Abstract:
The invention relates to a dimensionally stable, soft-rubbing adhesive stick consisting of a water-based preparation of starch derivatives and a soap gel as the shaping gel-forming component and, optionally, other auxiliaries. To obtain an adhesive stick which is largely based on natural raw materials and which may therefore be regarded as safe from ecological and toxicological standpoints, the invention is characterized in that viscosity-reduced starch ethers are present as the starch derivatives.

Description:
This application is a 371 of PCT/EP92/01665, filed Jul. 21, 1992. 
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     An adhesive stick based on starch ethers 
     This invention relates to an adhesive stick consisting of a water-based preparation of starch derivatives and a soap gel as the shaping gel-forming component and, optionally, other auxiliaries. The invention also relates to a process for the production of such sticks and to their use. 
     2. Discussion of Related Art 
     Adhesive sticks (=stick-like adhesives which are displaceably mounted in a closeable tube which leave behind a tacky film when rubbed onto a receiving surface) are now part of everyday life. They contain in particular (see DE-PS 18 11 466) water-soluble or water-dispersible synthetic high polymers of adhesive character, more particularly polyvinyl pyrrolidone (PVP), dissolved in an aqueous/organic liquid phase together with a shaping gel-forming component. The gel-forming component is selected in particular from alkali metal or ammonium salts of aliphatic carboxylic acids, more particularly containing from about 12 to 22 carbon atoms. If the basically high-tack water-based preparations of the polymer substances of adhesive character are heated together with small quantities of the gel-forming component based on fatty acid soaps to relatively high temperatures, more particularly above 50° C., and if this solution is subsequently left standing to cool, the mixture solidifies to a more or less stiff soap gel in which the shaping and comparatively rigid micelle structure of the soap gels is predominantly in evidence at first. This provides for the known production and handling of such adhesives in stick form in closeable tubes. When the stick is rubbed onto a receiving surface, the micelle structure if destroyed so that the rigid mixture is converted into a paste-like state in which its adhesive character is predominant. 
     Numerous attempts have been made to modify adhesive sticks of this type by changing the shaping gel-forming component and/or by changing the solvent-activated adhesive-forming component. DE-OS 22 04 482 uses the reaction product of sorbitol and benzaldehyde as the shaping gel-forming component. According to DE-OS 26 20 721, salts of substituted terephthalic acid amides are said to be used as the gelling agent. According to DE-OS 20 54 503, free long-chain aliphatic acids or esters thereof are said to form the gel-forming component instead of the alkali metal salts of aliphatic carboxylic acids. DE-OS 22 19 697 seeks to improve adhesive sticks of the type in question by incorporation of anionic non-soap-like wetting agents in the stick, particularly with a view to improving its rubbing onto the substrate. According to DE-OS 24 19 067, a reaction product of aromatic diisocyanates with monoalkanolamines and/or dialkanolamines is said to be used as the gel-forming agent. 
     Despite all these proposals, the oldest form of adhesive sticks of the type in question based on soap gels, which are described in DE-PS 18 11 466 cited at the beginning, are still in use to by far the predominant extent to this day. A solution of PVP in an aqueous organic solvent mixture is converted into the form of the soft-rubbing adhesive stick by incorporation of alkali metal soaps of aliphatic carboxylic acids. 
     Gelman patent application DE 36 06 382 describes an improved adhesive stick which, to improve its soft-rubbing characteristics, additionally contains a limited quantity of lactams of lower aminocarboxylic acids and/or the corresponding ring-opened aminocarboxylic acids. 
     Other patents and patent applications relating to adhesive sticks include DE 39 21 554, DE 37 02 871, DE 33 28 099, DE 26 13 935, DE 30 15 268 and DE 20 53 674. According to the last of these documents, film-forming, natural and synthetic polymers are used as the adhesive component. Among a number of compounds, carboxymethyl starch is mentioned as an Example of starch derivatives. Water-soluble or water-dispersible adhesives such as, for example, ethoxylated and propoxylated starch derivatives are known from DE 18 11 466 as a constituent of adhesive sticks. If compounds such as these are used in their commercial form as the predominant or sole adhesive component of adhesive sticks, the adhesive stick may be useable in principle, but is not satisfactory in regard to dimensional stability, soft rubbing and minimum tackiness because it is generally friable in its constitution, is difficult to apply and lacks sufficient tack. 
     The problem addressed by the present invention was to remedy these deficiencies and to provide an adhesive stick which would be dimensionally stable and easy to rub onto substrates and which would show sufficient adhesive power although it was to be formulated without solvents on the basis of ecologically safe raw materials of native origin. However, the necessary changes would not make it any more difficult to produce, but on the contrary would facilitate its production. 
     SUMMARY OF THE INVENTION 
     It has surprisingly been found that an adhesive stick of the type in question can be obtained if starch ethers degraded to a defined extent are used in a certain viscosity range as the adhesive component. 
