EP4077448A1 - Composé adhésif à base de polyéther-polyuréthane modifié, appliqué par couchage, à stabilité dimensionnelle - Google Patents

Composé adhésif à base de polyéther-polyuréthane modifié, appliqué par couchage, à stabilité dimensionnelle

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Publication number
EP4077448A1
EP4077448A1 EP20816530.8A EP20816530A EP4077448A1 EP 4077448 A1 EP4077448 A1 EP 4077448A1 EP 20816530 A EP20816530 A EP 20816530A EP 4077448 A1 EP4077448 A1 EP 4077448A1
Authority
EP
European Patent Office
Prior art keywords
weight
adhesive
carbon atoms
polyurethanes
polyether
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.)
Pending
Application number
EP20816530.8A
Other languages
German (de)
English (en)
Inventor
Adrian BRANDT
Horst Beck
Alexander Kux
Kerstin Schroeder
Christoph Lohr
Andreas Brenger
Nils Hellwig
Mathias Schriefers
Anna KAULISCH
Jennifer Schmidt
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP4077448A1 publication Critical patent/EP4077448A1/fr
Pending 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
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C09J175/08—Polyurethanes from polyethers
    • 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
    • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/358—Applications of adhesives in processes or use of adhesives in the form of films or foils for garments and textiles

Definitions

  • the present invention relates to a dimensionally stable adhesive which is largely water- and solvent-free and can be applied as a thin adhesive film by rubbing in contact with the substrate to be bonded, which is particularly suitable for bonding materials obtained from vegetable fibers.
  • the organic constituent of the adhesive of the invention consists essentially of a mixture of polyether polyurethanes which are end-group-capped with at least two monohydric aliphatic alcohols of different chain lengths.
  • the invention also relates to a method for applying a tacky film to a sheet-like substrate, preferably to paper, by rubbing off the adhesive at the point of contact with the substrate.
  • WO 99/51699 A1 describes adhesive sticks that can be rubbed off gently but are dimensionally stable, consisting of an aqueous preparation of starch ethers and sucrose as the adhesive component and a soap gel as the structural substance that gives the shape and, if desired, additional auxiliaries.
  • Such adhesives set after a thin film has been rubbed off solely through the loss of water and thus in a purely physical manner.
  • the packaging means is often also an applicator at the same time, which, as a rigid structure into which the adhesive is filled, is also form-stabilizing, so that there is also greater latitude in the formulation of the dimensionally stable adhesive.
  • DE 10047069 A1 describes such an applicator for a water-based, dimensionally stable glue stick.
  • water-free, dimensionally stable adhesives are also known which are likewise formulated to be rubable.
  • WO 96/37566 A1 describes partially crystalline, dimensionally stable adhesives based on polyether polyurethanes whose partially crystalline structure is broken up by the heat released during friction on a substrate surface, so that a thin adhesive film can be applied which, after a short time, forms partially crystalline areas again in this way sets and is able to glue the substrate.
  • Adhesives of this type are added there to improve the profile of properties, which additives modify the crystallinity or increase the tack or represent pigments, fillers, plasticizers, dyes, antioxidants and preservatives.
  • the adhesives disclosed in WO are already suitable for being marketed largely without packaging and being applied manually to substrates, in particular paper, without a special applicator.
  • Such a largely water- and solvent-free, dimensionally stable adhesive must, however, meet a complex requirement profile that includes both application-specific, consumer-specific and environmental hygiene aspects.
  • the profile of properties of dimensionally stable adhesives which can be activated by friction must be further improved in order to be able to establish packaging-free sales units in the consumer market.
  • the adhesive is suitable for bonding materials obtained from vegetable fibers.
  • This profile of properties is also intended to be retained even after the adhesive is stored or stored in the usual commercial and typical manner.
  • a dimensionally stable adhesive which can be rubbed off by hand on the substrate directly without an applicator, has no stickiness, the skin is not soiled with adhesive and skin compatibility is guaranteed.
  • the consumer is also expected to use such an adhesive in the form of a pen like a crayon guide the substrate and a continuous adhesive film can be applied.
