CA2826831C - Glue stick based on starch mixed ethers - Google Patents
Glue stick based on starch mixed ethers Download PDFInfo
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- CA2826831C CA2826831C CA2826831A CA2826831A CA2826831C CA 2826831 C CA2826831 C CA 2826831C CA 2826831 A CA2826831 A CA 2826831A CA 2826831 A CA2826831 A CA 2826831A CA 2826831 C CA2826831 C CA 2826831C
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- CA
- Canada
- Prior art keywords
- starch
- glue stick
- stick according
- hydroxyalkylcarboxymethyl
- starches
- 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.)
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- 229920002472 Starch Polymers 0.000 title claims abstract description 140
- 235000019698 starch Nutrition 0.000 title claims abstract description 140
- 239000008107 starch Substances 0.000 title claims abstract description 102
- 239000004836 Glue Stick Substances 0.000 title claims abstract description 88
- 150000002170 ethers Chemical class 0.000 title description 30
- 239000000344 soap Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000005304 joining Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000000123 paper Substances 0.000 claims abstract description 5
- 239000011111 cardboard Substances 0.000 claims abstract description 4
- 229920003023 plastic Polymers 0.000 claims abstract description 4
- 239000004033 plastic Substances 0.000 claims abstract description 4
- 239000002023 wood Substances 0.000 claims abstract description 4
- -1 hydroxyethylcarboxymethyl Chemical group 0.000 claims description 35
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 15
- 229920002521 macromolecule Polymers 0.000 claims description 10
- 239000002671 adjuvant Substances 0.000 claims description 9
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 claims description 9
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 9
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920001592 potato starch Polymers 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 description 30
- 239000000853 adhesive Substances 0.000 description 28
- 239000000126 substance Substances 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 13
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920000881 Modified starch Polymers 0.000 description 8
- 235000019426 modified starch Nutrition 0.000 description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 8
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 235000010980 cellulose Nutrition 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000010338 mechanical breakdown Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- 240000003183 Manihot esculenta Species 0.000 description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004026 adhesive bonding Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 229920000926 Galactomannan Polymers 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000057 Mannan Polymers 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- LUEWUZLMQUOBSB-GFVSVBBRSA-N mannan Chemical class O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](O[C@H]3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-GFVSVBBRSA-N 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 244000303965 Cyamopsis psoralioides Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 102100022624 Glucoamylase Human genes 0.000 description 1
- 108050008938 Glucoamylases Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001612 Hydroxyethyl starch Polymers 0.000 description 1
- 240000008375 Hymenaea courbaril Species 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000001341 hydroxy propyl starch Substances 0.000 description 1
- 235000021374 legumes Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
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
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/04—Starch derivatives
- C09J103/08—Ethers
-
- 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
Abstract
The subject matter of the present invention is glue stick, containing an aqueous preparation of at least one hydroxyalkylcarboxymethyl starch having a viscosity less than 2,000,000 mPas, determined as a 40-wt% aqueous solution using a Brookfield RVT viscosimeter at 20°C, spindle 7, 20 rpm, and soap, the manufacture thereof, and the use thereof for planar joining of substrates, in particular for joining paper, cardboard, wood, and/or plastic to one another.
Description
. CA 02826831 2013-08-08 GLUE STICK BASED ON STARCH MIXED ETHERS
[0002] The invention is in the field of adhesives, in particular glue sticks, and relates to a glue stick based on special mixed starch ethers, to the manufacture thereof, and to the use thereof.
[0003] Glue sticks (rod-shaped adhesives that are received slidably in a closable casing and leave behind a tacky film when rubbed off onto a substrate surface) are commonly used objects in contemporary everyday life. They contain, for example, water-soluble resp. water-dispersible synthetic polymers of an adhesive nature -- in particular polyvinylpyrrolidone (PVP) -- dissolved in an aqueous-organic liquid phase, together with a shape-imparting structural substance. Alkali resp.
ammonium salts of aliphatic carboxylic acids, in particular in the range of number of carbons from 12 to 22, are used in particular as a structural substance. If the aqueous preparations of the polymer substances of an adhesive nature, which are inherently highly tacky, are heated to higher temperatures, in particular above 50 C, together with small quantities of the structural substance based on fatty acid soaps, and if that solution is left to cool undisturbed, the substance mixture solidifies into a more or less rigid soap gel in which the shape-imparting and comparatively rigid micelle structure of such soap gels is at first predominantly apparent. This makes possible the known forming and handling of such substances in stick form in closable casings. Upon rubbing off, the micelle structure becomes destroyed and the rigid mass is thus converted into the pasty state in which the adhesive nature of the substance mixture then becomes paramount.
ammonium salts of aliphatic carboxylic acids, in particular in the range of number of carbons from 12 to 22, are used in particular as a structural substance. If the aqueous preparations of the polymer substances of an adhesive nature, which are inherently highly tacky, are heated to higher temperatures, in particular above 50 C, together with small quantities of the structural substance based on fatty acid soaps, and if that solution is left to cool undisturbed, the substance mixture solidifies into a more or less rigid soap gel in which the shape-imparting and comparatively rigid micelle structure of such soap gels is at first predominantly apparent. This makes possible the known forming and handling of such substances in stick form in closable casings. Upon rubbing off, the micelle structure becomes destroyed and the rigid mass is thus converted into the pasty state in which the adhesive nature of the substance mixture then becomes paramount.
[0004] Polymers based on natural raw materials are also used as an adhering component instead of the water-soluble resp. water-dispersible synthetic polymers of an adhesive nature.
[0005] WO 93/03109 Al, for example, discloses glue sticks based on reduced-viscosity starch derivatives. Nonionic starch ethers that are obtained by reacting natural starch with ethylene oxide, propylene oxide, butylene oxide, and/or glycide are preferably used. Hydroxyalkyl starches are described as being particularly suitable, and mixed etherification products can also be used successfully.
Hydroxyethyl starches and hydroxypropyl starches are used predominantly in the Examples, but the use of hydroxyethyl-hydroxypropyl starch can also be gathered from the Examples.
Hydroxyethyl starches and hydroxypropyl starches are used predominantly in the Examples, but the use of hydroxyethyl-hydroxypropyl starch can also be gathered from the Examples.
[0006] WO 99/51699 Al describes glue sticks that are likewise based on reduced-viscosity starch derivatives. These correspond to the derivatives known from WO 93/03109 Al. The glue stick comprises as an adhesive component an aqueous preparation that besides the aforementioned starch ethers also contains sucrose, as well as a soap gel as a structural substance.
[0007] The known glue sticks possess a level of performance that is satisfactory for most applications. From a production-engineering standpoint, however, it is usually necessary to add adjuvants to the glue sticks. Cellulose ethers in particular are thus introduced as adjuvants in order to stabilize the viscosity of the mass. This is significant in particular for the decanting process, since a mass with too low a viscosity would run out of the casings that are made available. At the same time, the cellulose ethers result in shortcomings in terms of the rub-off properties of the stick, in that small particles detach during use and the stick smears.