     Accordingly, the problem addressed by the present invention is solved by an adhesive stick consisting of a water-based preparation of macromolecular substrates as the adhesive component and a soap gel as the shaping gel-forming component and, optionally, other auxiliaries, characterized in that the adhesive component contains viscosity-reduced starch ethers. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     &#34;Viscosity-reduced&#34; starch ethers are understood to be starch ethers which not only have been etherified in largely polymer-analog form, but in addition have been chemically or physically destructured so that their viscosity is below about 2,000,000 mPas (30% solution, 20° C., Brookfield). 
     According to Ullmann, Encyklopadie der technischen Chemie, 4th Edition, Verlag Chemie, Weinheim/Bergstrasse (1974), starch ethers are formally products of the condensation between the hydroxy groups of the anhydroglucose units (AGU) of starch molecules and alcoholic hydroxy groups of other compounds. Only a few water-soluble starch ethers of this type are produced on a relatively large scale and industrially used. They include certain hydroxyalkyl starches, more particularly hydroxyethyl and hydroxypropyl starch and also carboxymethyl starch. Reaction products of native starches with ethylene oxide, propylene oxide, butylene oxide and/or glycidols have proved to be particularly suitable for the purposes of the invention. More particularly, starch derivatives having relatively high degrees of substitution, preferably nonionic starch ethers, can advantageously be adjusted to a relatively low viscosity level by mechanical treatment in aqueous systems which promotes the degradation of crystalline structures and/or oxidative, acid-hydrolytic, enzymatic and thermal degradation and are therefore particularly suitable. Accordingly, viscosity-reduced nonionic starch ethers, particularly hydroxyalkyl starch, are particularly preferred because the desired adhesive sticks are best obtained with them. The degree of substitution (DS) should preferably be 0.1 to 2.0 and, more preferably, 0.2 to 1.0. Mixed etherification products may of course also be successfully used in accordance with the invention. The adhesive sticks according to the invention preferably contain 5% by weight to 50% by weight viscosity-reduced starch ethers. These percentages by weight are based on the total weight of the stick. 
     In addition to the viscosity-reduced starch ethers according to the invention, the adhesive stick may contain other macromolecular substances (for example polyurethane dispersions, polyvinyl pyrrolidone and/or polyacrylates) as the adhesive component. The total percentage content of the adhesive components should be 15 to 50% by weight. 
     In principle, any native starches may be used for the production of the starch derivatives used in accordance with the invention. Suitable starches can be found in Ullmann, loc. cit., Vol. 22, sub-chapters 6.2 to 6.4 to the chapter entitled &#34;Starke (Starch)&#34;. In addition to cereal starches, such as cornstarch, wheat starch or rice starch, and also tuber or root starches, such as potato or tapioca starch, pulse starches, such as pea starch or bean starch, are also suitable. 
     The adhesive sticks according to the invention best contain sodium salts of C 12-22  fatty acids of natural or synthetic origin as the soaps for forming the gel structure. C 14-18  fatty acids and mixtures thereof are preferred. The sodium salts of the fatty acids, i.e. the soaps, are present in quantities of 3 to 20% by weight, based on the weight of the adhesive stick, and preferably in quantities of 5 to 10% by weight. 
     The auxiliaries typically used in adhesive sticks may also be used in the adhesive sticks according to the invention in quantities of 0 to 25% by weight, based on the adhesive stick. The auxiliaries in question are, for example, plasticizers and/or moisture regulators, i.e. organic water-soluble solvents, which are normally used in adhesive sticks. Other suitable auxiliaries are polyfunctional alcohols, such as propylene glycol, glycerol, polyglycerols, trimethylol propane, polyether glycols and also sorbitol and/or low molecular weight starch hydrolyzates which have been converted into the corresponding polyols by reduction with hydrogen. For example a mixture of glycerol and polyethylene glycol may be used. The non-volatile organic solvents mentioned should be used in quantities of at most up to 50% by weight, based on the water content of the sticks. 
     In addition to the main components mentioned, typical auxiliaries, for example substances which promote easy and soft rubbing, may also be used. Substances such as these are, for example, aminocarboxylic acids and/or their lactams. Suitable aminocarboxylic acids or lactams should contain up to 12 carbon atoms and, more particularly, from 4 to 8 carbon atoms. The preferred representative in terms of practical application is ε-caprolactam or the 7-aminocaproic acid derived therefrom. The quantity in which the lactams or corresponding aminocarboxylic acids are used is normally no more than 15% by weight and, for example, between 1% by weight and 10% by weight, based on the stick as a whole. 
     The adhesive sticks according to the invention may contain pigments, dyes, fragrances, preservatives and the like as further auxiliaries. These auxiliaries are present in the usual small quantities. Other possible additives are, for example fillers, optical brighteners, dextrins, cellulose derivatives and non-destructured starch derivatives. Mannans, more particularly galactomannans, may be present as further additives in the adhesive sticks according to the invention. Galactomannans from the fruit of the carob tree and from guar flour are particularly suitable. The destructured ethers may also be replaced to a small extent by destructured mannans. 