  • the abrasion of the adhesive on a flat substrate must be possible with little effort, so that flexible thin substrates such as paper are not curled or torn when the adhesive is applied.
  • the present invention thus sets itself the task of providing a dimensionally stable, abradable adhesive which can be formulated water- and solvent-free and skin-friendly and yet can be easily applied without a separate applicator and for this purpose in particular has a low abrasion resistance
  • the adhesive at 30.degree should not be permanently sticky and ideally also be translucent. Temperature stability of up to 70 ° C is also required for storage and transport.
  • the adhesive should have a high bond strength for materials obtained from vegetable fibers, in particular paper and cardboard.
  • an adhesive film rubbed off by the adhesive should generate sufficient initial adhesion so that the user does not have to press the substrates to be bonded until they set in order to achieve adequate bonding.
  • the present invention accordingly relates to a dimensionally stable adhesive, the organic component of which consists essentially of a mixture of polyether polyurethanes which are end-capped with two different monohydric aliphatic alcohols, the at least two different monohydric aliphatic alcohols being selected on the one hand from those having at least 4, but not more than 8 carbon atoms and on the other hand are selected from those with at least 16 but less than 22 carbon atoms.
  • the organic constituent of the adhesive of the invention particularly preferably consists essentially of a mixture of polyether polyurethanes, each of which is end-group-capped with the two different monohydric aliphatic alcohols mentioned above.
  • an organic compound or a constituent of an organic compound is considered to be aliphatic if it or the constituent, in addition to oxygen atoms, is composed exclusively of carbon and hydrogen atoms.
  • the mixture of polyether polyurethanes which is the essential constituent of the adhesive, is end-capped with primary monohydric aliphatic alcohols, which in turn are preferably linear, that is to say have neither tertiary nor quaternary carbon atoms.
  • a carbon atom is quaternary when it is covalently bonded to four other carbon atoms, while a tertiary carbon atom is covalently bonded to three other carbon atoms.
  • polyether polyurethanes are addition products of polyfunctional isocyanates with polyether polyols, the molar ratio of isocyanate to hydroxyl groups in the polyether polyols being greater than 1.0, preferably greater than 2.0, particularly preferably greater than 2.5, but preferably less than 4, 0, particularly preferably less than 3.5, and the addition product is end-capped and thus has no free isocyanate groups.
  • a polyether polyurethane does not contain any free isocyanate groups if it contains less than 0.1% NCO, based on the total amount of polyether polyurethanes.
  • the polyether polyols which form the basis of the polyether polyurethanes are selected from those whose ether functions via aliphatic divalent radicals, which in turn are preferably linear and unbranched, i.e. have neither tertiary nor quaternary carbon atoms, are bridged with one another, the divalent radicals in turn preferably having at least 4 carbon atoms, but preferably not more than 8 carbon atoms, particularly preferably not more than 6 carbon atoms in the main chain, and very particularly preferably 4 carbon atoms in the main chain.
  • Such adhesives are distinguished by very good temperature stability and, at the same time, good abrasion properties.
  • the polyether polyols which form the basis of the mixture of polyether polyurethanes of the adhesive according to the invention, have a hydroxyl number of less than 200 mg KOH / g, particularly preferably less than 120 mg KOH / g, but preferably at least 30 mg KOH / g, particularly preferably at least 40 mg KOH / g, based in each case on the totality of the polyether polyols which constitute the basis for the mixture of the polyether polyurethanes.
  • the hydroxyl number is a measure of the number of free hydroxyl groups in the respectively defined reference amount, for example per gram of the polyether polyols which form the mixture of polyether polyurethanes, which can be determined experimentally by potentiometric titration.
  • a weighed sample of the reference amount is heated in a reaction solution of 0.1 mol / l phthalic anhydride in pyridine at 130 ° C for 45 minutes and first with 1.5 times the volume of the reaction solution of pyridine and then with the 1.5- times the volume of the reaction solution of deionized water (K ⁇ 1 pScnr 1 ).
  • the amount of phthalic acid released is titrated in this mixture using 1 M sodium hydroxide solution.