Important utilization properties perceptible to the user, such as the strength and rub-off of these glue sticks, are therefore still capable of improvement.
Important utilization properties perceptible to the user, such as the strength and rub-off of these glue sticks, are therefore still capable of improvement.
[0008] A demand therefore exists for glue sticks that do not exhibit the disadvantages set forth above and that possess optimized processing and utilization properties.
[0009] The object of the present invention is therefore to make available a glue stick that on the one hand exhibits good strength in combination with outstanding rub-off properties, as well as good adhesive strength and shelf stability. On the other hand, the mixture on which the stick is based is intended to exhibit, under the ' CA 02826831 2013-08-08 conditions that exist during manufacture (i.e. in particular at temperatures above 50 C), a viscosity that is suitable for problem-free introduction of the adhesive masses into the stick casings, with no need to use cellulose derivatives for viscosity stabilization.
[0010] The manner in which the object is achieved is evident from the fundamental idea of the invention, that of adding special mixed starch ethers to the formulations of the glue sticks.
[0011] The subject matter of the invention is therefore a glue stick that contains an aqueous preparation of at least one hydroxyalkylcarboxymethyl starch having a viscosity less than 2,000,000 mPas, determined as a 40-wt% aqueous solution using a Brookfield RVT viscosimeter at 20 C, spindle 7, 20 rpm, and soap.
[0012] Surprisingly, the use of hydroxyalkylcarboxymethyl starch results both in stabilizing properties during production and in improved rub-off properties, while the adhesive results of the resulting glue sticks remain at least the same. The initial adhesive strength of commercially usual glue sticks based on reduced-viscosity hydroxyalkyl starches can be reached without difficulty, and in fact slightly exceeded. The initial adhesive strength of commercially usual glue sticks based on polyvinylpyrrolidone is appreciably exceeded. The addition of usual substances for viscosity stabilization, in particular cellulose ethers, can be omitted.
[0013] A glue stick according to the present invention is notable for improved strength and a more uniform rub-off as compared with known glue sticks, with outstanding adhesive and storage properties. Even over longer storage times, the adhesive bonds retain their white color and do not become yellow. At temperatures around 80 C the adhesive mixture on which the stick is based moreover exhibits a viscosity such that on the one hand it can easily be introduced into the stick casings, but on the other hand also does not emerge from the casing again through unsealed points in the stick screw seating region.
q . CA 02826831 2013-08-08
q . CA 02826831 2013-08-08
[0014]
Permanent adhesive bonding of substrates can be effected using the glue sticks according to the present invention. They can be used in particular for permanent planar joining of paper, cardboard, wood, and/or plastic to one another.
Permanent adhesive bonding of substrates can be effected using the glue sticks according to the present invention. They can be used in particular for permanent planar joining of paper, cardboard, wood, and/or plastic to one another.
[0015] The glue sticks according to the present invention contain as an adhesive component an aqueous preparation of at least one hydroxyalkylcarboxymethyl starch having a viscosity less than 2,000,000 mPas, determined as a 40-wt% aqueous solution using a Brookfield RVT viscosimeter at 20 C, spindle 7, rpm.
[0016]
Hydroxyalkylcarboxymethyl starches belong the group of the starch ethers, and can also be referred to as "mixed starch ethers." When mixed starch ethers are discussed hereinafter, they are to be understood as hydroxyalkylcarboxymethyl starches.
Hydroxyalkylcarboxymethyl starches belong the group of the starch ethers, and can also be referred to as "mixed starch ethers." When mixed starch ethers are discussed hereinafter, they are to be understood as hydroxyalkylcarboxymethyl starches.
[0017] According to Ullmann, "Encyklopadie der technischen Chemie"
[Encyclopedia of chemical engineering], 4th edition, Verlag Chemie, Weinheim/Bergstrafle (1974), starch ethers are formally products of condensation between the hydroxy groups of the anhydroglucose units (AGUs) of starch molecules and alcoholic hydroxy groups of other compounds. Only a few water-soluble ones of these types of starch ethers are manufactured and industrially used on a large scale. These include specific hydroxyalkyl starches, especially hydroxyethyl and hydroxypropyl starches, as well as carboxymethyl starch. A
number of different hydroxyalkylcarboxymethyl starches are, however, also commercially available.
[Encyclopedia of chemical engineering], 4th edition, Verlag Chemie, Weinheim/Bergstrafle (1974), starch ethers are formally products of condensation between the hydroxy groups of the anhydroglucose units (AGUs) of starch molecules and alcoholic hydroxy groups of other compounds. Only a few water-soluble ones of these types of starch ethers are manufactured and industrially used on a large scale. These include specific hydroxyalkyl starches, especially hydroxyethyl and hydroxypropyl starches, as well as carboxymethyl starch. A
number of different hydroxyalkylcarboxymethyl starches are, however, also commercially available.
[0018] By preference, hydroxy-C1 to C10 alkylcarboxymethyl starches, particularly preferably hydroxy-C2 to C6 alkylcarboxymethyl starches, are used according to the present invention as hydroxyalkylcarboxymethyl starches. Very particularly preferably, the hydroxyalkylcarboxymethyl starch is selected from hydroxyethylcarboxymethyl starches, hydroxypropylcarboxymethyl starches, and/or ' CA 02826831 2013-08-08 hydroxyethylhydroxypropylcarboxymethyl starches, the hydroxypropylcarboxymethyl starches in turn being preferred.
[0019]
Hydroxypropylcarboxmethyl starches used with particular preference are obtained by reacting a starch with monochloroacetic acid and/or monochloroacetate and propylene oxide, where monochloroacetic acid and/or monochloroacetate on the one hand and propylene oxide on the other hand are used at a molar ratio from : 1 to 1 : 100, by preference from 5 : 1 to 1 : 50, particularly preferably from 5 : 1 to 1 : 10. As a rule, the reaction occurs in two steps, in a first step the starch being reacted with monochloroacetic acid and/or monochloroacetate, and in a second step the resulting starch derivative then being reacted with propylene oxide. In the first step, carboxymethyl groups are introduced into the starch molecule. By reaction with propylene oxide, hydroxypropyl groups resp. hydroxy-terminated polypropylene oxide chains are linked to these carboxymethyl groups and/or to those free hydroxy groups of the anhydroglucose units (AGUs) of the starch molecules which are still present. The molar ratio of carboxymethyl groups and hydroxypropyl groups in the starch molecule is determined by the corresponding molar ratio of the educts used. If hydroxy-terminated polypropylene oxide chains are constructed, then the molar content of hydroxypropyl groups in the starch molecule is understood as the sum of the molar content of terminal hydroxypropyl groups and of the molar content of propylene oxide units in the polypropylene oxide chain. One mol of a -CH2CH(CH3)-0-CH2CH(CH3)-OH group therefore corresponds, for example, to two mol hydroxypropyl groups in the starch molecule.
