EP4077449A1 - Composé adhésif à base de polyester semi-cristallin à stabilité dimensionnelle, pouvant être essuyé - Google Patents

Composé adhésif à base de polyester semi-cristallin à stabilité dimensionnelle, pouvant être essuyé

Info

Publication number
EP4077449A1
EP4077449A1 EP20817006.8A EP20817006A EP4077449A1 EP 4077449 A1 EP4077449 A1 EP 4077449A1 EP 20817006 A EP20817006 A EP 20817006A EP 4077449 A1 EP4077449 A1 EP 4077449A1
Authority
EP
European Patent Office
Prior art keywords
weight
adhesive
polyurethanes
polyester
particularly preferably
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
EP20817006.8A
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 EP4077449A1 publication Critical patent/EP4077449A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
    • C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
    • 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
    • C08G18/28—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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3221—Polyhydroxy compounds hydroxylated esters of carboxylic acids other than higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic 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
    • 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
    • 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

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 composition of the invention consists essentially of polyester polyurethanes which are at least partially based on partially crystalline polyester polyols.
  • 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.
  • WO 96/37566 A1 describes semicrystalline, dimensionally stable adhesives based on polyesters and / or polyurethanes, the semicrystalline structure of which is broken up by the heat released during the friction on a substrate surface, so that a thin adhesive film can be applied which will reappear after a short time forms partially crystalline areas and in this way sets and is able to produce the To glue 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 for 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. It is also expected by the consumer that such an adhesive in the form of a pen can be guided over the substrate like a wax crayon when used and a continuous adhesive film can be applied in the process. 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 has in particular a low abrasion resistance, the adhesive being at 30 ° C should not be permanently sticky. Temperature stability of up to 70 ° C is also required for storage and transport. Above all, the adhesive should have a high bond strength for materials obtained from vegetable fibers, in particular paper and cardboard. In addition, 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.
  • this range of tasks is achieved by formulating an adhesive whose organic constituent comprises polyester-polyurethanes which are at least partially based on partially crystalline polyester polyols.
  • the present invention accordingly relates to a dimensionally stable adhesive, the organic constituent of which consists essentially of polyester polyurethanes which are at least partially based on partially crystalline polyester polyols.
  • partially crystalline polyester polyols are those which, 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”) are obtainable.
  • component A dicarboxylic acids selected from terminal dicarboxylic acids that are both saturated, linear and aliphatic, with an even number of at least 8 methylene groups
  • component B diols selected from terminal diols that are both saturated, linear and aliphatic and contain at least one ether function
  • 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.
  • An aliphatic compound is linear if it contains neither tertiary nor quaternary carbon atoms, with one carbon atom being quaternary when it is covalently attached to four other carbon atoms is bonded, while a tertiary carbon atom is covalently bonded to three other carbon atoms.
  • polyester-polyurethanes based on partially crystalline polyester polypoles which are necessarily contained according to the invention, have crystalline phases below their ring-ball softening point, measured in accordance with DIN EN 1238: 2011, which by means of differential scanning calorimetry (DSC) at a heating rate of not more than 10 Kelvin per minute as an endothermic melting peak Reaching the softening point can be demonstrated.
  • 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
  • the polyester-polyurethanes produced on the basis of these partially crystalline polyester polyols which recrystallize on melting act as a constituent of the adhesive of the invention excellent abrasion behavior with high temperature stability at the same time.
  • the application of an adhesive thin film to the substrate to be bonded is thus facilitated without the softening point of the adhesive being significantly lowered and the packaging-free, dimensionally stable adhesive being perceived by the end user as tacky in use.
  • the dicarboxylic acids according to component A do not have more than 24 methylene groups, especially preferably no more than 18 methylene groups, particularly preferably no more than 16 methylene groups, regardless of this, the dicarboxylic acids according to component A should preferably comprise at least 10 methylene groups in order to provide those partially crystalline polyester polyols which, due to their pronounced tendency to recrystallize as Based on the polyester-polyurethanes, give the adhesive excellent abrasion properties.
  • 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 also 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, however have neither a tertiary nor a quaternary carbon atom.
  • Aromatic dicarboxylic acids are in particular isophthalic acid, terephthalic acid, orthophthalic acid, furandicarboxylic acid, especially 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 fewer than 9 carbon atoms can be contained in the adhesive.
  • the proportion of polyester polyurethanes based on partially crystalline polyester polyols is based on the totality of the Polyester polyurethanes predominate.
  • this is the case when the proportion of dicarboxylic acids according to component A that can be split off formally from the polyester-polyurethanes by hydrolysis of the ester functions and splittable diols according to component B, based on the polyester polyol content of all polyester polyurethanes present in the adhesive of the invention, is at least 60% by weight, preferably at least 80% by weight and particularly preferably at least 90% by weight.
  • those partially crystalline polyester polyols have proven to be ideal 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 a molar excess based on the Dicarboxylic acids are included, 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 amount in a solvent mixture of methanol and distilled water in a volume ratio of 3: 1 and then potentiometrically titrating it 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, particularly preferably at least 80 mg / g KOH is, but preferably, a hydroxyl number below 200 mg / g KOH, particularly preferred below 140 mg / g KOH, particularly preferably below 120 mg / g KOH, in each case per gram of the reaction mixture comprising components A and B.
  • the hydroxyl number can be determined experimentally by potentiometric titration as a measure of the number of free hydroxyl groups in the respectively defined reference amount, for example per gram of the reaction mixture.
