AU763054B2 - Rubber adhesive based on a stabilized polyvinyl acetate dispersion - Google Patents
Rubber adhesive based on a stabilized polyvinyl acetate dispersion Download PDFInfo
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- AU763054B2 AU763054B2 AU12663/00A AU1266300A AU763054B2 AU 763054 B2 AU763054 B2 AU 763054B2 AU 12663/00 A AU12663/00 A AU 12663/00A AU 1266300 A AU1266300 A AU 1266300A AU 763054 B2 AU763054 B2 AU 763054B2
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- adhesive
- weight
- whole
- gumming
- polyvinyl alcohol
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 80
- 239000000853 adhesive Substances 0.000 title claims abstract description 78
- 239000006185 dispersion Substances 0.000 title claims abstract description 28
- 229920002689 polyvinyl acetate Polymers 0.000 title claims abstract description 25
- 239000011118 polyvinyl acetate Substances 0.000 title claims abstract description 25
- 229920002472 Starch Polymers 0.000 claims abstract description 24
- 235000019698 starch Nutrition 0.000 claims abstract description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008107 starch Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 239000000084 colloidal system Substances 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 229920001353 Dextrin Polymers 0.000 claims abstract description 4
- 239000004375 Dextrin Substances 0.000 claims abstract description 4
- 235000019425 dextrin Nutrition 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 8
- -1 hydroxypropyl Chemical group 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- LYKRIFJRHXXXDZ-UHFFFAOYSA-N 4-(4-hydroxybutoxy)butan-1-ol Chemical compound OCCCCOCCCCO LYKRIFJRHXXXDZ-UHFFFAOYSA-N 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 claims 3
- 238000001035 drying Methods 0.000 abstract description 18
- 230000004913 activation Effects 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract 1
- 239000000123 paper Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 230000000903 blocking effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002313 adhesive film Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 3
- 229920001592 potato starch Polymers 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 210000003811 finger Anatomy 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- IQBLWPLYPNOTJC-FPLPWBNLSA-N (z)-4-(2-ethylhexoxy)-4-oxobut-2-enoic acid Chemical compound CCCCC(CC)COC(=O)\C=C/C(O)=O IQBLWPLYPNOTJC-FPLPWBNLSA-N 0.000 description 1
- TURGQPDWYFJEDY-UHFFFAOYSA-N 1-hydroperoxypropane Chemical compound CCCOO TURGQPDWYFJEDY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 108010068370 Glutens Proteins 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 101710171321 Neuraminyllactose-binding hemagglutinin Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 244000062793 Sorghum vulgare 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
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000021312 gluten Nutrition 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000002023 wood Substances 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
- C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
- C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09J131/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/28—Non-macromolecular organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Materials For Medical Uses (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The aim of the invention is to simplify the production of conventional rubber adhesives based on stabilized polyvinyl acetate dispersions and to improve the drying and adhesive properties thereof. To these ends, the concentration of the protective colloid polyvinyl alcohol or starch ether is increased without adding an aqueous polymer solution of polyvinyl alcohol or dextrin. Adding an interfacially active substance accelerates the activation of the adhesive after drying the same at temperatures above 160 DEG C.
Description
WO 00/27943 PCT/EP99/08106 Rubber Adhesive Based on a Stabilized Polyvinyl Acetate Dispersion "Adhesive Based on a Polyvinyl Acetate Dispersion" This invention relates to an adhesive based on a polyvinyl acetate dispersion stabilized with protective colloids, to its production and to its use.
There are numerous publications concerned with the production of polyvinyl acetate dispersions and their use. DE 33 23 851 describes an aqueous polymer dispersion of vinyl esters and optionally 50% by weight of other ethylenically unsaturated compounds in the presence of starch ethers as protective colloid. In addition, other protective colloids, for example polyvinyl alcohol, may be added. However, these auxiliaries are preferably added if at all to the final dispersion, i.e. on completion of polymerization, because otherwise they can often interfere undesirably with the polymerization process or can cause unwanted changes in the products.