     The individual components are preferably present in the adhesive stick in the following quantities: 3 to 10% by weight soaps, 5 to 40% by weight viscosity-reduced starch ethers and 0 to 25% by weight auxiliaries, of which 0 to 20% by weight may be water-soluble or water-dispersible polymers. The balance to 100% is water. 
     The mixture is processed in known manner from the mixtures of the water-based preparations of viscosity-reduced starch ethers, the soap component and the other auxiliaries, if any, heated to temperatures of at least 50° C. and preferably to temperatures of 80° C. These mixtures, which are readily pourable at temperatures in the range mentioned, are preferably introduced directly into stick tubes or similar containers and allowed to solidify to the desired gels in the absence of any mechanical action. The water-based preparations of the viscosity-reduced starch ethers are preferably prepared by mixing the starch ethers with water and--substantially irreversibly--degrading the superstructures of the starch ethers by mechanical action and/or by oxidative, acid-catalytic, enzymatic or thermal degradation of the starch ethers. Concentrated systems having a starch ether content of from about 20% by weight to 70% by weight are preferred because it has been found that the preparations are easiest to handle in these concentration ranges. The water-based preparations may then be combined with the other components in the described manner. If desired, the starch derivative preparations may be diluted before mixing with the other components, preferably to a starch ether content of 20% by weight to 40% by weight. 
     The aqueous systems may be mechanically destructured in machines known to the expert, preferably at the high concentrations mentioned. Suitable destructuring machines are headers, extruders, stator-rotor machines and/or stirrers. The degree to which the superstructures of the aqueous starch derivative systems are mechanically degraded is dependent on concentration, temperature, residence time and shearing. The degree of degradation of the starch superstructures should advantageously lie close to the limit. The degree of degradation can be determined by measurement of the solution viscosities. The starch superstructures can also be degraded without any disadvantages during the production of the adhesive sticks in mixing machines in which a sufficient degree of degradation of the starch superstructures can be achieved. In the context of the invention, the degree of degradation can be assumed to be sufficient when a 30% by weight aqueous solution of the starch ether used has a Brookfield viscosity at 20° C. in the range from about 100 to 1,000,000 mPas, preferably in the range from 2,000 to 100,000 mPas and, more preferably, in the range from 3,000 to 30,000 mPas. Adhesive sticks containing 5% by weight to 10% by weight of the starch ethers according to the invention with a viscosity of 1,000,000 to 50,000 mPas or 10 to 30% by weight with a viscosity of 100,000 to 2,000 mPas or 30 to 50% by weight with a viscosity of 30,000 to 100 mPas have proved to be particularly suitable. In addition, other polymers may be added as the adhesive component in a total quantity of up to 50% by weight. The percentages by weight are based on the total weight of the adhesive stick. 
     The mechanical degradation of the starch or starch ether superstructures can be supported or replaced by chemical degradation of the starch molecules to the viscosity level according to the invention. The partial chemical degradation of the starch or starch ether molecules may be carried out both before and after mechanical degradation of the starch superstructures. The two processes may also be carried out alone independently of one another. The viscosity reduction of the starch ether solution may also be carried out solely by chemical degradation to the viscosity level according to the invention. The starch molecules may be degraded by the oxidative, acid-hydrolytic, enzymatic or thermal methods of degradation known to the expert. 
     The processes normally used for degrading starches are described in detail in &#34;Ullmanns Encyklopadie der technischen Chemie&#34; 4th Edition, Verlag Chemie, Weinheim (1974). Preferred oxidizing agents for oxidative degradation are chromic acid, permanganate, hydrogen peroxide, nitrogen dioxide, hypochlorite, periodate and peracids such as, for ,example, peracetic acid. Preferred acids for acidhydrolyric degradation are hydrochloric acid, sulfuric acid and phosphoric acid, although other acids, such as for example acetic acid, oxalic acid, sulfurous acid, perchloric or trichloroacetic acid, may also be used. Alpha- and beta-amylases and also the glucoamylases and debranching enzymes may be used as starch-degrading enzymes. 
     The adhesive sticks according to the invention show high adhesive power and, in addition to the surface-to-surface bonding of substrates, may be used in particular for the bonding of paper and/or cardboard. In addition, they may also be produced, if desired, without using water-soluble plasticizers (water-soluble organic solvents) or moisturizers regulators (again water-soluble organic solvents). 
     The adhesive sticks according to the invention are distinguished by good soft-rubbing characteristics, a uniform film with no unevenness being obtained with little effort. 
     The compressive strengths are in the range from about 30 to 70 N/16 mm .0.. 
     EXAMPLES 
     In a twin-screw Z header, various starch ethers (solids concentration=70% by weight to 75% by weight) were sheared for 3 hours at approx. 80° C. in a water-based system and subsequently diluted with water to a solids content of 30% by weight. The solution viscosities were determined at room temperature (RT) using a Brookfield viscosimeter: 
     
