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
  • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
  • C09J9/005—Glue sticks
• • 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
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/28—Non-macromolecular organic substances
  • C08L2666/34—Oxygen-containing compounds, including ammonium and metal salts

Definitions

• Pen-shaped rigid adhesives which are slidably mounted in a sealable sleeve and leave a sticky film when rubbed onto a recipient surface, are everyday objects of daily use. They contain in particular - see DE-PS 1811 466 water-soluble or water-dispersible synthetic high polymers with adhesive character - in particular polyvinylpyrrolidone (PVP) - dissolved in an aqueous-organic liquid phase together with a shaping framework.
• PVP polyvinylpyrrolidone
• Alkali or ammonium salts of aliphatic carboxylic acids in particular in the C number range from about 12 to 22, are used in particular as the framework.
• DE-AS 2204482 uses the reaction product of sorbitol and benzaldehyde as the shaping framework.
• salts of substituted terephthalic acid amides are to be used as gelling agents.
• DE-OS 2054503 instead of the alkali metal salts of aliphatic carboxylic acids, free long-chain aliphatic acids or their esters are to be the structural substance.
• DE-OS 2219697 intends to improve such glue sticks by incorporating anionic non-soap wetting agents into the stick, in particular in order to improve its abrasion on the base.
• DE-OS 2419067 a reaction product of aromatic diisocyanates with mono- and / or dialkanolamines is to be used as the gel-forming agent.
• German patent application DE 36 06 382 describes an improved glue stick which additionally contains a limited amount of lactams of lower aminocarboxylic acids and / or the corresponding ring-opened aminocarboxylic acids to improve the abrasion ability.
• Another very special object of the invention is to provide such an adhesive stick which can be formulated without the use of water-soluble plasticizers or organic solvents.
• the invention therefore relates to a dimensionally stable, soft, abradable glue stick, consisting of an aqueous preparation of a synthetic polymer and a soap gel as the shaping agent Framework substance and, if desired, other auxiliaries, characterized in that the aqueous preparation of a synthetic polymer contains an at least largely solvent-free aqueous polyurethane dispersion.
• the adhesive sticks according to the invention thus contain an aqueous polyurethane dispersion as the adhesive polymer component.
• Polyurethane dispersions are understood here to mean very broadly reaction products of polyfunctional alcohols, amino alcohols or amines on the one hand, with polyfunctional isocyanates on the other hand, which either contain additionally reacted building blocks which can form ionic groups after neutralization and additionally or instead of such groups hydrophilic nonionic Contain ingredients, making the polymers self-dispersing when water is added.
• particularly finely divided polyurethane dispersions are preferred starting materials for glue sticks, which look opaque to translucent to transparent, and in which the polymer should be at least partially in solution.
• the specialist knowledge of the polyurethane specialist applies here, who can influence the fine particle size via the proportion of ionic and / or non-ionic constituents.
• the polyurethane dispersions used as synthetic polymers in the glue sticks contain a reacted polyol or a polyol mixture as the starting product.
• the general rule here is that these polyols must have at least two reactive hydrogen atoms and are essentially linear.
• the molecular weight is between 300 and 40,000, preferably between 500 and 6,000.
• Polyester polyols, polyacetal polyols, polyether polyols, polythioether polyols, polyamide polyols or polyester amide polyols each having 2 to 4 hydroxyl groups, which can also be partially replaced by amino groups, can be used.
• monofunctional alcohols, in particular ether alcohols can also be used as nonionic hydrophilic modifiers.
• the reaction products of C 1 -C 10 alcohols with ethylene oxide in the molecular weight range up to 20,000, preferably 200 to 6,000, are preferred.
• polyethers e.g. the polymerization products of ethylene oxide, propylene oxide, butylene oxide and their mixed or graft polymerization products, and those obtained by the condensation of polyhydric alcohols or mixtures thereof and the polyethers obtained by alkoxylation of polyhydric alcohols, amines, polyamines and amino alcohols.