These known dispersions are used as such for the production of adhesives, more particularly for paper and films, and for the waterproof gluing of wood.
However, they are preferably used for the production of redispersible polymer powders for the production of wallpaper adhesives. There is no mention of their use as a gumming adhesive.
Gumming is understood to be the coating of a substrate with a water-reactivatable adhesive. The substrate is generally a water-absorbing product, more particularly of paper or paperboard. It may be used, for example, as a postage stamp, envelope, label, adhesive strip, etc. The gumming adhesive is applied to the substrate in liquid form and then dried, losing its tackiness in the process. Only when moistened with water does it become tacky again. Gumming adhesives are normally based, for example, on gluten or starch derivatives (dextrin), although fully synthetic WO 00/27943 2 PCT/EP99/08106 polymers, for example polyvinyl alcohol and polyvinyl acetate, may also be used.
The production of gumming adhesives based on a polyvinyl acetate dispersion is described in DD 275 069. According to this document, an aqueous solution of polyvinyl alcohol and, preferably, glycerol have to be added to the polyvinyl acetate dispersion. The remoistenable adhesive has the following composition by weight: 50 to 60% of a 20% polyvinyl alcohol solution, 40 to 50% of a polyvinyl acetate dispersion and 0 to 5% by weight of glycerol. The glycerol acts as a plasticizer and the polyvinyl alcohol improves reactivation by moisture. The production of a gumming adhesive is therefore complicated because the auxiliaries are added in a separate process step. In addition, some but not all of the requirements a gumming adhesive is expected to meet are satisfied to the required extent. This applies in particular to the stay-flat behavior of the gummed paper, to its blocking resistance and to the setting time after remoistening.
German patent application DE 196 36 590.2 describes an adhesive based on a stabilized polyvinyl acetate dispersion which is characterized in that it contains the following components: A) 35 to 45% by weight, based on the adhesive as a whole, of a copolymer of vinyl acetate and 25 to 60% by weight, based on the monomers as a whole, of at least one ester of fumaric, maleic, acrylic and/or methacrylic acid, the alkyl group being branched or unbranched and being said to contain 4 to 18 carbon atoms and B) a protective colloid, namely a) 0 to 30% by weight, based on the adhesive as a whole, of at least one nonionic starch ether and/or b) 0 to 12% by weight, based on the adhesive as a whole, of polyvinyl alcohol.
There is no reference to the problem which arises when drying is carried out at high temperatures, for example above 160 0 C, or to its solution.
Accordingly, one problem addressed by the present invention was to provide a gumming adhesive which would be easy to produce, which would dry more quickly after application of its solution and which would become tacky again more quickly when moistened, even if it has been dried at more than 1600C, but which would be largely blocking-resistant. In broad terms, the problem addressed by the invention was to provide a gumming adhesive with improved production, application and performance properties or to provide an alternative adhesive to the prior art.
The solution to this problem is defined in the claims and is essentially based on the fact that, to produce the gumming adhesive, an aqueous polymer solution, more particularly a solution of polyvinyl alcohol and starch ether, is not added to the polyvinyl acetate dispersion, instead the polyvinyl acetate dispersion is prepared under special conditions, among which the nature and quantity of the protective colloid are 15 particularly important.
In accordance with a first aspect of the present invention, there is provided a gumming adhesive based on a stabilized polyvinyl acetate dispersion which is characterized by the following components: A) 35 to 45% by weight, based on the adhesive as a whole, of a 20 copolymer of vinyl acetate and 25 to 50% by weight, based on the monomers as a whole, of at least one alkyl ester of fumaric, maleic, itaconic, crotonic, acrylic and/or methacrylic acid, the alkyl groups optionally being branched or unbranched and having to contain 4 to 18 carbon atoms, B) at least one protective colloid, namely a) 0 to 30% by weight, based on the adhesive as a whole, of a nonionic starch ether and/or LibC/558488speci.doc b) 0 to 12% by weight, based on the gumming adhesive as a whole, of a polyvinyl alcohol, C) 0.05 to 10% by weight of at least one surface-active agent.