                       TABLE 1______________________________________Viscosity of various aqueous starch ethersolutions (30% by weight) at room temperature           Viscosity [mPas]             After    BeforeStarting material shearing shearing______________________________________HES-K 250         11,700   &gt;2,000,000HES-K 500         9,000    &gt;2,000,000HES-K 750         5,700    &gt;2,000,000HES-K 1000        5,200    &gt;2,000,000HES-K 1250        2,700    &gt;2,000,000HPS-K 100         19,000   &gt;2,000,000HPS-K 250         12,000   &gt;2,000,000HPS-K 500         8,000    &gt;2,000,000HPS-K 750         3,400    &gt;2,000,000HPS-K 1000        4,500    &gt;2,000,000HPS-K 1250        3,600    &gt;2,000,000HE/HPS-K 250/250  10,000   &gt;2,000,000HE/HPS-K 500/500  11,800   &gt;2,000,000HE/HPS-K 1000/1000             16,200   &gt;2,000,000HBS-K 750         4,700    &gt;2,000,000HBS-K 1250        2,700    &gt;2,000,000DHPS-K 500        6,700    &gt;2,000,000DHPS-K 1000       18,000   &gt;2,000,000HPS-M 750         7,100    &gt;2,000,000HPS-t 750         7,700    &gt;2,000,000CMS-K 240/16      75,000   &gt;2,000,000______________________________________ 
    