  • the potentiometric measurement is carried out with a combination electrode (LL-Solvotrode® from Metrohm; reference electrolyte: 0.4 mol / l Tetraethylammonium bromide in ethylene glycol).
  • the hydroxyl number corresponds to the added amount of NaOH per gram of the reference amount at the turning point of the potentiometric titration curve.
  • the molar ratio of the two different monohydric aliphatic alcohols to one another defined as the molar amount of aliphatic alcohols with at least 4, but not more than 8 Carbon atoms, for the molar amount of aliphatic alcohols having at least 16 but less than 22 carbon atoms, in the range from 1: 2 to 3: 1, particularly preferably in the range from 1: 1 to 5: 2.
  • the mixture of polyether polyurethanes is preferably obtained by adding at least trifunctional, particularly preferably aliphatic, isocyanates, which are very particularly preferably selected from trimers of hexamethylene diisocyanate and / or pentamethylene diisocyanate, to polyether polyols.
  • isocyanates which are very particularly preferably selected from trimers of hexamethylene diisocyanate and / or pentamethylene diisocyanate
  • the free isocyanate groups formed in the addition reaction are reacted with the two monohydric aliphatic alcohols (hereinafter "end group closure"), the two monohydric aliphatic alcohols being selected on the one hand from those with at least 4 but not more than 8 carbon atoms and on the other hand are selected from those having at least 16 but fewer than 22 carbon atoms.
  • polyether polyurethanes with a dynamic Brookfield viscosity (spindle 27) at 80 ° C. of at least 2,000 mPas, particularly preferably at least 3,000 mPas, particularly preferably at least 5,000 mPas, but preferably less than 140,000 mPas, particularly preferably less than 60,000 mPas used.
  • Polyether polyurethanes with a dynamic viscosity in the lower preferred range are usually achieved by the end group closure being carried out predominantly with a long-chain monohydric aliphatic alcohol with a higher number of carbon atoms or at least partially by adding divalent isocyanates to the semicrystalline polyether polyols.
  • the mixture of polyether polyurethanes of the adhesive of the invention preferably has a number average molar mass of less than 6,000 g / mol, particularly preferably less than 5,000 g / mol, but preferably at least 1000 g / mol, particularly preferably at least 2000 g / mol, where the polydispersity is preferably greater than 4.0, but preferably less than 20.0, particularly preferably less than 15.0.
  • polyether polyurethanes are obtainable which give the adhesives of the invention, more than 40% by weight of such polyether polyurethanes, easy rubability and good tack with adequate temperature stability.
  • the number average molar mass can be determined on the basis of a sample of the reaction mixture by means of gel permeation chromatography after calibration against polystyrene standards.
  • chromatography is carried out at a column oven temperature of 40 ° C by elution with tetrahydrofuran, the distribution curve being recorded by means of a concentration-dependent RI detector, which continuously determines the refractive index in the eluate at a temperature of 40 ° C as well.
  • the polyether polyurethane constituent of the adhesive consists essentially of the mixture of polyether polyurethanes described above.
  • adhesives according to the invention are preferred in which the proportion of the mixture of polyether-polyurethanes which are end-group-capped with the two different monohydric aliphatic alcohols, based on the total of polyether-polyurethanes, is at least 80% by weight, preferably at least 90% by weight, particularly preferably at least Is 95% by weight.
  • the organic constituent of the adhesive of the invention in turn consists essentially of the mixture of polyether-polyurethanes if their proportion is greater than 40% by weight, based on the organic constituent of the adhesive.
  • the adhesives usually show particularly good temperature stability with good abrasion behavior at the same time when the proportion of polyether polyurethanes, as described above, based on the organic constituent of the adhesive, is greater than 50% by weight, better than 70% by weight or even better than 80% by weight is, so that such adhesives are preferred according to the invention.
  • Higher proportions of the mixture of polyether polyurethanes are also advantageous, in particular, for the translucency of the adhesive of the invention, which consumers find particularly attractive.