Preferably, the solids content is from 50 to 60% by weight and still more preferably from 55 to 60% by weight, based on the gumming adhesive.
Suitable "nonionic starch ethers" are, in particular, hydroxyalkyl ether starches, for example hydroxyethyl, hydroxypropyl and hydroxybutyl ether starches. The alkyl chains contain from 2 to 8 carbon atoms and, more particularly, from 2 to 4 carbon atoms. Both degraded starches, for example starches degraded by acidic hydrolysis, and native starches may be used as starting products for the starches mentioned. In general, no .ooo particular requirements have to be satisfied in selecting these starting .o products. Thus, virtually any starch of vegetable origin, for example corn 15 starch, wheat starch, potato starch, tapioca starch, rice starch, sago starch and millet starch, may be used. Basically, hydroxyalkylation is a known process and, for this reason, need not be described in any further detail here. The degrees of substitution are also not crucial to the success of the process and, in many cases, degrees of substitution of about two are sufficient. Many of the starch derivatives suitable for use in accordance with the invention are commercially available.
~The nonionic starch ether is preferably used as sole protective colloid in a quantity of 15 to 30% by weight and, more particularly, in a quantity of 15 to 25% by weight.
It is known that polyvinyl alcohol can be used in a quantity of about 2 to 5% by weight as protective colloid in the polymerization of polyvinyl acetate. According to the invention, this concentration should be increased despite the preconceived notion that this might adversely affect the properties of the polyvinyl acetate. It has surprisingly been found that LibC/558488speci.doc reactivation of the gum after moistening takes place just as quickly when 8 to 12% by weight of polyvinyl alcohol are added during the polymerization process as when more than 10% by weight of polyvinyl alcohol is subsequently added to the final polyvinyl acetate dispersion.
Accordingly, the polyvinyl alcohol content of the sodium acetate dispersion to be used in accordance with the invention is from 0 to 12% by weight, based on the gumming adhesive as a whole, preferably from 8 to 12% by weight and more preferably from 10.5 to 12% by weight. The percentage content can be larger during the polymerization process because, after polymerization, the final specification requirements are fulfilled by addition of water.
According to the invention, the polyvinyl acetate is a copolymer of vinyl acetate and 25 to 50% by weight, based on the monomers as a whole, of at least one mono- or di-ester of fumaric, maleic, itaconic, 15 crotonic, acrylic and/or methacrylic acid, the alkyl chain either being linear or branched and having to contain from 4 to 18 and, more particularly, from 4 to 8 carbon atoms. Preferred alkyl groups are ethyl, propyl, butyl and ethylhexyl or octyl groups. The preferred comonomer is an alkyl ester of maleic acid, more particularly monooctyl maleate.
20 Terpolymers of the above-mentioned comonomers may also be used. The third comonomer is used in a quantity of up to 10% by weight o* and preferably in a quantity of 0.1 to 2% by weight, based on the comonomers.
The copolymerization may largely be carried out by the process described in DE 33 23 851, the composition of the mixture having to be such that a solids content of 50 to 60% by weight and, more particularly, to 60% by weight, based on the dispersion to be used as a gumming adhesive in accordance with the invention, is obtained. More particularly, the polyvinyl acetate may be produced by suspension or emulsion polymerization, preferably by emulsion polymerization. The particular LibC/558488speci.doc WO 00/27943 6 PCT/EP99/08106 conditions of this process are generally known, cf. in particular DE 33 23 861.
The process for producing aqueous polymer dispersions comprises in particular polymerizing vinyl esters together with 25 to 50% by weight, based on the total weight of the monomers, of other ethylenically unsaturated compounds with at least partly water-soluble initiators which yield free radicals at reaction temperatures of +10 to +1000C in the presence of hydroxyalkylated starch and/or the other stabilizer, polyvinyl alcohol, at most one third of the monomer total being introduced at the beginning and the rest of the monomers being added during the polymerization reaction.