     
                       TABLE 2______________________________________Comparison of the viscosity of various aqueous starch ethersolutions (10% by weight), sheared and unsheared, at RT          Viscosity [mPas]            After    BeforeStarting material            shearing shearing______________________________________HES-K 1000       200      86,000HPS-K 1000       200      64,000HPS-M 750        350      48,000HPS-T 750        360      84,000DHPS-K 1000      730      96,000______________________________________ 
    
     As the examples in Table 1 and Table 2 show, the viscosity of a starch ether solution is several times higher before the treatment than after the treatment. 
     
         ______________________________________Definitions______________________________________HPS       hydroxypropyl starchHBS       hydroxybutyl starchDHPS      dihydroxypropyl starchK, M, T   basis potato starch, cornstarch, tapioca starch100       molar ratio starch:PO = 1:0.100750       molar ratio starch:PO = 1:0.7501000      molar ratio starch:PO = 1:1.000HES       hydroxyethyl starchHE/HPS    hydroxyethyl hydroxypropyl starchCMS       carboxymethyl starch240/16    molar ratio starch:MCAc = 1:0.240     molar ratio starch:GCH-PGE = 100:0.016     (GCH-PGE = bis-glycerol chlorohydrin poly-     glycol ether, MW = 780, MCAc = methyl     cellulose acetate).______________________________________ 
    
     I. Preparation of the starch ether solutions Examples of destructuring of the starch by mechanical treatment 
     Example 1 
     Degradation in a Z kneader (see also Tables 1 and 2): 
     1.8 kg of a starch ether HES-K 1250 (solids concentration =80.4% by weight) were sheared for 3 hours at approx. 80° C. with 440 ml water in a twin-screw Z kneader. After cooling with continued kneading, the starch ether was carefully diluted with water to a solids content of 30% by weight. The viscosity of the resulting solution as measured at room temperature was 3,600 mPas (Brookfield viscosimeter). 
     Example 2 
     Degradation in a cross-arm paddle mixer: 
     40 kg of a starch ether HPS-K 750 (solids concentration =41.5% by weight) were stirred for 5 hours at 60°-65° C. in a reactor equipped with a cross-arm paddle stirrer and flow baffles. 
     The starch ether was then diluted with water to a solids content of 30% by weight in the reactor. The viscosity of the resulting solution as measured at room temperature was 14,000 mPas (Brookfield viscosimeter). 
     Example 3 
     Degradation in a rotor/stator system: 
     From a storage vessel filled with 6 kg of a starch ether HPS-K 750 (solids concentration=42% by weight), the starch ether was continuously pumped to a high-speed rotor/stator machine at 75° to 80° C. and was then recirculated to the storage vessel. The test was terminated after shearing for about 1 hour at a rate of 120 to 160 kg/h and at a temperature of 75 to 80° C. After dilution to a solids content of 30% by weight, the viscosity of the solution as measured at room temperature was 6,000 mPas (Brookfield viscosimeter). 
     Example 4 
     Degradation in an extruder (twin-screw): 
     1.5 Parts by weight of a starch ether HES-K 1250 (solids concentration=75% by weight) were sheared for three hours at approx. 80° C. with 0.5 part by weight water in a twin-screw extruder. After cooling with continued kneading, the starch ether was carefully diluted with water to a solids content of 30% by weight. The viscosity of resulting solution as measured at room temperature was 4,000 mPas (Brookfield viscosmeter). 
     Example 5 
     Degradation by oxidation 
     41.8 g of a 32.1% hydrogen peroxide solution were added at 60° C. to 17.9 kg of a starch ether HPS-T750 (solids concentration=40.7%). The solution was heated to 83° C. and stirred for 2.5 h using a cross-arm paddle stirrer, the solution becoming more thinly liquid. The viscosity of the resulting solution as measured at 20° C. was 9,000 mPas (Brookfield viscosimeter) for a solids content of 30%. 
     Example 6 
     Degradation by acid hydrolysis 
     In a 1000 ml stirred glass flask, 432 g of a starch ether solution HPS-T750 (solids concentration=40.7%) were diluted with 28 g water and acidified with 126 ml 2-molar HCl to, a pH value of 1.2. The solution was then heated for 40 minutes at 65° C. 
     The viscosity of the resulting solution as measured at room temperature was 5,700 mPas (Brookfield viscosimeter). 
     Example 7 
     Degradation by enzymatic action In a 1000 ml stirred glass flask, 508 g of a starch ether solution HPS-T750 (solids concentration=40.7%) were diluted with 41 g water and 121 ml 2-molar HCl and, after heating to 65° C., were adjusted with 2-molar HCl solution to a pH value of 6. 6.6 mg alpha-amylase (BAN 800 MG, KNU/g) were added to the resulting solution, followed by stirring for 30 minutes at 65° C. The solution was then refluxed for 20 minutes to inactivate the enzyme. The viscosity of the resulting solution as measured at room temperature was 5,400 mPas (Brookfield viscosimeter). 
     II. Examples of starch ether sticks 
     A Viscosity-reduced starch ethers (invention) 
     B Non-viscosity-reduced starch ethers (comparison) 
     The starch ethers contain free alkali which is generally sufficient to saponify the fatty acids. 
     In the following Examples, therefore, sodiumhydroxide is only mentioned when it is additionally necessary for complete saponification. The sticks were produced as described in the Examples. 
     Examples of starch ether sticks 
     Example 1A 
     