  • polyester polyurethanes can be added, which are preferably based at least partially on partially crystalline polyester polyols, which in turn are obtainable by polycondensation of a reaction mixture comprising one or more dicarboxylic acids selected from terminal dicarboxylic acids that are both saturated, linear and aliphatic, with an even number of at least 8 methylene groups (hereinafter “component A”) and one or more diols selected from terminal diols that are both saturated, linear and aliphatic and contain at least one ether function (hereinafter “component B" ).
  • component A dicarboxylic acids selected from terminal dicarboxylic acids that are both saturated, linear and aliphatic
  • component B methylene groups
  • a dicarboxylic acid or a diol is considered to be aliphatic if, in addition to oxygen atoms, it is composed exclusively of carbon and hydrogen atoms, the term “dicarboxylic acid” also including the corresponding single or double methyl and / or ethyl esters as well as the corresponding single or double acid chlorides. In this context, it also applies that, in the case of a terminal dicarboxylic acid or a terminal diol, both carboxyl or hydroxyl groups are terminal.
  • polyester polyurethanes optionally present according to the invention based on partially crystalline polyester polypoles have a ring-sphere measured below their softening point according to DIN EN 1238: 2011 crystalline phases which can be detected by means of differential scanning calorimetry (DSC) at a heating rate of no more than 10 Kelvin per minute as an endothermic melting peak before the softening point is reached.
  • DSC differential scanning calorimetry
  • polyester polyurethanes based on partially crystalline polyester polyols that recrystallize when melting are formulated, which are obtainable by polycondensation of a reaction mixture comprising one or more dicarboxylic acids and one or more diols, where a) at least 50 mol%, preferably at least 60 mol.
  • component A terminal dicarboxylic acids with an even number of at least 8 methylene groups which are both saturated, linear and aliphatic
  • component B at least 40 mol%, preferably at least 60 mol%, particularly preferably at least 70 mol% of the diols are selected from terminal diols which are both saturated, linear and aliphatic and have at least one ether function
  • Such partially crystalline polyester polyols which recrystallize during melting, are distinguished by the fact that exothermic recrystallization occurs during the endothermic melting process before the softening point is reached, ie the transition to the liquid phase, so that differential scanning calorimetry (DSC) at a heating rate of no more an exothermic crystallization peak superimposed on the endothermic melting peak before the softening point is reached can also be detected as 10 Kelvin per minute.
  • DSC differential scanning calorimetry
  • Preferred representatives of the dicarboxylic acids according to component A are therefore 1,10-decamethylene dicarboxylic acid, 1,12-dodecamethylene dicarboxylic acid, 1,14-tetradecamethylene dicarboxylic acid and 1,16-hexadecamethylene dicarboxylic acid.
  • polyester-polyurethanes are additionally present which are based on polyester polyols which are obtained from the polycondensation of aromatic dicarboxylic acids or unsaturated dicarboxylic acids having fewer than 9 carbon atoms with aliphatic diols, which preferably have at least one ether function, but have neither a tertiary nor a quaternary carbon atom emerge.
  • Aromatic dicarboxylic acids are in particular isophthalic acid, terephthalic acid, orthophthalic acid, furandicarboxylic acid, in particular 2,5-furandicarboxylic acid, and itaconic acid, fumaric acid and / or maleic acid, which are also part of the polyesterpolyurethane as unsaturated dicarboxylic acids with less than 9 carbon atoms can be contained in the adhesive.
  • polyester-polyurethanes which have proven to be ideal with regard to the recrystallization behavior of the polyester-polyurethanes optionally contained in the adhesive according to the invention have been found as starting materials for the polyester-polyurethanes described above, which have an acid number preferably less than 50 mg KOH / g, particularly preferably less than 10 mg KOH / g, particularly preferably less than 5 mg KOH / g and very particularly preferably less than 2 mg KOH / g each per gram of the reaction mixture comprising components A and B and are obtainable from a reaction mixture of components A and B, the diols in molar excess based on the dicarboxylic acids, but not above a molar excess of 1.2: 1.
  • the acid number is a measured variable to be determined experimentally, which is a measure of the number of free acid groups in the respectively defined reference amount, for example per gram of the reaction mixture.
