CA2026427A1 - Synthetic resin plastic suspension or dispersion for use as a fusion adhesive - Google Patents
Synthetic resin plastic suspension or dispersion for use as a fusion adhesiveInfo
- Publication number
- CA2026427A1 CA2026427A1 CA002026427A CA2026427A CA2026427A1 CA 2026427 A1 CA2026427 A1 CA 2026427A1 CA 002026427 A CA002026427 A CA 002026427A CA 2026427 A CA2026427 A CA 2026427A CA 2026427 A1 CA2026427 A1 CA 2026427A1
- Authority
- CA
- Canada
- Prior art keywords
- suspension
- weight
- dispersion
- water
- meltable
- 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.)
- Abandoned
Links
- 239000000725 suspension Substances 0.000 title claims abstract description 23
- 239000000853 adhesive Substances 0.000 title claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 16
- 239000006185 dispersion Substances 0.000 title claims abstract description 10
- 229920003023 plastic Polymers 0.000 title description 3
- 239000004033 plastic Substances 0.000 title description 3
- 239000000057 synthetic resin Substances 0.000 title description 3
- 229920003002 synthetic resin Polymers 0.000 title description 3
- 230000004927 fusion Effects 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 239000000088 plastic resin Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 229920001897 terpolymer Polymers 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000010557 suspension polymerization reaction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 12
- 238000000576 coating method Methods 0.000 description 10
- 239000002250 absorbent Substances 0.000 description 8
- 230000002745 absorbent Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000004831 Hot glue Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- -1 aliphatic dicarboxylic acids Chemical class 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004026 adhesive bonding Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 159000000011 group IA salts Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 241001502050 Acis Species 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001643597 Evas Species 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011093 chipboard Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002084 enol ethers Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003443 succinic acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—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
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- 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
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
ABSTRACT
This is the description of an adhesive used in the form of a watery suspension or dispersion which is painted or otherwise applied to the selected substrate, the water is either removed or the suspension is dried, and finally the bonding is attained through the application of heat. The suspension is made by subjecting acetic-acid vinyl ester, alpha-olefinic unsaturated systems and similar compounds as well as other substances to a suspension polymerization in water.
This is the description of an adhesive used in the form of a watery suspension or dispersion which is painted or otherwise applied to the selected substrate, the water is either removed or the suspension is dried, and finally the bonding is attained through the application of heat. The suspension is made by subjecting acetic-acid vinyl ester, alpha-olefinic unsaturated systems and similar compounds as well as other substances to a suspension polymerization in water.
Description
r'~~ :
~ 1 ~
SYNTHETIC RESIN_PLASTIC SUSPENSION
~ OR DISPERSIQ~EQ~_~5~ FUSIO~ A_HESIVE
-~ The invention concerns a water plastic 5 suspension or dispersion which can be used as a meltable ;
adhesive.
There are different systems among adhesives.
Dispersions and suspensions for adhesive and sealing applications usually contain polyvinyl alcohol or derivatives of cellulose as protective colloids; these substances are not meltable. Also the polymers which contain these protective colloids are practically not meltable, or their melting point is in the range of the decomposition temperature, so that a reversible change of condition is not possible.
The dry films of dispersions containing `~
protective colloids develop at best only a slight surface taak after being heated.
With the appropriate formulations and the use of 2~0 ~emulsifiers,~ finely~dispersed synthetic plastic resin ;dispers~ions with low polymerization grade can be obtained which are meltable, but at temperatures just above room temperature, the coatings made from these dispersions are 'not block- and~tack free.
2~5 ~ They have poor heat resistance and exposed to higher temperatures. ~hese products have a very low ;-viacosity after melting. With these types of coatlngs or ` films, porous substrates cannot be glued together since these polymers will soak into the substrates at temperatures above the activating/melting temperature.
From the point of view of Hotmelt adhesives, these adhesives are by definition meltable and contain for instance EVA, resins and waxes.
The melt viscosity and blocking properties can be sufficiently regulated by adjusting the formulation.
However, because of the polymer structure of these types of products a broad softening range is obtained so that the heat resistance of such an application (glued as described - in DIN 53 254) does not exceed a temperature of 70--80- C.