         ______________________________________22.5 g    HPS-K 750, mechanically destructured4.2 g     monocarboxylic acid, C161.3 g     monocarboxylic acid, C181.0 g     monocarboxylic acid, C146.5 g     sorbitol solution10.0 g    glycerol54.5 g    water______________________________________ 
    
     Rubbing: pliant Open time: 50 seconds Setting time: 3.5 minutes Compressive strength: 45 N/16 mm .0. 
     Example 2A 
     
         ______________________________________23.2 g     HPS-T 750 degraded by oxidation5.5 g      monocarboxylic acids, C16/C189.5 g      sorbitol solution7.0 g      glycerol3.0 g      1,2-propylene glycol51.8 g     water______________________________________ 
    
     Rubbing: pliant Open time: 60 seconds Setting time: 3-4 minutes Compressive strength: 48 N/16 mm .0. 
     Example 3A 
     
         ______________________________________24.5 g   HE/HPS-K 1000 mechanically destructured6.0 g    monocarboxylic acids, C16/C1810.0 g   sorbitol solution10.0 g   glycerol0.2 g    sodium hydroxide49.3 g   water______________________________________ 
    
     Rubbing: smooth, pliant Open time: 50-60 seconds Setting time: 3.5 minutes Compressive strength: 46-48 N/16 mm .0. 
     Example 4A 
     
         ______________________________________23.7 g   HE/HPS-K 1000 mechanically destructured5.5 g    monocarboxylic acids, C16/C186.5 g    sorbitol solution8.0 g    glycerol56.3 g   water______________________________________ 
    
     Rubbing: pliant Open time: 50-60 seconds Setting time: 3 minutes Compressive strength: 43-44 N/16 mm .0. 
     Example 5A 
     
         ______________________________________24.3 g    HPS-M 750, mechanically destructured5.5 g     monocarboxylic acids, C16/C182.0 g     sodium hydroxide10.0 g    sorbitol solution9.0 g     glycerol49.2 g    water______________________________________ 
    
     Rubbing: pliant Open time: 50 seconds Setting time: 3-4 minutes Compressive strength: 48-50 N/16 mm .0. 
     Example 6A 
     
         ______________________________________24.3 g    HBS-K 750, mechanically destructured5.5 g     monocarboxylic acids, C16/C188.0 g     sorbitol solution9.0 g     glycerol4.0 g     1,2-propylene glycol1.0 g     sodium hydroxide48.2 g    water______________________________________ 
    
     Rubbing: pliant Open time: 45-60 seconds Setting time: 2.5-3 minutes Compressive strength: 45 N/16 mm .0. 
     Example 7A 
     
         ______________________________________24.5 g   DHPS-K 1000, mechanically destructured5.5 g    monocarboxylic acids C16/C189.0 g    sorbitol solution8.0 g    glycerol1.0 g    sodium hydroxide52.0 g   water______________________________________ 
    
     Rubbing:: pliant Open time: 50-60 seconds Setting time: 2.5-3 minutes Compressive strength: 44 N/16 mm .0. 
     Example 8A 
     
         ______________________________________5.5 g     monocarboxylic acid, C16/C1820.0 g    HPS-M750, mechanically destructured4.3 g     PVP K802.0 g     NaOH10.0 g    sorbitol solution8.0 g     glycerol2.0 g     caprolactam48.2 g    H.sub.2 O______________________________________ 
    
     Rubbing: pliant Open time: 50-60 seconds Setting time: 2.5-3 minutes Compressive strength: 50 N/16 mm .0. 
     Example 9A 
     
         ______________________________________5.5 g     monocarboxylic acid, C16/C1815.0 g    HPS-M750, mechanically destructured7.0 g     HPS-T750, degraded by acid hydrolysis3.3 g     PVP K8010.0 g    sorbitol solution8.0 g     glycerol1.0 g     caprolactam48.2 g    H.sub.2 O______________________________________ 
    
     Rubbing: pliant Open time: 50-60 seconds Setting time: 2-3 minutes Compressive strength: 43 N/16 mm .0. 
     Example 10A 
     
         ______________________________________5.5 g      monocarboxylic acids, C16/C1815.0 g     HPS-T750, degraded by oxidation7.0 g      HPS T750, enzyme-degraded3.0 g      PVP K9010.0 g     sorbitol solution7.0 g      glycerol3.0 g      caprolactam47.5 g     H.sub.2 O______________________________________ 
    