  • the acid number is determined by dissolving a weighed sample of the reference quantity in a solvent mixture of methanol and distilled water in a volume ratio of 3: 1 and then dissolving it is titrated potentiometrically with 0.05 mol / l KOH in methanol.
  • the potentiometric measurement is carried out with a combination electrode (LL-Solvotrode® from Metrohm; reference electrolyte: 0.4 mol / l tetraethylammonium bromide in ethylene glycol).
  • the acid number corresponds to the amount of KOH added per gram of the reference amount at the turning point of the potentiometric titration curve.
  • the hydroxyl number of the polyester polyols is at least 30 mg / g KOH, particularly preferably at least 60 mg / g KOH, in particular is preferably at least 80 mg / g KOH, but preferably a hydroxyl number below 200 mg / g KOH, particularly preferably below 140 mg / g KOH, particularly preferably below 120 mg / g KOH, each per gram of the reaction mixture comprising components A and B has.
  • polyester-polyurethanes of the adhesive of the invention optionally present in an adhesive of the invention are addition products of monofunctional or polyfunctional isocyanates with polyester polyols, the addition product being end-capped and thus not having any free isocyanate groups. It is preferred according to the invention if the addition is carried out in such a way that the molar ratio of isocyanate groups to hydroxyl groups of the polyester polyol is greater than 2, preferably greater than 2.5, but preferably less than 4, particularly preferably less than 3.5 is.
  • the end group closure is preferably carried out with monohydric alcohols.
  • a polyester polyurethane does not contain any free isocyanate groups if it contains less than 0.1% by weight of NCO, based on the total amount of polyester polyurethanes.
  • 4 milliliters of a 0.5 M dibutylamine solution in xylene are added to approx. 1 gram of the polyester polyurethane and then mixed with 50 milliliters of xylene and stirred at a temperature of 20 ° C. until completely homogenized . After adding 3 drops of bromophenol blue and 50 milliliters of isopropanol, titrate with 0.5 M hydrochloric acid until the color changes from blue to yellow.
  • the difference in the consumption of hydrochloric acid for titrating a blank value solution i.e. without adding the polyester polyurethane, multiplied by the value 2.1 and divided by the exact value
  • the weight of the polyester-polyurethane gives the percentage by weight of isocyanate groups.
  • the polyester polyurethanes are preferably obtained by adding at least trifunctional, particularly preferably aliphatic, isocyanates, which are very particularly preferably selected from trimers of hexamethylene diisocyanate and / or pentamethylene diisocyanate, to polyester polyols, preferably to the partially crystalline polyester polyols, with free isocyanate formed in the addition reaction.
  • Groups are preferably reacted with at least one monohydric alcohol, particularly preferably with at least one aliphatic, particularly preferably with at least one linear aliphatic alcohol, each preferably not having more than 24 carbon atoms in the main chain, but preferably at least 4 carbon atoms in the main chain.
  • the proportion of polyester-polyurethanes based on the organic constituent of the adhesive in a preferred inventive adhesive is not more than 50% by weight, particularly preferably not more than 30% by weight, particularly preferably not more than 20% by weight, very particularly preferably not more than 15% by weight, but preferably at least 2% by weight, particularly preferably at least 5% by weight, in order to optimize the abrasion behavior on paper and the temperature stability.
  • One advantage of the adhesives of the invention is accordingly that it is easy to add additives to the adhesive, which essentially consists of the mixture of polyether polyurethanes.
  • tackifiers that are not polyether polyurethanes or Represent polyester polyurethanes, are included.
  • tackifiers are organic compounds which preferably have a sum of hydroxyl and acid numbers above 100 mg KOH per gram of the respective organic compound.
  • the tackifiers are preferably resins, preferably natural resins which can be chemically modified because of their long-term availability and extensive environmental hygienic harmlessness.
  • a natural resin according to DIN 55958 comprises excretions secreted by animals and plants. Such resins are known to the person skilled in the art, for example as turpentine, balsam, gum lacquer, rosin, sandarac or mastic. According to the invention, the natural resins also include the modified natural resins which are obtained from the natural resins, for example, by hydrogenation, intrinsic addition reactions or esterification.