• Isotactic polypropylene glycol can also be used.
• the preferred polyether polyol is polytetrahydrofuran.
• Polytetrahydrofuran is understood here to mean polyethers which can theoretically or actually be prepared by ring-opening polymerization of tetrahydrofuran and which have a hydroxyl group on both chain ends.
• Suitable products have a degree of oligomerization of approximately 1.5 to 150, preferably 5 to 100.
• polystyrene resin Another preferred class of polyols are polycarbonate polyols.
• Aliphatic polycarbonate polyols ie esters of carbonic acid with difunctional alcohols of chain length C 2 to C 10, are preferred here.
• Polycarbonate polyols based on carbonic acid and bisphenol-A are less suitable.
• polyacetals such.
• B the compounds from glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyl-dimethylmethane, hexanediol and formaldehyde in question.
• Suitable polyacetals can also be prepared by polymerizing cyclic acetals.
• the polythioethers the condensation products of thiodiglycol with themselves and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular.
• the products are polythioethers, polythio mixed ethers, polythioether esters, polythioether ester amides.
• polyhydroxyl compounds can also be used in alkylated form or in a mixture with alkylating agents.
• the polyesters, polyester amides and polyamides include those obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated alcohols, amino alcohols, diamines, polyamines and their mixtures, predominantly linear condensates, and e.g. Polyterephthalates or polycarbonates. Lactone polyester, e.g. B. caprolactone or from hydroxycarboxylic acids can be used.
• the polyesters can have hydroxyl or carboxyl end groups. Higher molecular weight polymers or condensates, such as e.g. Polyethers, polyacetals, polyoxymethylenes (with) can be used.
• Polyhydroxyl compounds which already contain urethane or urea groups and, if appropriate, modified natural polyols such as castor oil can also be used.
• polyhydroxyl compounds which have basic nitrogen atoms can also be used, e.g. B. polyalkoxylated primary amines or polyesters or polythioethers which contain alkyl diethanolamine in condensed form.
• Sulfur-containing polyisocyanates are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol or dihydroxydihexyl sulfide.
• Other important diisocyanates are trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,2-diisocyanatododecane and dimer fatty acid diisocyanate.
• the aforementioned isocyanates can be used alone or in a mixture. Cyclic or branched aliphatic diisocyanates such as isophorone diisocyanate, but also hexamethylene diisocyanate, are preferred.
• tetramethylxylene diisocyanate tetramethylxylene diisocyanate (TMXDI) is preferred.
• Chain extenders with reactive hydrogen can also be used to build up the polyurethane dispersions used according to the invention.
• the chain extenders with reactive hydrogen atoms include: the usual saturated and unsaturated glycols, such as ethylene glycol or condensates of ethylene glycol, 1,3-butanediol, 1,4-butanediol, butenediol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol , Hexanediol, bis-hydroxymethyl-cyclohexane, dioxyethoxyhydroquinone, terephthalic acid bis-glycol ester, succinic acid di-2-hydroxyethyl amide, succinic acid di-N-methyl- (2-hydroxy-ethyl) -amide, 1,4-di (2-hydroxy-methyl-mercapto) -2,3,5,6-tetrachlorobenzene, 2-methylene-propanedi
• Special chain extenders with at least one basic nitrogen atom are, for example, mono-, bis- or polyoxalkylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, such as N-methyldiethanolamine, N-ethyl-diethanolamine, N-propyldiethanolamine, N-isopropyl-diethanolamine, N-butyl -diethanolamine, N-isobutyl-diethanolamine, N-oleyl-diethanolamine, N-stearyl-diethanolamine, ethoxylated coconut oil, N-allyl-diethanolamine, N-methyl-diisopropanolamine, N-ethyl-diisopropanolamine, N-propyl-diisopropanolamine, N- Butyl-diisopropanolamine, C-cyclohexyl-diisopropanolamine, N, N-dioxe
• the polyurethanes on which the polyurethane dispersions used according to the invention are based furthermore have, as an important constituent, a functional component capable of salt formation in aqueous solution.
