surrey UK.
  • the V4A stamp of the Texture Analyzer has a diameter of 5 mm.
  • the coated with the polymers aluminum plates were, first 5 min. heated to 70 ° C in a tempered laboratory drying oven. After removal from the
  • Drying cabinets cool the polymer layers to room temperature.
  • the first Tack measurements were made one minute after removal from the drying cabinet with the measuring device of the
  • Texture analyzer was tempered to 23 0 C. Further tack measurements were carried out at intervals of one minute each. The measurements were carried out until the tack value dropped to ⁇ 0, ln / mm 2 .
  • the Texture Analyzer's V4A stamp with a weight of 200 g (for the V4A stamp corresponds to a pressure of 1 bar) was pressed onto the polymer foam for 1 sec. Thereafter, the V4A stamp was punched at a rate of 0.1 mm / sec. subtracted at right angles from the polymer layer and the max. Force [N / mm 2 ] registered for the separation process.
  • Weight of 4000g (for the V4A stamp corresponds to a pressure of 20 bar) pressed over 60 seconds on the polymer shells. After that, the stamp became the speed 0, lmm / sec. deducted at right angles. The polymer is considered block-free if the max. Tack value ⁇ 0, lN / mm 2 .
  • Polyester II polyester diol from 1,6-hexanediol, neopentyl glycol and adipic acid
  • Desmodur ® H hexamethylene-1, 6 (Bayer MaterialScience AG, Leverkusen / D)
  • Desmodur ® I isophorone diisocyanate (Bayer MaterialScience AG, Leverkusen / D)
  • Example 1 (according to the invention): cationic polyester-polyurethane dispersion
  • a mixture of 450 g of polyester I and 42.5 g of polyester II are dehydrated for 1 hour at 110 0 C and 15 mbar.
  • At 60 0 C 15.49 g of N-methyldiethanolamine, 53.76 g of Desmodur ® H and then 35.52 g of Desmodur ® I are added.
  • the mixture is stirred at 80 0 C until a constant isocyanate content of 1.56% is reached.
  • the reaction mixture is dissolved in 896 g of acetone and cooled to 50 0 C.
  • the mixture is dispersed by adding a mixture of 14.3 g of 85% phosphoric acid and 894 g of water within 20 minutes. After distillative removal of the acetone, a solvent-free, aqueous, cationically hydrophilicized polyurethane-polyurea dispersion having a solids content of 40.2% by weight and an average particle size of the disperse phase, determined by laser correlation, of 193 nm is obtained.
  • Example 2 (according to the invention): cationic polyester-polyurethane dispersion
  • a mixture of 450 g of polyester I and 42.5 g of polyester II are dehydrated for 1 hour at 110 0 C and 15 mbar.
  • At 60 0 C 15.49 g of N-methyldiethanolamine, 53.76 g of Desmodur ® H and then 35.52 g of Desmodur ® I are added.
  • the mixture is stirred at 80 0 C until a constant isocyanate content of 1.58% is reached.
  • the reaction mixture is dissolved in 896 g of acetone while cooled to 50 ° C.
  • the mixture is dispersed by adding a mixture of 14.3 g of 85% phosphoric acid and 889 g of water within 20 minutes. After distillative removal of the acetone, a solvent-free, aqueous, cationically hydrophilicized polyurethane-polyurea dispersion having a solids content of 40.3% by weight and an average particle size of the disperse phase, determined by laser correlation, of 180 nm is obtained.
  • Example 3 (comparative example): anionic dispersion Dispercoll U 56 ® (Bayer MaterialScience AG, Leverkusen / D):
  • Example 4 Dispercoll U XP 2682 anionic dispersion (Bayer MaterialScience AG, Leverkusen / D):
  • Comparative Examples 3 and 4 show a strong dependence of the tack values on the layer thickness. In addition, these samples also very quickly lose their tack (stickiness).
  • tack values of Inventive Examples 1 and 2 are largely dependent on the layer thickness. These polymers retain their tack over a much longer period of time. Seven minutes after removal from the drying cabinet (70 ° C.), the tack of these samples is still> 0.1 N / mm 2 .
  • the polymer layers of the inventive examples have at 40 0 C and a pressure of 20 bar no tack (stickiness).
  • the polymer layers are thus "free from blocking.”
  • the polymers according to the invention will not lead to an adhesion of the winding layers.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une composition d'adhésif à base de dispersions aqueuses semi-cristallines de polyuréthanne ou de polyurée qui présentent une hydrophilisation cationique, un matériau plan comportant des couches d'adhésif à base de ladite composition d'adhésif, et l'utilisation de ladite composition pour fabriquer des étiquettes exemptes de papier de séparation.
PCT/EP2009/005268 2008-07-29 2009-07-21 Adhésifs à dispersion de polyuréthanne cationique WO2010012400A2 (fr)