.
lOTheoretically it would be possible to overcome these disadvantages by using EVAs with a very low melt flow index. In practice however it is not possible to apply such highly viscous polymers as hotmelt adhesives in the desired thickness of < 200 ~m. This eliminates these lS products for the majority of uses because of their low heat ~ resistance. Hotmelt adhesives must be heated and melted in .~ vessels for a long period of time during their manufacture for optimum homogenization of the raw materials -, and -i before application - in order to attain optimum processing 20 properties. These procedures often lead to the thermal -~
degradatlon of these systems. -~;
Hotmelt adhesives based on fatty acid polyamides - i.e. the condensation products oP dimerized, higher unsaturated fatty acids and diamines or saturated ~` 25 polyesters - i.e. the condensation products of aromatic ,~ ,and/or aliphatic dicarboxylic acids and glycols and/or -~
other diols - will improve the heat stability, with ~; appropriate adjustment of the formulation, by approximately 15^C however, the high price of these products limits their ~ -use to exceptional cases, and the application technique becomes too complicatedj since at the required higher working temperatures the adhesives tend to degrade more rapidly on the use of a protective gas is necessary. `
:.~. ~ :. :
'~' ` '.'``'~"'':
~ s~
~-~
~ 1 ~
SYNTHETIC RESIN_PLASTIC SUSPENSION
~ OR DISPERSIQ~EQ~_~5~ FUSIO~ A_HESIVE
-~ The invention concerns a water plastic 5 suspension or dispersion which can be used as a meltable ;
adhesive.
There are different systems among adhesives.
Dispersions and suspensions for adhesive and sealing applications usually contain polyvinyl alcohol or derivatives of cellulose as protective colloids; these substances are not meltable. Also the polymers which contain these protective colloids are practically not meltable, or their melting point is in the range of the decomposition temperature, so that a reversible change of condition is not possible.
The dry films of dispersions containing `~
protective colloids develop at best only a slight surface taak after being heated.
With the appropriate formulations and the use of 2~0 ~emulsifiers,~ finely~dispersed synthetic plastic resin ;dispers~ions with low polymerization grade can be obtained which are meltable, but at temperatures just above room temperature, the coatings made from these dispersions are 'not block- and~tack free.
2~5 ~ They have poor heat resistance and exposed to higher temperatures. ~hese products have a very low ;-viacosity after melting. With these types of coatlngs or ` films, porous substrates cannot be glued together since these polymers will soak into the substrates at temperatures above the activating/melting temperature.
From the point of view of Hotmelt adhesives, these adhesives are by definition meltable and contain for instance EVA, resins and waxes.
The melt viscosity and blocking properties can be sufficiently regulated by adjusting the formulation.
However, because of the polymer structure of these types of products a broad softening range is obtained so that the heat resistance of such an application (glued as described - in DIN 53 254) does not exceed a temperature of 70--80- C.
.
lOTheoretically it would be possible to overcome these disadvantages by using EVAs with a very low melt flow index. In practice however it is not possible to apply such highly viscous polymers as hotmelt adhesives in the desired thickness of < 200 ~m. This eliminates these lS products for the majority of uses because of their low heat ~ resistance. Hotmelt adhesives must be heated and melted in .~ vessels for a long period of time during their manufacture for optimum homogenization of the raw materials -, and -i before application - in order to attain optimum processing 20 properties. These procedures often lead to the thermal -~
degradatlon of these systems. -~;
Hotmelt adhesives based on fatty acid polyamides - i.e. the condensation products oP dimerized, higher unsaturated fatty acids and diamines or saturated ~` 25 polyesters - i.e. the condensation products of aromatic ,~ ,and/or aliphatic dicarboxylic acids and glycols and/or -~
other diols - will improve the heat stability, with ~; appropriate adjustment of the formulation, by approximately 15^C however, the high price of these products limits their ~ -use to exceptional cases, and the application technique becomes too complicatedj since at the required higher working temperatures the adhesives tend to degrade more rapidly on the use of a protective gas is necessary. `
:.~. ~ :. :
'~' ` '.'``'~"'':
~ s~
~-~
In systems based on solvents, the dissolution with organic solvents makes it possible to manufacture the desired coatings for later use, however the use of organic solvents makes this procedure so expensive, that it is only used in exceptional cases. Also the use of solvents should be avoided at all cost for environmental reasons, particularly since not just the application procedure is ....
very expensive - i.e. the protective measures to avoid explosion.
:~
The purpose of the present invention is to if~ propose an adhesive which does not have these disadvantages, does not require expensive devices for its manufacture and processing, and which can be handled and used in an environmentally safe manner.