  • the natural resins as component a) of the adhesive of the invention are in turn preferably selected from resin acids and / or resin esters, particularly preferably from resin acids and / or resin esters based on the di- and / or triterpenes, which are preferably hydrogenated and / or are present as intrinsic addition products .
  • the term resin ester describes the resin acids which are modified once or several times via the carboxyl groups of the resin acids in condensation reactions with the formation of ester groups.
  • Preferred representatives of the diterpene-based resin acids and / or resin esters are accordingly abietic acid, neoabietic acid, levopimaric acid, pimaric acid, palustric acid, agathenic acid, llluric acid and podocarpic acid, and the triterpene-based resin acids are elemic acid, sumarresinoleic acid and, preferably, each with their esters no more than 6 carbon atoms in the alkyl residue of the ester group.
  • tackifiers gives the adhesive, after it has been rubbed off as a thin film on a paper surface, increased initial tack, which, for example, when gluing opposite sides of a paper fold, ensures that the paper surfaces connected by the adhesive film are connected without exerting any pressure until the glue has set stay.
  • polyolefin waxes can also have a positive effect on the initial adhesion of the adhesive due to their largely non-polar character.
  • the polyolefin waxes improve the long-term stability of the bond, so that preferably up to 20% by weight, particularly preferably up to 10% by weight, based in each case on the adhesive, of polyolefin waxes can be present according to the invention, with a proportion of at least 1% by weight, in particular of at least 2% by weight, based in each case on the adhesive, is preferred.
  • an inventive adhesive additionally comprising polyolefin waxes
  • these are selected from copolymer waxes composed of propylene and ethylene and / or at least one branched or unbranched 1-alkene having 4 to 20 carbon atoms, and can additionally be modified with carboxyl groups for improved compatibility with the adhesive be
  • the acid number is preferably below 20 mg KOH per gram of the polyolefin wax. It is also advantageous if the polyolefin wax with additive is amorphous and therefore has no crystals in the range from 20 ° C. to the softening point.
  • the polyolefin waxes also increase the elasticity of the adhesive, so that, for example, glue sticks based on a correspondingly additized adhesive of the invention can be provided which are less susceptible to breakage, which is particularly advantageous in the case of packaging-free forms of administration and use of the adhesive of the invention.
  • the addition of pyrogenic silicas up to an amount of 15% by weight, based on the adhesive can be suitable while maintaining the other parameters such as initial adhesion, rubability and setting behavior, to reduce the stickiness of the dimensionally stable dosage form, in which case at least 1% by weight of the pyrogenic silica should preferably be added for a noticeable reduction in stickiness.
  • the adhesive in order to improve the abrasion of the adhesive on a flat substrate, it can be advantageous for the adhesive to additionally contain up to 5% by weight of nonionic surfactants, which preferably have an HLB value in the range of 12-18 and are particularly preferably selected from multiply alkoxylated C12-C22 fatty alcohols, very particularly preferably from multiply ethoxylated C12-C22 fatty alcohols with preferably more than 20 EO units.
  • nonionic surfactants which preferably have an HLB value in the range of 12-18 and are particularly preferably selected from multiply alkoxylated C12-C22 fatty alcohols, very particularly preferably from multiply ethoxylated C12-C22 fatty alcohols with preferably more than 20 EO units.
  • the adhesive of the invention is distinguished by the fact that it can be formulated solvent-free and water-free and the cohesive connection due to the setting of the adhesive does not require any physical loss of solvent or water.
  • the adhesive of the invention therefore contains less than 5% by weight, preferably less than 1% by weight, of water, based on the adhesive.
  • the proportion of water in the adhesive can be determined using the Karl Fischer method in xylene as a solvent.
  • Such virtually water-free adhesive formulations according to the invention have the advantage that after an adhesive film has been rubbed off on a thin, flat substrate of a water-absorbent material, for example paper, it does not curl and retains its flat shape even after setting.
  • the adhesive of the invention contains less than 5% by weight, particularly preferably less than 1% by weight, based in each case on the adhesive, of organic compounds having a boiling point below 100 ° C. at 1013 mbar.