Besides the polyvinyl acetate, the gumming adhesive according to the invention contains 0.05 to 10%.by weight and more particularly 0.1 to by weight of at least one surface-active agent, based on the adhesive as a whole. Surface-active agents are substances which reduce the interfacial tension to water. Generally, they contain a hydrophilic group and a hydrophobic group, more particularly a lipophilic group or groups. Actual examples of such substances are anionic surfactants, such as fatty alcohol sulfates, fatty alcohol ether sulfates and alkyl phenolether sulfates and alkyl benzene or alkylaryl sulfonates and sulfosuccinates, and nonionic surfactants, such as fatty alcohol polyglycol ethers, fatty alcohol EO/PO adducts and alkyl phenol EO/PO adducts.
The surface-active agent is added during the polymerization.
The gumming adhesive according to the invention additionally contains up to 10% by weight and more particularly 1 to 5% by weight of at least one hygroscopic substance, based on the adhesive as a whole. A hygroscopic substance in the context of the invention is one which attracts moisture from the air up to a certain equilibrium when stored under normal conditions. The hygroscopic substances are preferably organic substances such as, for example, sugars, glycerol or polyethylene glycol.
WO 00/27943 PCT/E P99/081 06 Auxiliaries may also be added to meet special requirements and include, for example, dyes, perfumes, biocides, etc. Since they are only optionally present in the adhesive, they are not included in the weightrelated expression "based on the adhesive as a whole".
There is no need to add an aqueous polymer solution, for example of polyvinyl alcohol or dextrin, in order to improve activation behavior after moistening, nor is such an addition appropriate.
The gumming adhesive according to the invention is distinguished by quick drying and by quick activation after moistening despite drying temperatures of more than 1600C and also by a very intensive adhesive effect by comparison with known gumming adhesives. A particularly surprising feature is that, in spite of this, it still gives a high-gloss film characterized by high blocking resistance. Last but not least, the production of the gumming adhesive according to the invention is easier because, for example, polyvinyl alcohol only has to be added once.
The adhesive according to the invention increases the operational reliability of automatic inserting machines during the sealing of envelopes because it can be activated sufficiently quickly irrespective of the drying conditions. The other properties are not impaired.: Thus, gloss ranges from glossy to high-gloss, the color is slightly yellowish, blocking resistance at 400C is at least 85% and the stay-flat behavior of a test paper with a 40 pm thick adhesive film is good to very good.
The invention is illustrated by the following Examples.
A) Production of the polyvinyl acetate dispersion a) Prior art In a reaction vessel equipped with a stirrer, thermometer, two metering vessels and a reflux condenser, a pH buffer, 22.5 kg of a modified potato starch (hydroxypropyl ether) and 0.05 kg of a commercial defoamer WO 00/27943 PCT/EP99/08106 are dissolved at >80°C in 36.275 kg of deionized water. A solution of 10 kg of deionized water and 0.5 kg of K 2
S
2 0 8 is separately prepared at room temperature. This solution is placed in metering vessel 1. A mixture of 24.26 kg of vinyl acetate and 16.165 kg of dibutyl maleate is prepared at room temperature in metering vessel 2. The polymerization reaction begins at a temperature of >650C by simultaneous introduction of the components from metering vessels 1 and 2 into the reaction vessel. After the onset of polymerization, the continuous introduction from vessels 1 and 2 is controlled so that a reaction temperature of 80 to 850C is established.
The reaction time is about 3.5 to 4 h.
On completion of polymerization, the characteristic data of the dispersion are adjusted with'water to a solids content of about 55% by weight.
b) Invention Besides water, modified potato starch and defoamer, the solution contains 0.2 kg of sulfosuccinate. Besides vinyl acetate and dibutyl maleate, the monomer mixture contains 0.125 kg of acrylic acid.