Hydroxypropylcarboxmethyl starches used with particular preference are obtained by reacting a starch with monochloroacetic acid and/or monochloroacetate and propylene oxide, where monochloroacetic acid and/or monochloroacetate on the one hand and propylene oxide on the other hand are used at a molar ratio from : 1 to 1 : 100, by preference from 5 : 1 to 1 : 50, particularly preferably from 5 : 1 to 1 : 10. As a rule, the reaction occurs in two steps, in a first step the starch being reacted with monochloroacetic acid and/or monochloroacetate, and in a second step the resulting starch derivative then being reacted with propylene oxide. In the first step, carboxymethyl groups are introduced into the starch molecule. By reaction with propylene oxide, hydroxypropyl groups resp. hydroxy-terminated polypropylene oxide chains are linked to these carboxymethyl groups and/or to those free hydroxy groups of the anhydroglucose units (AGUs) of the starch molecules which are still present. The molar ratio of carboxymethyl groups and hydroxypropyl groups in the starch molecule is determined by the corresponding molar ratio of the educts used. If hydroxy-terminated polypropylene oxide chains are constructed, then the molar content of hydroxypropyl groups in the starch molecule is understood as the sum of the molar content of terminal hydroxypropyl groups and of the molar content of propylene oxide units in the polypropylene oxide chain. One mol of a -CH2CH(CH3)-0-CH2CH(CH3)-OH group therefore corresponds, for example, to two mol hydroxypropyl groups in the starch molecule.
[0020] All natural starches can be used in principle to manufacture the mixed starch ethers usable according to the present invention. Suitable starches may be gathered from the aforementioned Ullmann, volume 22, sub-chapters 6.2 to 6.4 of the "Starch" chapter. In addition to cereal starches such as corn, wheat, or rice starch, as well as tuber or root starches such as potato, cassava, or tapioca starch, legume starches such as pea or bean starches are also suitable. The mixed starch ethers usable according to the present invention are, however, preferably based on tuber or root starches, particularly preferably on potato starch.
[0021] The aqueous preparations of reduced-viscosity mixed starch ethers are preferably manufactured by mixing the mixed starch ethers with water and (very largely irreversibly) breaking down the higher-order structures of the mixed starch ethers by physical, in particular mechanical action, and/or chemically breaking down the mixed starch ethers, for example by oxidation, acid catalysis, or enzymatically resp. thermally. A combination of actions is also possible.
Concentrated systems having a starch ether content from approximately 20 to 70 wt% are preferred in this context, since it has been proven that technical handling is easiest in these concentration ranges. The aqueous preparations can then be brought together with the remaining constituents in the manner described. If desired, the starch derivative preparations can be diluted prior to mixing with the other constituents, by preference to a mixed starch ether content from 30 to wt%.
Concentrated systems having a starch ether content from approximately 20 to 70 wt% are preferred in this context, since it has been proven that technical handling is easiest in these concentration ranges. The aqueous preparations can then be brought together with the remaining constituents in the manner described. If desired, the starch derivative preparations can be diluted prior to mixing with the other constituents, by preference to a mixed starch ether content from 30 to wt%.
[0022] Mechanical breakdown of the structures of such aqueous systems can be accomplished in mechanical apparatuses known to one skilled in the art.
Kneaders, extruders, stator/rotor machines, and/or agitators are suitable, for example, as such apparatuses. The degree of mechanical breakdown of the higher-order structures of the aqueous starch derivative systems depends on concentration, temperature, residence time, and shear. The degree of breakdown of the higher-order starch structures should advantageously be close to the achievable limit value. The degree of breakdown can be ascertained by determining the solution viscosity values. Without disadvantages, the breakdown of the higher-order starch structures can also occur during manufacture of the glue stick substances in batch apparatuses in which a sufficient degree of breakdown of the higher-order starch structures can be achieved.
Kneaders, extruders, stator/rotor machines, and/or agitators are suitable, for example, as such apparatuses. The degree of mechanical breakdown of the higher-order structures of the aqueous starch derivative systems depends on concentration, temperature, residence time, and shear. The degree of breakdown of the higher-order starch structures should advantageously be close to the achievable limit value. The degree of breakdown can be ascertained by determining the solution viscosity values. Without disadvantages, the breakdown of the higher-order starch structures can also occur during manufacture of the glue stick substances in batch apparatuses in which a sufficient degree of breakdown of the higher-order starch structures can be achieved.
[0023] The mechanical breakdown of the higher-order starch structures or *4 higher-order starch ether structures can be supplemented with or replaced by a chemical breakdown of the starch molecules to the viscosity level according to the present invention. The (partial) chemical breakdown of the starch molecules resp.
starch ether molecules can be carried out both before and after the mechanical breakdown of the higher-order starch structures. Both processes can also be carried out alone, independently of one another. The reduction in the viscosity of the mixed starch ether solution can also be accomplished exclusively by chemical breakdown to the viscosity level according to the present invention. The breakdown of the starch molecules can occur in accordance with methods known to one skilled in the art, by oxidative, acid-hydrolytic, enzymatic, or thermal breakdown.
starch ether molecules can be carried out both before and after the mechanical breakdown of the higher-order starch structures. Both processes can also be carried out alone, independently of one another. The reduction in the viscosity of the mixed starch ether solution can also be accomplished exclusively by chemical breakdown to the viscosity level according to the present invention. The breakdown of the starch molecules can occur in accordance with methods known to one skilled in the art, by oxidative, acid-hydrolytic, enzymatic, or thermal breakdown.
[0024] Ullmann's "Encyklopadie der technischen Chemie" [Encyclopedia of chemical engineering], 4th edition, Verlag Chemie, Weinheim (1974) describes in further detail the usual methods for breaking down starches. Preferred oxidizing agents for oxidative breakdown are chromic acid, permanganate, hydrogen peroxide, nitrogen dioxide, hypochlorite, periodate, and peracids such as, for example, peracetic acid. Hydrochloric acid, sulfuric acid, or phosphoric acid are preferably used as acids for acid-hydrolytic breakdown, but the use of other acids such as, for example, acetic acid, oxalic acid, sulfurous acid, perchloric acid, or trichloroacetic acid is also possible. Enzymes that can be used to break down starches are a- and 3-amylases, as well as the glucoamylases and debranching enzymes.
[0025] A sufficient degree of breakdown for purposes of the invention is usefully achieved when a 40-wt% aqueous solution of the mixed starch ether being used exhibits at 20 C a viscosity (Brookfield method) of less than 2,000,000 mPas, for example 100 to 1,000,000 mPas, by preference 2,000 to 100,000 mPas, in particular 10,000 to 80,000 mPas.