These problems are solved with the meltable adhesive described in the claims.
According to the invention the application is ,~; made out of the watery phase, which is simpler and less expensive than the application in the molten or dissolved phase.
The watery synthetic plastic resin suspension or disperaion has the following advantages:
The suspension contains water and not an environmentally hazardous solvent.
- The applied and dried coating is tack- and block free at room temperature.
,r5 ' : ~
he polymer can be molten to a mass with real measurable rheological properties by means of a heated ~; press or also in small melting containers.
-~
~ ` ~
, - The melting range can be adjusted according to the monomer compound and the degree of polymerization.
- The synthetic plastic resin of the dispersion does not soak into porous absorbent substrate when applied because the size of the particles is controlled, but instead remains in the area where it is needed for the gluing process.
- The adhesive provides heat resistance values which cannot be attained with conventional hotmelt adhesives.
- The adhesive does not need to endure long temperature exposure during the manufacturing process and during the application, as is the case with hotmelt adhesives, and therefore does not tend to degrade.
;~ 15 The suspension/dispersion forms a tack- and `~block free coating at room temperature after it is applied ;
to any smooth, absorbent or non-absorbent substrate after the water in the mixture has been separated or evaporated.
; When heated, the coating melts forming a sticky, highly viscous liquid with very good cohesion and adhesion.
The molten adhesive film is a genuine molten mass with a viscosity, depending on the formulation of between 50,000 -1,000,000 mPas at approximately 220- C. The melt flow indexes of the water-free polymers, depending on the ~; 25 formulation and according to DIN 53 735 are between 0.1 to 400 g/10 min. The gluing process, the properties attained ; during the gluing process only take place because of physical processes (change of state), which does not exclude that if reactive monomers are used, a chemical reaction like polymerization could take place. According to the known procedure of the suspension of polymerization, the monomers are emulsified in water with the alpha- -olefinic unsaturated compounds under the effect of shearing stresses, and are polymerized with the help of a monomer soluble initiators.
The following can be used as olefinic unsaturated compounds: vinyl esters or organic carboxylic acid whose carbon structure contains 1-20 C-atoms; esters of acrylic or methacrylic acid with C1- to C20 alcohols, alipathic or preferably aromatic alpha-beta unsaturated hydrocarbons, mono and/or di-esters of the cis or trans-dibutene acid, alpha-beta unsaturated carboxylic acids as well as their derivatives. Preferred are acetic acid, `~:
` propionic acid, isononic aci~, dodecane acid vinyl ester, styrene, vinyl toluene, cis-dodecane acid butyl ester, acrylic acid or crotonic acid.
1 ~ .
lS In addition to the mentioned alpha-olefinic unsaturated compounds, also polyfunctional monomers can be used, which allow a partial cross-linking in polymers.
The following are examples of that type of monomers: Esters from unsaturated carboxylic acids with alcohols which contain functional groups, such as glycidyl alcohol, several function alcohols such as ethylene- -~
propylene or butylene glycol, vinyl and allyl compounds as well as modlfied acryl amides.
Dispersing agents, sometimes also called 2S suspension stabilizers, are used in the manufacture of the plastic resin suspension, some for instance based on fine, insoluble, mostly inorganic substances such as kaolin, talcum, bentonite, montmorillonite, metal hydroxides or phosphates, or based on highly molecular, organic substances which are water soluble but not soluble in monomers - i.e. cellulose derivatives, starch ether, polyvinyl alcohols or their co-polymers, polyacrylic acid or of poly-methacryIic acid salts and their derivatives, butylene acid derivatives, polyvinyl pyrrolidine or their co-polymers, polystyrene or its co-polymers, as well as different condensation resins.
:;
In order to increase stability, and to control the size of the particles, modulators and surface active ~;
substances are added such as alkaline salts of alkane and alkylaren sulphonic acids, alkaline salts of alkyl sulphates with long alkyl groups, alkaline salts of fatty acis, ethoxilated products of the above mentioned surface active substances, succinic acid derivatives, ethoxilated fatty amines.
The molecular weights of the polymers can be regulated by means of regulators such as aldehydes, ketones, thiols, terpenes or cyclo-alipathic enol ether. -The monomer soluble catalysts used are peroxides - -~
or azo compounds.
