EP0479845A1

EP0479845A1 - Adhesive stick with improved adhesive strength

Info

Publication number: EP0479845A1
Application number: EP19900909715
Authority: EP
Inventors: Gerhard Dr. Gierenz; Wolfgang Dr. Klauck; Rainer Dr. Höfer; Roland Grützmacher
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1989-06-30
Filing date: 1990-06-21
Publication date: 1992-04-15
Also published as: CA2062950A1; NO305130B1; EP0405329B1; DE3921554A1; CZ320690A3; MX174480B; FI916132A0; JPH04506533A; KR0136267B1; US5371131A; IE902361A1; HU905536D0; KR920702709A; ZA905130B; DE59001295D1; AU5856890A; HUT59177A; AU635754B2; BR9007443A; EP0405329A1

Abstract

Afin d'améliorer la force d'adhérence d'un crayon adhésif indéformable mou que l'on use en frottant, composé d'une préparation aqueuse d'un polymère synthétique et d'un savon colloïdal qui sert de structure saponacée et lui donne sa forme, ainsi que le cas échéant d'autres additifs, on utilise comme composition aqueuse de polymère synthétique une dispersion aqueuse de polyuréthanne exempte au moins dans une large mesure de solvants.In order to improve the adhesion strength of a soft non-deformable adhesive pencil which is used by rubbing, composed of an aqueous preparation of a synthetic polymer and of a colloidal soap which serves as a saponaceous structure and gives it its In the form, as well as, where appropriate, of other additives, an aqueous polyurethane dispersion which is free at least to a large extent of solvents is used as the aqueous synthetic polymer composition.

Description

"Glue stick with improved adhesive strength"

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

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. 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. Are the highly sticky aqueous preparations of the polymer substances with adhesive character together with small amounts of the scaffold based on fatty acid soaps heated to higher temperatures, especially above 60 ° C and then allowed to cool this solution at rest, the mixture solidifies to a more or less stiff soap gel in which the shaping and comparatively rigid micelle structure of such Soap gels initially appear predominantly. This enables the known design and handling of such masses in stick form in closable sleeves. When rubbed off, the micelle structure is destroyed, transforming the rigid mass into the pasty state, in which the adhesive character of the mixture of substances comes to the fore.

Numerous attempts have been made to change glue sticks of this type by changing the shaping framework and / or by changing the solvent-activated adhesive-forming component. DE-AS 2204482 uses the reaction product of sorbitol and benzaldehyde as the shaping framework. According to the teaching of DE-OS 2620721, salts of substituted terephthalic acid amides are to be used as gelling agents. According to 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. According to DE-OS 2419067, a reaction product of aromatic diisocyanates with mono- and / or dialkanolamines is to be used as the gel-forming agent.

Despite all of these suggestions, the oldest form of the glue sticks concerned, based on soap gels, as described in the initially cited DE-PS 1811466, has been used at least to a large extent to this day. A solution of PVP in an aqueous-organic solvent mixture is passed through Incorporation of alkali soaps of aliphatic carboxylic acids into the form of the soft, abradable glue stick.

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.

Although the glue sticks mentioned offer sufficient strength for paper gluing, there is still a desire to obtain sticks which can be used more universally and with which gluing can produce higher strengths. In particular, it is to be avoided that, under climatically unfavorable conditions, the paper bonds produced with the pins become detached again.

Another disadvantage of the known glue sticks can be seen in the fact that the stick mass is highly viscous in the heated state before the formation of soap gel, which leads to the formation of bubbles and also otherwise complicates the processing.

It is therefore an object of the invention to provide a glue stick which is improved in this regard and which is based on an aqueous polyurethane dispersion and is suitable for bonds of higher strength. 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. For the purposes of the invention, 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. In addition, 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.

As 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.

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.