     Rubbing: pliant Open time: 45-50 seconds Setting time: 1.5-2.5 minutes Compressive strength: 41 N/16 mm .0. 
     PVP K80 and PVP K90 are polyvinyl pyrrolidones of BASF. 
     The sorbitol solution is a 70% aqueous solution. 
     Examples of starch ether sticks B 
     Example 1B 
     
         ______________________________________21.5 g     HPS-K 7506.6 g      monocarboxylic acids, C16/C188.0 g      sorbitol solution7.0 g      glycerol5.0 g      1,2-propylene glycol51.9 g     water______________________________________ 
    
     Example 2B 
     
         ______________________________________21.5 g     HPS-T 7506.5 g      monocarboxylic acids, C16/C188.0 g      sorbitol solution7.0 g      glycerol5.0 g      1,2-propylene glycol51.9 g     water______________________________________ 
    
     Example 3B 
     
         ______________________________________23.8 g     HPS-K 7506.6 g      monocarboxylic acids, C16/C187.5 g      sorbitol solution6.0 g      glycerol6.0 g      1,2-propylene glycol1.5 g      polyethylene glycol48.6 g     water______________________________________ 
    
     In all three Comparison Examples with starch ethers having a viscosity of at least 2,000,000 mPas, the adhesive sticks obtained were unsuitable for practical use: 
     Rubbing was greasy and stringy. 
     The constitution was friable so that the adhesive film obtained was so lacking in uniformity that the uneven areas could still be seen after the bonding of paper. 
     Tackiness was so poor that paper could not be firmly bonded. 
     In addition, it was difficult to produce adhesive sticks: 
     The filling was uneven and contained air bubbles. 
     Anchorage at the base of the stick was inadequate. 
     The adhesive formed threads during filling. 
     Tests for the quality control of adhesive sticks Compressive strength 
     Compressive strength is understood to be the maxmimum load measured parallel to the longitudinal axis on collapse of the stick under pressure. 
     Compressive strength is measured with an Erichsen Model 464L compressive strength tester, measuring head 709 (manufacturer: Erichsen, Simonshofchen 31, 56 Wuppertal 11). The adhesive cut off with a minimum length of 30 mm immediately above the piston is placed between two holders in the form of approx. 10 mm thick disks of rigid PVC which are formed with a circular 3 mm deep depression adapted to the particular stick diameters. The stick provided with the holders is placed centrally on the table of the compressive strength tester. The height of the force measuring instrument over the table is adapted to the height of the stick to be tested. The measuring head is then advanced against the stick to be tested at a rate of approx. 70 mm per minutes. On reaching the maximum compressive force, the value is read off from the digital display. 
     Setting time 
     To determine whether the adhesive properties of the sticks; are sufficient for the application envisaged, bonding tests are carried out by hand under certain processing conditions and evaluated. The following procedure is adopted: 
     A supply of white chrome paper (weight per unit area approx. 100 g/m 2 ) coated on one side and adhesive sticks to be tested are conditioned for at least 24 hours at 20° C./65% relative air humidity. The test paper is cut into strips 5 cm side and approx. 30 cm long. An adhesive stick is rubbed twice longitudinally under uniform pressure over the uncoated side of a paper strip and should produce a uniform film. Immediately afterwards, a second paper strip which has not been coated with adhesive is placed on the coated strip with its uncoated side facing inwards and rubbed on by hand. An attempt is then made to peel the paper strips slowly from one another. The time at which separation in the adhesion zone is only possible with tearing of paper over entire width characterizes the setting time. 
     Open time 
     The open time is the time after application of the adhesive within which the materials to be bonded have to be fitted together in order, after setting, to obtain complete tearing of paper in the separation test. The method is the same as that used to determine setting time except that the strips of paper are only fitted together after defined times following application of the adhesive. Beginning with 15 seconds, the open time may be graduated, for example, in intervals of 15 seconds. With slow-setting adhesives having predictably longer open times, correspondingly longer intervals will be selected. 
     Rubbing 
     Rubbing is subjectively evaluated by at least two examiners. The performance properties are characterized and classified as follows: smooth, pliable, flat, crumbly, greasy, hard, soft and stringy.