  • 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 partially crystalline polyester polyols obtainable from the reaction mixture containing the components A and B defined above preferably have a number average molar mass of less than 5,000 g / mol, particularly preferably less than 2,000 g / mol, but preferably at least 500 g / mol, the Polydispersity is preferably less than 2.5.
  • polyester polyurethanes can be obtained which give the adhesives of the invention, at least 50% by weight of such polyester polyurethanes, easy rubability and good tack combined 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.
  • Polyester-polyurethanes of the 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 The 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. 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.
  • 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 compounds 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 (hereinafter "end group closure"), 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 end group closure is carried out with monohydric aliphatic alcohols which have at least 4 carbon atoms, but less than 8 carbon atoms in the main chain, whereas an increased temperature stability of the adhesive is achieved when the end group closure is carried out with monohydric, preferably linear, alcohols aliphatic alcohols takes place which have at least 12 carbon atoms, but fewer than 24 carbon atoms in the main chain.
  • monohydric preferably linear, alcohols aliphatic alcohols takes place which have at least 12 carbon atoms, but fewer than 24 carbon atoms in the main chain.
  • the end group closure takes place Polyester polyurethanes both with monohydric aliphatic, preferably linear aliphatic alcohols with at least 4, but less than 10, preferably not more than 8 carbon atoms, and with monohydric aliphatic, preferably linear aliphatic alcohols with at least 10, preferably at least 12, particularly preferably at least 14, however no more than 24 carbon atoms.
  • Polyester-polyurethanes with a dynamic viscosity in the lower preferred range are usually achieved by at least partially carrying out the end group closure with long-chain monohydric alcohols or at least partially adding mono- or divalent isocyanates to the semicrystalline polyester polyols.
  • the organic constituent of the adhesive of the invention consists essentially of polyester-polyurethanes if their proportion is greater than 50% 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 if the proportion of polyester-polyurethanes, as described above, based on the organic constituent of the adhesive, is at least 60% by weight, better at least 70% by weight or even better at least 80% by weight .-%, so that such adhesives are preferred according to the invention.
  • polyether polyurethanes can be added, preferably by addition of at least trifunctional isocyanates to polyether polyols, particularly preferably to polytetramethylene ether glycol, and end group closure with at least one monohydric alcohol, preferably with at least one aliphatic, particularly preferably with at least one linear aliphatic monohydric alcohol, which is preferably not more than 24 carbon atoms in the main chain, but preferably at least 4 carbon atoms in the main chain, are available.
  • the at least trifunctional isocyanate can be added to a mixture of the partially crystalline polyester polyols described above, which also contains the polyether polyols.
  • polyester-polyether-polyurethanes which also meet the requirements for an adhesive of the invention and provide good rubability with excellent temperature stability, provided that the proportion of polyester polyols predominates and is more than 50% by weight based on the polyol proportion of the reaction mixture of the addition reaction .
  • the proportion of polyether polyurethanes based on the organic constituent of the adhesive in a preferred inventive adhesive is not more than 40% 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 be able to obtain colorless, translucent adhesives.
  • One advantage of the adhesives of the invention is accordingly that it is easy to add additives to the adhesive, which consists essentially of polyester-polyurethanes.
  • tackifiers that are not polyester-polyurethanes or polyether-polyurethanes.
  • 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 according to the invention excreta 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.
  • 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, palustrinic acid, agathenic acid, llluric acid and podocarpic acid, and the triterpene-based resin acids are elemic acid, sumarresinoleic acid and preferably their esters, respectively 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 bring about better long-term stability of the bond, so that preferably up to 20% by weight, particularly preferably up to 10% by weight, in each case based on the adhesive, of polyolefin waxes can be included according to the invention, with a proportion for a significant effect of at least 1% by weight, in particular at least 2% by weight, based in each case on the adhesive, is preferred.
  • an adhesive according to the invention 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 crystallinities in the area 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 composition of organic compounds with a boiling point below 100 ° C. at 1013 mbar.
  • the adhesive of the invention contains: a) at least 50% by weight, preferably at least 60% by weight, particularly preferably at least 70% by weight, particularly preferably at least 80% by weight, of polyester-polyurethanes, at least partially arise from 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 with an even number of at least 8 methylene groups that are both saturated, linear and aliphatic, and one or more Diols selected from terminal diols that are both saturated, linear and aliphatic and contain at least one ether function; b) up to 50% by weight, preferably 5 to 30% by weight, of polyether 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 alkoxyl
  • the inorganic constituent corresponds to the solids content of the adhesive after pyrolysis in a reaction furnace with the supply of a C0 2 -free oxygen stream at 900 ° C. without the addition of catalysts or others Aggregates remain, with pyrolysis taking place until an infrared sensor in the outlet of the reaction furnace delivers a signal identical 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 effect 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 tacky film to a sheet-like substrate, preferably to paper, by pressing a dimensionally stable adhesive of the invention onto the sheet-like substrate Substrate and subsequent relative change in 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.
  • the raw materials 0.369 kg isophthalic acid, 1.876 kg dodecanedioic acid and 1.421 kg diethylene glycol were placed in a 5 liter four-necked flask equipped with nitrogen inlet, thermostat, paddle stirrer and distillation arm.
  • the reaction mixture was heated and stirred at a temperature of 220 ° C. in a stream of nitrogen for several hours and then the pressure in the reaction flask was gradually reduced to 30 mbar.
  • the acid number was continuously checked, as explained in detail above in the description of the invention. As soon as the acid number fell below a value of 3 mg KOH / g based on the reaction mixture, the reaction mixture was first cooled to 80 ° C.
  • the reaction mixture was allowed to cool further to room temperature.
  • the acid number and hydroxyl number were then finally determined at 20 ° C. and the mixture was characterized by chromatography.
  • the hydroxyl number was 102 mg KOH / g; the acid number was 0.3 mg KOH / g and the dynamic viscosity at 50 ° C. was 1900 mPas.
  • 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.