• Dihydroxy or diamino compounds which contain an ionizable carboxylic acid, sulfonic acid or ammonium group can be used as such. These compounds can either be used as such or they can be prepared in situ.
• dihydroxycarboxylic acids is, for example, dimethylolpropionic acid.
• a diaminosulfonic acid can be added to the polyols.
• examples are 2,4-diminobenzenesulfonic acid but also the N- (w-aminoalkane) -w'-aminoalkanesulfonic acids as described in DE 2035732.
• the polyurethane prepolymers it is preferred to make the polyurethane prepolymers to be used water-soluble with the aid of carboxylic acid or sulfonic acid groups, it also being possible to use the nonionic modifiers already mentioned, for example the ether alcohols or their derivatives, with or instead of the anionic modifiers.
• the polymers if anionically modified, are present in salt form.
• the neutralizing agents it is preferred to use the neutralizing agents in a stoichiometric ratio, based on acid groups or in excess.
• the groups capable of salt formation can therefore be partially or completely neutralized by the counterions. An excess of neutralizing agent is also possible.
• the polyols and an excess of diisocyanate are reacted to form a polymer having terminal isocyanate groups, suitable reaction conditions and reaction times and temperatures being able to be varied depending on the isocyanate concerned.
• suitable reaction conditions and reaction times and temperatures being able to be varied depending on the isocyanate concerned.
• the person skilled in the art knows that the reactivity of the constituents to be reacted necessitates an appropriate balance between the reaction rate and undesirable side reactions which lead to discoloration and a reduction in molecular weight.
• the reaction is carried out with stirring at about 50 to about 120 ° C in about 1 to 6 hours.
• the preferred production process is the so-called acetone process (D. Dietrich, Angew. Makromol. Chem. 98, 133 (1981)).
• the polyurethane dispersions used according to the invention can also be prepared by the process of DE 1595602.
• a newer process for the production of polyurethane dispersions is in DE 3603996 and in the prior art specified therein, namely: DE-PS 880485, DE-AS 1044404, US-PS 3036 998, DE-PS 11 78586, DE-PS 1184946, DE-AS 1237306, DE-AS 1495745, DE-OS 1595602, DE-OS 17 70068, DE-OS 2019324, DE-OS 2035 732, DE-OS 2446440, DE-OS 2345256, DE-OS 2427274, US -PS 34 79310 and Angewandte Chemie 82, 53 (1970) and Angew. Macromol. Chem. 26.85 ff. (1972).
• a prepolymer with -NCO end groups is first prepared in an inert solvent, followed by chain extension in solution to the higher molecular weight polyurethane.
• the hydrophilic groups required for the dispersion are preferably incorporated either by incorporating diols bearing ionic, potentially ionic or nonionic hydrophilic groups into the prepolymer or by using appropriate amines as chain extenders.
• the dispersion is carried out discontinuously in stirred tanks with stirrers and possibly baffles.
• the solvent used is generally distilled from the stirred kettle immediately after being dispersed in water.
• the polyurethane dispersions used in the glue sticks according to the invention can also be prepared without the use of acetone as a solvent.
• the polyols based on polytetrahydrofuran or copolymers thereof with ethylene oxide or propylene oxide which are preferred for the purposes of the invention, preferably low molecular weight polyols, such as those with a molecular weight of up to 2,000 or up to 1,000, being used.
• the polyols are then reacted in a 0H: NCO ratio in the presence of a polyol which carries acid groups, for example dimethylolpropionic acid, in an OH: NCO ratio greater than 1: 1.2, with stirrable resins being formed which then directly form Water can be dispersed.
• a polyol which carries acid groups for example dimethylolpropionic acid
• OH: NCO ratio greater than 1: 1.2
• stirrable resins being formed which then directly form Water can be dispersed.
• the person skilled in the art must pay attention to a certain ratio between the component capable of salt formation and the other substances that make up the polyurethane.