As 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. Among 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. Depending on the co-components, the products are polythioethers, polythio mixed ethers, polythioether esters, polythioether ester amides. Such 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. In principle, 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. It is also possible to use polyols which can be produced by completely or partially ring opening epoxidized triglycerides with primary or secondary hydroxyl compounds, for example the reaction product of epoxidized soybean oil with methanol. All aromatic and aliphatic diisocyanates are suitable as polyisocyanates in the PU dispersions according to the invention, such as. B. 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, the isomers of tolylene diisocyanate, optionally in mixture, 1-methyl-2,4-diisocyanato-cyclohexane, 1,6-diisocyanato-2,2,4-trimethy1-hexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatomethyl-3 -isocyanato-1,5,5-trimethyl-cyclohexane, chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, 4,4'-diisocyanatophenylperfluoroethane, tetramethoxy-butane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1, 6-diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate, bis-isocyanatoethyl phthalate, furthermore polyisocyanates with reactive halogen atoms, such as 1-chloromethylphenyl2,4-diisocyanate, 1-bromomethylphenyl-2,6-diisocyanate, 3 , 3-bis-chloromethyl ether-4,4'-diphenyl diisocyanate. 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. Among the aromatic diisocyanates, 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-propanediol- (1,3), 2-methyl-propanediol- (1,3); - Aliphatic, cycloaliphatic and aromatic diamines such as ethylenediamine, hexamethylenediamine, 1,4-cyclohexylenediamine, benzidine, diamino-diphenylmethane, dichloro-diamino-diphenylmethane, the isomers of phenylenediamine, hydrazine, ammonia, carbohydrazide, adipic acid, dihydrazide, sebic acid dihydrazide, sebic acid dihydrazide -Methyl-propylenediamine, diaminodiphenyl sulfone, diaminodiphenyl ether, diaminodiphenyldimethylmethane, 2,4-diamino-6-phenyltriazine; - amino alcohols such as ethanolamine, propanolamine, butanolamine, N-methylethanolamine, N-methylisopropanolamine; - Aliphatic, cycloaliphatic, aromatic and heterocyclic mono- and diaminocarboxylic acids such as glycine, 1- and 2-alanine, 6-aminocaproic acid, 4-aminobutyric acid, the isomeric mono- and diaminobenzoic acids, the isomeric mono- and diaminonaphthoic acids;

water It should be emphasized that within the scope of the present invention it is not possible to distinguish strictly between the compounds with reactive hydrogen atoms with a molecular weight of 300 to 20,000 and the so-called "chain extenders", since the transitions between the two classes of compounds are fluid. Compounds that are not made up of several monomer units but have a molecular weight above 300, such as 3,3'-dibrorn-4,4'-diaminodiphenylmethane, are included in the chain extenders, but also pentaethylene glycol, although the composition of the latter is actually one Is polyether diol.

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-dioxethylaniline, N, N-dioxethyltoluidine, N, N-dioxethyl-1-aminopyridine, N, N'-dioxethylpiperazine, dimethyl-bis-oxethylhydrazine, N, N '-Bis- (2-hydroxy-ethyl) -N, N'-diethyl-hexahydro-p-phenylenediamine, N-12-hydroxyethyl-piperazine, polyalkoxylated amines such as oxypropylated methyl-diethanolamine, furthermore compounds such as N-methyl-N, N-bis-3-aminopropylamine, N- (3-aminopropyl) -N, N'-dimethylethylenediamine, N- (3rd -Aminopropyl) -N-methylethanolamine, N, N'-bis (3-aminopropyl) -N, N'-dimethylethylenediamine, N, N'-bis (3-aminopropyl) piperazine, N- (2-aminoethyl ) -piperazine, N, N'-bisoxyethyl-propylenediamine, 2,6-diaminopyridine, diethanolamino-acetamide, diethanolamidopropionamide, N, N-bis-oxyethyl-phenyl-thiosemicarbazide, N, N-bis-oxethyl-methyl-semicarbazide, p, p'-bis-aminomethyl-dibenzylmethylamine, 2,6-diaminopyridine, 2-dimethylaminomethyl-2-methyl-propanediol-1,3.

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. In order to introduce compounds which can contain ionizable carboxylic acid groups into the polyurethane, the person skilled in the art can add dihydroxycarboxylic acids to the polyols. A preferred dihydroxycarboxylic acid is, for example, dimethylolpropionic acid.

In order to introduce sulfonic acid groups capable of salt formation, 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.

According to the invention, 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.

In the polyurethane dispersions used according to the invention, the polymers, if anionically modified, are present in salt form. In the preferred polymers modified with carboxylic acids or sulfonic acids, alkali metal salts, ammonia or amines, ie primary, secondary or tertiary amines, are present as counterions. For the purposes of the invention, 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.

To produce the polyurethanes which are particularly suitable for the purposes of the invention, 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. 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. Typically, 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)). Furthermore, 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). Of the processes mentioned, the "acetone process" in analogy to the teaching of DE-OS 1495745 (= US-PS 3479310) or to DE-OS 1495847 (GB-PS 1067788) is of particular importance. In general, 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.

Further processes for the production of polyurethane prepolymers, in particular for the continuous production of polyurethane prepolymers, are described in German Offenlegungsschriften 2260870, 23 11 635 and 2344 135.

However, the polyurethane dispersions used in the glue sticks according to the invention can also be prepared without the use of acetone as a solvent. For this purpose, one can start from 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. For the purposes of the invention, it is preferred to use polyurethane dispersions which are clear to opaque.

To be essentially clear, i.e. H. To obtain transparent opaque to water-clear polyurethane dispersions, 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. It is expedient to use 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. Furthermore, the transparency depends on the degree of neutralization. The person skilled in the art can determine by a few preliminary tests from what amount of modifying agent capable of ion formation or from what amount of neutralizing agent a sufficient degree of transparency has been achieved. In general, as little as possible of these substances is used, since they can interfere with the water resistance of the adhesive film when used too high.