[0026] The hydroxyalkylcarboxymethyl starches contained in the glue sticks therefore by preference exhibit a viscosity from 100 to 1,000,000 mPas, by ' CA 02826831 2013-08-08 preference from 2,000 to 100,000 mPas, particularly preferably from 10,000 to 80,000 mPas, determined in each case as a 40-wt% aqueous solution using a Brookfield RVT viscosimeter at 20 C, spindle 7, 20 rpm.
[0027] The glue sticks contain the hydroxyalkylcarboxymethyl starch by preference in a total quantity from 5 to 50, particularly preferably from 10 to 40 wt%, based on the total mass of the glue stick. If mixtures of several hydroxyalkylcarboxymethyl starches are used, the total quantity is of course to be understood as the sum of the quantities of each hydroxyalkylcarboxymethyl starch that is used.
[0028] Glue sticks that contain 5 to 10 wt% mixed starch ethers having a viscosity from 1,000,000 mPas to 50,000 mPa, or 10 to 30 wt% having a viscosity from 100,000 to 2,000 mPas, or 30 to 50 wt% having a viscosity from 30,000 to mPas, have proven particularly suitable. The "wt%" refers to the total weight of the glue stick.
[0029] It is preferred to use hydroxyalkylcarboxymethyl starches whose degree of substitution (DS) is 0.1 to 2.0, by preference 0.2 to 1Ø
[0030] The glue stick according to the present invention can contain at least two different hydroxyalkylcarboxymethyl starches. The glue stick according to the present invention by preference contains at least two different hydroxpropylcarboxymethyl starches, particularly preferably at least two different hydroxypropylcarboxymethyl starches that differ from one another in terms of the molar ratio of hydroxypropyl groups to carboxymethyl groups. By preference, what is used as a first hydroxypropylcarboxymethyl starch is a hydroxypropylcarboxymethyl starch that is obtained by a reacting a starch with monochloroacetic acid and/or monochloroacetate and propylene oxide, the monochloroacetic acid and/or monochloroacetate on the one hand and the propylene oxide on the other hand being used at a molar ratio from 1 : 2 to 1 :
. . , 100, by preference from 1 : 2 to 1 :50, particularly preferably from 1 : 2 to 1 : 5.
The second hydroxypropylcarboxymethyl starch used is by preference a hydroxypropylcarboxymethyl starch that is obtained by reacting a starch with monochloroacetic acid and/or monochloroacetate and propylene oxide, the monochloroacetic acid and/or monochloroacetate on the one hand and the propylene oxide on the other hand being used at a molar ratio from 10: 1 to 1 : 1, by preference from 8 : 1 to 2 : 1, particularly preferably from 5 : 1 to 3 :
1. In other words, in the one case the hydroxyalkyl groups, and in the other case the carboxymethyl groups, are present at a molar excess. The first and the second hydroxypropylcarboxymethyl starch are used by preference in quantities such that the weight ratio of the first to the second hydroxypropylcarboxymethyl starch is 100 : 1 to 1 : 1, by preference 50: 1 to 2: 1, particularly preferably 25: 1 to 5:
1.
. . , 100, by preference from 1 : 2 to 1 :50, particularly preferably from 1 : 2 to 1 : 5.
The second hydroxypropylcarboxymethyl starch used is by preference a hydroxypropylcarboxymethyl starch that is obtained by reacting a starch with monochloroacetic acid and/or monochloroacetate and propylene oxide, the monochloroacetic acid and/or monochloroacetate on the one hand and the propylene oxide on the other hand being used at a molar ratio from 10: 1 to 1 : 1, by preference from 8 : 1 to 2 : 1, particularly preferably from 5 : 1 to 3 :
1. In other words, in the one case the hydroxyalkyl groups, and in the other case the carboxymethyl groups, are present at a molar excess. The first and the second hydroxypropylcarboxymethyl starch are used by preference in quantities such that the weight ratio of the first to the second hydroxypropylcarboxymethyl starch is 100 : 1 to 1 : 1, by preference 50: 1 to 2: 1, particularly preferably 25: 1 to 5:
1.
[0031] The mixed starch ethers used according to the present invention can be present in uncrosslinked or crosslinked fashion. Crosslinked mixed starch ethers additionally exhibit water-retarding properties, with the result that the viscosity of the stick substance is increased. Surprisingly, however, further positive effects also occur. Better strength values and rub-off properties are achieved. The glue stick applies very uniformly, i.e. shedding only a very few chunks, without losing too much mass.
[0032] A
glue stick according to the present invention contains an aqueous preparation of at least one hydroxyalkylcarboxymethyl starch. In addition to the hydroxyalkylcarboxymethyl starch, at least one further macromolecular substance can also be provided. The further macromolecular substance can be selected, for example, from starch derivatives other than hydroxyalkylcarboxymethyl starch, from polyvinyl acetals, polyacrylates, polyurethanes, polyvinylpyrrolidone, alcohols, celluloses, proteins, and/or from mixtures thereof.
glue stick according to the present invention contains an aqueous preparation of at least one hydroxyalkylcarboxymethyl starch. In addition to the hydroxyalkylcarboxymethyl starch, at least one further macromolecular substance can also be provided. The further macromolecular substance can be selected, for example, from starch derivatives other than hydroxyalkylcarboxymethyl starch, from polyvinyl acetals, polyacrylates, polyurethanes, polyvinylpyrrolidone, alcohols, celluloses, proteins, and/or from mixtures thereof.
[0033]
Preferred further macromolecular substances are selected from reduced-viscosity starch ethers, polyvinylpyrrolidone, polyurethanes, polyvinyl alcohols, and/or from mixtures thereof. Particularly preferred further macromolecular substances are selected from reduced-viscosity starch ethers and polyurethanes.
"Reduced-viscosity" starch ethers are understood as starch ethers that not only have been etherified in largely polymer-analogous fashion, but moreover have also been chemically or physically destructured in such a way that their viscosity is less than approx. 2,000,000 mPas (40-percent solution, 20 C, Brookfield).
Preferred further macromolecular substances are selected from reduced-viscosity starch ethers, polyvinylpyrrolidone, polyurethanes, polyvinyl alcohols, and/or from mixtures thereof. Particularly preferred further macromolecular substances are selected from reduced-viscosity starch ethers and polyurethanes.
"Reduced-viscosity" starch ethers are understood as starch ethers that not only have been etherified in largely polymer-analogous fashion, but moreover have also been chemically or physically destructured in such a way that their viscosity is less than approx. 2,000,000 mPas (40-percent solution, 20 C, Brookfield).