  • the proportion of organic constituents is at least 70% by weight, preferably at least 80% by weight, based on the adhesive.
  • the adhesive of the invention contains: a) at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight, of a mixture of polyether polyurethanes made with two different monohydric aliphatic alcohols are end-capped, the two different monohydric aliphatic alcohols being selected on the one hand from those having at least 4 but not more than 8 carbon atoms and on the other hand being selected from those having at least 16 but less than 22 carbon atoms; b) up to 50% by weight, preferably 5 to 30% by weight, of polyester polyurethanes; c) up to 20% by weight, preferably 1 to 10% by weight, of polyolefin waxes; d) up to 5% by weight of tackifiers; and e) up to 5% by weight of multiply alkoxylated C12-C22 fatty alcohols; each based on the organic constituent, the proportion of the organic constituents at least 80% by weight based on the adhesive and the proportion of inorganic components
  • the inorganic constituent corresponds to the solids content of the adhesive that remains after pyrolysis in a reaction oven with the supply of a C0 2 -free oxygen stream at 900 ° C without the addition of catalysts or other additives, with pyrolysis being carried out until an infrared sensor is inserted in the outlet of the reaction oven delivers an identical signal to the C0 2 -free carrier gas (blank value).
  • the organic constituent of the adhesive is the adhesive minus the amount of water determined by the Karl Fischer method in the solvent xylene and minus the inorganic constituent as defined above.
  • an adhesive is considered to be dimensionally stable if a mass of the preparation shaped into a cylinder (10 grams) with a base area of 2 cm 2 under the action of a steadily increasing force perpendicular to the base area of the cylinder at 30 ° C. and 50% more relative Humidity is irreversibly deformed only above a pressure of 20 N / cm 2.
  • the action of the force and the Determination of the occurrence of the deformation can be followed by means of a force measuring device, for example by means of the texture analyzer TA-XT HiR (Stable Micro Systems Ltd.).
  • dimensional stability is closely linked to the required temperature stability of adhesives according to the invention; in such a way that adhesives with a ring-ball softening point measured according to DIN EN ISO 4625-1: 2006-04 of preferably at least 40 ° C., particularly preferably of at least 60 ° C., but preferably of less than 150 ° C., particularly preferred of less than 100 ° C are considered to be temperature-stable to the extent that dimensionally stable adhesives can be provided at 30 ° C.
  • At least 80% by weight of the organic constituents of the adhesive of the invention have a ring-ball softening point, measured according to DIN EN ISO 4625-1: 2006-04, of preferably at least 40 ° C., particularly preferably at least 60 ° C., in order to be as shaped as possible - and provide temperature-stable adhesive.
  • the dimensionally stable adhesive composition provided according to the present invention has a low tack at 30 ° C. and can easily be rubbed off on substrates.
  • the transfer of material brought about by rubbing off takes place in such a way that a thin, tacky film of the adhesive results on flat substrates which sets after a short time so that substrates can be bonded to one another with sufficient adhesion to the adhesive.
  • the present invention therefore relates to a method for applying a sticky film to a sheet-like substrate, preferably on paper, by pressing a dimensionally stable adhesive according to the invention onto the sheet-like substrate and subsequently changing its position while maintaining a contact pressure perpendicular to the surface normal of the substrate.
  • Suitable substrates are preferably obtained from vegetable fibers, flat and flexible, in particular paper.
  • mixtures of polyether polyurethanes is first set out which, as such, were cast into cylindrical, dimensionally stable adhesives according to the invention and characterized with regard to abrasion behavior and the bonding of paper.
  • Mixtures A and B of the polyester-polyurethanes were melted at 110 ° C. and poured into a cylindrical stick shape (diameter 2 cm, length 6-8 cm) and stored for 24 hours at 20 ° C. before the stick-type adhesives were able to be handled and the adhesive film rubbed off were determined.
  • the paper tear determined after gluing a sheet of paper with a weight of 80 g / m 2 , which was provided with an adhesive film according to the abrasion test and then folded for gluing and pulled apart again after 1 hour at 20 ° C., was given the value “5 “(1: no paper tear, 2: less than 30%, 3: less than 60%, 4: less than 90%, 5: more than 90% of the adhesive surface shows paper tear).