Applications Claiming Priority (2)

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DE102008035207.1 2008-07-29
DE200810035207 DE102008035207A1 (de) 2008-07-29 2008-07-29 Kationische Polyurethan-Dispersionsklebstoffe

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WO2010012400A2 true WO2010012400A2 (fr) 2010-02-04
WO2010012400A3 WO2010012400A3 (fr) 2010-03-25

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TW (1) TW201016814A (fr)
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DE102013113134A1 (de) 2013-11-27 2015-05-28 Synthopol Chemie Dr.Rer.Pol. Koch Gmbh & Co Kg Wässrige, kationisch stabilisierte Polyurethandispersionen, ihre Herstellung und Verwendung in Beschichtungsmitteln
CN107955126A (zh) * 2017-12-01 2018-04-24 万华化学（宁波）有限公司 一种聚氨酯-聚脲多元醇的水分散体及其制备方法
WO2024020779A1 (fr) * 2022-07-26 2024-02-01 万华化学集团股份有限公司 Dispersion aqueuse de polyuréthane-polyurée, son procédé de préparation et utilisation associée

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CN111320743B (zh) * 2020-03-26 2021-04-27 中国科学院长春应用化学研究所 一种高固体含量二氧化碳基阳离子水性聚氨酯及其制备方法

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US3686108A (en) * 1970-04-22 1972-08-22 Bayer Ag Light fast quaternized or amine salt polyurethanes from 2-alkyl - 2 - dialkylaminomethyl-1,3-propane diols
US4861826A (en) * 1986-12-20 1989-08-29 Basf Aktiengesellschaft Aqueous polyurethane adhesive dispersions
US5561187A (en) * 1991-11-01 1996-10-01 Witco Corporation Cationic polyurethane compositions, quaternary ammonium salts and methods for their preparation
WO2000052080A1 (fr) * 1999-03-02 2000-09-08 Avery Dennison Corporation Revetements anti-adhesifs imprimables et constructions de timbres
WO2006110265A2 (fr) * 2005-04-08 2006-10-19 Cytec Technology Corp. Procede de preparation de dispersions de polyurethane
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GB1214773A (en) * 1968-05-03 1970-12-02 Bayer Ag Process for treating sheet structures with aqueous polyurethane dispersions and colloidal solutions
US3686108A (en) * 1970-04-22 1972-08-22 Bayer Ag Light fast quaternized or amine salt polyurethanes from 2-alkyl - 2 - dialkylaminomethyl-1,3-propane diols
US4861826A (en) * 1986-12-20 1989-08-29 Basf Aktiengesellschaft Aqueous polyurethane adhesive dispersions
US5561187A (en) * 1991-11-01 1996-10-01 Witco Corporation Cationic polyurethane compositions, quaternary ammonium salts and methods for their preparation
WO2000052080A1 (fr) * 1999-03-02 2000-09-08 Avery Dennison Corporation Revetements anti-adhesifs imprimables et constructions de timbres
EP1798248A1 (fr) * 2004-10-05 2007-06-20 Adeka Corporation Preparation de polyurethane hydrodispersee
WO2006110265A2 (fr) * 2005-04-08 2006-10-19 Cytec Technology Corp. Procede de preparation de dispersions de polyurethane

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013113134A1 (de) 2013-11-27 2015-05-28 Synthopol Chemie Dr.Rer.Pol. Koch Gmbh & Co Kg Wässrige, kationisch stabilisierte Polyurethandispersionen, ihre Herstellung und Verwendung in Beschichtungsmitteln
EP2878610A1 (fr) 2013-11-27 2015-06-03 SYNTHOPOL CHEMIE Dr. rer. pol. Koch GmbH & CO. KG Dispersions de polyuréthane aqueuses, cationiques et stabilisées, leur fabrication et leur utilisation dans des produits de revêtement
CN107955126A (zh) * 2017-12-01 2018-04-24 万华化学（宁波）有限公司 一种聚氨酯-聚脲多元醇的水分散体及其制备方法
WO2024020779A1 (fr) * 2022-07-26 2024-02-01 万华化学集团股份有限公司 Dispersion aqueuse de polyuréthane-polyurée, son procédé de préparation et utilisation associée

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WO2010012400A3 (fr) 2010-03-25
TW201016814A (en) 2010-05-01

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