[0034] Preferred reduced-viscosity starch ethers are nonionic starch ethers that are obtainable by reacting natural starches with ethylene oxide, propylene oxide, butylene oxide, and/or glycide. The reaction can occur with only one of the substances recited, with mixtures of the substances, or sequentially with several of the substances, for example first with ethylene oxide and then with propylene oxide.
The result is to add on an ethylene oxide block to which a propylene oxide block is then attached. Starch derivatives in particular having higher degrees of substitution, by preference nonionogenic starch ethers, can advantageously be adjusted to a relatively low viscosity level by mechanical treatment in aqueous systems by breaking down crystalline structures and/or by oxidative, acid-hydrolytic, enzymatic, and thermal breakdown, and are thus suitable to a particular degree.
Hydroxyalkyl starches are particularly preferred in this context. The degree of substitution (DS) should by preference be 0.1 to 2.0, in particular 0.2 to 1Ø The desired viscosity can be established using the methods that have already been described above in the context of manufacture of the hydroxyalkylcarboxymethyl starches used according to the present invention.
The result is to add on an ethylene oxide block to which a propylene oxide block is then attached. Starch derivatives in particular having higher degrees of substitution, by preference nonionogenic starch ethers, can advantageously be adjusted to a relatively low viscosity level by mechanical treatment in aqueous systems by breaking down crystalline structures and/or by oxidative, acid-hydrolytic, enzymatic, and thermal breakdown, and are thus suitable to a particular degree.
Hydroxyalkyl starches are particularly preferred in this context. The degree of substitution (DS) should by preference be 0.1 to 2.0, in particular 0.2 to 1Ø The desired viscosity can be established using the methods that have already been described above in the context of manufacture of the hydroxyalkylcarboxymethyl starches used according to the present invention.
[0035] If the glue stick according to the present invention also contains at least one further macromolecular substance in addition to at least one hydroxyalkylcarboxymethyl starch, the total quantity of macromolecular substances, i.e. hydroxyalkylcarboxymethyl starch and further macromolecular substances, is by preference 5 to 50 wt%, particularly preferably 10 to 40 wt%, based in each case on the total mass of the stick.
,or
,or
[0036] The addition of further macromolecular substances is not necessary according to the present invention, however. In particular, the addition of polyvinylpyrrolidones and cellulose derivatives can be omitted. In a special embodiment, the glue stick according to the present invention is free of carboxymethyl celluloses. A glue stick of this kind is notable in particular for more economical application with no change in adhesive performance and with additionally improved long-term stability of the adhesive bond. The glue stick according to the present invention is preferably free of polyvinylpyrrolidones and of any cellulose derivatives. "Free of" is to be understood literally as 0 wt%.
Very particularly preferably, the glue stick according to the present invention contains as rnacromolecular substances exclusively the mixed starch ethers to be used according to the present invention.
Very particularly preferably, the glue stick according to the present invention contains as rnacromolecular substances exclusively the mixed starch ethers to be used according to the present invention.
[0037] A
glue stick according to the present invention furthermore contains soap.
glue stick according to the present invention furthermore contains soap.
[0038] The soap is preferably the sodium salt of C12 to C22 fatty acids, in particular of C14 to C18 fatty acids, of natural or synthetic origin. The soap resp. the soap gel serves chiefly as a shape-imparting structural substance. Sodium salts of fatty acids are harder than, for example, the corresponding potassium salts and are therefore well-suited as structuring agents.
[0039] The soap is contained by preference in quantities from 3 to 20 wt%, particularly preferably from 4 to 10 wt%, based on the total mass of the glue stick.
At these proportions the soap gel can optimally form the desired physical structure that constitutes the basis for the outstanding strength of the glue stick according to the present invention. On the other hand, however, the physical structure can also be destroyed sufficiently easy when rubbed off on the surface to be adhesively bonded, so that the adhesive nature of the preparation then, as desired, becomes predominant.
At these proportions the soap gel can optimally form the desired physical structure that constitutes the basis for the outstanding strength of the glue stick according to the present invention. On the other hand, however, the physical structure can also be destroyed sufficiently easy when rubbed off on the surface to be adhesively bonded, so that the adhesive nature of the preparation then, as desired, becomes predominant.
[0040] A
glue stick according to the present invention can additionally contain gelatin. The quantity of gelatin is by preference 0 to 10 wt% and in particular 1.5 to wt%, based on the total mass of the glue stick. Any grades of gelatin can be used in this context.
glue stick according to the present invention can additionally contain gelatin. The quantity of gelatin is by preference 0 to 10 wt% and in particular 1.5 to wt%, based on the total mass of the glue stick. Any grades of gelatin can be used in this context.
[0041] A combination of mineral filler, in particular barium sulfate, and gelatin can also be used in a glue stick according to the present invention. The result here can be a synergistic improvement in adhesive properties thanks to the combination of a mineral filler, in particular barium sulfate, and gelatin.
[0042] The glue stick can furthermore contain sucrose. Sucrose, being an economical and moreover entirely harmless substance, is outstandingly suitable as a filler for a glue stick according to the present invention. In a preferred embodiment of the glue stick according to the present invention, the latter therefore contains sucrose, the sucrose content being by preference 15 to 25, particularly preferably 17 to 22 wt%, based on the total mass of the glue stick.
[0043] The glue sticks can furthermore contain superabsorbers.
"Superabsorbers" are understood in the context of the present invention as particles of synthetic or at least partly synthetic materials that can absorb at least 4 times, preferably at least 10 times, and particularly preferably at least 100 times their mass of water. A feature common to all superabsorbers, despite differences in chemical structure, is that they are capable of absorbing and retaining the aforementioned multiple of their mass of aqueous liquids even under a moderate pressure load. Superabsorbers such as those that can be used in the context of the present invention have been known hitherto in particular from their utilization in baby diapers and in special hygiene products.
"Superabsorbers" are understood in the context of the present invention as particles of synthetic or at least partly synthetic materials that can absorb at least 4 times, preferably at least 10 times, and particularly preferably at least 100 times their mass of water. A feature common to all superabsorbers, despite differences in chemical structure, is that they are capable of absorbing and retaining the aforementioned multiple of their mass of aqueous liquids even under a moderate pressure load. Superabsorbers such as those that can be used in the context of the present invention have been known hitherto in particular from their utilization in baby diapers and in special hygiene products.
[0044] The superabsorber can be contained, for example, in the form of particles having a particle size from 1 to 1000 pm. The permeability and thus the absorption properties of the superabsorbers are advantageously manifested in this particle-size range. It is preferred to use superabsorbers that have an average particle diameter of at most 150 pm, preferably 100 pm, and particularly preferably 70 pm.
A glue stick containing such superabsorbers is notable in particular for more economical application with no change in adhesive performance and with further improved long-term stability of the adhesive bond.
A glue stick containing such superabsorbers is notable in particular for more economical application with no change in adhesive performance and with further improved long-term stability of the adhesive bond.