B) Properties The polyvinyl acetate dispersions described above were used unchanged as a gumming adhesive. The properties are set out in the following Table and were determined as follows: SViscosity was determined by the Brookfield method according to ISO 2555 under the following conditions: RVT, spindle 4, 20 250C.
The solids content was determined in accordance DIN 53189, Method C, after 3 hours at 1050C by weighing out.
To determine the drying time, a 40 pm thick film of a dispersion having a solids content of 55% by weight was applied using a box knife coater WO 00/27943 PCT/EP99/08106 and was dried in non-circulated air at 23 0 C/55% relative air humidity.
The drying time (wet tack time) is the time elapsing from application to the moment when the coating is no longer tacky. This time was determined by different methods according to the substrates used (glass plate or 70 g/m 2 writing paper according to DIN 19307, use class 4a): In the case of the glass plate, the degree of drying of an adhesive film can be visually determined by sliding a finger over the surface of that film. As drying progresses, the finger test is repeated at approximately2 second intervals until the film surface shows no sign of damage. This time is measured in seconds and represents the drying time of an adhesive on glass.
In the case of writing paper, the time in seconds after which the surfaceof the adhesive is dry is determined by pressing one corner at a time ofa ZK form folded crosswise 4 times onto the film surface with the thumb. The adhesive is dry when the paper does not lift and tear.
The time measured in seconds is the drying time of an adhesive on paper.
In order to imitate the rigorous drying conditions in the production of envelopes, the adhesive film dried at room temperature was additionally exposed for 10 secs. to temperatures of 150 to 200 0 C, after which the setting time after remoistening and wettability were determined. To determine wettability, the heat-treated adhesive film was wiped with a sponge soaked with water and its wetting behavior was visually determined: water film over entire adhesive film water film over ca. 50 to 80% of the adhesive film no water film WO 00/27943 10 PCT/EP99/08106 To determine the setting time after remoistening, a dry adhesive film of a 40 pm thick layer of a 55% by weight dispersion on a paper (see drying time) is moistened with water using a sponge. Strips of paper g, wood-free) are applied to the adhesive thus reactivated. The strips are removed every half second. The time at which fibers are torn out when the strip of paper is removed counts as the end of the setting time.
In order to determine the beginning of blocking, 40 pm thick films were applied to writing paper using a surface coater and dried for 24 hours under ambient conditions. The paper is then cut into pieces measuring x 10 cm. An uncoated sheet of paper of the same type and size is placed on a coated sheet. The stack obtained should consist of coated sheets and 15 uncoated sheets. Two equally large pieces of paperboard are added as top and bottom covers. The stack is then placed in a conditioning cabinet (400C/70% relative humidity) and a weight of 1 kg is attached. The test specimen remains in this atmosphere for 48 hours. For inspection, the weight is removed and the stack is examined for blocking. Blocking is said to have started when the adhesive film becomes tacky. If there is no sign of blocking, the weight is re-attached to the test specimen. The relative air humidity is then increased by followed by storage for another 48 hours.
This procedure is continued until blocking occurs.
The quantity applied represents the quantity of solids per unit area.
The pH value is determined with a glass electrode in accordance with DIN 53785/ISO 1148.
To determine gloss, an Erichsen surface coater and writing paper g/m 2 for example "Multi Bright", a product of Stora Fine Papier, NYMOLLA, SE) are required. A 40 pm thick, 6 cm wide strip of adhesive is applied by coating knife to a sheet of writing paper measuring 20 x 20 cm. It is important that the strip of adhesive is WO 00/27943 PCT/EP99/08106 applied without interruption in the direction of travel of the paper. After drying (ca. 15 minutes), the adhesive film is evaluated for gloss. The gloss is differentiated as follows: Standard very high gloss DH 4094 high gloss DH 4093 glossy DH 4084 mat A 4520 Gloss was always evaluated against one of the above standards.