; In addition to being influenced by the dispersing agent, the size of the forming beads can also be influenced by the stirring speed and by the geometry of the r~eartor~vessel The size of the particles varies according - ;-to~the application between 0.5 ~m and up to several mm.
Depending~on the variation one can obtain polymers which tend~to~phaae~separation or products which resemble stable finely dispersed dispers1ons~
The suspension/dispersion prepared by means of polymerization can be used directly for the gluing and coating applications. Compounding with thixotropic agents ~-or othor bin~dlng substances is also possible. -The~suspension resulting directly from the ~` ~ polymerization or the prepared suspension can be applied by means of a coating bar, by roller application, with low pressure~or roller machines, using nozzle application by ` spraying or dipping or also using a transfer process, to ~;~
~ .
~.
any smooth, absorbent or non-absorbent sur~aces such as pl~stic foils, paper, sheets impregnated with synthetic resins, wood or chip board substrates; fleece made ~f synthetic or natural fibres; foam materials, e.g. based on PE, PUR, PVC - or to metals.
~ ecause the particle size is adjusted during the polymerization process, the synthetic plastic resin soaks only to a small extent into any eventual absorbent substrate. After the drying or the removal of the water a synthetic resin film remains with low cohesion and adhesion. The water can be removed by evaporation, e.g.
through a change of state, for instance in a drying tunnel, or by means of a suction procedure similar to a filtration ; procedure. Contrary to the systems known to this date, ~- lS after the application and drying a block free coating is obtained. After heating the polymer with tempered presses, hot rollers, calenders or heated air, the previously block free surface melts forming an adhesive of high cohesion and good adhesion. As long as the adhesive remains in liquid state the coated substrate can be glued to other parts/surfaces simultaneously, or immediately after the heating procésses.
..,.. ,~
EXAMPLE
650 g deionized water is placed in a 1.5 1 laboratory vessel which can be heated or cooled, and which i equipped with a condenser, an agitator and an apportioning device, and 9.0 g of polyacrylic acid - a 50%
paste in 60 crystal oil (molecular weight 2,800,000) is added while stirring vigorously. After 10 minutes of homogenization the mixture is brought to a pH value of 7 .~ ~
~-~ with concentrated ammonia.
:
~' ~ '. ' ' . .
1~ ~ ."V~"
~ - 8 -~.~
In another mixing container 220 g of acetic acid vinyl ester are mixed with gO g of acrylic acid butyl-ester, 0.6 g of dibenzoyl peroxide and 15 g of ethoxilated fatty amine C1gH37N-(CH2CH20-)x, yHr where x+y= 20 (molecular weight 1149) are dissolved in the monomers. The monomer mixture is pre-emulsified in the reactor in the above mentioned watery solution at room temperature and under vigorous stirring. After adding another 0.1 g of dibenzoyl peroxide, the mixture is heated to the point of slight reflux while stirring, 0.1 g dibenzoyl peroxide are added to the reaction mixture three times at intervals of 2 hours each time. After the completion of the reflux (approximately 6 hours~ the mixture is left for 1 hour at 80 C for the final polymerization of the preparation, while ~ 15 heat is being supplied from an outside source. In order to `- -~ adjust the pH-value, 2 ml of concentrated ammonia added after the suspension polymer has cooled down. A synthetic ~ -~ plastic resin suspension is obtained which has a solid -~-`~ content of approximately 28%, a viscosity of approximately 1000 mPas, a neutral pH-value, and which tends to precipitate. However, the precipitate may be stirred again resulting in a preparation with the same properties. The ~` homogenized mixture can be applied onto paper foil with a 200;~m spiral coating bar. After the water had dried up, ; 2S the coatlng remained totally block free following a test commonly conducted in this industry which consists of the following: 10 round, coated, dry foil cutouts each with a surface of 100 cm2 are stacked on each other for 72 hours under a load of 5 kg. After the weights were removed the ; ~ ~ 30 fi ~ were not sticky or glued together.
y means of tempered presses the coated foils can be pressed onto an absorbent or non absorbent substrate with their;coated sides facing the substrate, at a ~` ~ temperature of 160-C and a press time of 3 seconds. During this procedure the coating melts and the foil is glued to `,'' ~ ,~4~ ,. ' ~ S~
the substrate, showing excellent adhesion, cohesion and heat resistance.
: Coated, dried plastic films or separated, dried suspension polymers will melt in an oven at a temperature S of 250 C forming a liquid flowing mass.