In addition to or instead of the modification with components capable of salt formation, 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.

When producing the polyurethane dispersions on which the adhesive sticks according to the invention are based, 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. For the purposes of the invention, however, it is preferred not to use 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 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. For example, if desired, 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.

In addition to the main components described here, customary auxiliaries can also be used, for example substances that promote light and soft abrasion. Such 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.

B e i s p i e l e

example 1

Production of the polyurethane solutions or dispersions

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 (polyether diol and dimethylolpropionic acid) are placed in acetone and stirred at about 65-80 ° C. under reflux until the NCO value is constant. After the reaction has ended, 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. After stirring for several hours, 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.

Table I

Polyurethane system no. A B C D

- ^{- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -}

Parts by weight water 233 230 200 200

"" Isophorone diisocyanate 49 - 5B.4 29.7

"" Trlmethylhexamethy.

lene diisocyanate - 49.5 - - "" PIHF 2000 * 100 90 - - "" Polyurax PPG 1025 ** - 10 100 - "" Pluronic L 61 *** - - - 100

"" Dimethyloipropionic acid 1155..66 15.6 13 6.B

"" NaOH (100%) 4.7 3.5 4.1 2.2

"" NH, (100%) - 0.5 - - "" Aetton 50 60 50 50

Solids content after

Distillation (%) 46 47 41 36

Viscosity at 20 ° C

after distillation (mPas) 4000 3800 14000 12000 * polytetrahydrofuran M _w = 2000 (BASF)

* * Polypropylene glycol M _w = 1000 (BP)

* * * Polyethylene propylene glycol (EO content 10%) M _w = 2000 (BASF)

Example 2

Production of the pen masses

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.

Claims

1. Dimensionally stable, soft, abradable glue stick, consisting of an aqueous preparation of a synthetic polymer and a soap gel as shaping framework and, if desired, further auxiliaries, characterized in that an aqueous solvent dispersion which is at least largely solvent-free is present as the aqueous preparation of a synthetic polymer.

2. Glue stick according to claim 1, characterized in that the aqueous polyurethane dispersion is a reaction product of a polyol or a polyol mixture, a bifunctional or polyfunctional isocyanate component, a component capable of salt formation in an alkaline aqueous solution and / or a non-ionic hydrophilic modifier and if desired, contains a chain extender.

3. Glue stick according to one of claims 1 or 2, characterized in that the aqueous polyurethane dispersion contains a reaction product of a polyether and / or polyester polyol as a polyol.

4. Glue stick according to one of claims 1 to 3, characterized in that the aqueous polyurethane dispersion contains a reaction product of a polyethylene oxide, polypropylene oxide or a polytetrahydrofuran and / or a copolymer of the above.

5. Glue stick according to one of claims 1 to 3, characterized in that the aqueous polyurethane dispersion contains as a polyol mixture a reaction product of a polycarbonate diol, in particular an aliphatic polycarbonate diol.

6. Glue stick according to one of claims 1 to 5, characterized in that the aqueous polyurethane dispersion is a reaction product of a polyol mixture, a component capable of salt formation in alkaline solution and a polyisocyanate in an OH: NCO ratio of 1.0: 0, 8 to 1.0: 4.0, preferably 1.0: 1.1 to 1.0: 2.0, in particular 1.0: 1.1 to 1.0: 1.8.

7. Glue stick according to one of claims 1 to 6, characterized in that the aqueous polyurethane dispersion is a reaction product of a bifunctional or polyfunctional aliphatic isocyanate.

8. Glue stick according to one of claims 1 to 7, characterized in that the aqueous polyurethane dispersion contains a reaction product of a dihydroxycarboxylic acid capable of salt formation.

9. Glue stick according to one of claims 1 to 8, characterized in that the polyurethane dispersion contains a reaction product that the groups capable of salt formation in amounts of 5 to 35 wt .-%, preferably from 5 to 20 wt .-% and contains in particular from 5 to 15% by weight, based on polyurethane solid, and calculated as dimethylolpropionic acid.

10. Glue stick according to one of claims 1 to 9, characterized in that sodium salts of C ₁₂ to C ₂₀ fatty acids of natural or synthetic origin are contained as the gel structure-forming soap.

11. Glue stick according to one of claims 1 to 10, characterized in that the sodium salts of C ₁₂ to C ₂₀ fatty acids are contained in amounts of 3 to 20, preferably 5 to 12 wt .-%, based on the total preparation.

12. Glue stick according to one of claims 1 to 11, characterized in that water-soluble plasticizers, dyes, fragrances and / or moisture-regulating substances are contained as further auxiliaries.

13. A process for the preparation of glue sticks according to claims 1 to 12, characterized in that the soap gel-forming constituents and the polyurethane dispersion are mixed with one another, heated to temperatures above 60 ° C until a uniform mixture has been formed and this without mechanical influence can cool with gel formation.