To determine stay-flat behavior, a 40 pm thick, 6 cm wide strip of adhesive (55% dispersion) is applied by coating knife to a 20 x 20 cm sheet of writing paper (80 g/m 2 wood-free). It is important that the strip of adhesive is applied without interruption in the direction of travel of the paper. The adhesive is dried at 23°C/55% relative air humidity.
The stay-flat behavior should be evaluated after ca. 5 minutes, 1 hour and 24 hours. It is important to ensure that the coated papers are not exposed to circulated air. The evaluation should also include a direct comparison with a standard adhesive because the stay-flat behavior changes as a function of ambient temperatures and atmospheric humidity. The stay-flat behavior is differentiated according to the following criteria: paper stays flat paper curls slightly paper curls fairly sharply paper rolls up paper turns wavy paper develops folds Adhesin A 4520 of Henkel KGaA is used as a standard adhesive with very good stay-flat behavior. The stay-flat evaluation should be carried out at the same ambient temperature and atmospheric humidity.
WO 00/27943 PCT/EP99/08106 Other properties, such as color and the beginning of blocking, were in a favorable range.
Table 1. Characterization and processing/performance properties Example a) Example b) Characteristics: Viscosity [mPas] 6250 6400 pH value 4.0 4.1 Solids by weight] 56 57 Properties: Drying times [mins.] on paper 1.4 1.3 on glass 3.0 Setting time after remoistening [secs.] drying at 230 only 2.5 additional drying for 10 secs.
a) at 150 0 C 2.5 b) at 160°C 3 c) at 170 0 C d) at 180 0 C 2 e) at 190 0 C 2 f) at 200 0 C 2 a) There could be no question of wetting No water film was formed, only water droplets, as on siliconized paper for example. By contrast, the film of the adhesive according to the invention was completely covered with a film of water at all temperatures.
Claims (15)
1. A gumming adhesive based on a stabilized polyvinyl acetate dispersion, which is characterized by the following components: A) 35 to 45% by weight, based on the adhesive as a whole, of a copolymer of vinyl acetate and 25 to 50% by weight, based on the monomers as a whole, of at least one alkyl ester of fumaric, maleic, itaconic, crotonic, acrylic and/or methacrylic acid, the alkyl groups optionally being branched or unbranched and having to contain 4 to 18 carbon atoms, B) at least one protective colloid, namely a) 0 to 30% by weight, based on the adhesive as a whole, of a nonionic starch ether and/or b) 0 to 12% by weight, based on the gumming adhesive as a whole, of polyvinyl alcohol, C) 0.05 to 10% by weight of at least one surface-active agent.
2. The adhesive as claimed in claim 1, wherein the comonomer is an alkyl ester of maleic acid containing 4 to 8 carbon atoms.
3. The adhesive as claimed in claim 1, wherein the copolymer is a terpolymer of vinyl acetate and 25 to 50% by weight of a second and up to 10% by weight of a third comonomer.
4. The adhesive as claimed in claim 1, 2 or 3, wherein the protective colloid is a nonionic starch ether selected from the following group consisting of hydroxyethyl, hydroxypropyl and hydroxybutyl ether starch.
5. The adhesive as claimed in any one of claims 1 to 4, wherein the nonionic starch ether makes up from 15 to 25% by weight of the adhesive as a whole.
6. The adhesive as claimed in any one of claims 1 to 5, wherein the percentage polyvinyl alcohol content is 8 to 12% by weight based on the adhesive as a whole. 30
7. The adhesive as claimed in claim 6, wherein the percentage polyvinyl alcohol content is 10.5 to 12% by weight based on the adhesive as a whole. LibC/558488speci.doc id, a -k' 14
8. The adhesive as claimed in any one of the preceding claims, wherein the solids content is from 50 to 60% by weight based on the adhesive as a whole.
9. The adhesive as claimed in claim 8, wherein the solids content is from 55 to 60% by weight based on the adhesive as a whole.
A gumming adhesive based on a stabilized polyvinyl acetate dispersion substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples.