Landscapes

  • 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)
  • Adhesive Tapes (AREA)

Abstract

La présente invention concerne un composé adhésif à stabilité dimensionnelle qui est formulé principalement sans eau ni solvants et qui peut être mis en contact avec le substrat à coller en étant essuyé 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 de polyester-polyuréthanes qui sont au moins partiellement à base de polyesterpolyols semi-cristallins. L'invention concerne également un procédé d'application d'un film adhésif sur un substrat planiforme, de préférence sur du papier, par essuyage de l'adhésif sur le point de contact avec le substrat.
EP20817006.8A 2019-12-16 2020-12-07 Composé adhésif à base de polyester semi-cristallin à stabilité dimensionnelle, pouvant être essuyé Pending EP4077449A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19216370 2019-12-16
PCT/EP2020/084842 WO2021122091A1 (fr) 2019-12-16 2020-12-07 Composé adhésif à base de polyester semi-cristallin à stabilité dimensionnelle, pouvant être essuyé

Publications (1)

Publication Number Publication Date
EP4077449A1 true EP4077449A1 (fr) 2022-10-26

Family

ID=68917502

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20817006.8A Pending EP4077449A1 (fr) 2019-12-16 2020-12-07 Composé adhésif à base de polyester semi-cristallin à stabilité dimensionnelle, pouvant être essuyé

Country Status (9)