  • the adhesives were therefore sufficiently temperature-stable to be able to be offered free of packaging.

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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)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne un composé adhésif dimensionnellement stable qui est principalement formulé sans eau et sans solvant et qui peut être mis en contact avec le substrat à coller en étant couché sous la forme d'un film adhésif mince qui est particulièrement approprié pour lier des matériaux obtenus à partir de fibres végétales. Le composant organique du composé adhésif selon l'invention est essentiellement constitué d'un mélange de polyéther-polyuréthanes qui ont au niveau des extrémités terminales au moins deux alcools aliphatiques monovalents ayant des longueurs de chaîne différentes. L'invention concerne également un procédé d'application d'un film adhésif sur un substrat planiforme, de préférence sur du papier, par couchage de l'adhésif sur le point de contact avec le substrat.
EP20816530.8A 2019-12-16 2020-12-07 Composé adhésif à base de polyéther-polyuréthane modifié, appliqué par couchage, à stabilité dimensionnelle Pending EP4077448A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19216371 2019-12-16
PCT/EP2020/084841 WO2021122090A1 (fr) 2019-12-16 2020-12-07 Composé adhésif à base de polyéther-polyuréthane modifié, appliqué par couchage, à stabilité dimensionnelle

Publications (1)

Publication Number Publication Date
EP4077448A1 true EP4077448A1 (fr) 2022-10-26

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Country Status (9)

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US (1) US20220306918A1 (fr)
EP (1) EP4077448A1 (fr)
JP (1) JP2023506873A (fr)
CN (1) CN114846048B (fr)
BR (1) BR112022011696A2 (fr)
CA (1) CA3164944A1 (fr)
CL (1) CL2022001601A1 (fr)
MX (1) MX2022007234A (fr)
WO (1) WO2021122090A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE3921554A1 (de) * 1989-06-30 1991-01-17 Henkel Kgaa Klebestift mit verbesserter klebkraft
JPH11511774A (ja) 1995-05-26 1999-10-12 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン 結合方法
ATE231526T1 (de) * 1996-02-24 2003-02-15 Henkel Kgaa Feste, haftende und geschmeidig abreibende masse in form eines klebestifts
DE19908561A1 (de) * 1998-03-26 1999-09-30 Henkel Kgaa Klebestift auf der Basis eines Seifengels
DE19908560A1 (de) 1998-04-01 1999-10-07 Henkel Kgaa Klebestift auf Stärkeetherbasis
DE10047069C2 (de) 2000-09-22 2002-11-14 Henkel Kgaa Vorrichtung zur Aufnahme und Abgabe eines streichfähigen Materials
US7112631B2 (en) * 2002-10-24 2006-09-26 National Starch And Chemical Investment Holding Corporation Moisture cured reactive hot melt adhesive with monofunctional reactants as grafting agents
CN101220252B (zh) * 2008-01-25 2011-09-14 中北大学 一种固体胶棒及其制备方法
CN102942674B (zh) * 2012-11-26 2014-05-07 山东一诺威聚氨酯股份有限公司 三组分聚氨酯弹性体组合物
WO2017165652A1 (fr) * 2016-03-23 2017-09-28 H.B. Fuller Company Composition adhésive thermofusible réactive
ES2762076T3 (es) 2017-07-13 2020-05-22 Henkel Ag & Co Kgaa Mezcla semicristalina de polioles de poliéster y su uso
EP3717585A4 (fr) * 2017-11-27 2021-09-08 Henkel IP & Holding GmbH Composés d'uréthane et de polysiloxane et compositions adhésives optiquement transparentes

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CN114846048B (zh) 2024-07-02
CL2022001601A1 (es) 2023-02-10
WO2021122090A1 (fr) 2021-06-24
US20220306918A1 (en) 2022-09-29
CN114846048A (zh) 2022-08-02
MX2022007234A (es) 2022-07-12
JP2023506873A (ja) 2023-02-20
BR112022011696A2 (pt) 2022-09-06
CA3164944A1 (fr) 2021-06-24

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