~: A viscosity of 800,000 mPas at 220 C was :~ determined using the Thermosel ~VT Brookfield viscosimeter. ::
-. :
~""~
very expensive - i.e. the protective measures to avoid explosion.
:~
The purpose of the present invention is to if~ propose an adhesive which does not have these disadvantages, does not require expensive devices for its manufacture and processing, and which can be handled and used in an environmentally safe manner.
These problems are solved with the meltable adhesive described in the claims.
According to the invention the application is ,~; made out of the watery phase, which is simpler and less expensive than the application in the molten or dissolved phase.
The watery synthetic plastic resin suspension or disperaion has the following advantages:
The suspension contains water and not an environmentally hazardous solvent.
- The applied and dried coating is tack- and block free at room temperature.
,r5 ' : ~
he polymer can be molten to a mass with real measurable rheological properties by means of a heated ~; press or also in small melting containers.
-~
~ ` ~
, - The melting range can be adjusted according to the monomer compound and the degree of polymerization.
- The synthetic plastic resin of the dispersion does not soak into porous absorbent substrate when applied because the size of the particles is controlled, but instead remains in the area where it is needed for the gluing process.
- The adhesive provides heat resistance values which cannot be attained with conventional hotmelt adhesives.
- The adhesive does not need to endure long temperature exposure during the manufacturing process and during the application, as is the case with hotmelt adhesives, and therefore does not tend to degrade.
;~ 15 The suspension/dispersion forms a tack- and `~block free coating at room temperature after it is applied ;
to any smooth, absorbent or non-absorbent substrate after the water in the mixture has been separated or evaporated.
; When heated, the coating melts forming a sticky, highly viscous liquid with very good cohesion and adhesion.
The molten adhesive film is a genuine molten mass with a viscosity, depending on the formulation of between 50,000 -1,000,000 mPas at approximately 220- C. The melt flow indexes of the water-free polymers, depending on the ~; 25 formulation and according to DIN 53 735 are between 0.1 to 400 g/10 min. The gluing process, the properties attained ; during the gluing process only take place because of physical processes (change of state), which does not exclude that if reactive monomers are used, a chemical reaction like polymerization could take place. According to the known procedure of the suspension of polymerization, the monomers are emulsified in water with the alpha- -olefinic unsaturated compounds under the effect of shearing stresses, and are polymerized with the help of a monomer soluble initiators.
The following can be used as olefinic unsaturated compounds: vinyl esters or organic carboxylic acid whose carbon structure contains 1-20 C-atoms; esters of acrylic or methacrylic acid with C1- to C20 alcohols, alipathic or preferably aromatic alpha-beta unsaturated hydrocarbons, mono and/or di-esters of the cis or trans-dibutene acid, alpha-beta unsaturated carboxylic acids as well as their derivatives. Preferred are acetic acid, `~:
` propionic acid, isononic aci~, dodecane acid vinyl ester, styrene, vinyl toluene, cis-dodecane acid butyl ester, acrylic acid or crotonic acid.
1 ~ .
lS In addition to the mentioned alpha-olefinic unsaturated compounds, also polyfunctional monomers can be used, which allow a partial cross-linking in polymers.
The following are examples of that type of monomers: Esters from unsaturated carboxylic acids with alcohols which contain functional groups, such as glycidyl alcohol, several function alcohols such as ethylene- -~
propylene or butylene glycol, vinyl and allyl compounds as well as modlfied acryl amides.
Dispersing agents, sometimes also called 2S suspension stabilizers, are used in the manufacture of the plastic resin suspension, some for instance based on fine, insoluble, mostly inorganic substances such as kaolin, talcum, bentonite, montmorillonite, metal hydroxides or phosphates, or based on highly molecular, organic substances which are water soluble but not soluble in monomers - i.e. cellulose derivatives, starch ether, polyvinyl alcohols or their co-polymers, polyacrylic acid or of poly-methacryIic acid salts and their derivatives, butylene acid derivatives, polyvinyl pyrrolidine or their co-polymers, polystyrene or its co-polymers, as well as different condensation resins.
:;
In order to increase stability, and to control the size of the particles, modulators and surface active ~;
substances are added such as alkaline salts of alkane and alkylaren sulphonic acids, alkaline salts of alkyl sulphates with long alkyl groups, alkaline salts of fatty acis, ethoxilated products of the above mentioned surface active substances, succinic acid derivatives, ethoxilated fatty amines.