• the salt-forming component - calculated as dimethylolpropionic acid - in amounts of 1 to 30, preferably 2 to 20, and in particular 10 to 18% by weight, based on polyol.
• Based on polyurethane solids and calculated as dimethylolpropionic acid these are 5 to 35% by weight, preferably 5 to 20% by weight and in particular 5 to 15% by weight.
• the transparency depends on the degree of neutralization.
• a non-ionic modification can also take place.
• Monoalcohols which are obtained by reacting primary alcohols with ethylene oxide, are primarily suitable for the nonionic modification.
• the required amount of non-ionic modifiers depends on the hydrophilicity of the overall system, ie it is lower if polyols based on polyethylene glycol have already been used as polyols to build up the polymer. Of course, the amount is also lower if additional ionic groups are incorporated.
• the upper limit is given by the water resistance of the adhesive film. For example, based on solids, up to 85% by weight of the Derive polyurethane from ethylene oxide. If ionic modification is dispensed with, the usual values are 5 to 50% by weight. If ionic modifiers are also used, however, any other underlying value can be set.
• the person skilled in the art must pay attention to the ratio of hydroxyl groups to isocyanate groups. This can be between 1.0: 0.8 and 1.0: 4.0. Ratios of 1.0: 1.1 to 1.0: 2.0, in particular 1.0: 1.1 to 1.0: 1.8, are preferred. Corresponding polyurethane dispersions can be produced in a wide range of concentrations. Preparations with a solids content of between 20 and 80% by weight, in particular 35 to 60% by weight, are preferred.
• the adhesive sticks according to the invention contain sodium salts of C 12 to C 20 fatty acids of natural or synthetic origin as soaps for forming the gel structure.
• C 12 to C 18 fatty acid mixtures are preferred here.
• the sodium salts of the fatty acids, ie the soaps, are present in amounts of 3 to 20% by weight, based on the mass of glue stick, preferably 5 to 12% by weight.
• the auxiliaries customary for glue sticks can be used in the glue sticks according to the invention.
• plasticizers and / or moisture-regulating substances which are organic water-soluble solvents which are normally used in glue sticks. Nevertheless, these compounds can, if desired, be present in minor amounts.
• these compounds are polyglycol ethers, in particular polyethylene glycol and polypropylene glycol, the preferred polyethers having an average molecular weight in the range from 200 to 1,000, in particular in the range from 500 to 800.
• Polyfunk can still be used tional alcohols such as glycerol, trimethylolpropane and the like and / or polyether glycols.
• a mixture of glycerin and polyethylene glycol can also be used.
• the non-volatile organic solvents mentioned should be used at most in amounts of up to 50% by weight, based on the water content of the sticks.
• customary auxiliaries can also be used, for example substances that promote light and soft abrasion.
• substances are, for example, aminocarboxylic acids and / or their lactams.
• Suitable aminocarboxylic acids or their lactams should contain up to 12 carbon atoms, in particular 4 to 8 carbon atoms.
• the preferred representative for practical use is epsilon-caprolactam or the 7-aminocaproic acid derived therefrom.
• the amount of the lactams or the corresponding aminocarboxylic acids to be used is usually not more than 15% by weight, for example 2.5 to 15% by weight, based on the total stick mass.
• the adhesive sticks according to the invention can contain pigments, dyes, odor improvers and the like as further auxiliaries. As usual, the quantities of these substances are subordinate.
• Other possible additives are, for example, fillers, dextrins, cellulose derivatives, starch derivatives.
• the mixture is processed in a manner known per se from the mixtures heated to temperatures of 60 ° C., preferably above 80 ° C., from the polyurethane dispersions, the soap constituent and, if desired, the other auxiliaries. It is preferred to fill these mixtures, which are easy to pour, directly into pencil sleeves or similar containers and to set them to the desired gels without mechanical influence.