11. A process for the production of the adhesive as claimed in any one of the preceding claims, wherein the copolymerization of the vinyl acetate is carried out in the presence of the surface-active agent and the nonionic starch ether and/or polyvinyl alcohol.
12. The process as claimed in claim 11, wherein, on completion of the copolymerization, no aqueous polymer solution is added to the polyvinyl acetate dispersion.
13. The process as claimed in claim 12, wherein the aqueous polymer solution is polyvinyl alcohol or dextrin.
14. Use of a gumming adhesive as claimed in any one of claims 1 to for gumming in automatic inserting machines.
15. A process for the production of a gumming adhesive substantially as hereinbefore described with reference to any one of the examples but excluding the comparative examples. Use of an adhesive substantially as hereinbefore described with reference to any one of the examples but excluding the comparative 25 examples for gumming in automatic inserting machines. Dated 19 May, 2003 Henkel Kommanditgesellschaft auf Aktien Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON bC558488speci.doc LibC/558488speci.doc
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19850887 | 1998-11-05 | ||
DE19850887 | 1998-11-05 | ||
PCT/EP1999/008106 WO2000027943A1 (en) | 1998-11-05 | 1999-10-27 | Rubber adhesive based on a stabilized polyvinyl acetate dispersion |
Publications (2)
Publication Number | Publication Date |
---|---|
AU1266300A AU1266300A (en) | 2000-05-29 |
AU763054B2 true AU763054B2 (en) | 2003-07-10 |
Family
ID=7886706
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU12663/00A Ceased AU763054B2 (en) | 1998-11-05 | 1999-10-27 | Rubber adhesive based on a stabilized polyvinyl acetate dispersion |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1127097B1 (en) |
AT (1) | ATE274041T1 (en) |
AU (1) | AU763054B2 (en) |
DE (2) | DE59910303D1 (en) |
WO (1) | WO2000027943A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2006222333B2 (en) * | 2005-03-08 | 2011-06-30 | Henkel Kommanditgesellschaft Auf Aktien | Gum adhesive based on a filled polymer dispersion |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0705896A1 (en) * | 1994-10-03 | 1996-04-10 | National Starch and Chemical Investment Holding Corporation | Synthetic remoistenable adhesive compositions |
AU4301397A (en) * | 1996-09-10 | 1998-04-02 | Henkel Kommanditgesellschaft Auf Aktien | Use of an adhesive dispersion for gumming in inserting machines |
-
1999
- 1999-10-27 EP EP99955888A patent/EP1127097B1/en not_active Expired - Lifetime
- 1999-10-27 DE DE59910303T patent/DE59910303D1/en not_active Expired - Lifetime
- 1999-10-27 WO PCT/EP1999/008106 patent/WO2000027943A1/en active IP Right Grant
- 1999-10-27 AT AT99955888T patent/ATE274041T1/en not_active IP Right Cessation
- 1999-10-27 AU AU12663/00A patent/AU763054B2/en not_active Ceased
- 1999-10-28 DE DE19951803A patent/DE19951803A1/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0705896A1 (en) * | 1994-10-03 | 1996-04-10 | National Starch and Chemical Investment Holding Corporation | Synthetic remoistenable adhesive compositions |
AU4301397A (en) * | 1996-09-10 | 1998-04-02 | Henkel Kommanditgesellschaft Auf Aktien | Use of an adhesive dispersion for gumming in inserting machines |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2006222333B2 (en) * | 2005-03-08 | 2011-06-30 | Henkel Kommanditgesellschaft Auf Aktien | Gum adhesive based on a filled polymer dispersion |
Also Published As
Publication number | Publication date |
---|---|
AU1266300A (en) | 2000-05-29 |
DE59910303D1 (en) | 2004-09-23 |
EP1127097A1 (en) | 2001-08-29 |
WO2000027943A1 (en) | 2000-05-18 |
ATE274041T1 (en) | 2004-09-15 |
EP1127097B1 (en) | 2004-08-18 |
DE19951803A1 (en) | 2000-05-11 |
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