[0045] The glue stick can contain the superabsorber, for example, in a quantity from 0.2 to 3 wt%, based on the total mass of the glue stick. Within this range a particularly balanced relationship is achieved between outstanding strength of the solidified stick mass and good shelf stability. The superabsorber is contained particularly preferably in a quantity from 0.3 to 2 wt%, based on the total mass of the glue stick. The proportion of superabsorber is in particular 0.4 to 1.2 wt%, based on the total mass of the glue stick. Optimum strength values with consistently good shelf stability are obtained within this range.
[0046] In addition to the components listed so far, further usual adjuvants can concurrently be used, for example substances that promote easy and smooth rub-off. Such substances are, for example, aminocarboxylic acids and/or lactams thereof. Suitable aminocarboxylic acids resp. lactams thereof should contain up to 12 carbon atoms, in particular 4 to 8 carbon atoms. The representative preferred for practical use is caprolactam-epsilon resp. 7-aminocaproic acid deriving therefrom. The quantity of lactams or of corresponding aminocarboxylic acids to be used is usually not more than 15 wt%, for example 0.5 wt% to 5 wt%, based on the total stick mass.
[0047] As further adjuvants the glue sticks according to the present invention can contain (further) pigments, dyes, scents, preservatives, and the like. The quantities of these substances are, as usual, subordinate. Further possible additives are, for example, further fillers, optical brighteners, dextrins, and non-destructured starch derivatives. Mannans, in particular galactomannans, can also be contained in the glue sticks according to the present invention. The galactomannans from the fruits of the locust tree and from guar flour are particularly *
suitable. The destructured starch ethers can also be replaced, in a subordinate proportion, by destructu red man nans.
suitable. The destructured starch ethers can also be replaced, in a subordinate proportion, by destructu red man nans.
[0048] Also to be recited as suitable adjuvants are, for example, plasticizers and/or moisture-regulating substances, for example organic water-soluble solvents that are usually used in glue sticks. The nonvolatile organic solvents should be used at most in quantities of up to 50 wt%, based on the water content of the sticks.
Concurrent use of polyvalent (polyfunctional) alcohols such as propylene glycol, glycerol, polyglycerols, trimethylolpropane, polyether glycols, and sorbitol, and/or low-molecular-weight starch hydrolysates that have been converted by hydrogen reduction into corresponding polyols, is also possible. For example, a mixture of glycerol and polyethylene glycol can be concurrently used. The concentration of glycerol and propylene glycol, especially propylene glycol, is by preference 0 to 15 wt%, in particular 5 to 10 wt%, based on the total glue stick.
Concurrent use of polyvalent (polyfunctional) alcohols such as propylene glycol, glycerol, polyglycerols, trimethylolpropane, polyether glycols, and sorbitol, and/or low-molecular-weight starch hydrolysates that have been converted by hydrogen reduction into corresponding polyols, is also possible. For example, a mixture of glycerol and polyethylene glycol can be concurrently used. The concentration of glycerol and propylene glycol, especially propylene glycol, is by preference 0 to 15 wt%, in particular 5 to 10 wt%, based on the total glue stick.
[0049] The quantities indicated above of the individual ingredients, together with the water that is additionally present, add up in each case to a total of 100 wt%.
[0050] In a preferred embodiment, the glue stick according to the present invention is made up of:
- 5 to 50 wt% macromolecular substance containing at least one hydroxyalkylcarboxymethyl starch, - 3 to 20 wt% soap, - 0 to 30 wt% sucrose, - 0 to 25 wt% further adjuvants, and - 25 to 92 wt% water, the total quantity of the ingredients yielding 100 wt%.
- 5 to 50 wt% macromolecular substance containing at least one hydroxyalkylcarboxymethyl starch, - 3 to 20 wt% soap, - 0 to 30 wt% sucrose, - 0 to 25 wt% further adjuvants, and - 25 to 92 wt% water, the total quantity of the ingredients yielding 100 wt%.
[0051] The statements already made above apply analogously regarding preferred ingredients and preferred quantities of the individual constituents.
[0052] A further subject of the present invention is a method for manufacturing a 11, =
glue stick according to the present invention, which method is characterized in that the aqueous preparation of at least one hydroxyalkylcarboxymethyl starch is mixed with the soap or with the soap-forming constituents and optionally with the fillers and/or adjuvants, optionally while being heated, until a homogeneous mixture has resulted, and the mixture is allowed to stand or is cooled without mechanical influence. It is preferred to decant the homogeneous mixture, after heating to temperatures of at least 50 C, by preference up to 80 C, directly into stick casings or similar containers, and to allow it to solidify into the desired gels without mechanical influence. This method is advantageous because the mixtures are easy to pour in the aforementioned temperature range. The glue sticks according to the present invention are notable for even further optimized viscosity values at around 80 C as compared with the existing art, and can therefore be processed particularly effectively.
glue stick according to the present invention, which method is characterized in that the aqueous preparation of at least one hydroxyalkylcarboxymethyl starch is mixed with the soap or with the soap-forming constituents and optionally with the fillers and/or adjuvants, optionally while being heated, until a homogeneous mixture has resulted, and the mixture is allowed to stand or is cooled without mechanical influence. It is preferred to decant the homogeneous mixture, after heating to temperatures of at least 50 C, by preference up to 80 C, directly into stick casings or similar containers, and to allow it to solidify into the desired gels without mechanical influence. This method is advantageous because the mixtures are easy to pour in the aforementioned temperature range. The glue sticks according to the present invention are notable for even further optimized viscosity values at around 80 C as compared with the existing art, and can therefore be processed particularly effectively.
[0053] A glue stick according to the present invention exhibits outstanding compressive strength. At the same time it possesses optimized rub-off properties.
This is to be understood to mean that the stick on the one hand applies uniformly and on the hand applies sufficient mass that good adhesive bonding of the substrates is achieved, but almost no excess adhesive is delivered, i.e. the stick loses almost no clumps and the formation of local adhesive excesses and irregularities on the substrate surface is minimized. In addition, the optimized rub-off is expressed as more pleasant utilization for the user, and the stick slides better over the surface to be bonded. The adhesive properties of a glue stick according to the present invention are likewise outstanding. Shelf stability is moreover enhanced, and even over longer storage times the adhesive bonds retain their white color and do not become yellow.
This is to be understood to mean that the stick on the one hand applies uniformly and on the hand applies sufficient mass that good adhesive bonding of the substrates is achieved, but almost no excess adhesive is delivered, i.e. the stick loses almost no clumps and the formation of local adhesive excesses and irregularities on the substrate surface is minimized. In addition, the optimized rub-off is expressed as more pleasant utilization for the user, and the stick slides better over the surface to be bonded. The adhesive properties of a glue stick according to the present invention are likewise outstanding. Shelf stability is moreover enhanced, and even over longer storage times the adhesive bonds retain their white color and do not become yellow.