Country Link
US (1) US20220306919A1 (fr)
EP (1) EP4077449A1 (fr)
JP (1) JP2023507345A (fr)
CN (1) CN114829439A (fr)
BR (1) BR112022011683A2 (fr)
CA (1) CA3179492A1 (fr)
CL (1) CL2022001602A1 (fr)
MX (1) MX2022006830A (fr)
WO (1) WO2021122091A1 (fr)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3921554A1 (de) * 1989-06-30 1991-01-17 Henkel Kgaa Klebestift mit verbesserter klebkraft
CZ295465B6 (cs) * 1995-05-26 2005-08-17 Henkel Kommanditgesellschaft Auf Aktien Způsob lepení a lepidlo
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
CN101220252B (zh) * 2008-01-25 2011-09-14 中北大学 一种固体胶棒及其制备方法
ES2755097T3 (es) * 2014-05-16 2020-04-21 Henkel Ag & Co Kgaa Adhesivo de fusión en caliente de poliuretano termoplástico
WO2016116376A1 (fr) * 2015-01-20 2016-07-28 Covestro Deutschland Ag Prépolymères de polyester résistant à la cristallisation
CN104804698B (zh) * 2015-04-27 2017-04-05 武汉戴尔惠科技有限公司 一种太阳能背板用双组分复合胶粘剂及其制备方法
EP3347396A1 (fr) * 2015-09-08 2018-07-18 Resinate Materials Group, Inc. Polyester polyols pour adhésifs thermofusibles réactifs
EP3428209B1 (fr) * 2017-07-13 2019-10-30 Henkel AG & Co. KGaA Mélange semi-cristallin de polyester polyol et son utilisation

Also Published As

Publication number Publication date
CL2022001602A1 (es) 2023-02-10
CA3179492A1 (fr) 2021-06-24
US20220306919A1 (en) 2022-09-29
CN114829439A (zh) 2022-07-29
WO2021122091A1 (fr) 2021-06-24
BR112022011683A2 (pt) 2022-09-06
JP2023507345A (ja) 2023-02-22
MX2022006830A (es) 2022-07-12

Similar Documents

Publication Publication Date Title
EP0828801B1 (fr) Procede de collage
DE2435863B2 (fr)
DE2401320A1 (de) Schmelzklebemassen
DE2601692C3 (de) Thermoplastische Copolyester und deren Verwendung für Heißschmelzklebstoffe
DE2328430C2 (de) Verfahren zur Herstellung von Haftklebern
DE3328099C2 (de) Klebestift und Verfahren zu seiner Herstellung
WO2021122091A1 (fr) Composé adhésif à base de polyester semi-cristallin à stabilité dimensionnelle, pouvant être essuyé
EP4077448A1 (fr) Composé adhésif à base de polyéther-polyuréthane modifié, appliqué par couchage, à stabilité dimensionnelle
EP1218332A1 (fr) Polyols de transesterification pour prepolymeres de polyurethanne a viscosite pouvant etre regulee de maniere ciblee
AT405647B (de) Thixotrope alkydharz-zusammensetzungen
DE19957351A1 (de) Polyurethan-Zusammensetzungen mit niedrigem Gehalt an Isocyanatmonomeren
WO2009077229A1 (fr) Adhésif biodégradable pour stratification
EP3401378B1 (fr) Mélange d'adhésif abrasif stable au stockage
EP1098947B1 (fr) Melange de resine de colophane et de cire
DE19921331A1 (de) Verfahren zur Herstellung von Papierverbunden und befeuchtungsklebrigen Materialien
EP0035666B1 (fr) Procédé de préparation de résines à mélange pour rendre thixotropes des résines d'alkydes longues en huile
DE19519391A1 (de) Klebeverfahren
EP0001400B1 (fr) Résines alkydes séchant à l'air
DE19648756A1 (de) Wasserfreier bzw. wasserarmer, teilkristalliner, bei Raumtemperatur fester Klebstoff
EP1264861B1 (fr) Compositions aqueuses thixotropiques de résine alkyde
DE2002457B2 (de) Verfahren zur Herstellung von Haftklebern auf Basis von Polyalkylenoxid und Polylsocyanat
DD211689A3 (de) Verfahren zur herstellung thixotroper polyisocyanate
WO2013102583A1 (fr) Préparations de polyuréthane réactives
WO2023218010A1 (fr) Adhésif sensible à la pression contenant une résine liquide comprenant une composition d'oligoester
DE19548842A1 (de) Klebeverfahren

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220516

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230530