• the glue sticks according to the invention have the advantage of higher adhesive strength and can therefore not only be used for paper gluing. If desired, they can also be prepared without the use of water-soluble plasticizers (water-soluble organic solvents) or moisture-regulating substances (also water-soluble organic solvents). Glue sticks according to the invention have significantly lower inherent tack in a humid and warm climate (for example 30 ° C., 75% relative atmospheric humidity) and are therefore easy to handle even under these conditions.
• the polyurethane adhesive raw materials are produced by the acetone process, although other production processes, such as, for example, dispersing the extruded prepolymer melt (melt extrusion process), are also possible.
• Polyisocyanates and diol components are placed in acetone and stirred at about 65-80 ° C. under reflux until the NCO value is constant.
• the indicated amount of water is added, with vigorous stirring, which contains the calculated alkali and possibly chain extenders.
• the introduction of high shear forces is of great importance for the quality and especially the homogeneity of the dispersion.
• the solvent is distilled off until the acetone concentration is clearly below 0.1 and until the viscosities and solids contents contained in Table I are reached.
• the stick masses 1-10 are obtained by mixing the individual components from Table II at 65 - 80 ° C and then filled into pencil sleeves for cooling. If necessary, the pH of the mass is adjusted in the range pH 8-11 by adding a small amount of dilute sodium hydroxide solution.
• the comparison pen 11 is made by mixing 26% by weight of PVP (molecular weight approx. 700,000), 8% by weight of sodium myristate, 6% by weight of glycerol, 9% by weight of polypropylene glycol 600 and 51% by weight of water at 75 ° C manufactured and also filled into pen sleeves for cooling. In the comparative pen 12, the glycerin and polypropylene glycol portions are replaced by water.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Polyurethanes Or Polyureas (AREA)
• Materials For Medical Uses (AREA)
• Detergent Compositions (AREA)

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• 1989
  • 1989-06-30 DE DE3921554A patent/DE3921554A1/de not_active Withdrawn
• 1990
  • 1990-06-21 JP JP2509173A patent/JP2836957B2/ja not_active Expired - Lifetime
  • 1990-06-21 DK DK90111738.2T patent/DK0405329T3/da active
  • 1990-06-21 KR KR1019910702012A patent/KR0136267B1/ko not_active IP Right Cessation
  • 1990-06-21 AU AU58568/90A patent/AU635754B2/en not_active Ceased
  • 1990-06-21 ES ES199090111738T patent/ES2042146T3/es not_active Expired - Lifetime
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  • 1990-06-21 HU HU905536A patent/HU212188B/hu unknown
  • 1990-06-21 EP EP19900909715 patent/EP0479845A1/de active Pending
  • 1990-06-21 US US07/778,971 patent/US5371131A/en not_active Expired - Lifetime
  • 1990-06-21 DE DE9090111738T patent/DE59001295D1/de not_active Expired - Lifetime
  • 1990-06-21 WO PCT/EP1990/000982 patent/WO1991000322A1/de active IP Right Grant
  • 1990-06-21 EP EP90111738A patent/EP0405329B1/de not_active Expired - Lifetime
  • 1990-06-27 CZ CS903206A patent/CZ283445B6/cs not_active IP Right Cessation
  • 1990-06-27 SK SK3206-90A patent/SK279178B6/sk not_active IP Right Cessation
  • 1990-06-28 PT PT94531A patent/PT94531B/pt not_active IP Right Cessation
  • 1990-06-29 AR AR90317271A patent/AR248288A1/es active
  • 1990-06-29 MX MX021407A patent/MX174480B/es unknown
  • 1990-06-29 IE IE236190A patent/IE64413B1/en not_active IP Right Cessation
  • 1990-06-29 ZA ZA905130A patent/ZA905130B/xx unknown
  • 1990-06-29 DD DD90342353A patent/DD297993A5/de unknown
  • 1990-07-17 TR TR90/0589A patent/TR24605A/xx unknown
• 1991
  • 1991-10-29 NO NO914241A patent/NO305130B1/no unknown
  • 1991-12-27 FI FI916132A patent/FI100986B/fi active

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