[0054] A further subject of the present invention is the use of a glue stick according to the present invention for planar joining, in particular for adhesive bonding, of substrates, in particular for joining paper, cardboard, wood, and/or plastic to one another.
[0055] The invention will be explained in further detail below with reference to exemplifying embodiments. Unless otherwise indicated, percentages and quantitative ratios refer to weight.
EXAMPLES
Starting materials
EXAMPLES
Starting materials
[0056] - Mixed starch ether A: Hydroxypropylcarboxymethyl starch based on potato starch; molar ratio of hydroxypropyl to carboxymethyl > 1; viscosity, determined as a 40-wt% aqueous solution using a Brookfield RVT viscosimeter at 20 C, spindle 7, 20 rpm: approx. 70,000 mPas;
[0057] - Mixed starch ether B: Hydroxypropylcarboxymethyl starch based on a mixture of potato starch and tapioca starch; molar ratio of hydroxypropyl to carboxymethyl > 1; viscosity, determined as a 40-wt% aqueous solution using a Brookfield RVT viscosimeter at 20 C, spindle 7, 20 rpm: approx. 80,000 mPas;
[0058] - Mixed starch ether C: Hydroxypropylcarboxymethyl starch based on potato starch; molar ratio of hydroxypropyl to carboxymethyl < 1; viscosity, determined as a 10-wt% aqueous solution using a Brookfield RVT viscosimeter at 20 C, spindle 4 or 5, 20 rpm: approx. 5,000 mPas.
[0059] - Fatty acids: commercially obtainable fatty acids having 14 to 18 carbon atoms.
Manufacturing the glue sticks
Manufacturing the glue sticks
[0060] The components according to Table I were mixed at 80 C and processed into glue sticks in accordance with the description. The respective compositions are indicated in parts by weight.
III. Properties of the glue sticks a) Compressive strength
III. Properties of the glue sticks a) Compressive strength
[0061] The term "compressive strength" is to be understood as the maximum load measured upon collapse of the stick shape under compressive stress parallel to the longitudinal axis.
[0062] An Erichsen model 464L tester, measurement head 709, is used to measure compressive strength.
[0063] The adhesive, cut off directly above the piston and having a minimum length of 30 mm, is inserted between two holding pieces; these are disks of hard PVC whose thickness is approx. 10 mm and which exhibit a circular depression of about 3 mm adapted to the respective stick diameter. The stick, fitted with the holding pieces, is placed centeredly onto the test stage of the compressive strength tester. The height of the force measurement instrument above the test stage is adapted to the height of the test article. The measurement head is then advanced onto the stick to be tested at a feed rate of approx. 70 mm per minute. Once the maximum compressive force is reached, the value (in newtons) is read from the digital display.
b) Application characteristics (lumps)
b) Application characteristics (lumps)
[0064] The so-called "lump test" describes the (undesirable) shedding of smaller and larger lumps, deviating from a continuous adhesive film, upon application of the glue stick onto paper,. Here the sticks are moved over a DIN A4 sheet in several tracks under the load of a defined test weight. The sliding characteristics are assessed qualitatively. The uniformity of the adhesive film and the formation of lumps are assessed visually.
IV. Results
IV. Results
[0065] The results are summarized in Table II.
, .
, .
[0066] Table I: Compositions (indications in wt%) Component Example Mixed starch ether A (44% aqueous preparation) - 54.0 Mixed starch ether B (44% aqueous preparation) 53.0 -Mixed starch ether C (solid) - 2.4 Sodium hydroxide (10%) 1.4 -Fatty acids 5.7 5.7 Sucrose 20.0 20.3 Caprolactam 1.0 1.0 Adjuvants 2.7 0.3 Demineralized water to 100 to 100
[0067] Table II: Test results with sticks manufactured from compositions according to Table I
Property Example Compressive 86 92 strength (20 g) [N]
Application (lumps, minimal clumping; minimal minimal clumping; minimal visual) smearing; good sliding smearing; very good sliding characteristics characteristics
Property Example Compressive 86 92 strength (20 g) [N]
Application (lumps, minimal clumping; minimal minimal clumping; minimal visual) smearing; good sliding smearing; very good sliding characteristics characteristics
[0068] The results presented in Table II shows that the glue sticks according to the present invention have outstanding compressive strength and application characteristics. Thanks to the use of a mixture of two mixed starch ethers based entirely on potato starch, the hydroxyalkyl groups in one case and the carboxymethyl groups in the other case being present at a molar excess, the compressive strength and sliding characteristics can be further optimized. The initial adhesive strength that is achieved corresponds to, resp. slightly exceeds, the initial adhesive strength that can be achieved when using commercially usual glue sticks based on reduced-viscosity hydroxyalkyl starches. The initial adhesive strength of commercially usual glue sticks based on polyvinylpyrrolidone is appreciably exceeded.
Claims (15)
1. A glue stick, containing an aqueous preparation of at least one hydroxyalkylcarboxymethyl starch having a viscosity less than 2,000,000 mPas, determined as a 40-wt% aqueous solution using a Brookfield RVT viscosimeter at 20°C, spindle 7, 20 rpm, and soap.
2. The glue stick according to claim 1, wherein the hydroxyalkylcarboxymethyl starch is selected from hydroxyethylcarboxymethyl starches, hydroxypropylcarboxymethyl starches, and/or hydroxyethylhydroxypropylcarboxymethyl starches.
3. The glue stick according to claim 1 or 2, wherein the hydroxyalkylcarboxymethyl starch is selected from hydroxypropylcarboxymethyl starches.
4. The glue stick according to claim 3, wherein the hydroxypropylcarboxymethyl starches are obtained by reacting a starch with monochloroacetic acid and/or monochloroacetate and propylene oxide, where monochloroacetic acid and/or monochloroacetate on the one hand and propylene oxide on the other hand are used at a molar ratio from 10 : 1 to 1 : 100.
5. The glue stick according to any one of claims 1 to 4, wherein the degree of substitution (DS) of the hydroxyalkylcarboxymethyl starch is 0.1 to 2Ø
6. The glue stick according to any one of claims 1 to 4, wherein the degree of substitution (DS) of the hydroxyalkylcarboxymethyl starch is 0.2 to 1Ø
7. The glue stick according to any one of claims 1 to 6, wherein hydroxyalkylcarboxymethyl starch is contained in a total quantity from 5 to 50 wt%, based on the total mass of the glue stick.
8. The glue stick according to any one of claims 1 to 6, wherein hydroxyalkylcarboxymethyl starch is contained in a total quantity from 10 to 40 wt%, based on the total mass of the glue stick.