The molecular weights of the polymers can be regulated by means of regulators such as aldehydes, ketones, thiols, terpenes or cyclo-alipathic enol ether. -The monomer soluble catalysts used are peroxides - -~
or azo compounds.
; In addition to being influenced by the dispersing agent, the size of the forming beads can also be influenced by the stirring speed and by the geometry of the r~eartor~vessel The size of the particles varies according - ;-to~the application between 0.5 ~m and up to several mm.
Depending~on the variation one can obtain polymers which tend~to~phaae~separation or products which resemble stable finely dispersed dispers1ons~
The suspension/dispersion prepared by means of polymerization can be used directly for the gluing and coating applications. Compounding with thixotropic agents ~-or othor bin~dlng substances is also possible. -The~suspension resulting directly from the ~` ~ polymerization or the prepared suspension can be applied by means of a coating bar, by roller application, with low pressure~or roller machines, using nozzle application by ` spraying or dipping or also using a transfer process, to ~;~
~ .
~.
any smooth, absorbent or non-absorbent sur~aces such as pl~stic foils, paper, sheets impregnated with synthetic resins, wood or chip board substrates; fleece made ~f synthetic or natural fibres; foam materials, e.g. based on PE, PUR, PVC - or to metals.
~ ecause the particle size is adjusted during the polymerization process, the synthetic plastic resin soaks only to a small extent into any eventual absorbent substrate. After the drying or the removal of the water a synthetic resin film remains with low cohesion and adhesion. The water can be removed by evaporation, e.g.
through a change of state, for instance in a drying tunnel, or by means of a suction procedure similar to a filtration ; procedure. Contrary to the systems known to this date, ~- lS after the application and drying a block free coating is obtained. After heating the polymer with tempered presses, hot rollers, calenders or heated air, the previously block free surface melts forming an adhesive of high cohesion and good adhesion. As long as the adhesive remains in liquid state the coated substrate can be glued to other parts/surfaces simultaneously, or immediately after the heating procésses.
..,.. ,~
EXAMPLE
650 g deionized water is placed in a 1.5 1 laboratory vessel which can be heated or cooled, and which i equipped with a condenser, an agitator and an apportioning device, and 9.0 g of polyacrylic acid - a 50%
paste in 60 crystal oil (molecular weight 2,800,000) is added while stirring vigorously. After 10 minutes of homogenization the mixture is brought to a pH value of 7 .~ ~
~-~ with concentrated ammonia.
:
~' ~ '. ' ' . .
1~ ~ ."V~"
~ - 8 -~.~
In another mixing container 220 g of acetic acid vinyl ester are mixed with gO g of acrylic acid butyl-ester, 0.6 g of dibenzoyl peroxide and 15 g of ethoxilated fatty amine C1gH37N-(CH2CH20-)x, yHr where x+y= 20 (molecular weight 1149) are dissolved in the monomers. The monomer mixture is pre-emulsified in the reactor in the above mentioned watery solution at room temperature and under vigorous stirring. After adding another 0.1 g of dibenzoyl peroxide, the mixture is heated to the point of slight reflux while stirring, 0.1 g dibenzoyl peroxide are added to the reaction mixture three times at intervals of 2 hours each time. After the completion of the reflux (approximately 6 hours~ the mixture is left for 1 hour at 80 C for the final polymerization of the preparation, while ~ 15 heat is being supplied from an outside source. In order to `- -~ adjust the pH-value, 2 ml of concentrated ammonia added after the suspension polymer has cooled down. A synthetic ~ -~ plastic resin suspension is obtained which has a solid -~-`~ content of approximately 28%, a viscosity of approximately 1000 mPas, a neutral pH-value, and which tends to precipitate. However, the precipitate may be stirred again resulting in a preparation with the same properties. The ~` homogenized mixture can be applied onto paper foil with a 200;~m spiral coating bar. After the water had dried up, ; 2S the coatlng remained totally block free following a test commonly conducted in this industry which consists of the following: 10 round, coated, dry foil cutouts each with a surface of 100 cm2 are stacked on each other for 72 hours under a load of 5 kg. After the weights were removed the ; ~ ~ 30 fi ~ were not sticky or glued together.
y means of tempered presses the coated foils can be pressed onto an absorbent or non absorbent substrate with their;coated sides facing the substrate, at a ~` ~ temperature of 160-C and a press time of 3 seconds. During this procedure the coating melts and the foil is glued to `,'' ~ ,~4~ ,. ' ~ S~
the substrate, showing excellent adhesion, cohesion and heat resistance.