9. The glue stick according to any one of claims 1 to 8, wherein the hydroxyalkylcarboxymethyl starch has a viscosity from 100 to 1,000,000 mPas, determined as a 40-wt% aqueous solution using a Brookfield RVT viscosimeter at 20°C, spindle 7, 20 rpm.
10. The glue stick according to any one of claims 1 to 8, wherein the hydroxyalkylcarboxymethyl starch has a viscosity from 2000 to 100,000 mPas, determined as a 40-wt% aqueous solution using a Brookfield RVT viscosimeter at 20°C, spindle 7, 20 rpm.
11. The glue stick according to any one of claims 1 to 8, wherein the hydroxyalkylcarboxymethyl starch has a viscosity from 10,000 to 80,000 mPas, determined as a 40-wt% aqueous solution using a Brookfield RVT viscosimeter at 20°C, spindle 7, 20 rpm.
12. The glue stick according to any one of claims 1 to 11, wherein the hydroxyalkylcarboxymethyl starch is a corresponding derivative of potato starch.
13. The glue stick according to any one of claims 1 to 12, wherein it is made up of:
- 5 to 50 wt% macromolecular substance containing at least one hydroxyalkylcarboxymethyl starch, - 3 to 20 wt% soap, - 0 to 25 wt% further adjuvants, and - 25 to 92 wt% water, - and further comprising 0 to 30 wt% sucrose, the total quantity of the ingredients yielding 100 wt%.
- 5 to 50 wt% macromolecular substance containing at least one hydroxyalkylcarboxymethyl starch, - 3 to 20 wt% soap, - 0 to 25 wt% further adjuvants, and - 25 to 92 wt% water, - and further comprising 0 to 30 wt% sucrose, the total quantity of the ingredients yielding 100 wt%.
14. Use of a glue stick according to any one of claims 1 to 13 for planar joining of substrates.
15. Use of a glue stick according to claim 14 for joining paper, cardboard, wood, and/or plastic to one another.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE201110004340 DE102011004340A1 (en) | 2011-02-17 | 2011-02-17 | Glue stick based on starch mix ethers |
DE102011004340.3 | 2011-02-17 | ||
PCT/EP2012/052675 WO2012110594A1 (en) | 2011-02-17 | 2012-02-16 | Glue stick based on starch mixed ethers |
Publications (2)
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CA2826831A1 CA2826831A1 (en) | 2012-08-23 |
CA2826831C true CA2826831C (en) | 2019-03-12 |
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CA2826831A Active CA2826831C (en) | 2011-02-17 | 2012-02-16 | Glue stick based on starch mixed ethers |
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EP (1) | EP2675858B1 (en) |
JP (1) | JP6073814B2 (en) |
CN (1) | CN103370386B (en) |
CA (1) | CA2826831C (en) |
DE (1) | DE102011004340A1 (en) |
ES (1) | ES2532716T3 (en) |
MX (1) | MX341383B (en) |
WO (1) | WO2012110594A1 (en) |
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US10165781B2 (en) | 2014-08-28 | 2019-01-01 | The Johns Hopkins University | Compositions and methods useful for the prevention of malaria and dengue virus transmission |
CN104403010A (en) * | 2014-12-09 | 2015-03-11 | 兰州大学 | Preparation method for carboxymethyl hydroxyethyl potato modified starch |
DE102015219309B4 (en) | 2015-10-06 | 2018-01-18 | Henkel Ag & Co. Kgaa | Dimensionally stable, abradable preparation containing platelet-shaped particles |
CN106349819A (en) * | 2016-10-26 | 2017-01-25 | 苏州吉谷新材料有限公司 | Environment-friendly non-toxic thermal sublimation ink |
EP3725859B1 (en) | 2019-04-16 | 2023-03-29 | Société BIC | Glue stick composition |
CN110156901A (en) * | 2019-06-06 | 2019-08-23 | 哈尔滨坤丰生物工程有限公司 | A kind of pea hydroxypropyl carboxy methyl starch and preparation method |
DE102020109777B3 (en) | 2020-04-08 | 2021-07-29 | Uhu Gmbh & Co. Kg | Adhesive composition for a glue stick and glue stick |
EP4101885A1 (en) | 2021-06-08 | 2022-12-14 | Henkel AG & Co. KGaA | Dimensionally stable adhesive composition containing enzymatically modified starch |
CN114213997A (en) * | 2021-12-29 | 2022-03-22 | 得力集团有限公司 | Environment-friendly degradable plant solid glue stick and preparation method thereof |
TW202342677A (en) * | 2022-02-17 | 2023-11-01 | 日商國譽股份有限公司 | Liquid paste for paper |
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JPH0623355B2 (en) * | 1988-08-01 | 1994-03-30 | 松谷化学工業株式会社 | Adhesive composition for corrugated board |
DE4125122C2 (en) | 1991-07-30 | 1994-06-23 | Henkel Kgaa | Starch ether-based glue stick |
DE19908560A1 (en) * | 1998-04-01 | 1999-10-07 | Henkel Kgaa | Adhesive pencil for gluing substrate surfaces together, especially paper and cardboard |
DE102006008001A1 (en) * | 2006-02-21 | 2008-05-15 | Henkel Kgaa | Liquid adhesive concentrate |
AT505928B1 (en) * | 2007-11-20 | 2009-05-15 | Tulln Zuckerforschung Gmbh | BUILDING MATERIAL COMPOSITION |
DE102009012667A1 (en) * | 2009-03-13 | 2010-09-30 | Henkel Ag & Co. Kgaa | Glue stick with superabsorbers |
-
2011
- 2011-02-17 DE DE201110004340 patent/DE102011004340A1/en not_active Ceased
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2012
- 2012-02-16 JP JP2013553942A patent/JP6073814B2/en active Active
- 2012-02-16 EP EP12705831.1A patent/EP2675858B1/en active Active
- 2012-02-16 CA CA2826831A patent/CA2826831C/en active Active
- 2012-02-16 CN CN201280008832.7A patent/CN103370386B/en active Active
- 2012-02-16 MX MX2013009505A patent/MX341383B/en active IP Right Grant
- 2012-02-16 ES ES12705831.1T patent/ES2532716T3/en active Active
- 2012-02-16 WO PCT/EP2012/052675 patent/WO2012110594A1/en active Application Filing
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DE102011004340A1 (en) | 2012-08-23 |
JP6073814B2 (en) | 2017-02-01 |
CN103370386B (en) | 2016-12-21 |
WO2012110594A1 (en) | 2012-08-23 |
CN103370386A (en) | 2013-10-23 |
EP2675858B1 (en) | 2014-12-24 |
MX341383B (en) | 2016-08-18 |
JP2014508831A (en) | 2014-04-10 |
ES2532716T3 (en) | 2015-03-31 |
CA2826831A1 (en) | 2012-08-23 |
MX2013009505A (en) | 2013-09-26 |
EP2675858A1 (en) | 2013-12-25 |
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