: Coated, dried plastic films or separated, dried suspension polymers will melt in an oven at a temperature S of 250 C forming a liquid flowing mass.
~: A viscosity of 800,000 mPas at 220 C was :~ determined using the Thermosel ~VT Brookfield viscosimeter. ::
-. :
~""~
Claims (2)
1. Water synthetic plastic resin suspension or dispersion of homo-, co-, or terpolymers containing alpha-olefinic monomers mixed with protective colloids and surface active substances to be used as meltable adhesives, characterized by the fact that the following mixture:
48 - 98 Weight - % acetic acid vinyl ester 0 - 50 Weight - % other alpha-olefinic unsaturated systems 1 - 10 Weight - % dispersing agents 0 - 10 Weight - % protective colloids 1 - 10 Weight - % surface active substances are polymerized in a watery suspension procedure, and that the suspension can be used as such.
48 - 98 Weight - % acetic acid vinyl ester 0 - 50 Weight - % other alpha-olefinic unsaturated systems 1 - 10 Weight - % dispersing agents 0 - 10 Weight - % protective colloids 1 - 10 Weight - % surface active substances are polymerized in a watery suspension procedure, and that the suspension can be used as such.
2. Meltable adhesives according to claim 1, characterized by the fact that the synthetic plastic resin suspension can be applied to surfaces by painting, spraying, pressing, wiping, dipping or by using the transfer procedure, forming a block free meltable adhesive after the water has dried up or has been absorbed.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEEP89118181.0 | 1989-09-30 | ||
EP89118181A EP0420998B1 (en) | 1989-09-30 | 1989-09-30 | Aqueous resin suspension or dispersion, and its use as a melt adhesive |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2026427A1 true CA2026427A1 (en) | 1991-03-31 |
Family
ID=8201969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002026427A Abandoned CA2026427A1 (en) | 1989-09-30 | 1990-09-27 | Synthetic resin plastic suspension or dispersion for use as a fusion adhesive |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0420998B1 (en) |
AT (1) | ATE139786T1 (en) |
CA (1) | CA2026427A1 (en) |
DE (1) | DE58909696D1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5292844A (en) * | 1991-05-22 | 1994-03-08 | Minnesota Mining And Manufacturing Company | Vinyl acetate modified suspension polymer beads, adhesives made therefrom and a method of making |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005039830B4 (en) * | 2005-08-22 | 2020-12-17 | Endress+Hauser SE+Co. KG | Method of joining two elements by means of an adhesive |
DE102006037317A1 (en) | 2006-08-08 | 2008-02-14 | Celanese Emulsions Gmbh | Vinyl ester copolymer dispersions, process for their preparation and use |
DE102006037318A1 (en) * | 2006-08-08 | 2008-02-14 | Celanese Emulsions Gmbh | Method of applying a dispersion adhesive by means of nozzle application and use of dispersion adhesives |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3856734A (en) * | 1971-05-03 | 1974-12-24 | Air Prod & Chem | Aqueous emulsion of interpolymer of vinyl acetate n-methylol acrylamide and acrylic acid |
US4113540A (en) * | 1977-01-21 | 1978-09-12 | Celanese Corporation | Use of multifunctional monomers in the preparations of emulsions to be used in adhesives |
-
1989
- 1989-09-30 AT AT89118181T patent/ATE139786T1/en not_active IP Right Cessation
- 1989-09-30 DE DE58909696T patent/DE58909696D1/en not_active Expired - Fee Related
- 1989-09-30 EP EP89118181A patent/EP0420998B1/en not_active Expired - Lifetime
-
1990
- 1990-09-27 CA CA002026427A patent/CA2026427A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5292844A (en) * | 1991-05-22 | 1994-03-08 | Minnesota Mining And Manufacturing Company | Vinyl acetate modified suspension polymer beads, adhesives made therefrom and a method of making |
Also Published As
Publication number | Publication date |
---|---|
EP0420998A1 (en) | 1991-04-10 |
DE58909696D1 (en) | 1996-08-01 |
ATE139786T1 (en) | 1996-07-15 |
EP0420998B1 (en) | 1996-06-26 |
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FZDE | Discontinued |